WO2026034603A1 - Light-transmitting absorption filter, organic electroluminescence display element, and organic electroluminescence display device - Google Patents

Light-transmitting absorption filter, organic electroluminescence display element, and organic electroluminescence display device

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Publication number
WO2026034603A1
WO2026034603A1 PCT/JP2025/028193 JP2025028193W WO2026034603A1 WO 2026034603 A1 WO2026034603 A1 WO 2026034603A1 JP 2025028193 W JP2025028193 W JP 2025028193W WO 2026034603 A1 WO2026034603 A1 WO 2026034603A1
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WO
WIPO (PCT)
Prior art keywords
group
light
layer
laminate
wavelength
Prior art date
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Pending
Application number
PCT/JP2025/028193
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French (fr)
Japanese (ja)
Inventor
伸隆 深川
匡広 渥美
隆宏 小倉
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2026034603A1 publication Critical patent/WO2026034603A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/86Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30Devices specially adapted for multicolour light emission
    • H10K59/38Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to a light-transmitting/absorbing filter, an organic electroluminescent display element, and an organic electroluminescent display device.
  • OLED organic electroluminescence
  • inorganic electroluminescence display devices inorganic EL display devices
  • liquid crystal display devices have been used as image display devices.
  • Liquid crystal display devices are becoming more and more popular as space-saving, low-power image display devices. Because the liquid crystal panel that displays images is a non-emissive element, a liquid crystal display device is equipped with a backlight unit that is placed behind the liquid crystal panel and supplies light to the liquid crystal panel.
  • OLED display devices also referred to as "organic EL display devices" are devices that display images by utilizing the spontaneous emission of OLED elements.
  • OLED display devices are being actively researched and developed as next-generation display devices due to their flexibility.
  • Inorganic EL display devices are devices that display images by utilizing the spontaneous emission of inorganic EL elements instead of the OLED elements used in OLED display devices as fluorescent materials. Recent research has raised hopes that inorganic EL display devices will be superior to OLED display devices in terms of larger screens and longer life.
  • Patent Document 1 discloses a method of preventing reflection of external light without reducing the transmittance of display light by combining a plurality of dyes with different maximum absorption wavelengths.
  • light-absorbing filter incorporated into an image display device As another form of light-absorbing filter incorporated into an image display device, research is also being conducted on optical filters that have both light-absorbing portions with a light-absorbing effect and portions where light absorption has been eliminated (hereinafter simply referred to as "light-absorbency-eliminated portions") by eliminating the light-absorbency in desired portions.
  • light-absorbency-eliminated portions optical filters that have both light-absorbing portions with a light-absorbing effect and portions where light absorption has been eliminated (hereinafter simply referred to as "light-absorbency-eliminated portions" by eliminating the light-absorbency in desired portions.
  • non-light-emitting portions (portions from which display light is not emitted) of OLED display devices have metal wiring or the like arranged therein, and therefore often have a higher reflectance than light-emitting portions (portions from which display light is emitted).
  • Patent Document 2 describes a light-absorbing filter containing a resin, a compound having an acid group, a compound that forms a hydrogen bond with the compound having an acid group and generates radicals upon irradiation with ultraviolet light, and a dye having a main absorption wavelength band in the range of 400 to 700 nm.
  • Patent Document 2 The light-absorbing filter described in Patent Document 2 is said to exhibit a high decolorization rate upon ultraviolet irradiation, and to exhibit high decolorization performance with almost no absorption (hereinafter also referred to as "secondary absorption") resulting from a new colored structure associated with decomposition of the dye upon ultraviolet irradiation.
  • Patent Document 3 also describes a light-absorbing filter containing a resin, a dye having a main absorption wavelength band in the range of 400 to 700 nm, and a compound that generates radicals upon ultraviolet irradiation, wherein the dye includes at least one of an azo dye represented by any one of general formulas (i) to (iv) and an indoaniline dye represented by general formula (v).
  • Patent Document 4 discloses a configuration in which, in a multicolor light-emitting organic EL display device, magenta color filters (first dimming layers) are arranged on blue light-emitting sections, red light-emitting sections, and non-light-emitting sections, and the magenta color filters are not arranged on green light-emitting sections, and further, first dimming layers that have selective absorption properties for light of wavelengths intermediate between red light and green light (specifically, the wavelength at which the transmittance is at a minimum exists in the range of 580 to 600 nm) are arranged on the blue light-emitting sections, red light-emitting sections, green light-emitting sections, and non-light-emitting sections.
  • magenta color filters first dimming layers
  • the light-absorbing filter described in Patent Document 1 has a problem in that the transmittance of display light is impaired when the absorbance is increased to the point where reflection of external light can be sufficiently suppressed. Also, the methods described in Patent Documents 2 and 3 do not sufficiently suppress reflection of external light caused by light-emitting sections in display devices, and improvements have been desired.
  • OLED display devices having a microcavity structure can improve the color purity of display light, they are known to have high viewing angle dependency, resulting in significant color changes depending on the viewing angle.
  • the multicolor light-emitting organic EL display device described in Patent Document 4 shows a certain improvement effect in reducing color changes due to viewing angle, but has a problem in that it does not sufficiently suppress the reflection of blue external light, resulting in a change in the color of the reflected light compared to a display that does not contain a dye (the color of the reflected light deviates from neutral).
  • the present invention aims to provide a light-transmitting-absorbing filter that, when incorporated into a display device, ensures the desired transmittance of display light; when incorporated into a display device, it suppresses external light reflection and also suppresses changes in the color of reflected light compared to when the filter does not contain a dye (hereinafter referred to as "the color of reflected light is adjusted to be neutral"), and suppresses changes in the color of display light compared to when the filter does not contain a dye (hereinafter referred to as "the color of display light is adjusted to be neutral”); an organic electroluminescent display element including this light-transmitting-absorbing filter; and an organic electroluminescent display device equipped with this light-transmitting-absorbing filter or organic electroluminescent display element.
  • the inventors conducted extensive research and discovered that by configuring a light-transmitting/absorbing filter that exhibits the desired high light transmittance, having a first light-transmitting/absorbing section whose transmittance at specific wavelengths is equal to or greater than a specific value, and a second light-transmitting/absorbing section whose chromaticity satisfies a specific relationship with the first light-transmitting/absorbing section, it is possible to suppress external light reflection when incorporated into a display device, and further adjust the color of both the reflected light and the displayed light to be neutral.
  • the present invention was completed after further research based on this finding.
  • ⁇ 1> having a first light-transmitting-absorbing portion and a second light-transmitting-absorbing portion;
  • the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm of the first light transmitting/absorbing site each satisfy the following relationships:
  • T(460) ⁇ 30% T(530) ⁇ 40% T(620) ⁇ 30% ⁇ 2> The light transmission-absorption filter according to ⁇ 1>, wherein a * and b * of the transmitted light of the first light transmission-absorption site satisfy the following relationship: ⁇ 20.0 ⁇ a * ⁇ +20.0 ⁇ 20.0 ⁇ b * ⁇ +20.0 ⁇ 3>
  • ⁇ 4> ⁇ 1> ⁇ 2>
  • An organic electroluminescence display element comprising the light-transmitting/absorbing filter according to any one of ⁇ 1> to ⁇ 2>.
  • the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation, the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order;
  • the organic electroluminescent display element according to ⁇ 4> wherein a distance d between the laminate III and the light-emitting element layer, an average area S of each light-emitting element constituting the light-emitting element layer, and an average area Sf of the first light-transmitting/absorbing portion located directly above each light-emitting element satisfy the relationship of the following formulas (1) and (2):
  • Formula (1) 0.6 ⁇ d/ ⁇ S ⁇ 7.5
  • the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing
  • substituents, etc. when there are multiple substituents or linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol or formula, or when multiple substituents, etc. are specified simultaneously, unless otherwise specified, the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. Furthermore, when multiple substituents, etc. are adjacent to each other (particularly when adjacent), they may be linked to each other to form a ring, unless otherwise specified. Furthermore, unless otherwise specified, rings, such as alicyclic rings, aromatic rings, and heterocyclic rings, may be further condensed to form a condensed ring.
  • any of the upper and lower limits can be appropriately combined to form a specific numerical range.
  • the upper and lower limits forming the numerical range are not limited to the combination of the specific upper and lower limits written before and after "to” as a specific numerical range, but can be a numerical range obtained by appropriately combining the upper and lower limits of each numerical range.
  • a numerical range expressed using "to” means a range that includes the numerical values written before and after "to” as the upper and lower limits.
  • the term "composition” includes not only a mixture in which the component concentrations are constant (each component is uniformly dispersed), but also a mixture in which the component concentrations vary within a range that does not impair the intended function.
  • the term “laminate” includes a form in which each layer is laminated directly or via another layer, as well as a form in which each layer is bonded to form a laminate structure.
  • having a main absorption wavelength band in the wavelength range of XX to YY nm means that the wavelength showing maximum absorption (i.e., the maximum absorption wavelength) is present in the wavelength range of XX to YY nm.
  • the entire absorption band including this wavelength may be within the above wavelength range, or may extend outside the above wavelength range.
  • the maximum absorption wavelength showing the greatest absorbance referred to as the "maximum maximum absorption wavelength” in the present invention
  • maximum absorption wavelengths other than the maximum maximum absorption wavelength may be present either inside or outside the above wavelength range of XX to YY nm.
  • resin when the term "resin” is simply mentioned, it includes elastomers.
  • (meth)acrylate refers to either or both of acrylate and methacrylate
  • (meth)acrylic acid refers to either or both of acrylic acid and methacrylic acid
  • (meth)acryloyl refers to either or both of acryloyl and methacryloyl.
  • the light transmission-absorption filter of the present invention is a light transmission-absorption filter that ensures a desired transmittance of display light when incorporated into a display device, and when incorporated into a display device, it suppresses reflection of external light and also adjusts the color of both the reflected light and the display light to be neutral. Furthermore, the organic electroluminescent display element of the present invention and the organic electroluminescent display device of the present invention are equipped with the light transmission-absorption filter constituting them, which ensures a desired transmittance of display light, suppresses reflection of external light, and can adjust the color of both the reflected light and the display light to be neutral.
  • FIG. 1 is a schematic cross-sectional view showing an outline of a light transmission-absorption filter I, which is one embodiment of the light transmission-absorption filter of the present invention, and an outline of the positional relationship with a light emitting element.
  • the light transmission-absorption filter of the present invention has a first light transmission-absorption region and a second light transmission-absorption region, the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm of the first light transmitting/absorbing site each satisfy the following relationships,
  • This is a light-transmitting-absorbing filter in which the first light-transmitting-absorbing portion and the second light-transmitting-absorbing portion satisfy a relationship in which the sign of at least one of the values a * and b * in the L * a * b * color space of transmitted light is opposite.
  • the light transmission-absorption filter of the present invention may be in the form of a film having a certain thickness, and may be a film that stands on its own, or may be a film that is disposed on a substrate film, etc. When the film-shaped light transmission-absorption filter of the present invention is observed in the thickness direction, it is sufficient that a first transmission portion and a second transmission portion are present. Furthermore, the light transmission-absorption filter of the present invention may have a single-layer structure or a multi-layer structure of two or more layers, as long as it has the first light transmission-absorption region (hereinafter also simply referred to as the "first region”) and the second light transmission-absorption region (hereinafter also simply referred to as the "second region").
  • first region hereinafter also simply referred to as the "first region”
  • second region the second light transmission-absorption region
  • a multi-layer structure of two or more layers is preferred because it makes it easier to realize the first region and the second region having different light transmission-absorption properties.
  • the light transmission-absorption filter of the present invention having a multi-layer structure of two or more layers, a structure including two or more layers with different light absorption-transmission properties is preferred.
  • preferred examples include light transmission-absorption filter I obtained by mask-exposing a laminate including a wavelength-selective absorption layer and a light-absorbing-disappearing layer described below with ultraviolet light irradiation, and light transmission-absorption filter II including a laminate obtained by mask-exposing a laminate including a light-absorbing-disappearing layer with ultraviolet light irradiation, and a laminate including a wavelength-selective absorption layer.
  • the light transmission-absorption filter of the present invention may have light transmission-absorption regions having different light transmission-absorption characteristics, defined as the first region and the second region.
  • the light transmission-absorption filter of the present invention is used by arranging the first region on a light-emitting region (also simply referred to as a "light-emitting region” in the present invention) in the display region of an organic electroluminescence display element (OLED display element), and the second region on a non-light-emitting region (such as a substrate, thin metal wires (metal wiring), and a black bank (black partition wall); also simply referred to as a "non-light-emitting region” in the present invention) in the display region of the OLED display element.
  • a light-emitting region also simply referred to as a "light-emitting region” in the present invention
  • OLED display element organic electroluminescence display element
  • the light transmission-absorption filter of the present invention may further have other light transmission-absorption regions (hereinafter referred to as "other regions") having light transmission-absorption characteristics different from those of the first region and the second region.
  • other regions light transmission-absorption regions
  • the first and second areas may be arranged on the display area as described above, and other areas may be arranged on the non-display area (for example, a frame area surrounding the display area, an area covered by a fixing member such as a housing, etc.).
  • the light transmission and absorption characteristics of the other areas may be adjusted as appropriate in accordance with the configuration of the non-display area of the OLED display element.
  • the light-emitting portion of the OLED display element means a portion in the display area from which display light is emitted
  • the non-light-emitting portion of the OLED display element means a portion in the display area from which display light is not emitted. Therefore, the first and second regions of the light transmission absorption filter of the present invention are configured in accordance with the arrangement of the light emitting portions and non-light emitting portions of the OLED display element into which the light transmission absorption filter of the present invention is incorporated.
  • the light transmission-absorption filter of the present invention usually has a plurality of the above-mentioned first regions in accordance with the number of light-emitting sections of the OLED display element into which the light transmission-absorption filter of the present invention is incorporated, and the light transmission-absorption filter of the present invention may have a plurality of the above-mentioned second regions in accordance with the number of non-light-emitting sections of the OLED display element into which the light transmission-absorption filter of the present invention is incorporated.
  • the provisions relating to the first portion, the second portion, and the relationship between the first portion and the second portion of the light transmission/absorption filter of the present invention all hold true for all of the multiple first portions and the multiple second portions that may be present.
  • the relationship between the first portion and the second portion in which the signs of a * and/or b * are opposite satisfies the relationship with the second portion in any of the multiple first portions.
  • the light transmission-absorption filter of the present invention is a light transmission-absorption filter that, due to its configuration having the above-mentioned first and second sections, ensures a desired transmittance of display light when incorporated into a display device, and when incorporated into a display device, external light reflection is suppressed, and the color of both the reflected light and the color of the display light are adjusted to be neutral. This is thought to be due to the following reasons.
  • the light transmission-absorption filter of the present invention has transmittances at wavelengths of 460 nm, 530 nm, and 620 nm that satisfy the relationships described below (30% or more at wavelengths of 460 nm and 620 nm, and 40% or more at wavelength 530 nm), thereby ensuring the desired transmittance of display light.
  • the light transmission-absorption filter of the present invention has transmittances at wavelengths of 460 nm, 530 nm, and 620 nm that satisfy the relationships described below (30% or more at wavelengths of 460 nm and 620 nm, and 40% or more at wavelength 530 nm), thereby ensuring the desired transmittance of display light.
  • a decrease in the utilization efficiency of display light is suppressed.
  • the first and second regions satisfy a relationship in which the signs of at least one of the values of a * and b * in the L * a * b * color space of transmitted light are opposite. Therefore, the chromaticity (a * and b * ) of the first region and the chromaticity (a * and b * ) of the second region are adjusted to be complementary, and by arranging the first region of the light-transmitting-absorbing filter of the present invention on the light-emitting portion of the OLED display element and the second region on the non-light-emitting portion of the OLED display element, the light-transmitting-absorbing filter of the present invention can be one in which external light reflection is suppressed and the color of the reflected light is adjusted to be neutral.
  • the first portion of the light transmission-absorption filter of the present invention has transmittances at wavelengths of 460 nm, 530 nm, and 620 nm that satisfy the relationships described below, and each transmittance is at least 30% or more (at least 40% or more at a wavelength of 530 nm). Therefore, the first portion is a portion that exhibits light transmittance different from that of any of the R (red), G (green), and B (blue) color filters, each of which has a transmittance of less than 30% at a wavelength of 460 nm, 530 nm, or 620 nm.
  • the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm each satisfy the following relationships: T(460) ⁇ 30% T(530) ⁇ 40% T(620) ⁇ 30%
  • the first portion of the light transmission-absorption filter of the present invention is a portion that exhibits light transmittance different from that of any of the R (red), G (green), and B (blue) color filters, in that the transmittance at wavelengths of 460 nm, 530 nm, or 620 nm is less than 30%.
  • the upper limit values of the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm are not particularly limited, and can be, for example, 80% or less, preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less.
  • the range of the transmittance T(460) at a wavelength of 460 nm and the range of the transmittance T(620) at a wavelength of 620 nm can be 30 to 80%, preferably 30 to 70%, more preferably 30 to 65%, and even more preferably 30 to 60%
  • the range of the transmittance T(530) at a wavelength of 530 nm can be 40 to 80%, preferably 40 to 70%, more preferably 40 to 65%, and even more preferably 40 to 60%.
  • the transmittance T(460) of the first portion at a wavelength of 460 nm is preferably 45% or more, and more preferably 50% or more. That is, the transmittance T(460) at a wavelength of 460 nm is preferably in the range of 45 to 80%, more preferably 50 to 70%, even more preferably 50 to 65%, and particularly preferably 50 to 60%.
  • the relationship in which the sign of at least one of the values of a * and b * in the L * a * b * color space of transmitted light is opposite between the first region and the second region specifically means that the following (1) and/or (2) is satisfied: (1) The sign of the a * value in the L * a * b * color space of the first region is opposite to the sign of the a * value in the L * a * b * color space of the second region, one being + (plus) and the other being ⁇ (minus).
  • the sign of the b * value in the L * a * b * color space of the first region is opposite to the sign of the b * value in the L * a * b * color space of the second region, one being + (plus) and the other being ⁇ (minus).
  • the light transmission-absorption filter of the present invention satisfies a relationship in which the sign of at least one of the values of a * and b * in the L * a * b * color space of transmitted light is opposite between the first region and the second region, and therefore the first region and the second region can be said to be regions with different hues.
  • the light transmission/absorption filter of the present invention satisfy a relationship in which the signs of both the a * and b * values in the L * a * b * color space of the transmitted light between the first and second regions are opposite, i.e., that both of the above (1) and (2) are satisfied.
  • the L * a * b * color space refers to the L * a * b * color space standardized by the CIE (International Commission on Illumination) in 1976.
  • a * and b * in the L * a * b * color space of transmitted light are values calculated for each of the first and second regions by multiplying the transmittance of the light-transmitting/absorbing filter in the wavelength range of 380 to 780 nm by the standard relative luminous efficiency for photopic vision and then summing (luminous efficiency correction).
  • a * and b * in the L * a * b * color space of transmitted light refer to a * and b * of transmitted light at a polar angle of 0° and an azimuthal angle of 0°.
  • the first portion of the light transmission/absorption filter of the present invention is used by being disposed above the light-emitting portion of an OLED display element.
  • the light-emitting and non-light-emitting portions of the display element are typically arranged with a width of about 10 to 30 ⁇ m in one pixel, and when the light-transmitting and -absorbing filter of the present invention is applied to an OLED display element, the distance between the light-transmitting and -absorbing filter of the present invention and the OLED display element layer is typically set to, for example, about 2 to 40 ⁇ m. In such a configuration, the color of the display light can be evaluated by evaluating a * and b * of the first portion.
  • a * and b * of the transmitted light through the first portion usually satisfy the following relationship: ⁇ 30.0 ⁇ a * ⁇ +30.0 ⁇ 30.0 ⁇ b * ⁇ +30.0
  • the following relationship be satisfied: ⁇ 20.0 ⁇ a * ⁇ +20.0 ⁇ 20.0 ⁇ b * ⁇ +20.0
  • the following relationship is satisfied: ⁇ 10.0 ⁇ a * ⁇ +10.0 ⁇ 10.0 ⁇ b * ⁇ +10.0
  • the following relationship is satisfied: ⁇ 8.0 ⁇ a * ⁇ +8.0 ⁇ 8.0 ⁇ b * ⁇ +8.0
  • a * and b * in the formula in this paragraph are respectively synonymous with a * and b* in the L * a * b * color space of the transmitted light through the first portion.
  • a * and b * in the L * a * b * color space of the transmitted light through the first portion satisfy the above relationship means that a * and b * both satisfy the above relationship. Furthermore, whether or not the above relationship is satisfied is determined based on a * and b * obtained by rounding off to one decimal place.
  • the second portion of the light transmission-absorption filter of the present invention is disposed on a non-light-emitting portion of an OLED display element, and therefore the transmittance of the second portion is not particularly limited in a specific wavelength range, as is the transmittance of the first portion.
  • a * and b * of the transmitted light in the second region satisfy the following relationship: ⁇ 30.0 ⁇ a * ⁇ +30.0 ⁇ 30.0 ⁇ b * ⁇ +30.0 It is more preferable that the following relationship is satisfied: ⁇ 25.0 ⁇ a * ⁇ +25.0 ⁇ 25.0 ⁇ b * ⁇ +25.0 It is more preferable that the following relationship is satisfied: ⁇ 20.0 ⁇ a * ⁇ +20.0 ⁇ 20.0 ⁇ b * ⁇ +20.0
  • a * and b * in the formula in this paragraph are respectively synonymous with a * and b* in the L * a * b * color space of the transmitted light through the second portion.
  • a * and b * in the L * a * b * color space of the transmitted light through the second portion satisfy the above relationship means that a * and b * both satisfy the above relationship. Furthermore, whether or not the above relationship is satisfied is determined based on a * and b * obtained by rounding off to one decimal place.
  • the area ratio between the first region and the second region corresponds to the area ratio between the light-emitting region and the non-light-emitting region of the OLED display element to which the light transmission/absorption filter of the present invention is applied.
  • the reflection color exhibited by the light transmission/absorption filter of the present invention it is preferable that at least one of a * and b * in the L * a * b * color space is ⁇ 5.0 to 5.0, more preferably both a * and b * in the L * a*b* color space are ⁇ 5.0 to 5.0, and even more preferably both a * and b * in the L*a * b * color space are ⁇ 2.0 to 2.0.
  • the reflectance exhibited by the light transmission/absorption filter of the present invention is preferably 8.0% or less, more preferably 7.5% or less, and even more preferably 7.0% or less. There is no particular lower limit, and a reflectance of 4.0% or more is practical.
  • the a * and b * and reflectance in the L * a * b * color space of the reflected light exhibited by the light transmission/absorption filter of the present invention are values calculated by the method described in the Examples below, as the sum of the reflection spectra of the light-emitting portions and the reflection spectra of the non-light-emitting portions multiplied by the area ratio of the light-emitting portions to the non-light-emitting portions, and then multiplying the resulting reflection spectra by the CIE standard illuminant D65 spectrum and the photopic standard relative luminous efficiency and taking the sum (luminous efficiency correction).
  • the thickness of the light transmission/absorption filter of the present invention is not particularly limited and can be, for example, 2 to 130 ⁇ m.
  • Light transmission/absorption filter I described below, is preferably 2 to 80 ⁇ m, more preferably 2 to 70 ⁇ m, and even more preferably 2 to 60 ⁇ m.
  • Light transmission/absorption filter II described below, is preferably 5 to 120 ⁇ m, more preferably 7 to 110 ⁇ m, and even more preferably 9 to 110 ⁇ m.
  • the thickness is a value measured based on the method for measuring the film thickness of the light-absorbing/dissipating layer and wavelength-selective absorption layer, described below.
  • a light transmission-absorption filter obtained by mask-exposing a laminate including a wavelength-selective absorption layer and a light-absorbing-disappearing layer (hereinafter also referred to as “laminate I”) to ultraviolet light
  • laminate I a light transmission-absorption filter obtained by mask-exposing a laminate including a wavelength-selective absorption layer and a light-absorbing-disappearing layer
  • a light transmission-absorption filter comprising a laminate (hereinafter also referred to as “laminate III”) obtained by mask-exposing a laminate (hereinafter also referred to as “laminate pre-III”) containing a light-absorbing and disappearing layer with ultraviolet light irradiation, and a laminate (hereinafter also referred to as “laminate II”) containing a wavelength-selective absorption layer
  • laminate III laminate obtained by mask-exposing a laminate
  • laminate pre-III containing a light-absorbing and disappearing layer with ultraviolet light irradiation
  • laminate II hereinafter also referred to as “laminate II”
  • the light transmission/absorption filter of the present invention is not limited to these forms at all.
  • the light transmission/absorption filter I is a light transmission/absorption filter obtained by exposing a laminate I including a wavelength-selective absorption layer and a light-absorbing/disappearing layer to ultraviolet light using a mask.
  • the wavelength-selective absorption layer means a layer that has light absorption properties that are almost the same as those of the wavelength-selective absorption layer in the laminate I before exposure to ultraviolet light using a mask, regardless of the exposure to ultraviolet light using a mask.
  • the light-absorbing and dissipative layer refers to a layer that has the property of being discolorable due to a chemical change of the dye contained in the light-absorbing and dissipative layer when irradiated with ultraviolet light. Therefore, the light-absorbing and dissipative layer in the light-transmitting and absorbing filter I of the present invention has light-absorbing portions that have a light-absorbing effect and portions where the light-absorbency has been eliminated (light-absorbency-eliminating portions) according to the pattern of mask exposure by ultraviolet light irradiation (hereinafter also referred to as the "mask pattern"). The light-absorbing portions can exhibit the desired absorbance.
  • the masked portions of the laminate I are not exposed and exist as light-absorbing portions with a light-absorbing effect, while the unmasked portions are exposed, and the light-absorbing and dissipating layer in the unmasked portions is discolored to become light-absorbing and dissipating portions, resulting in portions with low light absorption.
  • the region including the wavelength selection absorption layer and the light-absorbing and dissipating layer (light-absorbing and dissipating region) in the unmasked region becomes the first region
  • the region including the wavelength selection absorption layer and the light-absorbing and dissipating layer (light-absorbing region) in the masked region becomes the second region.
  • the light-absorbing and dissipating layer in light-transmitting and absorbing filter I can exhibit optical properties that are close to colorless, and the first portion can exhibit light-absorbing properties that are specific to the wavelength-selective absorption layer.
  • the description of laminate I can be preferably applied to light transmission-absorption filter I, except that the layer corresponding to the light-absorbing-disappearing layer in laminate I has a light-absorbing-disappearing site formed by ultraviolet irradiation.
  • the laminate I for example, a laminate including a configuration in which a wavelength selective absorption layer, a diffusion-preventing layer described below, and a light-absorbing and dissipating layer are arranged in this order can be mentioned.
  • Light transmission-absorption filter II is a light transmission-absorption filter comprising laminate III obtained by mask-exposing laminate pre-III, which includes a light-absorbing and dissipating layer, to ultraviolet light, and laminate II, which includes a wavelength-selective and absorbent layer. Note that laminate pre-III does not include a wavelength-selective and absorbent layer, and laminate II does not include a light-absorbing and dissipating layer.
  • the wavelength-selective absorption layer like the wavelength-selective absorption layer in the above-described light-transmitting-absorbing filter I, means a layer that has light absorption properties that are almost the same as those of the wavelength-selective absorption layer in the laminate II before mask exposure, regardless of whether or not it is subjected to mask exposure by ultraviolet irradiation.
  • the light-absorbing and dissipative layer refers to a layer that has the property of being discolorable due to a chemical change of the dye contained in the light-absorbing and dissipative layer when irradiated with ultraviolet light, similar to the light-absorbing and dissipative layer in the light-transmitting and absorbing filter I described above.
  • the light-absorbing and dissipative layer in the light-transmitting and absorbing filter II of the present invention has light-absorbing portions that have a light-absorbing effect and portions where the light-absorbency has been eliminated (light-absorbency-eliminating portions) according to the pattern of mask exposure by ultraviolet irradiation (hereinafter also referred to as the "mask pattern").
  • the light-absorbing portions can exhibit the desired absorbance.
  • the masked areas of the laminate pre-III are not exposed and exist as light-absorbing parts with a light-absorbing effect, while the unmasked areas are exposed, and the light-absorbing and dissipating layer in the unmasked areas is discolored to become light-absorbing and dissipating parts and exist as parts with low light absorption, resulting in the laminate III.
  • the region including the wavelength selection/absorption layer and the light-absorbing/disappearing layer (light-absorbing/disappearing region) in the unmasked region becomes the first region
  • the region including the wavelength selection/absorption layer and the light-absorbing/disappearing layer (light-absorbing region) in the masked region becomes the second region.
  • the light-absorbing and dissipating layer in the light-transmitting and absorbing filter II can exhibit optical properties that are close to colorless, and the first portion can exhibit light-absorbing properties that are specific to the wavelength-selective and absorbing layer.
  • the description of laminate pre-III can be preferably applied to laminate III in light transmission-absorption filter II, except that the layer corresponding to the light-absorbing and dissipating layer in laminate pre-III has a light-absorbing and dissipating site formed by ultraviolet irradiation.
  • a preferred example of the laminate II is a laminate including a configuration in which a first wavelength selective absorption layer (described later), a gas barrier layer (described later), and a first wavelength selective absorption layer (described later) are arranged in this order.
  • a preferred example of the laminate pre-III is a laminate including a configuration in which a diffusion-preventing layer (described later), a light-absorbing and dissipating layer (described later), and a gas barrier layer (described later) are arranged in this order.
  • the positional relationship between the first and second portions in the light transmission-absorption filter of the present invention and the OLED display element, which is a light-emitting element, will be explained below with reference to Fig. 1.
  • the above positional relationship is not limited to light transmission-absorption filter I, but is also applicable to light transmission-absorption filters of the present invention such as light transmission-absorption filter II.
  • the light-transmitting-absorbing filter I (10) is obtained by mask-exposing the laminate I (not shown), and has a mask-exposed wavelength-selective-absorbing layer 3 and a mask-exposed light-absorbing and decolorizable layer 4.
  • the unmasked areas become light-absorbent loss areas 5, and the masked areas become light-absorbing areas 6.
  • the mask pattern is applied so as to correspond to the arrangement of the light-emitting sections 7 and non-light-emitting sections 8 of the OLED display element, and specifically, the pattern is such that the areas of the laminate I located above the light-emitting sections 7 of the OLED display element are masked, and the areas of the laminate I located above the non-light-emitting sections 8 of the OLED display element are not masked.
  • the light-transmitting-absorbing filter I (10) has a first region 1 including the masked wavelength-selective-absorbing layer 3 and the light-absorbency-disappearing region 5 at a location corresponding to the top of the light-emitting region 7 of the OLED display element, and a second region 2 including the masked wavelength-selective-absorbing layer 3 and the light-absorbent region 6 at a location corresponding to the top of the non-light-emitting region 8 of the OLED display element.
  • the mask-exposed light-absorbing and decolorizing layer 4, the mask-exposed wavelength-selective absorption layer 3, and the light-emitting portion 7 of the OLED display element are arranged in this order, but they may also be arranged in this order: the mask-exposed wavelength-selective absorption layer 3, the mask-exposed light-absorbing and decolorizing layer 4, and the light-emitting portion 7 of the OLED display element.
  • laminate I which includes a wavelength-selective absorption layer and a light-absorbing and dissipating layer
  • laminate II which includes a wavelength-selective absorption layer
  • laminate pre-III which includes a light-absorbing and dissipating layer.
  • the laminate I is a laminate including a light-absorbing and dissipating layer and a wavelength-selective and absorbing layer, specifically, a light-absorbing and dissipating layer containing a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light; It is preferable that the laminate includes a wavelength selective absorption layer that contains a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and does not contain a compound that generates radicals when irradiated with ultraviolet light.
  • the laminate II is a laminate including a wavelength-selective absorption layer, and specifically, it is preferably a laminate including a wavelength-selective absorption layer that contains a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and does not contain a compound that generates radicals upon irradiation with ultraviolet light, however, the laminate II does not include a light-absorbing and disappearing layer.
  • the laminate pre-III is a laminate including a light-absorbing and dissipating layer, and more specifically, it is preferably a laminate including a light-absorbing and dissipating layer containing a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light, however, the laminate pre-III does not include a wavelength-selective absorption layer.
  • the components constituting the light-absorbing and dissipating layers in Laminate I and Laminate pre-III may each be contained in the light-absorbing and dissipating layers in Laminate I and Laminate pre-III, either singly or in combination of two or more.
  • the components constituting the wavelength-selective absorption layers in Laminate I and Laminate II may each be contained in the wavelength-selective absorption layers in Laminate I and Laminate II, either singly or in combination of two or more. This also applies to a light-transmitting and absorbing filter I produced using Laminate I and a light-transmitting and absorbing filter II produced using Laminate II and Laminate pre-III.
  • the main absorption wavelength band of the dye refers to the main absorption wavelength band of the dye measured in the state of laminate I, for each of laminates II and pre-III, or for the laminate of laminates II and pre-III. Specifically, the measurement is performed in the state of laminate I, for each of laminates II and pre-III, or for the laminate of laminates II and pre-III under the conditions described in [Measurement of absorbance of first and second portions] in the Examples described later.
  • the "dye” is dispersed (preferably dissolved) in the resin contained in the same layer (light-absorbing and dissipating layer or wavelength-selective and absorbing layer), thereby making the laminate I, II, and pre-III filters exhibiting a specific absorption spectrum derived from the dye.
  • This dispersion may be random, regular, or the like.
  • the light-absorbing and dissipating layer has a compound that generates radicals when irradiated with ultraviolet light dispersed (preferably dissolved) in the resin, so that when irradiated with ultraviolet light, radicals are generated, and the generated radicals react with the dye, causing a chemical change in the dye, fading and decolorizing the dye.
  • the light-absorbing and dissipative layers constituting the laminate I and laminate pre-III contain, as compounds that generate radicals upon ultraviolet irradiation, compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, as described below, the efficiency of generating radical species upon ultraviolet irradiation is improved compared to when a commonly used photoradical generator such as a benzophenone compound is used. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose, thereby fading and discoloring the dye.
  • compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A forms a hydrogen bond with compound A and is dispersed (preferably dissolved) in the resin, or, when compound A containing the acid group is bonded to a polymer constituting the resin, forms a hydrogen bond with compound A in the resin, and when irradiated with ultraviolet light, generates a radical, and the generated radical reacts with a nearby dye, making the radical more likely to react with the dye, thereby enabling the dye to be faded and decolorized more efficiently.
  • the light-absorbing and dissipative layers constituting the laminate I and the laminate pre-III will be described in detail below.
  • SQ squaraine
  • CY cyanine
  • benzylidene benzylidene
  • cinnamylidene cinnamylidene
  • azo indoaniline coloring matter
  • the light-absorbing and dissipative layer preferably contains at least one of an azo dye represented by any one of general formulas (i) to (iv) below and an indoaniline dye represented by general formula (v) below, because these dyes are less likely to produce secondary colored structures due to dye decomposition.
  • the azo dye represented by general formula (i) below is a dye having a main absorption wavelength band in the wavelength range of approximately 400 to 500 nm
  • the azo dye represented by any one of general formulas (ii) to (iv) below is a dye having a main absorption wavelength band in the wavelength range of approximately 450 to 650 nm
  • the indoaniline dye represented by general formula (v) below is a dye having a main absorption wavelength band in the wavelength range of approximately 580 to 700 nm.
  • the azo dye represented by the following general formula (i), the azo dye represented by the following general formula (ii), the azo dye represented by the following general formula (iii), the azo dye represented by the following general formula (iv), and the indoaniline dye represented by the following general formula (v), which can be contained in the light-absorbing and disappearing layer, may each be one type or two or more types.
  • the light-absorbing and disappearing layer may contain a squaraine dye represented by general formula (1) which will be described later in relation to the wavelength-selective absorption layer.
  • the light-absorbing and disappearing layer may also contain a dye other than the azo dye represented by any one of general formulas (i) to (iv), the indoaniline dye represented by general formula (v), and the squaraine dye represented by general formula (1) described below.
  • a dye other than the azo dye represented by any one of general formulas (i) to (iv), the indoaniline dye represented by general formula (v), and the squaraine dye represented by general formula (1) described below By optimizing the blending ratio of the azo dye represented by any one of general formulas (i) to (iv) described below and the indoaniline dye represented by general formula (v) described below, in combination with a wavelength-selective absorption layer described below, it is possible to suppress a change in the color of reflected light compared to when no dye is contained (hereinafter, also referred to as "adjusting the color of reflected light to be more neutral").
  • the light-absorbing and disappearing layer contains a dye that has absorption in a wavelength region with low absorbance compared to the main absorption wavelength band of each dye contained in the wavelength-selective absorption layer described below, from the viewpoint of more easily achieving both suppression of external light reflection and suppression of brightness reduction.
  • the light-absorbing and dissipating layer preferably contains a dye having a main absorption wavelength band that is 5 nm or more away from any of the main absorption wavelength bands of the dyes contained in the wavelength-selective and absorbent layer described below.
  • the "dye" contained in the light-absorbing and dissipative layer preferably includes at least one of the following dyes E to G, which have main absorption wavelength bands in different wavelength regions.
  • Dye E a dye having a main absorption wavelength band in a wavelength range of 430 to 480 nm
  • Dye F a dye having a main absorption wavelength band in a wavelength range of 500 to 590 nm
  • Dye G a dye having a main absorption wavelength band in a wavelength range of 600 to 660 nm
  • the dye E that can be contained in the light-absorbing and disappearing layer may be one type or two or more types.
  • the dyes F and G that can be contained in the light-absorbing and disappearing layer may each independently be one type or two or more types.
  • the wavelength range in which the dye E has its main absorption wavelength band is preferably 430 to 475 nm, more preferably 430 to 470 nm, and even more preferably 430 to 465 nm.
  • the wavelength range in which the dye F has its main absorption wavelength band is preferably 505 to 585 nm, more preferably 510 to 580 nm, and even more preferably 515 to 580 nm.
  • the wavelength range in which the dye G has a main absorption wavelength band is preferably 610 to 655 nm, more preferably 610 to 650 nm, and even more preferably 610 to 640 nm.
  • the light-absorbing and dissipative layer may contain dyes other than the dyes E to G.
  • the dyes E, F, and G are a combination of at least two types, and examples include a combination that includes at least dyes E and F and may further include dye G.
  • the wavelength-selective absorption layer described below contains all of the dyes A to D described below, and the light-absorbing and disappearing layer contains at least two types of dyes E to G, from the viewpoints that the suppression of external light reflection and the suppression of brightness reduction of the light transmission-absorption filters I and II can be more highly realized, and that when the obtained light transmission-absorption filters I or II are applied to a display device, the color of the reflected light can be adjusted to a neutral color.
  • the main absorption wavelength band of the dye E is preferably 5 to 70 nm (more preferably 5 to 60 nm) away from the main absorption wavelength band of the dye A described below, and 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below.
  • the main absorption wavelength band of the dye E is preferably 1 to 70 nm (more preferably 1 to 60 nm) away from the main absorption wavelength band of the dye A described below, and 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below.
  • the main absorption wavelength band of the dye F is preferably 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below, and is preferably 5 to 60 nm (more preferably 5 to 50 nm) away from the main absorption wavelength band of the dye C described below.
  • the main absorption wavelength band of the dye G is preferably 5 to 60 nm (more preferably 10 to 50 nm) away from the main absorption wavelength band of the dye C described below, and is preferably 5 to 80 nm (more preferably 10 to 60 nm) away from the main absorption wavelength band of the dye D described below.
  • the cation exists in a delocalized state, and multiple tautomeric structures exist. Therefore, in the present invention, if at least one tautomeric structure of a dye corresponds to one of the general formulas, the dye is considered to be a dye represented by that general formula. Therefore, a dye represented by a specific general formula can also be said to be a dye whose at least one tautomeric structure can be represented by that specific general formula. In the present invention, the dye represented by a general formula may have any tautomeric structure, as long as at least one of the tautomeric structures corresponds to that general formula.
  • R 17 and R 18 each independently represent a hydrogen atom or a monovalent substituent.
  • R 19 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.
  • Q represents a residue of a diazo component.
  • Examples of the monovalent substituent which may be taken as R 17 and R 18 include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an amino group (—NH 2 ), an aliphatic amino group, an arylamino group, a heterocyclic amino group, an acylamino group, a carbamoylamino group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, an
  • an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an arylamino group is preferred.
  • substituents that can be taken as R 17 and R 18 may be further substituted.
  • the aliphatic groups that can be represented by R 17 to R 19 may further have a monovalent substituent, and may be saturated or unsaturated, or may be cyclic. Specific examples include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups.
  • the total number of carbon atoms in the aliphatic group is preferably 1 to 30, and more preferably 1 to 16.
  • the aliphatic group examples include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2-(2-(acetyloxy)ethoxy)ethyl group, a cyclohexyl group, a benzyl group, a 2-phenethyl group, a vinyl group, and an allyl group.
  • Examples of the monovalent substituent that may be present include the monovalent substituents that may be present as R 17 and R 18 , and the same applies to the following description of the monovalent substituent that may be present.
  • Preferred examples of the monovalent substituent that may be present include an alkoxy group, an acyloxy group, and a hydroxy group. These substituents may further have a substituent, and preferred examples thereof include an alkoxy group, an acyloxy group, and a hydroxy group.
  • the aryl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and is preferably an aryl group having a total carbon number of 6 to 30, more preferably 6 to 16.
  • the heterocyclic group that can be taken as R 17 to R 19 may be a saturated or unsaturated aliphatic ring group or an aromatic ring group, with an aromatic heterocyclic group being preferred.
  • ring-constituting atoms that constitute the heterocyclic group include those containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and may further have a monovalent substituent.
  • the heterocyclic group is preferably a heterocyclic group having a total of 1 to 30 carbon atoms, and more preferably a heterocyclic group having 1 to 15 carbon atoms. Specific examples include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.
  • the carbamoyl groups that can be taken as R 17 to R 19 include unsubstituted carbamoyl groups (—CONH 2 ) as well as carbamoyl groups substituted with an aliphatic group, aryl group, or the like.
  • the carbamoyl groups which can be represented by R 17 to R 19 may further have a monovalent substituent, and are preferably carbamoyl groups having a total of 1 to 30 carbon atoms, and more preferably carbamoyl groups having 1 to 16 carbon atoms. Specific examples include methylcarbamoyl groups, dimethylcarbamoyl groups, phenylcarbamoyl groups, and N-methyl-N-phenylcarbamoyl groups.
  • the aliphatic oxycarbonyl group which can be represented by R 17 and R 18 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and is preferably an aliphatic oxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an aliphatic oxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.
  • the alkoxycarbonyl group that can be taken as R 19 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and is preferably an alkoxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an alkoxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.
  • the aryloxycarbonyl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and is preferably an aryloxycarbonyl group having a total of 7 to 30 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms.
  • Specific examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.
  • the acyl group that can be taken as R 17 to R 19 includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably has a total of 1 to 30 carbon atoms, more preferably has a total of 1 to 16 carbon atoms. Specific examples include an acetyl group, a methoxyacetyl group, a thienoyl group, and a benzoyl group.
  • the aliphatic sulfonyl group which can be represented by R 17 and R 18 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.
  • the alkylsulfonyl group that can be taken as R 19 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.
  • the arylsulfonyl group which can be represented by R 17 to R 19 may further have a monovalent substituent, and preferably has a total of 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Specific examples include benzenesulfonyl and toluenesulfonyl groups.
  • the sulfamoyl groups that can be taken as R 17 to R 19 include unsubstituted sulfamoyl groups (—SO 2 NH 2 ) as well as sulfamoyl groups substituted with an aliphatic group, aryl group, or the like.
  • the sulfamoyl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and preferably has a total of 0 to 30 carbon atoms, more preferably 0 to 16 carbon atoms. Specific examples include an unsubstituted sulfamoyl group, a dimethylsulfamoyl group, and a di-(2-hydroxyethyl)sulfamoyl group.
  • the imido group which can be taken as R 17 and R 18 may further have a monovalent substituent, and is preferably a 5- or 6-membered ring imido group.
  • the imido group preferably has a total of 4 to 30 carbon atoms, more preferably 4 to 20. Specific examples include succinimide and phthalimide groups.
  • aliphatic group in the aliphatic oxy group aliphatic amino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group and aliphatic thio group which can be taken as R 17 and R 18
  • the descriptions of the aliphatic groups which can be taken as R 17 to R 19 can be applied.
  • the aryl group in the aryloxy group arylamino group, aryloxycarbonylamino group, arylsulfonylamino group and arylthio group which can be taken as R 17 and R 18
  • the descriptions of the aryl group which can be taken as R 17 to R 19 can be applied.
  • the descriptions of the acyl groups which can be taken as R 17 to R 19 can be applied.
  • the carbamoyl group in the carbamoyloxy group and carbamoylamino group which can be taken as R 17 and R 18 the descriptions of the carbamoyl groups which can be taken as R 17 to R 19 can be applied.
  • the heterocyclic group in the heterocyclic oxy group heterocyclic amino group and heterocyclic thio group which can be taken as R 17 and R 18 , the descriptions of the heterocyclic groups which can be taken as R 17 to R 19 can be applied.
  • the description of the sulfamoyl group which can be taken as R 17 to R 19 can be applied.
  • the diazo component residue represented by Q means a residue of the diazo component "Q-NH 2 ".
  • Q is preferably an aryl group or an aromatic heterocyclic group.
  • the aromatic hydrocarbon ring constituting the aryl group that can be taken as Q may be a monocyclic ring or a fused ring, and is preferably a monocyclic ring.
  • An aryl group having a total of 6 to 30 carbon atoms is preferred, and an aryl group having a total of 6 to 16 carbon atoms is more preferred.
  • a phenyl group is preferred.
  • the aryl group that can be taken as Q may have a substituent, and preferred examples of the substituent that may be had include a sulfamoyl group (preferably an alkylsulfamoyl group or a dialkylsulfamoyl group), a sulfonyl group (preferably an alkylsulfonyl group), and a cyano group.
  • a sulfamoyl group preferably an alkylsulfamoyl group or a dialkylsulfamoyl group
  • a sulfonyl group preferably an alkylsulfonyl group
  • cyano group cyano group
  • the aromatic heterocyclic group that can be taken as Q is preferably an aromatic ring group containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom as a ring-constituting atom constituting the heterocyclic group, and is preferably constituted by a 5- or 6-membered ring.
  • the number of carbon atoms in the aromatic heterocyclic group is preferably 1 to 25, more preferably 1 to 15.
  • the aromatic heterocycle constituting the aromatic heterocyclic group may be a monocycle or a fused ring, and is preferably a monocycle.
  • aromatic heterocyclic group examples include a pyrazole group, a 1,2,4-triazole group, an isothiazole group, a benzisothiazole group, a thiazole group, a benzothiazole group, an oxazole group, and a 1,2,4-thiadiazole group.
  • R 21 to R 24 , R 26 and R 27 each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 108 , —SR 109 , —NR 110 R 111 , —S( ⁇ O) 2 NR 112 R 113 , —C( ⁇ O)NR 114 R 115 , —NHC( ⁇ O)R 116 , —C( ⁇ O)OR 117 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups.
  • R 108 to R 121 each represent a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group, and n is a positive integer.
  • the acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 108 , —SR 109 , —NR 110 R 111 , —S( ⁇ O) 2 NR 112 R 113 , —C( ⁇ O)NR 114 R 115 , —NHC( ⁇ O)R 116 , —C( ⁇ O)OR 117 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2
  • the acyclic hydrocarbon group which can be taken as R 21 to R 24 , R 26 , R 27 and R 108 to R 121 means an acyclic alkyl group in which one hydrogen atom has been removed from an acyclic alkane.
  • the acyclic alkyl group may have a ring structure as a substituent.
  • the number of carbon atoms in the acyclic alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 12, particularly preferably 1 to 8, and of these, 1 to 6 is preferred.
  • the monocyclic hydrocarbon group which may be taken as R 21 to R 24 , R 26 , R 27 and R to R 121 means a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a monocyclic cycloalkynyl group or a monocyclic aryl group, which is a group in which one hydrogen atom has been removed from a monocyclic aliphatic hydrocarbon ring (which may be any of a monocyclic cycloalkane, a monocyclic cycloalkene and a monocyclic cycloalkyne) or a monocyclic aromatic hydrocarbon ring.
  • the number of carbon atoms in the monocyclic cycloalkyl group, monocyclic cycloalkenyl group, and monocyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 16.
  • the number of carbon atoms in the monocyclic aryl group is more preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 16.
  • the fused polycyclic hydrocarbon group which may be taken as R 21 to R 24 , R 26 , R 27 and R to R 121 means a fused polycyclic cycloalkyl group, a fused polycyclic cycloalkenyl group, a fused polycyclic cycloalkynyl group or a fused polycyclic aryl group, which is a group in which one hydrogen atom has been removed from a fused polycyclic aliphatic hydrocarbon ring (which may be any of a fused polycyclic cycloalkane, a fused polycyclic cycloalkene and a fused polycyclic cycloalkyne) or a fused polycyclic aromatic hydrocarbon ring.
  • the number of carbon atoms in the fused polycyclic cycloalkyl group, fused polycyclic cycloalkenyl group, and fused polycyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is preferably 8 to 30, and more preferably 8 to 20.
  • the number of carbon atoms in the fused polycyclic aryl group is more preferably 12 to 30, and more preferably 12 to 20.
  • the heterocyclic groups which can be taken as R 21 to R 24 , R 26 , R 27 and R 108 to R 121 the descriptions of the heterocyclic groups which can be taken as R 17 to R 19 in the above general formula (i) can be applied.
  • n is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 3.
  • R 1 to R 4 , R 6 , R 7 , and R 8 to R 21 in the compounds represented by general formula [1] described in JP-A-5-257180 can be applied as they are to R 21 to R 24 , R 26 , R 27 , and R 108 to R 121 , respectively.
  • R 21 is preferably a cyano group, a nitro group, —OR 108 , an acyclic hydrocarbon group (preferably an acyclic alkyl group or an acyclic alkenyl group) or a heterocyclic group, more preferably a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom (preferably an alkyl group substituted with a fluorine atom), and still more preferably a cyano group.
  • an acyclic hydrocarbon group preferably an acyclic alkyl group or an acyclic alkenyl group
  • a heterocyclic group more preferably a cyano group or a nitro group
  • a halogen atom preferably an alkyl group substituted with a fluorine atom
  • R 22 is preferably a hydrogen atom, a cyano group, an acyclic hydrocarbon group (preferably an acyclic alkyl group) or a monocyclic hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably an alkyl group or an aryl group. At least one of R 21 and R 22 is preferably a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom, a cyano group, or a nitro group.
  • R 23 is preferably a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —C( ⁇ O)NR 114 R 115 , —NHC( ⁇ O)R 116 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), and a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —NHC( ⁇ O)R 116 or an acyclic alkyl group is more preferred, and —NHC( ⁇ O)R 116 is even more preferred.
  • R 108 to R 111 , R 116 and R 118 to R 121 are preferably acyclic alkyl groups.
  • R 24 and R 27 are preferably hydrogen atoms.
  • R 26 is preferably a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —NHC( ⁇ O)R 116 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), more preferably a hydrogen atom, —OR 108 or —SR 109 , and even more preferably a hydrogen atom.
  • R 108 to R 111 , R 116 , and R 118 to R 121 are preferably acyclic alkyl groups.
  • R 110 is preferably an acyclic alkyl group
  • R 111 is preferably an acyclic alkyl group, more preferably an unsubstituted acyclic alkyl group, or an acyclic alkyl group having —OR 108 , a monocyclic hydrocarbon group, or a fused polycyclic hydrocarbon group as a substituent, wherein R 108 is preferably a hydrogen atom or an acyclic alkyl group.
  • dyes represented by general formula (ii) include the compounds used in the examples described below, as well as the compounds described in paragraphs [0023] to [0034] of JP-A No. 5-257180, the compounds described in paragraphs [0050] and [0052] of JP-A No. 2013-129712, compound D-18 described in paragraph [0055], and the compound described in paragraph [0056].
  • the present invention is not limited to these.
  • R 31 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group, or a heterocyclic group.
  • R 32 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group or a heterocyclic group.
  • R 34 and R 35 each independently represent a hydrogen atom, an alkyl group, or an aromatic group.
  • R 37 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an acylamino group or an aromatic group.
  • R 34 and R 35 may be bonded to each other to form a ring.
  • R 1 and R 2 in general formula (1) described in JP-A-2013-129712 can be applied directly to R 31 and R 32 , respectively, and the descriptions regarding R 4 , R 5 and R 7 in general formula (3) described in JP-A-2013-129712 can be applied directly to R 34 , R 35 and R 37 , respectively.
  • R 37 may be the following acylamino group in addition to the hydrogen atom, alkyl group, alkoxy group, cyano group, carbonyl group, and aromatic group that R 7 in the general formula (3) described in JP-A-2013-129712 can be.
  • the acylamino group that can be taken as R 37 preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkyl group which can be taken as R 31 , R 32 and R 37 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the alkoxy group which can be represented by R 31 , R 32 and R 37 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the alkyloxycarbonyl group which can be represented by R 31 , R 32 and R 37 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 7 carbon atoms.
  • the alkyl group that can be taken as R 34 and R 35 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.
  • R 31 is preferably an alkyl group or an aryl group, more preferably an alkyl group.
  • R 32 is preferably an alkyl group or a cyano group, more preferably a cyano group.
  • R 34 and R 35 are preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • R 37 is preferably a hydrogen atom, an alkyl group, an acylamino group or an aromatic group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group.
  • dyes represented by general formula (iii) include the specific examples of azo dyes represented by general formula (iii) described in paragraphs [0056] to [0058] of WO 2023/234353.
  • the present invention is not limited to these examples.
  • R 41 to R 44 , R 46 and R 47 each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 208 , —SR 209 , —NR 210 R 211 , —S( ⁇ O) 2 NR 212 R 213 , —C( ⁇ O)NR 214 R 215 , —NHC( ⁇ O)R 216 , —C( ⁇ O)OR 217 , —O(CH 2 CH 2 O) n R 218 , —O(CH 2 CH 2 S) n R 219 , —S(CH 2 CH 2 O) n R 220 , —S(CH 2 CH 2 S) n R 221 , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups.
  • R 208 to R 221 each represent a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group, and n is a positive integer.
  • the acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR 208 , -SR 209 , -NR 210 R 211 , -S( ⁇ O) 2 NR 212 R 213 , -C( ⁇ O)NR 214 R 215 , -NHC( ⁇ O)R 216 , -C( ⁇ O)OR 217 , -O(CH 2 CH 2 O) n R 218 , -O(CH 2 CH 2 S) n R 219 , -S(CH
  • R 21 to R 24 , R 26 , R 27 , R 108 to R 121 and n in the general formula (ii) above can be applied as they are to R 41 to R 44 , R 46 , R 47 , R 208 to R 221 and n in the general formula (iv), respectively.
  • R 43 is preferably a hydrogen atom, —OR 208 , —SR 209 , —NR 210 R 211 , —NHC( ⁇ O)R 216 , —O(CH 2 CH 2 O) n R 218 , —O(CH 2 CH 2 S) n R 219 , —S(CH 2 CH 2 O) n R 220 , —S(CH 2 CH 2 S) n R 221 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), more preferably a hydrogen atom, —OR 208 , —SR 209 , —NR 210 R 211 , —NHC( ⁇ O)R 216 or an acyclic alkyl group, and even more preferably —NHC( ⁇ O)R 216 or an acyclic alkyl group.
  • R 208 to R 211 , R 216 and R 218 to R 221 are preferably acyclic alkyl groups.
  • R 210 is preferably an acyclic alkyl group
  • R 211 is preferably an acyclic alkyl group, more preferably an unsubstituted acyclic alkyl group (including an acyclic alkyl group substituted with an acyclic alkyl group), or an acyclic alkyl group having —OR 208 , a monocyclic hydrocarbon group or a fused polycyclic hydrocarbon group as a substituent.
  • R 208 is preferably a hydrogen atom or an acyclic alkyl group.
  • R 44 and/or R 46 may be bonded to R 210 and/or R 211 in -NR 210 R 211 located at the ortho position relative to R 44 and R 46 on the benzene ring to form a ring.
  • the ring that may be formed is preferably a 5- or 6-membered ring, and may be saturated or unsaturated, with a saturated 6-membered ring being preferred.
  • the ring that may be formed may further have a substituent, and preferably has, for example, an alkyl group.
  • the ring is preferably formed by bonding R 46 to R 211 in —NR 210 R 211 located at the ortho position relative to R 44 and R 46 on the benzene ring to form a saturated 6-membered ring.
  • Q 1 represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which it is attached, including at least one nitrogen atom.
  • R 51 represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group or a sulfonyl group
  • R 52 represents a hydrogen atom or an alkyl group
  • R 53 to R 57 represent a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group or a halogen atom
  • R 58 and R 59 represent a hydrogen atom, an alkyl group or an aryl group.
  • R51 and R53 , R54 and R55 and/or R55 and R59 , or R58 and R59 may be bonded to each other to form a ring. That is, R51 and R53 may be bonded to each other to form a ring, R54 and R55 and/or R55 and R59 may be bonded to each other to form a ring, or R58 and R59 may be bonded to each other to form a ring.
  • R 1 to R 6 , R 8 , R 9 and Q 1 in general formula (I) described in JP-A-2-92686 can be directly applied to R 51 to R 56 , R 58 , R 59 and Q 1 , respectively.
  • R 53 to R 56 can be the following acylamino group and alkylsulfonylamino group in addition to the hydrogen atom, alkyl group, alkoxy group and halogen atom that R 3 to R 6 in general formula (I) described in JP-A-2-92686 can be.
  • the acylamino group represented by R 53 to R 57 preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkylsulfonylamino group represented by R 53 to R 57 preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms.
  • the alkyl group, alkoxy group and halogen atom that can be taken as R 57 the descriptions of the alkyl group, alkoxy group and halogen atom that can be taken as R 53 to R 56 can be applied as they are.
  • R 16 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a hydrogen atom is preferred. With regard to the definition and preferred range of each substituent of R 16 , the descriptions regarding R 16 in relation to general formula (I) described in JP-A-2-92686 can be applied as is.
  • R 51 is preferably an acyl group having 2 to 7 carbon atoms or an alkoxycarbonyl group having 2 to 7 carbon atoms.
  • R 52 is preferably a hydrogen atom, and R 53 to R 56 are preferably hydrogen atoms.
  • R 57 is preferably an alkoxy group, an acylamino group or an alkylsulfonylamino group, more preferably an alkoxy group or an acylamino group.
  • R 58 and R 59 are preferably alkyl groups having 1 to 6 carbon atoms.
  • the indoaniline dye represented by the above general formula (v) is preferably represented by the following general formula (va):
  • R 51 , R 53 , R 57 to R 59 and Q 2 have the same meanings as R 51 , R 53 , R 57 to R 59 and Q 2 in the above general formula (v).
  • Q 2 is preferably —CR 11 R 12 CR 13 R 14 —, —CR 11 R 12 — or —NR 11 —, and more preferably —CR 11 R 12 CR 13 R 14 —.
  • R 11 to R 14 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and it is preferred that R 11 and R 12 are hydrogen atoms and R 13 and R 14 are alkyl groups having 1 to 4 carbon atoms. It is preferable that —CR 11 R 12 CR 13 R 14 — is bonded to >C ⁇ O on the side of the carbon atom to which R 11 and R 12 are bonded.
  • dyes represented by general formula (v) include the compounds used in the examples described below, as well as compounds No. 1 to 51 listed on pages 5 and 6 of JP-A No. 2-92686. However, the present invention is not limited to these.
  • the total content of the dyes in the light-absorbing and dissipative layer is preferably 0.10 to 50% by mass, more preferably 0.15 to 40% by mass, even more preferably 0.20 to 30% by mass, particularly preferably 0.25 to 15% by mass, and especially preferably 0.30 to 15% by mass.
  • the content of the azo dye represented by general formula (i) in the light-absorbing and dissipating layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass.
  • the content of the azo dye represented by general formula (ii), the azo dye represented by general formula (iii), the azo dye represented by general formula (iv), and the indoaniline dye represented by general formula (v) in the light-absorbing and dissipating layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass.
  • all of the dyes in the light-absorbing and dissipating layer may be composed of at least one of the azo dyes represented by any of general formulas (i) to (iv) and the indoaniline dye represented by general formula (v).
  • the light-absorbing and dissipative layer contains a compound that generates radicals upon irradiation with ultraviolet light (also simply referred to as a "radical generator" in the present invention).
  • the radical generator is not particularly limited as long as it is a compound that generates radicals when irradiated with ultraviolet light and has the function of decolorizing the dye.
  • a photoradical generator that may be used in combination with compound B described below can be used as the radical generator.
  • the radical generator may be a combination of two or more compounds, and the two or more compounds may form a complex or other interaction in the light-absorbing/disappearing layer to generate radicals upon ultraviolet irradiation.
  • the types of compounds to be combined may be two or more compounds that exhibit different functions in the mechanism of generating radicals upon ultraviolet irradiation, and two types are preferred.
  • a preferred example of such a combination is a combination of a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A.
  • the efficiency of generating radical species upon ultraviolet irradiation is improved compared to when the above-mentioned photoradical generator is used. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose and fade or disappear.
  • the azo dye represented by any of the above general formulas (i) to (iv), the indoaniline dye represented by the above general formula (v), and the squaraine dye represented by the below-mentioned general formula (1) which can be contained in the light-absorbing and dissipating layer, are discolored with almost no secondary absorption associated with dye decomposition.
  • Compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A will be described in detail below.
  • Compound A having an acid group The light-absorbing and disappearing layer preferably contains, as the radical generator, a compound A having an acid group (also simply referred to as "compound A" in the present invention), together with a compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, which will be described later.
  • the acid group contained in compound A is preferably a proton dissociative group having a pKa of 12 or less.
  • pKa means the negative common logarithm (-log Ka) of the acid dissociation constant (Ka) in water at 25°C, and can be calculated in the same manner as in the pKa of compound B described below, except that the 50/50 (volume ratio) mixed solvent of water/methanol is changed to water.
  • Compound A may be a low molecular weight compound or a high molecular weight compound (hereinafter also referred to as a "polymer”), and is preferably a polymer.
  • the compound A being a polymer means that the compound A is chemically bonded to a polymer that constitutes the resin contained in the light-absorbing and dissipating layer.
  • the molecular weight of compound A is less than 5,000, preferably 2,000 or less, more preferably 1,000 or less, even more preferably 500 or less, and particularly preferably 400 or less.
  • a practical value is 100 or more and less than 5,000, and a range of 200 to 2,000 is preferred, more preferably 200 to 1,000, even more preferably 200 to 500, and particularly preferably 200 to 400.
  • the lower limit of the weight-average molecular weight of compound A is 5,000 or more, and from the viewpoint of the physical properties of the light transmission/absorption filter I, it is preferably 10,000 or more, and more preferably 15,000 or more.
  • the upper limit is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 500,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less. That is, a range of 5,000 to 500,000 is practical, with 10,000 to 200,000 being preferred, and 15,000 to 150,000 being more preferred.
  • Compound A may or may not be anionized in the light-absorbing and dissipative layers that constitute Laminate I and Laminate pre-III, and in the present invention, both anionized and non-anionized acid groups are referred to as acid groups.
  • acid groups both anionized and non-anionized acid groups are referred to as acid groups.
  • Compound A may or may not be anionized in Laminate I and Laminate pre-III.
  • Compound A is preferably a compound having a carboxy group, in view of excellent film-forming properties of the light-absorbing and disappearing layer.
  • the compound having a carboxy group is preferably a monomer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing monomer”) or a polymer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing polymer”), and from the viewpoint of film-forming properties of the light-absorbing and disappearing layer, it is more preferably a carboxy group-containing polymer.
  • carboxy groups (—COOH) possessed by the carboxy group-containing monomer and the carboxy group-containing polymer may or may not be anionized in the laminate I and the laminate pre-III, and the term “carboxy group” includes both anionized carboxy groups (—COO ⁇ ) and non-anionized carboxy groups.
  • carboxyl group-containing polymer in the light-absorbing and dissipative layer constituting the laminate I and laminate pre-III may be anionized or not, and both anionized and not anionized carboxyl group-containing polymers are referred to as the carboxyl group-containing polymer.
  • the content of compound A in the light-absorbing and disappearing layer is preferably 1% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 45% by mass or more, and especially preferably 50% by mass or more.
  • the upper limit of the content of compound A is preferably less than 100% by mass, more preferably 99% by mass or less, and even more preferably 97% by mass or less. That is, the content is preferably 1% by mass or more but less than 100% by mass, more preferably 25 to 99% by mass, more preferably 30 to 97% by mass, particularly preferably 45 to 97% by mass, and especially preferably 50 to 97% by mass.
  • the content of compound A in the light-absorbing and dissipating layer is preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass or more and less than 100% by mass, and even more preferably 70% by mass or more and less than 100% by mass.
  • the upper limit is also preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass or less.
  • the compound A may be used alone or in combination of two or more kinds.
  • the carboxy group-containing monomer may be a polymerizable compound that contains a carboxy group and one or more (for example, 1 to 15) ethylenically unsaturated groups.
  • the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred.
  • the carbonyl bond in the (meth)acryloyl group and the carbonyl bond in the carboxy group may share one carbonyl bond.
  • the carboxyl group-containing monomer is preferably a difunctional or higher functional monomer containing a carboxyl group.
  • the difunctional or higher functional monomer refers to a polymerizable compound having two or more (e.g., 2 to 15) ethylenically unsaturated groups in one molecule.
  • the number of carboxy groups contained in the carboxy group-containing monomer may be one or more, and for example, 1 to 8 is preferred, 1 to 4 is more preferred, and 1 or 2 is even more preferred.
  • the carboxyl group-containing monomer may further have an acid group other than a carboxyl group, such as a phenolic hydroxyl group, a phosphoric acid group, or a sulfonic acid group.
  • the di- or higher functional monomer containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional or higher functional monomers containing a carboxy group include trade names such as Aronix M-520 and Aronix M-510 (both manufactured by Toagosei Co., Ltd.).
  • trifunctional or higher functional monomers containing a carboxy group it is also preferable to use them in combination with difunctional or higher functional monomers containing a carboxy group, from the perspective of achieving better
  • difunctional or higher functional monomers containing a carboxy group and difunctional or higher functional monomers containing an acid group include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP 2004-239942 A. The contents of this publication are incorporated herein by reference.
  • the carboxyl group-containing polymer may further have an acid group other than a carboxyl group, such as a phenolic hydroxyl group, a phosphoric acid group, or a sulfonic acid group.
  • the carboxy group-containing polymer is a copolymer
  • the structure of the polymer may be a random polymer or a regular polymer such as a block polymer.
  • the carboxy group-containing polymer preferably has a structural unit having a carboxy group.
  • structural units having a carboxy group include structural units derived from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, or fumaric acid. Among these, structural units derived from (meth)acrylic acid are preferred because of their excellent decolorization properties.
  • the content of the structural unit having a carboxy group in the carboxy group-containing polymer is preferably 1 to 100 mol%, more preferably 3 to 65 mol%, still more preferably 5 to 60 mol%, particularly preferably 10 to 60 mol%, and of these, 20 to 55 mol% is preferred, when the total of all structural units of the carboxy group-containing polymer is taken as 100 mol%.
  • the structural unit having a carboxy group may be used alone or in combination of two or more types.
  • the carboxyl group-containing polymer preferably also contains a structural unit having an aromatic ring (preferably an aromatic hydrocarbon ring), such as a structural unit derived from a (meth)acrylate having an aromatic ring (specifically, benzyl (meth)acrylate, phenethyl (meth)acrylate, or phenoxyethyl (meth)acrylate).
  • a structural unit having an aromatic ring preferably an aromatic hydrocarbon ring
  • a structural unit derived from a (meth)acrylate having an aromatic ring specifically, benzyl (meth)acrylate, phenethyl (meth)acrylate, or phenoxyethyl (meth)acrylate.
  • the content of the structural unit having an aromatic ring in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units of the carboxy group-containing polymer is 100 mol %.
  • the aromatic ring-containing structural unit may be used alone or in combination of two or more types.
  • the carboxyl group-containing polymer also preferably has a structural unit having an alicyclic structure.
  • alicyclic structures include a tricyclo[5.2.1.0 2,6 ]decane ring structure (also called tetrahydrodicyclopentadiene; the monovalent group is dicyclopentanyl), a tricyclo[5.2.1.0 2,6 ]decane-3-ene ring structure (also called 5,6-dihydrodicyclopentadiene; the monovalent group is dicyclopentenyl), an isobornane ring structure (the monovalent group is isobornyl), an adamantane ring structure (the monovalent group is adamantyl), and a cyclohexane ring structure (the monovalent group is cyclohexyl).
  • Examples of structural units having an alicyclic structure include structural units derived from (meth)acrylates having an alicyclic structure (specifically, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, methyl adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.).
  • the content of the structural unit having an alicyclic structure in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units in the carboxy group-containing polymer is 100 mol %.
  • the structural unit having an alicyclic structure may be used alone or in combination of two or more types.
  • the carboxyl group-containing polymer may have other structural units in addition to the structural units described above.
  • Examples of the other structural units include structural units derived from methyl (meth)acrylate.
  • the content of other structural units in the carboxy group-containing polymer is preferably 0 to 70 mol %, more preferably 0 to 50 mol %, and even more preferably 0 to 20 mol %, when the total of all structural units of the carboxy group-containing polymer is 100 mol %.
  • the other structural units may be used alone or in combination of two or more.
  • the light-absorbing and disappearing layer preferably contains, as the radical generator, together with the compound A, a compound B (also simply referred to as "compound B" in the present invention) having a structure capable of forming a hydrogen bond with an acid group contained in the compound A.
  • Compound B is preferably a compound having a structure that increases its basicity by absorbing ultraviolet light and becoming excited. The increased basicity of compound B in the excited state allows the acid group contained in compound A to form a complex with compound B through stronger interaction, thereby increasing the efficiency of radical generation.
  • the structure of compound B that can form a hydrogen bond with the acid group contained in compound A may be the entire structure of compound B or a partial structure that constitutes a part of compound B.
  • Compound B may be a high molecular weight compound (meaning a compound having a molecular weight of 5000 or more) or a low molecular weight compound (meaning a compound having a molecular weight of less than 5000), and is preferably a low molecular weight compound.
  • the molecular weight of compound B which is a low molecular weight compound, is less than 5,000, preferably less than 1,000, more preferably 500 or less, and even more preferably 350 or less. There is no particular restriction on the lower limit, but it is preferably 65 or more, and more preferably 75 or more.
  • a preferred range for the molecular weight of compound B, which is a low molecular weight compound is, for example, 65 or more and less than 5,000, preferably 65 or more and less than 1,000, more preferably 65 to 500, and even more preferably 75 to 350.
  • Compound B is preferably an aromatic compound because it has a large molar absorption coefficient for ultraviolet light.
  • the aromatic compound is a compound having one or more aromatic rings. Only one or more aromatic rings may be present in compound B. When more than one aromatic ring is present, the aromatic ring may be present, for example, in a side chain of a polymer constituting the resin.
  • the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic hetero ring.
  • the aromatic hetero ring (also referred to as a heteroaromatic ring) is used, it is a compound having one or more (e.g., 1 to 4) heteroatoms (at least one of nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms (ring-constituting atoms), and preferably has one or more (e.g., 1 to 4) nitrogen atoms as ring member atoms.
  • unsubstituted aromatic hydrocarbons do not have a structure capable of forming a hydrogen bond with the acid group contained in compound A, and therefore do not have the function of generating radicals upon ultraviolet irradiation, and do not fall under compound B.
  • unsubstituted aromatic hydrocarbon rings in a form in which an unsubstituted aromatic hydrocarbon ring is bonded to a side chain of a polymer constituting a resin do not have a structure capable of forming a hydrogen bond with the acid group contained in compound A, and therefore do not have the function of generating radicals upon ultraviolet irradiation, and do not fall under compound B.
  • the aromatic ring preferably has 5 to 15 ring atoms.
  • aromatic ring examples include monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; aromatic rings formed by condensing two rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring; and aromatic rings formed by condensing three rings such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.
  • monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring
  • aromatic rings formed by condensing two rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring
  • aromatic rings formed by condensing three rings such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.
  • the aromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group.
  • substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group.
  • the multiple substituents may be bonded to each other to form a non-aromatic ring.
  • the series of aromatic ring structures in which the above-mentioned multiple aromatic rings are bonded via a structure selected from a single bond, a carbonyl bond, and a multiple bond does not fall under the above-mentioned unsubstituted aromatic hydrocarbon ring, nor does it fall under the unsubstituted aromatic hydrocarbon ring in a form in which an unsubstituted aromatic hydrocarbon ring is bonded to a side chain of a polymer constituting the resin. It is also preferred that one or more of the aromatic rings constituting the series of aromatic ring structures be the heteroaromatic ring.
  • compound B include monocyclic aromatic compounds such as pyridine compounds (pyridine and pyridine derivatives), pyrazine compounds (pyrazine and pyrazine derivatives), pyrimidine compounds (pyrimidine and pyrimidine derivatives), and triazine compounds (triazine and triazine derivatives); compounds in which two rings are fused to form an aromatic ring, such as quinoline compounds (quinoline and quinoline derivatives), isoquinoline compounds (isoquinoline and isoquinoline derivatives), quinoxaline compounds (quinoxaline and quinoxaline derivatives), and quinazoline compounds (quinazoline and quinazoline derivatives); and compounds in which three or more rings are fused to form an aromatic ring, such as acridine compounds (acridine and acridine derivatives), phenanthridine compounds (phenanthridine and phenanthridine derivatives), phenanthroline compounds (phenanthroline and phenanthroline derivatives), and phen
  • the term "compound” is used to mean not only the compound itself, but also a compound having a substituent (referred to as a "derivative"), including an unsubstituted compound whose structure is partially modified within a range that does not impair the effects of the present invention. It is presumed that these compounds B form complexes with the aforementioned compound A, and when irradiated with ultraviolet light, generate two radical molecules through the following mechanism. 1) Compound B is generated in an excited state by absorbing ultraviolet light. 2) A hole moves from compound B in the excited state to compound A in the ground state (an electron from compound A moves to the lower energy orbital of the two half-occupied orbitals of compound B in the excited state).
  • a proton is transferred from compound A to compound B, generating a radical in which a hydrogen radical is added to compound B and a radical in which a hydrogen radical is released from compound A.
  • compound A is a compound having a carboxy group
  • the following reaction further occurs, and a radical is generated by a photodecarboxylation reaction.
  • Carbon dioxide is released from the radical resulting from the release of a hydrogen radical from compound A.
  • compound B is preferably at least one of quinoline compounds (quinoline and quinoline derivatives) and isoquinoline compounds (isoquinoline and isoquinoline derivatives).
  • the substituents which these compounds may have are preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group.
  • compound B When compound B is a polymer, it may be a polymer in which the specific structure is bonded to the polymer main chain via a single bond or a linking group.
  • Compound B, which is a polymer can be obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a heteroaromatic ring having a vinyl group and/or a (meth)acrylate monomer having a heteroaromatic ring). If necessary, it may be copolymerized with other monomers.
  • compound B examples include quinoline, 2-methylquinoline, 4-methylquinoline, 2,4-dimethylquinoline, 2-methyl-4-phenylquinoline, isoquinoline, 1-methylisoquinoline, 3-methylisoquinoline, and 1-phenylisoquinoline.
  • the content of Compound B is preferably from 0.1 to 50 mass %, more preferably from 2.0 to 40 mass %, still more preferably from 4 to 35 mass %, and particularly preferably from 8 to 30 mass %, relative to the total mass of the light-absorbing and disappearing layer.
  • the pKaH (pKa of the conjugate acid) which is a measure of the basicity of compound B is preferably 2.0 to 7.0, more preferably 3.0 to 6.0, and still more preferably 4.3 to 5.5.
  • the compound B may be used alone or in combination of two or more.
  • the resin contained in the light-absorbing and disappearing layer is not particularly limited as long as it can disperse (preferably dissolve) the dye, can exhibit the dye decolorizing action by radicals generated from a compound that generates radicals upon ultraviolet irradiation (preferably a radical generator containing compound B hydrogen-bonded with an acid group contained in compound A), and has the desired light transmittance (a light transmittance of 80% or more is preferred in the visible region of wavelengths of 400 to 800 nm).
  • the polymer constituting the resin various polymers can be used, and from the viewpoint of preventing the molecular weight of the resin from decreasing due to ultraviolet irradiation, a polymer having an aromatic ring or an alicyclic structure in the side chain is preferred, and a chain polymerization polymer such as a (meth)acrylic polymer containing a structural unit having an aromatic ring or an alicyclic structure is more preferred. Among them, from the viewpoint of further improving the decolorization rate and further improving the heat resistance and light resistance, a (meth)acrylic polymer containing a structural unit having an alicyclic structure is even more preferred.
  • the (meth)acrylic polymer refers to a polymer containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid ester.
  • the structural unit derived from (meth)acrylic acid becomes a structural unit having a carboxy group as the acid group in the above-mentioned compound A, and corresponds to the above-mentioned polymer in which the above-mentioned compound A is chemically bonded to the polymer constituting the resin.
  • the term "main chain” refers to the relatively longest bond chain in the molecule of a polymer compound
  • side chain refers to an atomic group branching off from the main chain.
  • Monomers that derive structural units having an aromatic ring include (meth)acrylates having an aromatic ring, such as benzyl acrylate, benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, naphthyl methyl acrylate, and naphthyl methyl methacrylate.
  • the content of structural units having an aromatic ring is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass, relative to the total mass of the polymer.
  • Examples of monomers that lead to structural units having an alicyclic structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
  • the content of the structural unit having an alicyclic structure is preferably 1 to 90 mass%, more preferably 5 to 90 mass%, and even more preferably 5 to 80 mass%, relative to the total mass of the polymer.
  • the polymer constituting the resin may contain a structural unit bonded to a compound A having an acid group.
  • the structural unit bonded to a compound A having an acid group can be the same as the structural unit having a carboxy group in the compound A described above, and a structural unit derived from (meth)acrylic acid is preferred.
  • the content of the structural unit bonded to a compound A having an acid group is preferably 1 to 70% by mass, more preferably 1 to 60% by mass, relative to the total mass of the polymer. More preferably, the content of the structural unit having a carboxy group in the carboxy group-containing polymer in the compound A described above is applied.
  • the polymer constituting the resin contains a structural unit bonded to a compound A having an acid group
  • the contents of structural units having an aromatic ring and structural units having an alicyclic structure in the carboxy group-containing polymer of compound A described above apply to the contents of structural units bonded to a compound A having an acid group, the content of structural units having an aromatic ring and the content of structural units having an alicyclic structure.
  • the polymer constituting the resin may contain a structural unit having an alkyl group having 1 to 14 carbon atoms, from the perspective of adjusting the glass transition temperature, etc.
  • structural units having an alkyl group having 1 to 14 carbon atoms include structural units derived from alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and
  • structural units having an alkyl group having 1 to 14 carbon atoms may be used alone, or two or more types may be used in combination.
  • the content of structural units having an alkyl group having 1 to 14 carbon atoms is preferably 0 to 95% by mass relative to the total mass of the polymers that make up the resin.
  • the weight-average molecular weight (Mw) of the polymer that constitutes the resin is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.
  • the wavelength-selective absorption layers constituting the laminates I and II contain a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and do not contain a compound that generates radicals upon ultraviolet irradiation.
  • the dye preferably does not have a main absorption wavelength band at any of the wavelengths of 460 nm, 530 nm, and 620 nm, and more preferably does not have a main absorption wavelength band at any of the wavelength ranges of 450 to 470 nm, more than 520 nm but not more than 540 nm, or more than 610 nm but not more than 630 nm.
  • the "dye" is dispersed (preferably dissolved) in the resin, thereby making the wavelength selective absorption layer a layer exhibiting a specific absorption spectrum derived from the dye.
  • the "dye" contained in the wavelength selective absorption layer preferably includes at least one of the following dyes A to D, each of which has a main absorption wavelength band in a different wavelength region.
  • Dye A a dye having a main absorption wavelength band in a wavelength range of 390 to 435 nm
  • Dye B a dye having a main absorption wavelength band in a wavelength range of 480 to 520 nm
  • Dye C a dye having a main absorption wavelength band in a wavelength range of 560 to 610 nm
  • Dye D a dye having a main absorption wavelength band in a wavelength range of 640 to 780 nm
  • the dye A that can be contained in the wavelength selective absorption layer may be one type or two or more types.
  • the dyes B to D that can be contained in the wavelength selective absorption layer may each independently be one type or two or more types.
  • the wavelength selective absorption layer may contain dyes other than the dyes A to D.
  • the wavelength-selective absorption layer may take any form so long as the dye in the wavelength-selective absorption layer exhibits an absorption spectrum, and in combination with the light-absorbing and dissipative layer described above, the resulting light-transmitting and absorbing filters I and II are able to simultaneously suppress external light reflection and brightness reduction, and preferably are also not likely to affect the original color of the displayed image.
  • One form of the wavelength-selective absorption layer is one in which a dye (preferably at least one of dyes A to D) is dispersed (preferably dissolved) in a resin. This dispersion may be random, regular, or otherwise.
  • the dyes A to D have their main absorption wavelength bands in the wavelength ranges of 390 to 435 nm, 480 to 520 nm, 560 to 610 nm, and 640 to 780 nm, respectively, which do not overlap with the wavelength ranges of B (Blue, 460 nm), G (Green, 530 nm), and R (Red, 620 nm) used as light sources in OLED display devices. Therefore, by containing at least one of these dyes A to D, the wavelength-selective absorption layer can suppress reflection of external light in the light-emitting section of the display device without compromising the color reproduction range of light emitted from the OLED display element.
  • the dyes A, B, C, and Dye D that can be contained in the wavelength selective absorption layer are preferably a combination of at least two types, more preferably a combination of at least three types, and even more preferably a combination of all four types.
  • the dyes A to D are contained in the wavelength-selective absorption layer as described above, a problem of reduced lightfastness due to mixing of the dyes may occur due to chain transfer of radicals generated during dye decomposition, etc.
  • the wavelength-selective absorption layer in the laminate I and laminate II, as well as the light-transmission-absorption filter I obtained by mask-exposing the laminate I, and the light-transmission-absorption filter II including the laminate II and laminate III, can exhibit an excellent level of lightfastness that overcomes the reduced lightfastness that accompanies mixing of the dyes by providing a specific gas barrier layer as described below or by having multiple dyes separated into two wavelength-selective absorption layers.
  • the wavelength-selective-absorption layer contains all of the four dyes A to D and satisfies the following relational formulas (I) to (VI):
  • Light-transmission-absorption filter I obtained from laminate I having a wavelength-selective-absorption layer with such a configuration and the above-mentioned light-absorbing-disappearing layer, and light-transmission-absorption filter II obtained from laminate II and laminate III including a wavelength-selective-absorption layer with such a configuration, can not only satisfactorily suppress external light reflection and brightness reduction, but also maintain the original color of an image of an OLED display device at an excellent level.
  • the upper limit of Ab(450)/Ab(430) in the relational formula (I) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, and particularly preferably 0.60 or less.
  • the lower limit is no particular restriction on the lower limit, but a practical value is 0.05 or more, preferably 0.10 or more, and more preferably 0.20 or more.
  • the upper limit of Ab(450)/Ab(500) in the relational formula (II) is preferably 0.90 or less, more preferably 0.80 or less, even more preferably 0.75 or less, particularly preferably 0.65 or less, and among these, 0.60 or less is preferable, and 0.50 or less is most preferable.
  • the upper limit of Ab(540)/Ab(500) in the relational formula (III) is preferably 0.90 or less, more preferably 0.80 or less, even more preferably 0.75 or less, particularly preferably 0.70 or less, and among these, 0.50 or less is preferable, and 0.20 or less is most preferable.
  • the upper limit of Ab(540)/Ab(600) in the relational formula (IV) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, particularly preferably 0.70 or less, and among these, 0.50 or less is preferable, and 0.25 or less is most preferable.
  • a practical value is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.
  • the upper limit of Ab(630)/Ab(600) in the relational formula (V) is preferably 0.40 or less, more preferably 0.30 or less, even more preferably 0.20 or less, and particularly preferably 0.15 or less.
  • the upper limit of Ab(630)/Ab(700) in the relational formula (VI) is preferably 0.95 or less, more preferably 0.90 or less, even more preferably 0.80 or less, and particularly preferably 0.75 or less.
  • the relational expressions (I) to (VI) each satisfy the above-mentioned preferred ranges, the change in color caused by the provision of the light-transmitting-absorbing filters I and II can be reduced, and the original color of the image of the OLED display device can be further enhanced.
  • the dyes A to D have a sharp absorption waveform in the main absorption wavelength band.
  • dye B is a squaraine dye represented by general formula (1) described below
  • the wavelength selective absorption layer can satisfy the above-mentioned preferred ranges for relational formulas (II) and (III), and can maintain the original color of the image of the OLED display device at a superior level.
  • the wavelength selective absorption layer can satisfy the above-mentioned preferable ranges of relational formulas (I) to (IV), and can maintain the original color of the image of the OLED display device at a superior level.
  • This is also thought to be due to the low absorbance at wavelengths around the absorption maximum (534 nm) of the green visual pigment in human cones, as described above.
  • satisfying the relational expression (V) is important in that it does not affect the original color of the image of the OLED display device. It is believed that the change in a * can be suppressed by satisfying the relational expression (V), and as a result, the above-mentioned color can be maintained at an excellent level.
  • the wavelength-selective absorption layer of Laminate I and Laminate II may be a single layer, or may be a two-layer structure from the viewpoint of suppressing a decrease in light resistance due to the mixing of the above-mentioned dyes.
  • the wavelength-selective absorption layer has a two-layer structure consisting of a first wavelength-selective absorption layer and a second wavelength-selective absorption layer, it is preferable that the dye contained in the first wavelength-selective absorption layer has a main absorption wavelength band in a wavelength range different from that of the dye contained in the second wavelength-selective absorption layer.
  • the dye contained in the first wavelength-selective absorption layer has a main absorption wavelength band in a wavelength range different from that of the dye contained in the second wavelength-selective absorption layer
  • the maximum absorption maximum wavelength of the dye contained in the first wavelength-selective absorption layer and the maximum absorption maximum wavelength of the dye contained in the second wavelength-selective absorption layer are separated by 50 nm or more.
  • the first-wavelength-selective-absorption layer contains a dye having a main absorption wavelength band on the shortest wavelength side (hereinafter referred to as "shortest-wavelength dye") among the dyes contained in the first-wavelength-selective-absorption layer and the second-wavelength-selective-absorption layer.
  • shortest-wavelength dye a dye having a main absorption wavelength band on the shortest wavelength side
  • the first-wavelength-selective-absorption layer located on the external light side contains the shortest-wavelength dye, photodecomposition of dyes other than the shortest-wavelength dye due to photoexcitation of the shortest-wavelength dye can be more effectively suppressed, and excellent lightfastness can be exhibited.
  • a combination of the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer is preferably one that can both suppress a decrease in brightness and suppress the influence of reflected color when the light transmission and absorption filter of the present invention is applied to a display device.
  • the first wavelength selective absorption layer and the second wavelength selective absorption layer preferably contain at least one dye having a main absorption wavelength band in a different wavelength region.
  • the first wavelength selective absorption layer may contain two or more dyes having different main absorption wavelength bands, and the second wavelength selective absorption layer may contain two or more dyes having different main absorption wavelength bands.
  • the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer have main absorption wavelength bands in different wavelength regions.
  • the first wavelength selective absorption layer containing two or more dyes having different main absorption wavelength bands means that the maximum absorption maximum wavelengths of the two or more dyes contained in the first wavelength selective absorption layer are different from each other by 50 nm or more.
  • the second wavelength selective absorption layer containing two or more dyes having different main absorption wavelength bands means that the maximum absorption maximum wavelengths of the two or more dyes contained in the second wavelength selective absorption layer are different from each other by 50 nm or more.
  • the shortest wavelength dye is preferably contained in the first wavelength selective absorption layer as described above, and the shortest wavelength dye is preferably dye A described above.
  • the above-mentioned descriptions relating to "dye” can be applied to the “dye” contained in the first wavelength selective absorption layer and the second wavelength selective absorption layer, and it is preferable that the “dye” contains at least one of the dyes A to D.
  • the dyes A to D that can be contained in two or more wavelength selective absorption layers may each independently be one type or two or more types.
  • it is preferable that the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer are combined to form a configuration containing all of the dyes A to D.
  • a preferred example of such a configuration is a configuration in which the first wavelength selective absorption layer contains the dyes A and C, and the second wavelength selective absorption layer contains the dyes B and D. Furthermore, with regard to the above-mentioned relational expressions (I) to (VI), it is preferable that the first wavelength selective absorption layer and the second wavelength selective absorption layer do not satisfy all of the above-mentioned relational expressions (I) to (VI) individually, and that the wavelength selective absorption layer as a whole including the first wavelength selective absorption layer and the second wavelength selective absorption layer satisfies all of the above-mentioned relational expressions (I) to (VI).
  • dye A there are no particular limitations on the dye A, so long as it has a main absorption wavelength band in the wavelength range of 390 to 435 nm in the laminate I and laminate II, and various dyes can be used.
  • the wavelength range in which dye A has its main absorption wavelength band is preferably 395 to 435 nm, more preferably 400 to 435 nm, and even more preferably 405 to 435 nm.
  • Specific examples of dye A include porphyrin-based, squaraine-based, cyanine (CY)-based, pyrrolmethine-based, and indoaniline-based pigments (dyes).
  • the dye A a dye represented by the following general formula (A1) is preferred because it has a sharp absorption waveform in the main absorption wavelength band.
  • R1 and R2 each independently represent an alkyl group or an aryl group
  • R3 to R6 each independently represent a hydrogen atom or a substituent
  • R5 and R6 may be bonded to each other to form a 6-membered ring.
  • each substituent in general formula (A1) can be directly applied to the descriptions of each substituent in the dye represented by general formula (A1) in paragraphs [0022] to [0056] of WO 2022/138925.
  • R 1 and R 2 in formula (A1) are both aryl groups.
  • R1 and R2 each independently represent an aryl group
  • R3 , R5 , and R6 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R3 and R6 is a hydrogen atom.
  • R3 represents a hydrogen atom
  • R5 and R6 each independently represent an alkyl group or an aryl group
  • R5 and R6 each independently represent an alkyl group
  • R3 represents a hydrogen atom
  • R5 and R6 each independently represent an alkyl group
  • R5 and R6 are bonded to each other to form a ring that is condensed with a pyrrole ring and forms an indole ring together with the pyrrole ring.
  • the dye represented by the above general formula (A1) is a dye represented by the following general formula (A2):
  • R 1 to R 4 have the same meanings as R 1 to R 4 in general formula (A1), respectively, and the preferred embodiments are also the same.
  • R 15 represents a substituent.
  • R 15 is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, or an alkoxycarbonyl group.
  • the alkyl group and aryl group which can be taken as R 15 have the same meanings as the alkyl group and aryl group which can be taken as R 3 , R 5 and R 6 , respectively, and the preferred embodiments are also the same.
  • halogen atoms that can be taken as R 15 include a chlorine atom, a bromine atom, and an iodine atom.
  • acyl groups that can be taken as R 15 include an acetyl group, a propionyl group, and a butyroyl group.
  • the amino group that can be taken as R 15 can be the same as the amino group that can be possessed by the substituted aryl group in R 4. Also preferred is a 5- to 7-membered nitrogen-containing heterocyclic group in which the alkyl group on the nitrogen atom of the amino group is bonded to form a ring.
  • the alkoxycarbonyl group that can be taken as R 15 is preferably an alkoxycarbonyl group having 2 to 5 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl, and isopropoxycarbonyl.
  • n is an integer from 0 to 4. There are no particular restrictions on n, but it is preferably 0 or 1, for example.
  • dyes represented by general formula (A1) include the compounds described in paragraphs [0063] to [0065] of WO 2022/138925 and the following compound (E-42). However, the present invention is not limited to these.
  • dyes represented by the following general formula (B) are also preferred as dyes A.
  • the compounds and specific examples represented by general formula (1), (3), or (6) described in paragraphs [0016] to [0097] of WO 2023/100715 can be applied as they are to dyes represented by the following general formula (B).
  • Dye A-321, used in the examples described below, is also preferred as dye A.
  • Q1 represents a group represented by the following formula (Q-1).
  • R q1 to R q3 represent a hydrogen atom or a substituent
  • R 1 and R 2 each represent a hydrogen atom or a substituent.
  • X 1 to X 4 each independently represent —S—, —NR X1 — or —SO 2 —, where R X1 represents a hydrogen atom or an alkyl group.
  • R 101 and R 102 represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
  • R 101 or R 102 when either R 101 or R 102 is a hydrogen atom, the other is an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond;
  • R 101 and R 102 When one of R 101 and R 102 is a methyl group, the other represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond
  • R 101 or R 102 is a phenyl group
  • the other represents a hydrogen atom, an alkyl group, an aralkyl group, a substituted aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated
  • the dye represented by the above general formula (B) is preferably a dye having a combination of the following substituents.
  • R 101 and R 102 are preferably an alkyl group or an aralkyl group, and more preferably an alkyl group having 2 or more carbon atoms.
  • R q2 and R q3 are preferably bonded to each other to form a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, more preferably a cyclobutane ring.
  • R 1 and R 2 are preferably —OC( ⁇ O)—Y 11 , —O—Y 11 or —OC( ⁇ O)NR y11 , and more preferably —OC( ⁇ O)—Y 11.
  • Y 11 is preferably an alkyl group, and more preferably a branched alkyl group.
  • R y11 is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
  • X 1 to X 4 are preferably —S—.
  • preferred examples of the dye A include porphyrin dyes represented by the following general formula (7), which contain copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide as a central metal.
  • X 1 to X 8 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted ethynyl group, an aryl group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or an acyl group.
  • Adjacent groups among X 1 to X 8 may be bonded to each other to form an aromatic ring together with the carbon atoms that substitute for them.
  • R 18 to R 21 each represent an aryl group.
  • M represents copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide.
  • the nitrogen atoms located above and below M on the paper indicate that they are coordinated to M via an unshared electron pair.
  • halogen atom alkyl group, alkoxy group, aryl group, aryloxy group, aryloxycarbonyl group, alkylthio group, arylthio group and acyl group which can be taken as X 1 to X 8
  • the descriptions of the halogen atom, alkyl group, alkoxy group (described as a form in which the aliphatic group in an aliphatic oxy group is an alkyl group), aryl group, aryloxy group, aryloxycarbonyl group, alkylthio group (described as a form in which the aliphatic group in an aliphatic thio group is an alkyl group), arylthio group and acyl group in the substituents which can be taken as R 17 and R 18 in the above-mentioned general formula (i) can be applied.
  • the alkyl groups that can be taken as X 1 to X 8 may have a substituent, and examples of the alkyl group substituted with a substituent include an aralkyl group, a halogenoalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an aralkyloxyalkyl group, and a halogenoalkoxyalkyl group.
  • the alkoxy groups that can be taken as X 1 to X 8 may have a substituent, and examples of the alkoxy group substituted with a substituent include an aralkyloxy group and a halogenoalkoxy group.
  • the same descriptions of the corresponding substituents in the substituents that can be taken as R 17 and R 18 in the general formula (i) above can also be applied to the substituents (aryl group, halogen atom) in the alkoxy group substituted with these substituents.
  • substituents which the substituted ethenyl group and substituted ethynyl group which can be taken as X 1 to X 8 can have, the substituents which can be taken as R 1 to R 6 in the above-mentioned general formula (P) can be applied.
  • the aryl groups that can be taken as R 18 to R 21 can be the same as those described above for the aryl groups in the substituents that can be taken as R 17 and R 18 in the general formula (i).
  • X 1 to X 8 are preferably a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms.
  • porphyrin dyes represented by general formula (7) can be used without any restrictions.
  • porphyrin compounds that satisfy the main absorption wavelength band of dye A sold by Tokyo Chemical Industry Co., Ltd., Yamada Chemical Co., Ltd., etc.
  • FDB-002 trade name, manufactured by Yamada Chemical Co., Ltd.
  • dye A in addition to the dye represented by the above general formula (A1), the porphyrin dye represented by the above general formula (7), and the dye represented by the above general formula (B), the compounds described in paragraphs 0012 to 0067 of JP-A No. 5-53241 and the compounds described in paragraphs 0011 to 0076 of Japanese Patent No. 2707371 can also be preferably used.
  • dye B there are no particular limitations on the dye B, so long as it has a main absorption wavelength band in the wavelength range of 480 to 520 nm in the laminate I and laminate II, and various dyes can be used.
  • dye C is not particularly limited as long as it has a main absorption wavelength band in the wavelength range of 560 to 610 nm in the laminate I and laminate II, and various dyes can be used.
  • the wavelength range in which dye B has its main absorption wavelength band is preferably 485 to 520 nm, more preferably 490 to 520 nm, and even more preferably 490 to 515 nm.
  • the wavelength range in which dye C has its main absorption wavelength band is preferably 580 to 615 nm, more preferably 580 to 610 nm, and even more preferably 580 to 610 nm.
  • dye B examples include pyrrole methine (PM)-based, rhodamine (RH)-based, boron dipyrromethene (BODIPY)-based, and squaraine (SQ)-based pigments (dyes).
  • dye C examples include tetraazaporphyrin (TAP)-based, squaraine-based, and cyanine (CY)-based pigments (dyes).
  • squaraine dyes are preferred as dye B and dye C because they have sharp absorption waveforms in the main absorption wavelength band, and squaraine dyes represented by the following general formula (1) are more preferred.
  • dyes with sharp absorption waveforms as dye B and dye C, the above-mentioned relational expressions (I) and (II) can be satisfied at a preferred level, and the original color of the image of the OLED display device can be maintained at an excellent level.
  • At least one of dye B and dye C in the wavelength selective absorption layer is a squaraine dye (preferably, a squaraine dye represented by the following general formula (1)), and it is more preferable that both dye B and dye C are squaraine dyes (preferably, squaraine dyes represented by the following general formula (1)).
  • G represents a heterocyclic group which may have a substituent.
  • each substituent in general formula (1) can be directly applied to the descriptions of each substituent in the dye represented by general formula (1) in paragraphs [0073] to [0095], [0099], and [0100] of WO 2021/221122.
  • a preferred embodiment of the dye represented by the above general formula (1) is a dye represented by the following general formula (2):
  • a 1 is the same as A in the general formula (1). Among them, a nitrogen-containing five-membered heterocyclic group is preferred.
  • R1 and R2 each independently represent a hydrogen atom or a substituent.
  • R1 and R2 may be the same or different, and may be bonded to each other to form a ring.
  • the substituents that can be taken as R1 and R2 are not particularly limited, and examples thereof include alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.), heteroaryl groups (furyl, thienyl, pyridyl, pyrid
  • arylsulfonyl groups phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.
  • amino groups amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.
  • alkylsulfonyloxy groups methanesulfonyloxy
  • cyano group nitro group, halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, etc.
  • an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group is preferred, an alkyl group, an aryl group, or a heteroaryl group is more preferred, and an alkyl group is even more preferred.
  • the substituents that can be taken as R 1 and R 2 may further have a substituent.
  • Examples of the substituents that may further have include the above-mentioned substituents that can be taken as R 1 and R 2 , and the substituent X that A, B, and G in the above-mentioned general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).
  • R 1 and R 2 may be bonded to each other to form a ring, and R 1 or R 2 and the substituents that B 2 or B 3 have may be bonded to form a ring.
  • the ring formed in this case is preferably a heterocycle or heteroaryl ring, and the size of the ring formed is not particularly limited, but is preferably a 5-membered or 6-membered ring.
  • the number of rings formed is also not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include a form in which the substituents carried by R1 and B2 , and the substituents carried by R2 and B3, are bonded to each other to form two rings.
  • B 1 , B 2 , B 3 and B 4 each independently represent a carbon atom or a nitrogen atom.
  • a ring including B 1 , B 2 , B 3 and B 4 is an aromatic ring. It is preferred that at least two of B 1 to B 4 are carbon atoms, and it is more preferred that all of B 1 to B 4 are carbon atoms.
  • the carbon atoms which can be taken as B 1 to B 4 have a hydrogen atom or a substituent. Of the carbon atoms which can be taken as B 1 to B 4 , the number of carbon atoms which have a substituent is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1.
  • B 1 and B 4 are carbon atoms and at least one of them has a substituent.
  • the substituents that the carbon atoms that can be taken as B 1 to B 4 have are not particularly limited, and examples include the above-mentioned substituents that can be taken as R 1 and R 2.
  • alkyl groups alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amido groups, sulfonylamido groups, carbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups
  • alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amido groups, sulfonylamido groups, carbamoyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amido groups, sulfonylamido groups, carbamoyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups.
  • the substituents possessed by the carbon atoms that can be taken as B 1 to B 4 may further have a substituent.
  • Examples of the substituents that may further be possessed include the substituents that may be further possessed by R 1 and R 2 in the general formula (2) described above, and the substituent X that may be possessed by A, B, and G in the general formula (1) described above (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).
  • the substituents that can be taken by the carbon atoms represented by B1 and B4 are more preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, a sulfonylamido group, or a carbamoyl group, particularly preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, or a sulfonylamido group, and most preferably a hydroxy group, an amide group, or a sulfonylamido group.
  • the substituents that the carbon atoms that can be taken as B2 and B3 have are more preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an amino group, a cyano group, a nitro group, or a halogen atom, and it is particularly preferred that either one of the substituents is an electron-withdrawing group (for example, an alkoxycarbonyl group, an acyl group, a cyano group, a nitro group, or a halogen atom).
  • the dye represented by the above general formula (2) is preferably a dye represented by any of the following general formulas (3), (4), and (5):
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
  • B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.
  • R3 and R4 each independently represent a hydrogen atom or a substituent.
  • the substituents that can be taken as R3 and R4 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
  • the substituent that can be taken as R3 is preferably an alkyl group, an alkoxy group, an amino group, an amido group, a sulfonylamido group, a cyano group, a nitro group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom, more preferably an alkyl group, an aryl group, or an amino group, and still more preferably an alkyl group.
  • the substituent that can be taken as R4 is preferably an alkyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a carbamoyl group, an amino group, or a cyano group, more preferably an alkyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or an aryl group, and still more preferably an alkyl group.
  • the alkyl group that can be taken as R3 and R4 may be linear, branched, or cyclic, but is preferably linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 8.
  • Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group, and more preferably a methyl group or a t-butyl group.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
  • B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.
  • R5 and R6 each independently represent a hydrogen atom or a substituent.
  • the substituents that can be taken as R5 and R6 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
  • the substituent that can be taken as R5 is preferably an alkyl group, an alkoxy group, an aryloxy group, an amino group, a cyano group, an aryl group, a heteroaryl group, a heterocyclic group, an acyl group, an acyloxy group, an amido group, a sulfonylamido group, a ureido group, or a carbamoyl group, more preferably an alkyl group, an alkoxy group, an acyl group, an amido group, or an amino group, and still more preferably an alkyl group.
  • the alkyl group that can be taken as R5 has the same meaning as the alkyl group that can be taken as R3 in general formula (3), and the preferred range is also the same.
  • the substituent that can be taken as R6 is preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a sulfonylamido group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an amino group, a cyano group, a nitro group, or a halogen atom, more preferably an alkyl group, an aryl group, a heteroaryl group, or a heterocyclic group, and still more preferably an alkyl group or an aryl group.
  • the alkyl group that can be taken as R6 has the same meaning as the alkyl group that can be taken as R4 in general formula (3), and the preferred range is also the same.
  • the aryl group that can be taken as R6 is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.
  • This aryl group may have a substituent, and examples of such a substituent include groups included in the following substituent group B, with alkyl groups having 1 to 10 carbon atoms, sulfonyl groups, amino groups, acylamino groups, sulfonylamino groups, and the like being particularly preferred. These substituents may further have a substituent.
  • the substituent is preferably an alkylsulfonylamino group.
  • Substituent group B examples include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an aminooxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a sulfonylamino group (including an alkyl or arylsulfonylamino group), a mercapto group, an alkylthio group, an arylthio group, a heterocyclic group, a cyano
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
  • B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.
  • R7 and R8 each independently represent a hydrogen atom or a substituent.
  • the substituents that can be taken as R7 and R8 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
  • the preferred range, more preferred range, and even more preferred range of the substituent that can be taken as R7 are the same as the substituent that can be taken as R5 in general formula (4).
  • the alkyl group that can be taken as R5 has the same definition as the alkyl group that can be taken as the above-mentioned R3 , and the preferred range is also the same.
  • the preferred range, more preferred range, and even more preferred range of the substituent that can be taken as R8 are the same as the substituent that can be taken as R6 in general formula (4).
  • the preferred range of the alkyl group and aryl group that can be taken as R8 are the same as the alkyl group and aryl group that can be taken as R6 in general formula (4) above, and the preferred ranges are also the same.
  • the squaraine dye can be any squaraine dye represented by any of the general formulas (1) to (5) and is not particularly limited. Examples include the compounds described in JP-A-2006-160618, WO-2004/005981, WO-2004/007447, Dyes and Pigment, 2001, 49, pp. 161-179, WO-2008/090757, WO-2005/121098, and JP-A-2008-275726.
  • Specific examples of the dyes represented by any of the general formulas (1) to (5) include the compounds described in paragraphs [0119] to [0122] of WO 2021/221122. However, the present invention is not limited to these. In addition to the above specific examples, specific examples of the dyes represented by any of the general formulas (3) to (5) include the compounds described in paragraphs [0124] to [0132] of WO 2021/221122. However, the present invention is not limited to these.
  • a preferred embodiment of the dye represented by the above general formula (1) is a dye represented by the following general formula (6):
  • R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meanings and preferred values as R3 and R4 in the general formula (3) above.
  • A2 is the same as A in the general formula (1). Among them, a nitrogen-containing five-membered heterocyclic group is preferred.
  • the dye represented by the above general formula (6) is preferably a dye represented by any of the following general formulas (7), (8), and (9):
  • R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meanings and preferred ranges as R3 and R4 in general formula (3).
  • Two R3s and two R4s may be the same or different.
  • R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meaning as R3 in formula (3) above, and the preferred range is also the same.
  • R5 and R6 each independently represent a hydrogen atom or a substituent, and have the same meanings as R5 and R6 in formula (4) above, and the preferred ranges are also the same.
  • R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meaning as R3 in formula (3) above, and the preferred range is also the same.
  • R 7 and R 8 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 7 and R 8 in formula (5) above, and the preferred ranges are also the same.
  • any squaraine dye represented by any of general formulas (6) to (9) can be used without any particular limitation.
  • squaraine dyes include the compounds described in JP-A-2002-97383 and JP-A-2015-68945.
  • Specific examples of the squaraine dyes represented by any of general formulas (6) to (9) include the compounds described in paragraphs [0145] to [0148] of WO 2021/221122.
  • the present invention is not limited to these.
  • the squaraine dye represented by the general formula (1) may be a quencher-containing dye in which a quencher moiety is covalently linked to the dye via a linking group.
  • the quencher-containing dye can also be preferably used as at least one of dyes B and C. That is, the quencher-containing dye is counted as dye B or dye C depending on the wavelength of its main absorption wavelength band.
  • the quencher moiety include the ferrocenyl group in the above-mentioned substituent X (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122). Further examples include the quencher moiety in the quencher compound described in paragraphs [0199] to [0212] and paragraphs [0234] to [0310] of WO 2019/066043.
  • squaraine dyes represented by general formula (1) that fall under the category of dyes with built-in quenchers include the compounds described in paragraphs [0151] to [0167] of WO 2021/221122 and the following compounds (C-121) and (C-122).
  • the present invention is not limited to these.
  • Tetraazaporphyrin dyes represented by the following general formula (8) are also preferred as dye C.
  • Y 1 to Y 8 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms,
  • the tetraazaporphyrin dye represented by general formula (8) can be any commercially available product and can be used without any restrictions.
  • tetraazaporphyrin dyes commercially available from Tokyo Chemical Industry Co., Ltd., Yamada Chemical Industry Co., Ltd., Yamamoto Chemical Industry Co., Ltd., etc. can be used.
  • dye D there are no particular limitations on the dye D, so long as it has a main absorption wavelength band in the wavelength range of 640 to 780 nm in the laminate I and laminate II, and various dyes can be used.
  • the wavelength range in which dye D has its main absorption wavelength band is preferably 640 to 750 nm, and more preferably 645 to 700 nm.
  • Specific examples of the dye D include porphyrin-based, squaraine-based, cyanine (CY)-based, indoaniline-based, and anthraquinone-based pigments (dyes).
  • Preferred examples of the squaraine dye include squaraine dyes represented by the following general formula (1).
  • dye D is a dye represented by general formula (1), it is preferably a dye represented by the following general formula (14):
  • R1 and R2 have the same meanings as R1 and R2 in general formula (2).
  • R41 and R42 also have the same meanings as R1 and R2 in general formula (2).
  • R 1 , R 2 , R 41 and R 42 are preferably an alkyl group, an alkenyl group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and further preferably an alkyl group or an aryl group.
  • R 1 , R 2 , R 41 and R 42 may further have a substituent.
  • substituents that may be further substituted include the substituent that R 1 and R 2 in the general formula (2) may have, and the substituent X that A, B and G in the general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).
  • B1 , B2 , B3 and B4 in general formula (14) are respectively defined as B1 , B2 , B3 and B4 in general formula (2) described above.
  • B5 , B6 , B7 and B8 in general formula (14) are respectively defined as B1 , B2 , B3 and B4 in general formula (2) described above.
  • the substituents on the carbon atoms that can be taken as B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , and B 8 may further have a substituent.
  • Examples of the substituents that may further have include the substituent X that A, B, and G in the general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).
  • R1 and R2 may be bonded to each other to form a ring, and R1 or R2 may be bonded to a substituent carried by B2 or B3 to form a ring.
  • R41 and R42 may be bonded to each other to form a ring, and R41 or R42 may be bonded to a substituent carried by B6 or B7 to form a ring.
  • the ring formed is preferably a heterocycle or heteroaryl ring, and the size of the ring formed is not particularly limited, but is preferably a 5-membered or 6-membered ring.
  • the number of rings formed is also not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include a form in which the substituents carried by R1 and B2 , and the substituents carried by R2 and B3, are bonded to each other to form two rings.
  • dye D represented by general formula (1) include the compounds described in paragraphs [0097] to [0099] of WO 2023/228799. However, the present invention is not limited to these.
  • an anthraquinone dye is preferred, and an anthraquinone dye represented by the following general formula (20) is more preferred, from the viewpoint of achieving a higher level of both suppression of brightness reduction and suppression of the influence of reflected color on the original color of the displayed image.
  • A represents a hydroxy group or —NH—R 62 .
  • R 61 and R 62 each represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group represented by the following formula (20b).
  • R 63 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, —SO 3 H, —CO 2 H, —CO 2 R 64 , —NHCOR 64 , —SO 3 R 64 or —SO 2 NR 64 R 65 .
  • R 64 represents a saturated hydrocarbon group having 1 to 10 carbon atoms.
  • R 65 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
  • r is an integer from 0 to 5.
  • X 61 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. * indicates a bond.
  • Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which can be taken as R 61 and R 62 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group.
  • Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms that can be taken as R 61 and R 62 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
  • the aliphatic hydrocarbon group having 1 to 10 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms which can be taken as R 61 and R 62 may have a substituent, and examples of the substituent that may be had include a hydroxy group and a halogen atom.
  • Examples of the alkyl group having 1 to 6 carbon atoms that can be taken as R 63 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a neopentyl group.
  • the —SO 3 H and —CO 2 H that can be taken as R 63 may each have an ionic structure in which a hydrogen ion is dissociated, or may each have a salt structure.
  • —CO 2 H is used to mean a carboxylate ion or a salt group thereof
  • —SO 3 H is used to mean a sulfonate ion or a salt group thereof.
  • salts include salts with alkali metals such as sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; ammonium salts; and the like.
  • saturated hydrocarbon groups having 1 to 10 carbon atoms that can be taken as R 64 and R 65 include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and saturated alicyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.
  • At least one hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms which can be taken as R 64 and R 65 may be substituted with a halogen atom, a hydroxy group or an amino group.
  • Examples of —CO 2 R 64 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.
  • Examples of —NHCOR 64 include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group, and an N-pivaloylamino group.
  • Examples of —SO 3 R 64 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
  • Examples of —SO 2 NR 64 R 65 include an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-isopropylsulfamoyl group, an N-butylsulfamoyl group, an N-isobutylsulfamoyl group, an N-sec-butylsulfamoyl group, an N-tert-butylsulfamoyl group, an N-pentylsulfamoyl group, an N-(1-ethylpropyl)sulfamoyl group, an N-(1,1-dimethylpropyl)sulfamoyl group, an N-(1,2-dimethylpropyl)sulfamoyl group, an N-(2,2-dimethylpropyl)sulfamoyl group, an N-(1-methylbut
  • N-1-substituted sulfamoyl groups such as an N-(1-methylhexyl)sulfamoyl group, an N-(1,4-dimethylpentyl)sulfamoyl group, an N-octylsulfamoyl group, an N-(2-ethylhexyl)sulfamoyl group, an N-(1,5-dimethyl)hexylsulfamoyl group, an N-(1,1,2,2-tetramethylbutyl)sulfamoyl group, or an N-(5-aminopentyl)sulfamoyl group;
  • the sulfamoyl group include N,N-disubstituted sulfamoyl groups such as N,N-dimethylsulfamoyl group, N-ethyl-N-methylsulfamoyl group, N,N-diethyl
  • alkanediyl group having 1 to 6 carbon atoms that can be taken as X 61 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.
  • Examples of the anthraquinone dye represented by the above general formula (20) include the following exemplary compounds (2-1) to (2-14). However, the present invention is not limited to these.
  • indoaniline dye represented by general formula (v) in the light-absorbing and dissipating layer described above can also be preferably used as dye D in the wavelength-selective absorption layer.
  • the total content of the dyes (preferably the dyes A to D) in the wavelength selective absorption layer is preferably 0.10 to 50 mass%, more preferably 0.15 to 50 mass%, still more preferably 0.20 to 40 mass%, particularly preferably 0.25 to 40 mass%, and particularly preferably 0.30 to 35 mass%.
  • the description regarding the total content of the dyes (preferably the dyes A to D) in the wavelength-selective absorption layer applies to each of the first wavelength-selective absorption layer and the second wavelength-selective absorption layer.
  • the content of each of the dyes A to D that can be contained in the wavelength selective absorption layer is preferably as follows.
  • the content of dye A in the wavelength selective absorption layer is preferably 0.05 to 50% by mass, and more preferably 0.2 to 40% by mass.
  • the content of dye B in the wavelength selective absorption layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass.
  • the content of dye C in the wavelength selective absorption layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass.
  • the content of dye D in the wavelength selective absorption layer is preferably 0.05 to 45% by mass, and more preferably 0.1 to 30% by mass.
  • the description regarding the contents of each of the dyes A to D that can be contained in the wavelength selective absorption layer applies to each of the first wavelength selective absorption layer and the second wavelength selective absorption layer.
  • the description regarding the content ratio of each of the dyes A to D in the wavelength selective absorption layer applies to the content ratio of each of the dyes A to D as a whole of the dyes contained in the first wavelength selective absorption layer and the second wavelength selective absorption layer.
  • the content of the dye containing a quencher is preferably 0.1 to 45% by mass relative to 100% by mass of the wavelength-selective absorption layer, in terms of anti-reflection effect.
  • the resin contained in the wavelength selective absorption layer (hereinafter also referred to as "matrix resin") is not particularly limited as long as it can disperse (preferably dissolve) the dye. Among them, a resin that can satisfactorily suppress external light reflection and brightness reduction and can also maintain the original color of the image of the OLED display device at an excellent level is preferred.
  • the matrix resin is preferably a low-polarity matrix resin that allows the squaraine dye to exhibit a sharper absorption peak.
  • low polarity preferably refers to an fd value defined by the following relational expression I of 0.50 or greater.
  • Relational expression I: fd ⁇ d/( ⁇ d+ ⁇ p+ ⁇ h)
  • ⁇ d, ⁇ p, and ⁇ h represent the terms corresponding to the London dispersion force, the dipole-dipole force, and the hydrogen bonding force, respectively, relative to the solubility parameter ⁇ t calculated by the Hoy method. Specific calculation methods are described below.
  • fd represents the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h.
  • wi represents the mass fraction of the i-th matrix resin
  • fd i represents the fd value of the i-th matrix resin.
  • ⁇ d corresponding to London dispersion force refers to the ⁇ d determined for Amorphous Polymers described in the section "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature "Properties of Polymers 3rd , Elsevier, (1990),” and is calculated according to the description in the above section of the literature.
  • ⁇ p corresponding to the dipole-dipole force refers to the ⁇ p determined for the amorphous polymers described in the section "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature "Properties of Polymers 3rd , Elsevier, (1990),” and is calculated according to the description in the above section of the literature.
  • ⁇ h corresponding to the hydrogen bonding strength refers to the ⁇ h determined for the Amorphous Polymers described in the literature "Properties of Polymers 3rd , Elsevier, (1990)" on pages 214 to 220, in the section “2) Method of Hoy (1985, 1989),” and is calculated according to the description in the above section of the literature.
  • the moisture content of the wavelength-selective absorption layer can be set to a low moisture content of, for example, 0.5% or less, which is preferable from the viewpoint of improving the light resistance of the laminate I (excluding the light-absorbing and disappearing layer) and the laminate II containing the wavelength-selective absorption layer.
  • the resin may contain any conventional component in addition to the polymer, but the fd of the matrix resin is a calculated value for the polymer that constitutes the matrix resin.
  • the matrix resin include polystyrene resin and cyclic polyolefin resin, with polystyrene resin being more preferred.
  • the fd value of polystyrene resin is 0.45 to 0.60
  • the fd value of cyclic polyolefin resin is 0.45 to 0.70.
  • resin components that impart functionality to the wavelength-selective absorption layer such as an extensible resin component and a release property-controlling resin component, which will be described later.
  • matrix resin is used to mean not only the resins described above, but also the extensible resin component and the release property-controlling resin component.
  • the matrix resin preferably contains a polystyrene resin in order to sharpen the absorption waveform of the dye.
  • the polystyrene contained in the polystyrene resin refers to a polymer containing a styrene component.
  • the polystyrene preferably contains 50% by mass or more of the styrene component.
  • the wavelength selective absorption layer may contain one type of polystyrene or two or more types of polystyrene.
  • the styrene component is a structural unit derived from a monomer having a styrene skeleton in its structure.
  • the polystyrene preferably contains 70% by mass or more, and more preferably 85% by mass or more, of a styrene component. It is also preferable that the polystyrene is composed only of a styrene component.
  • the description of the polystyrene resin described in [0106] to [0110] of WO 2023/228799 can be applied as is.
  • the wavelength selective absorption layer preferably contains a polyphenylene ether resin in addition to the polystyrene resin.
  • a polyphenylene ether resin By containing both the polystyrene resin and the polyphenylene ether resin, the toughness of the wavelength selective absorption layer can be improved and the occurrence of defects such as cracks can be suppressed even in harsh environments such as high temperature and high humidity.
  • the polyphenylene ether resin Zylon S201A, S202A, S203A (all trade names) manufactured by Asahi Kasei Corporation can be preferably used.
  • a resin prepared by pre-mixing polystyrene resin and polyphenylene ether resin can be used.
  • the wavelength selective absorption layer contains a polystyrene resin and a polyphenylene ether resin
  • the mass ratio of the two, polystyrene resin/polyphenylene ether resin is preferably 99/1 to 50/50, more preferably 98/2 to 60/40, and even more preferably 95/5 to 70/30.
  • the cyclic olefin compound forming the cyclic polyolefin contained in the cyclic polyolefin resin (also referred to as polycycloolefin resin) is not particularly limited as long as it is a compound having a ring structure containing a carbon-carbon double bond, and examples thereof include norbornene compounds, monocyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, and vinyl alicyclic hydrocarbon compounds.
  • cyclic polyolefins examples include (1) polymers containing structural units derived from norbornene compounds, (2) polymers containing structural units derived from monocyclic olefin compounds other than norbornene compounds, (3) polymers containing structural units derived from cyclic conjugated diene compounds, (4) polymers containing structural units derived from vinyl alicyclic hydrocarbon compounds, and hydrogenated polymers containing structural units derived from each of the compounds (1) to (4).
  • the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic olefin compound include ring-opened polymers of each compound.
  • the description of the cyclic polyolefin resin described in paragraphs [0112] to [0125] of WO 2023/228799 can be applied as is.
  • the resins described above in the section on the light-absorbing and dissipating layer can also be preferably used as the resin for the wavelength-selective absorption layer. Furthermore, the following descriptions can also be applied to the various structural units described in the resins described above in the section on the light-absorbing and dissipating layer (structural units having an aromatic ring, structural units having an alicyclic structure, structural units having an alkyl group with 1 to 14 carbon atoms), in addition to the above descriptions, and they can also contain structural units having a polar group, as described below.
  • the polymer constituting the resin of the wavelength selective absorption layer preferably contains a polymer having a structural unit with an aromatic ring.
  • examples include structural units derived from chain polymerization monomers having an aromatic ring and a carbon-carbon double bond, and preferred structural units are those derived from styrene; alkylstyrenes such as ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, and tert-butylstyrene; and substituted styrenes in which a hydroxy
  • the content of the structural unit having an aromatic ring is preferably 5 to 100 mol %, more preferably 10 to 100 mol %, and even more preferably 20 to 100 mol %, when the total of all structural units of the polymer having a structural unit having an aromatic ring is taken as 100 mol %.
  • the aromatic ring-containing structural unit may be used alone or in combination of two or more types.
  • the polymer constituting the resin of the wavelength selective absorption layer preferably contains a polymer having a structural unit with an alicyclic structure.
  • structural units derived from monomers that lead to structural units having an aromatic ring as described above in the section on the light-absorbing and dissipating layer structural units derived from dicyclopentenyl (meth)acrylate are preferred.
  • the content of the structural unit having an alicyclic structure is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 80 mol%, particularly preferably 20 to 80 mol%, and especially preferably 25 to 80 mol%, when the total of all structural units of the polymer having a structural unit having an alicyclic structure is taken as 100 mol%.
  • the structural unit having an alicyclic structure may be used alone or in combination of two or more types.
  • the polymer constituting the resin of the wavelength selective absorption layer may contain a structural unit having an alkyl group having 1 to 14 carbon atoms from the viewpoint of adjusting the glass transition temperature, etc.
  • the structural unit having an alkyl group having 1 to 14 carbon atoms the structural unit having an alkyl group having 1 to 14 carbon atoms described in the section on the light-absorbing and disappearing layer above is preferred.
  • the structural unit having an alkyl group having 1 to 14 carbon atoms may be used alone, or two or more types may be used in combination.
  • the content of the structural unit having an alkyl group having 1 to 14 carbon atoms is preferably 0 to 95 mol %, more preferably 0 to 70 mol %, still more preferably 0 to 50 mol %, and particularly preferably 0 to 20 mol %, when the total of all structural units of the polymer is 100 mol %.
  • the polymer constituting the resin of the wavelength selective absorption layer may contain a polymer having a polar group.
  • the polar group contained in the polymer having a polar group include a carboxy group, a hydroxy group (including a phenolic hydroxy group), a nitrogen-containing aromatic ring group such as an oxazoline ring group, an amide group, etc., and the carboxy group or the oxazoline ring group is preferred.
  • the polymer having a polar group preferably contains a structural unit having a polar group, and examples thereof include a structural unit derived from a chain polymerization monomer having a polar group and a carbon-carbon double bond, and preferred are structural units derived from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 4-vinylpyridine, 4-vinylpyrrolidone, 2-isopropenyl-2-oxazoline, 4-vinylphenol, or the like.
  • the content of the structural unit having a polar group is preferably 0.5 to 95 mol%, more preferably 1.0 to 70 mol%, even more preferably 1.5 to 50 mol%, and particularly preferably 2.0 to 45 mol%, when the total of all structural units of the polymer having a polar group is taken as 100 mol%.
  • the resin in at least one of the first wavelength-selective absorption layer and the second wavelength-selective absorption layer contains a polymer having a polar group, from the viewpoint of exhibiting excellent interlayer adhesion.
  • polymers having a polar group include polymers having a structural unit having the above-mentioned polar group and at least one of the above-mentioned structural units having an aromatic ring, structural units having an alicyclic structure, and structural units having an alkyl group having 1 to 14 carbon atoms.
  • Polymers having a structural unit having at least one polar group selected from a carboxy group, a hydroxy group (including a phenolic hydroxy group), a nitrogen-containing aromatic ring group such as an oxazoline ring group, and an amide group and at least one of the above-mentioned structural units having an aromatic ring and structural units having an alicyclic structure are preferred, and polymers having a structural unit having at least one polar group selected from a carboxy group and an oxazoline ring group, and the above-mentioned structural unit having an aromatic ring are more preferred.
  • an oil-soluble polymer having an oxazoline ring group is preferred, and an oil-soluble styrene copolymer containing an oxazoline ring group is more preferred.
  • a commercially available product may be used, for example, EPOCROS RPS-1005 (trade name) manufactured by Nippon Shokubai Co., Ltd.
  • the weight average molecular weight (Mw) of the polymer constituting the resin of the wavelength selective absorption layer is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.
  • the weight average molecular weight of the polymer can be measured as a molecular weight converted into polystyrene by gel permeation chromatography (GPC).
  • a GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation) is used, tetrahydrofuran is used as an eluent, and G3000HXL+G2000HXL columns (both trade names, manufactured by Tosoh Corporation) are used, and detection can be performed by RI (differential refractive index) at 23°C and a flow rate of 1 mL/min.
  • RI differential refractive index
  • the wavelength selective absorption layer preferably contains 5% by mass or more of the matrix resin, more preferably 20% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more.
  • the content of the matrix resin in the wavelength selective absorption layer is usually 99.90% by mass or less, and preferably 99.85% by mass or less.
  • the wavelength-selective absorption layer can contain an appropriately selected resin component exhibiting extensibility (also referred to as an extensible resin component).
  • resin component exhibiting extensibility also referred to as an extensible resin component.
  • specific examples include acrylonitrile-butadiene-styrene resin (ABS resin), styrene-butadiene resin (SB resin), isoprene resin, butadiene resin, polyether-urethane resin, and silicone resin. Furthermore, these resins may be further hydrogenated as appropriate.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • SB resin styrene-butadiene resin
  • isoprene resin butadiene resin
  • polyether-urethane resin polyether-urethane resin
  • silicone resin silicone resin
  • these resins may be further hydrogenated as appropriate.
  • the extensible resin component it is preferable to use an ABS resin or an SB resin, and it is more preferable to use an SB resin.
  • the above-mentioned SB resin can be, for example, a commercially available product.
  • commercially available products include TR2000, TR2003, and TR2250 (all trade names, manufactured by JSR Corporation), Clearen 210M, 220M, and 730V (all trade names, manufactured by Denka Company Limited), Asaflex 800S, 805, 810, 825, 830, and 840 (all trade names, manufactured by Asahi Kasei Corporation), and Eporex SB2400, SB2610, and SB2710 (all trade names, manufactured by Sumitomo Chemical Co., Ltd.).
  • the wavelength-selective absorption layer preferably contains 15 to 95% by mass of the extensible resin component in the matrix resin, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.
  • the extensible resin component When the extensible resin component is used alone to prepare a sample 30 ⁇ m thick and 10 mm wide, and the breaking elongation at 25°C is measured in accordance with JIS 7127, it is preferable that the extensible resin component exhibits a breaking elongation of 10% or more, and more preferably 20% or more.
  • the wavelength selective absorption layer preferably contains an adhesion improver to improve adhesion to the gas barrier layer.
  • the structure of the adhesion improver is not particularly limited as long as adhesion to the gas barrier layer is obtained.
  • the adhesion improver preferably has a structure that bonds with the hydroxyl group of the polyvinyl alcohol, more preferably a polymer having a boronic acid-containing group, and even more preferably a polymer containing a structural unit having a boronic acid-containing group.
  • the boronic acid-containing group is not limited to a group represented by -B(OH) 2 , but also refers to a group represented by -B( OR11 )( OR12 ) ( R11 and R12 may be linked together) in the structural unit represented by general formula (II) described in paragraph [0025] of Japanese Patent No. 6722602.
  • the boronic acid-containing polymer contained in the wavelength selective absorption layer is unevenly distributed in the wavelength selective absorption layer at the interface with the gas barrier layer, and —B—OH in the boronic acid-containing group forms a chemical bond such as a boronic acid ester with a hydrophilic group such as an —OH group in the gas barrier layer, thereby improving adhesion.
  • the boronic acid-containing polymer is not included in the polymer constituting the transparent resin in the wavelength selective absorption layer.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the phrase "the wavelength selective absorption layer further contains a polymer having a boronic acid-containing group” includes an embodiment in which the wavelength selective absorption layer contains a polymer having a boronic acid-containing group, as well as an embodiment in which the boronic acid-containing group of the polymer having the boronic acid-containing group is used to form a chemical bond with a hydrophilic group such as an —OH group in the gas barrier layer.
  • acid-modified resins such as the "Tuftec M series” manufactured by Asahi Kasei Chemicals Corporation, the “Admer series” and “Unistall series” manufactured by Mitsui Chemicals, Inc., the “Umex series” manufactured by Sanyo Chemical Industries, Ltd., and the “Hardlen series” manufactured by Toyobo Co., Ltd. can also be preferably used as adhesion improvers to be added to the wavelength-selective absorption layer.
  • the content of the adhesion improver in the wavelength selective absorption layer is, for example, preferably 0.1 to 15% by mass, more preferably 0.3 to 13% by mass, and even more preferably 0.5 to 10% by mass.
  • the light-absorbing and dissipating layer and wavelength-selective and absorbing layer of the present invention may contain a leveling agent (surfactant) and the like in addition to the above-mentioned components (dye, resin, and in the light-absorbing and dissipating layer, further a radical generator).
  • a leveling agent surfactant
  • the light-absorbing and dissipating layer and the wavelength-selective absorption layer may each appropriately contain a leveling agent (surfactant).
  • a leveling agent surfactant
  • Commonly used compounds may be used as the leveling agent, with fluorine-containing surfactants being particularly preferred. Specific examples include the compounds described in paragraphs [0028] to [0056] of JP-A No. 2001-330725.
  • commercially available products such as the Megafac F (trade name) series manufactured by DIC Corporation may also be used.
  • the content of the leveling agent in the light-absorbing and disappearing layer or the wavelength-selective absorbing layer is adjusted appropriately depending on the purpose.
  • the light-absorbing and dissipating layer and the wavelength-selective absorbing layer may each contain low-molecular-weight plasticizers, oligomeric plasticizers, retardation adjusters, ultraviolet absorbers, anti-degradants, peel promoters, infrared absorbers, antioxidants, fillers, compatibilizers, etc.
  • Fine particles may be added to the surfaces of the laminate I, and the laminates II and pre-III to impart slip properties and prevent blocking.
  • fine particles silica (silicon dioxide, SiO 2 ) whose surface is coated with hydrophobic groups and takes the form of secondary particles is preferably used.
  • fine particles such as titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate may also be used.
  • Examples of commercially available fine particles include R972 and NX90S (both manufactured by Nippon Aerosil Co., Ltd.).
  • microparticles function as a so-called matting agent, and the addition of the microparticles creates minute irregularities on the surface of laminate I and the laminate of laminate II and laminate pre-III. These irregularities prevent laminate I from sticking together, laminate II and laminate pre-III from sticking together, or laminate I from sticking to other films, or laminate II from sticking to other films, even when they are overlapped, ensuring smoothness.
  • the minute irregularities caused by protrusions of fine particles protruding from the filter surface have a particularly large effect of improving slip properties and anti-blocking properties when the number of protrusions having a height of 30 nm or more is 104 / mm2 or more.
  • Methods for applying fine particles to the surface layer of the laminate I, and the laminates of the laminate II and laminate pre-III include means such as multilayer casting and coating.
  • the content of the matting agent in the laminate I, and the laminate of the laminate II and the laminate pre-III is adjusted appropriately depending on the purpose.
  • the matting agent (fine particles) added to the surface of laminate I also referred to as being applied to the surface layer
  • laminates II and laminate pre-III can prevent light transmission-absorption filters II from sticking to each other, or light transmission-absorption filter II and other films, etc., when they are overlapped. It is also preferable to apply a matting agent to the surface layer of the light transmission/absorption filter of the present invention from the same viewpoint as in the case of the laminate I, and the laminate of the laminate II and the laminate pre-III.
  • the light-absorbing and dissipating layer in the laminate I and laminate pre-III and the wavelength-selective and absorbing layer in the laminate I and laminate II can be produced by a conventional method such as a solution film-forming method, a melt extrusion method, or a method of forming a coating layer on a substrate film (support film) by any method (coating method), and stretching can also be combined as appropriate.
  • the light-absorbing and dissipating layer and the wavelength-selective and absorbing layer are preferably produced by a coating method.
  • a solution of the material for the light-absorbing and disappearing layer or the wavelength-selective absorption layer is applied to a support film to form a coating layer.
  • a release agent or the like may be applied in advance to the surface of the support film as appropriate to control adhesion to the coating layer.
  • the coating layer may also be formed on the support film via an optional resin layer.
  • the coating layer can be used by laminating it to another member via an adhesive layer in a subsequent process and then peeling off the support film. Any adhesive can be used as the adhesive constituting the adhesive layer.
  • the support film can be stretched together with the solution of the material for the light-absorbing and disappearing layer or the wavelength-selective absorption layer, or with the coating layer laminated on the support film.
  • the solvent used in the solution of the material for the light-absorbing and dissipating layer or wavelength-selective absorption layer can be selected appropriately based on factors such as whether the solvent can dissolve or disperse the material for the light-absorbing and dissipating layer or wavelength-selective absorption layer, whether it can easily form a uniform surface during the coating and drying processes, whether the liquid can be stored, and whether it has an appropriate saturated vapor pressure.
  • the timing of adding the dye and the radical generator to the material of the light-absorbing and disappearing layer is not particularly limited as long as they are added at the time of film formation. For example, they may be added at the time of synthesis of the polymer constituting the matrix resin, or they may be mixed with the material of the light-absorbing and disappearing layer when preparing a coating solution for the material of the light-absorbing and disappearing layer. Note that when the radical generator contains a combination of compound A and compound B, and compound A is bonded to the polymer constituting the resin, compound A is added when the polymer constituting the resin is added.
  • the timing of adding the dye to the material for the wavelength selective absorption layer is not particularly limited as long as it is added at the time of film formation.
  • the dye may be added at the time of synthesis of the polymer constituting the resin, or may be mixed with the material for the wavelength selective absorption layer when preparing a coating solution for the material for the wavelength selective absorption layer.
  • the support film used to form the light-absorbing and disappearing layer or wavelength-selective absorption layer by a coating method or the like preferably has a film thickness of 2 to 100 ⁇ m, more preferably 5 to 100 ⁇ m, even more preferably 10 to 75 ⁇ m, and particularly preferably 15 to 65 ⁇ m.
  • the film thickness is equal to or greater than the above-mentioned preferable lower limit, sufficient mechanical strength is easily ensured, and defects such as curling, wrinkling, and buckling are unlikely to occur.
  • the film thickness is equal to or less than the above-mentioned preferable upper limit
  • a multilayer film comprising a light-absorbing and disappearing layer or wavelength-selective absorption layer and a support film or even a multilayer film comprising a light-absorbing and disappearing layer, a wavelength-selective absorption layer, and a support film, is stored, for example, in a long roll form, the surface pressure applied to the multilayer film is easily adjusted to an appropriate range, and adhesion defects are unlikely to occur.
  • the surface energy of the support film is not particularly limited, but the adhesive strength between Laminate I, Laminate II or Laminate pre-III and the support film can be adjusted by adjusting the relationship between the surface energy of the material and coating solution of the light-absorbing and dissipating layer or wavelength-selective absorption layer and the surface energy of the surface of the support film on which the light-absorbing and dissipating layer or wavelength-selective absorption layer is to be formed. Reducing the difference in surface energy tends to increase adhesive strength, while increasing the difference in surface energy tends to decrease adhesive strength, and these can be set appropriately.
  • the surface roughness of the support film is not particularly limited, but can be adjusted, for example, for the purpose of preventing adhesion failure when a multilayer film of Laminate I, Laminate II, or Laminate pre-III and a support film is stored in the form of a long roll, depending on the relationship between the surface energy, hardness, and surface roughness of the surface of Laminate I, Laminate II, or Laminate pre-III opposite the support film and the surface energy and hardness of the surface of the support film opposite the side on which Laminate I, Laminate II, or Laminate pre-III is formed.
  • Increasing the surface roughness tends to suppress adhesion failure, while decreasing the surface roughness tends to reduce the surface roughness of Laminate I, Laminate II, or Laminate pre-III and the haze of Laminate I, Laminate II, or Laminate pre-III, and can be set appropriately.
  • any suitable material or film can be used as such a support film.
  • Specific materials include polyester polymers (including polyethylene terephthalate), olefin polymers, cycloolefin polymers, (meth)acrylic polymers, cellulose polymers, and polyamide polymers.
  • the support film can be subjected to appropriate surface treatments to adjust its surface properties. For example, corona treatment, room temperature plasma treatment, and saponification treatment can be used to reduce surface energy, while silicone treatment, fluorine treatment, and olefin treatment can be used to increase surface energy.
  • the wavelength selective absorption layer, the diffusion-preventing layer, and the light absorbing and dissipating layer are preferably arranged in this order so as to be in direct contact with each other.
  • the diffusion-inhibiting layer is provided between the wavelength-selective absorption layer and the light-absorbing and dissipating layer, and has the effect of inhibiting components such as dyes contained in the wavelength-selective absorption layer from diffusing into the light-absorbing and dissipating layer, and may be any layer as long as it has the effect of inhibiting components such as dyes and radical generators contained in the light-absorbing and dissipating layer from diffusing into the wavelength-selective absorption layer.
  • Diffusion of the components in the wavelength-selective absorption layer into the light-absorbing and dissipating layer can occur either when the wavelength-selective absorption layer is formed on the light-absorbing and dissipating layer, or when the wavelength-selective absorption layer is formed on the light-absorbing and dissipating layer. Diffusion of the components in the light-absorbing and dissipating layer into the wavelength-selective absorption layer can occur either when the light-absorbing and dissipating layer is formed on the wavelength-selective absorption layer, or when the light-absorbing and dissipating layer is formed on the wavelength-selective absorption layer.
  • the laminate I can suppress the diffusion of components in the wavelength-selective absorption layer into the wavelength-selective absorption layer and the diffusion of components in the light-absorbing and dissipating layer into the wavelength-selective absorption layer, as described above.
  • This allows the fading and decolorization reaction of the dye in the light-absorbing and dissipating layer due to ultraviolet irradiation of the laminate I to occur as a fading and decolorization reaction of the dye in the light-absorbing and dissipating layer caused by a compound in the light-absorbing and dissipating layer that generates radicals upon ultraviolet irradiation.
  • the provision of the diffusion-preventing layer makes it possible for the light transmission and absorption filter I obtained using the laminate I to more effectively achieve the desired light absorption characteristics derived from the wavelength-selective absorption layer and the light-absorbing and dissipating layer, respectively.
  • the diffusion-preventing layer swells due to the solvent (solvent) in the coating solution for forming the light-absorbing/dissipating layer, and the free volume in the diffusion-preventing layer increases.
  • the resin constituting the diffusion-preventing layer provided between the wavelength-selective absorption layer and the light-absorbing/dissipating layer has low affinity for the solvent used when forming the wavelength-selective absorption layer or the light-absorbing/dissipating layer on the diffusion-preventing layer.
  • the resin constituting the diffusion-preventing layer be a resin with low affinity for organic solvents, i.e., a water-soluble resin.
  • the resin constituting the diffusion-preventing layer be a resin with low affinity for organic solvents, i.e., a water-soluble resin.
  • the affinity between the solvent used in forming the wavelength-selective absorption layer or the light-absorbing/dissipating layer and the resin constituting the diffusion-preventing layer can be evaluated by the solubility parameter ⁇ t calculated by the Hoy method.
  • the solubility parameter ⁇ t can be calculated, for example, by the method described in "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature “Properties of Polymers 3rd , Elsevier, (1990).”
  • the absolute value of the difference between the ⁇ t value of the solvent used when forming wavelength selective absorption layer or light absorbing and dissipating layer and the ⁇ t value of the resin that constitutes diffusion-inhibiting layer is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 3.0 or more, particularly preferably 4.0 or more.By adjusting the absolute value of the difference between the ⁇ t value of the solvent used when forming wavelength selective absorption layer or light absorbing and dissipating layer and the ⁇ t value of the resin that constitutes diffusion-inhibiting layer to be above the above-mentioned preferred value or more, when the solution that forms wavelength selective absorption layer or light absorbing and dissipating layer is applied on the diffusion-inhibiting layer
  • the upper limit of the absolute value of the difference between the ⁇ t value of the solvent used when forming the wavelength-selective absorption layer or the light-absorbing and disappearing layer and the ⁇ t value of the resin constituting the diffusion-preventing layer is practically 20.0 or less, and the absolute value of the difference between the ⁇ t value of the solvent used when forming the wavelength-selective absorption layer or the light-absorbing and disappearing layer and the ⁇ t value of the resin constituting the diffusion-preventing layer is preferably 1.0 to 20.0, more preferably 2.0 to 20.0, even more preferably 3.0 to 20.0, and particularly preferably 4.0 to 20.0.
  • the ⁇ t value of the solvent means the weight average of the ⁇ t values of the respective solvents.
  • the ⁇ t value of the resin means the weight average of the respective resins.
  • the resin constituting the diffusion-preventing layer is preferably a water-soluble resin.
  • the water-soluble resin may be either a thermosetting resin or a thermoplastic resin, and if it is a thermoplastic resin, it may be crystalline or amorphous.
  • preferred water-soluble resins include polyvinyl alcohol, polyvinylpyridine, (meth)acrylic resins, polyurethanes, polyesters, epoxy resins, cellulose resins, etc. These water-soluble resins may be at least partially modified.
  • the polyvinyl alcohol may be modified or unmodified. Examples of modified polyvinyl alcohol include modified polyvinyl alcohols into which groups such as acetoacetyl groups and carboxy groups have been introduced.
  • the degree of saponification of the polyvinyl alcohol is preferably 60.0 mol% or more, more preferably 80.0 mol% or more, and even more preferably 90.0 mol% or more, from the viewpoint of further improving the barrier properties (permeation suppression performance) of organic solvents. There is no particular upper limit, but 99.99 mol% or less is practical.
  • the degree of saponification of the polyvinyl alcohol is a value calculated based on the method described in JIS K 6726 (1994).
  • the (meth)acrylic resin may be any resin containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid ester, and is preferably a resin containing a structural unit derived from (meth)acrylic acid.
  • the proportion of the structural units derived from (meth)acrylic acid in all structural units constituting the (meth)acrylic resin is preferably 70 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 90 to 100 mol %.
  • the resin constituting the diffusion-preventing layer is preferably at least one of polyvinyl alcohol and (meth)acrylic resin, and more preferably at least one of polyvinyl alcohol and poly(meth)acrylic acid, because the crystalline portion can effectively suppress the permeation of solvent molecules and swelling due to the organic solvent used in the dye layer is unlikely to occur.
  • the resin constituting the diffusion-preventing layer is poly(meth)acrylic acid.
  • the weight average molecular weight (Mw) of the resin constituting the diffusion-preventing layer is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.
  • the content of the resin (preferably a water-soluble resin) in the diffusion-preventing layer is, for example, preferably 90% by mass or more, more preferably 95% by mass or more. There is no particular upper limit, but it can be 100% by mass.
  • the thickness of the diffusion-inhibiting layer is preferably 0.1 to 5.0 ⁇ m, and more preferably 0.2 to 4.0 ⁇ m.
  • the method for forming the diffusion-preventing layer is not particularly limited, but examples thereof include a method of forming the diffusion-preventing layer on the wavelength-selective absorption layer or the light-absorbing/disappearing layer by a conventional casting method such as spin coating or slit coating.
  • the solvent used in this case is not particularly limited as long as the desired diffusion-preventing layer can be obtained.
  • the resin constituting the diffusion-preventing layer is a water-soluble resin
  • water-soluble solvents such as water, alcohols such as ethanol and isopropyl alcohol can be preferably used.
  • the diffusion-preventing layer is not limited to being provided between the wavelength-selective absorption layer and the light-absorbing and dissipating layer in the laminate I, but may be provided as appropriate between two adjacent layers constituting each of the laminates I, II, and pre-III.
  • a preferred configuration is one in which the support film, the diffusion-preventing layer, and the light-absorbing and dissipating layer are arranged in this order so as to be in direct contact with each other.
  • the diffusion-preventing layer can be formed on the support film by the above-mentioned method.
  • the film thicknesses of the light-absorbing and disappearing layer and the wavelength-selective absorption layer are not particularly limited, but are preferably 1 to 18 ⁇ m, more preferably 1 to 12 ⁇ m, and even more preferably 1 to 8 ⁇ m.
  • the thickness is equal to or less than the above-mentioned preferred upper limit, the addition of a dye at a high concentration to a thin film can suppress a decrease in polarization degree due to fluorescence emitted by the dye (pigment). Furthermore, the effect of the quencher is also easily manifested in the light-absorbing and disappearing layer.
  • a film thickness of 1 to 18 ⁇ m means that the thickness of the light-absorbing and disappearing layer or the wavelength-selective and absorbing layer is within the range of 1 to 18 ⁇ m no matter where it is measured. This also applies to film thicknesses of 1 to 12 ⁇ m and 1 to 8 ⁇ m.
  • the film thickness can be measured using an electronic micrometer (for example, manufactured by Anritsu Corporation).
  • the largest absorbance at a wavelength showing maximum absorption within a wavelength range of 400 to 700 nm (hereinafter also simply referred to as "Ab( ⁇ max )”) is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.7 or more.
  • the absorbance of the laminate I, laminate II, and laminate pre-III can be adjusted by the type of dye, the amount added, or the film thickness.
  • the light-absorbing and dispersible layer in the laminate I and laminate pre-III preferably has a discoloration rate of 85% or more, more preferably 87% or more, and even more preferably 90% or more, when irradiated with ultraviolet light at 25° C. There is no particular upper limit, and a value of 100% is also preferred.
  • the decolorization rate is calculated from the following formula using the values of Ab( ⁇ max ) before and after the ultraviolet irradiation test.
  • Decolorization rate (%) 100- (Ab( ⁇ max ) after ultraviolet irradiation/Ab( ⁇ max ) before ultraviolet irradiation) ⁇ 100
  • the ultraviolet irradiation test is carried out by irradiating the laminate I and laminate pre-III with ultraviolet light at an illuminance of 100 mW/cm 2 and an irradiation dose of 2000 mJ/cm 2 at room temperature (45°C) using an ultra-high pressure mercury lamp (for example, UL750 manufactured by HOYA Corporation) under atmospheric pressure (101.33 kPa).
  • the absorbance and ultraviolet irradiation test can be measured and calculated by the method described in [Measurement of absorbance at first and second sites].
  • the light-absorbing and dissipative layer hardly generates absorption (secondary absorption) derived from a new colored structure accompanying decomposition of the dye.
  • the presence or absence of absorption due to a new colored structure accompanying decomposition of the dye can be confirmed based on the ratio of absorbance at a specific wavelength to the above Ab( ⁇ max ).
  • the specific wavelength is selected to be a wavelength at which the dye shows almost no absorption before UV irradiation and at which new absorption due to decomposition of the dye is observed.
  • the presence or absence of absorption due to the new colored structure accompanying the decomposition of the dye can be confirmed based on the ratio of absorbance at a specific wavelength to the above Ab( ⁇ max ).
  • the specific wavelength is selected to be a wavelength at which the dye shows almost no absorption before UV irradiation and at which new absorption due to the decomposition of the dye is observed.
  • the presence or absence of absorption derived from a new colored structure accompanying dye decomposition can be confirmed based on the ratio of the absorbance at a wavelength of 450 nm (hereinafter also simply referred to as "Ab(450)”) to the above Ab( ⁇ max ).
  • this value is preferably less than 8.5%, more preferably 7.0% or less, and even more preferably 5.0% or less.
  • the lower limit There is no particular restriction on the lower limit, but from the viewpoint of validating the evaluation of the presence or absence of secondary absorption accompanying dye decomposition, -10% or more is practical, and -6% or more is preferable.
  • the absorbance at a wavelength of 650 nm (hereinafter also referred to simply as "Ab(650)”) may be used instead of the absorbance at a wavelength of 450 nm, and the evaluation can also be performed based on the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV).
  • the preferred range of the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV) is the same as the value obtained by subtracting the ratio of the above formula (I) from the ratio of the above formula (II).
  • (III) (Ab(650) before ultraviolet irradiation/Ab( ⁇ max ) before ultraviolet irradiation) ⁇ 100%
  • (IV) (Ab(650) after ultraviolet irradiation/Ab( ⁇ max ) before ultraviolet irradiation) ⁇ 100%
  • the ultraviolet irradiation test can be preferably carried out in the same manner as described above for the extinction rate.
  • the light-absorbing and dissipative layer can exhibit excellent discoloration properties if both the discoloration rate and the value used to confirm the presence or absence of absorption due to the new colored structure resulting from the decomposition of the dye fall within the preferred ranges.
  • the ultraviolet-unirradiated portion of the light-absorbing and disappearing layer (the portion having the light-absorbing effect) satisfies the description of Ab( ⁇ max ) for the laminate I, laminate II, and laminate pre-III described above.
  • the laminate I, laminate II, and laminate pre-III may be subjected to a hydrophilization treatment such as a glow discharge treatment, a corona discharge treatment, or an alkaline saponification treatment, and the corona discharge treatment is preferably used. It is also preferable to apply the methods disclosed in JP-A-6-94915 or JP-A-6-118232.
  • the resulting film may be subjected to a heat treatment process, a superheated steam contact process, an organic solvent contact process, etc. as needed.
  • Surface treatment may also be performed as appropriate.
  • a layer made of a pressure-sensitive adhesive composition having a base polymer such as a (meth)acrylic resin, a styrene resin, a silicone resin, or the like, to which a crosslinking agent such as an isocyanate compound, an epoxy compound, or an aziridine compound has been added can also be applied.
  • a base polymer such as a (meth)acrylic resin, a styrene resin, a silicone resin, or the like
  • a crosslinking agent such as an isocyanate compound, an epoxy compound, or an aziridine compound has been added
  • the description of the adhesive layer in the OLED display device described later can be applied.
  • the laminate I may have a gas barrier layer on at least one surface.
  • the laminate I can be a laminate I that achieves both excellent decolorization properties and excellent light fastness, and can be suitably used to produce the light transmission-absorption filter I described above.
  • the laminate II may have a gas barrier layer.
  • the laminate II has two layers, the first wavelength selective absorption layer and the second wavelength selective absorption layer, it is preferable to have a gas barrier layer between these layers. This not only can suppress decomposition of the dye by oxygen gas, but also can suppress energy transfer between the first and second wavelength selective absorption layers, thereby further suppressing decomposition of the dye.
  • the laminate pre-III may have a gas barrier layer on at least one surface.
  • the laminate pre-III can be made to have both excellent decolorization properties and excellent light resistance, and can be suitably used to produce the light transmission-absorption filter II described above.
  • the material for forming the gas barrier layer is not particularly limited, and examples thereof include organic materials (preferably crystalline resins) such as polyvinyl alcohol and polyvinylidene chloride, organic-inorganic hybrid materials such as sol-gel materials, and inorganic materials such as SiO 2 , SiO x , SiON, SiN x and Al 2 O 3.
  • the gas barrier layer may be a single layer or a multilayer, and in the case of a multilayer, examples of the gas barrier layer include an inorganic dielectric multilayer film and a multilayer film in which organic materials and inorganic materials are alternately laminated.
  • the laminate I has a gas barrier layer at least on the surface that comes into contact with air when the above-described light transmission-absorption filter I is used, thereby making it possible to suppress a decrease in the absorption intensity of the dye in the light transmission-absorption filter I.
  • the gas barrier layer may be provided on only one surface of the laminate I or on both surfaces.
  • the laminate pre-III has a gas barrier layer at least on the surface of the light-absorbing and dissipating layer that comes into contact with air, so that a decrease in the absorption intensity of the dye in the light-absorbing and dissipating layer can be suppressed in the state of the laminate pre-III and the laminate III obtained by exposing the laminate pre-III with a mask.
  • the gas barrier layer may be provided on only one surface or both surfaces of the laminate pre-III. From the same viewpoint as in the case of the light transmission-absorption filter I obtained using the laminate I, it is preferable to provide a gas barrier layer in the light transmission-absorption filter of the present invention, and the description of the laminate I can be applied.
  • the gas barrier layer contains a crystalline resin
  • the gas barrier layer contains a crystalline resin, has a layer thickness of 0.1 ⁇ m to 10 ⁇ m, and has an oxygen permeability of 60 cc/ m2 day atm or less.
  • the "crystalline resin” is a resin that has a melting point at which it undergoes a phase transition from crystal to liquid when the temperature is increased, and is capable of imparting gas barrier properties to oxygen gas to the gas barrier layer.
  • gas barrier layer containing a crystalline resin having a layer thickness of 0.1 ⁇ m to 10 ⁇ m, and having an oxygen permeability of 60 cc/ m2 ⁇ day ⁇ atm or less
  • gas barrier layer described in paragraphs [0180] to [0184] of WO 2022/149510, and the descriptions therein can be applied as is.
  • the method for forming the gas barrier layer is not particularly limited, but may be a conventional method.
  • examples include a casting method such as spin coating or slit coating.
  • Other examples include a method of laminating a commercially available resin gas barrier film or a pre-prepared resin gas barrier film.
  • examples include a plasma enhanced chemical vapor deposition (CVD) method, a sputtering method, and a vapor deposition method.
  • CVD plasma enhanced chemical vapor deposition
  • the gas barrier layer can be formed directly on the laminate I that has no gas barrier layer and that has been produced by the above-mentioned production method. In this case, it is also preferable to subject the surface of the laminate I on which the gas barrier layer is to be formed to a corona treatment.
  • the gas barrier layer may be formed directly on the first wavelength selective absorption layer or the second wavelength selective absorption layer produced by the above-mentioned production method.
  • the gas barrier layer may be formed directly on the light-absorbing and disappearing layer formed by the above-mentioned production method.
  • the laminate I, laminate II, and laminate pre-III may appropriately include the gas barrier layer or any optically functional film as long as the effects of the present invention are not impaired.
  • the optical properties and materials of the above-mentioned optional optical functional film are not particularly limited, but a film containing (or having as its main component) at least one of cellulose ester resin, acrylic resin, cyclic olefin resin, and polyethylene terephthalate resin can be preferably used. Note that either an optically isotropic film or an optically anisotropic retardation film can be used.
  • the optional optical functional film for example, Fujitac TD80UL (trade name, manufactured by Fujifilm Corporation) can be used as the film containing a cellulose ester resin.
  • examples of the film containing an acrylic resin include an optical film containing a (meth)acrylic resin containing a styrene-based resin as described in Japanese Patent No. 4570042, an optical film containing a (meth)acrylic resin having a glutarimide ring structure in the main chain as described in Japanese Patent No. 5041532, an optical film containing a (meth)acrylic resin having a lactone ring structure as described in Japanese Patent Laid-Open No. 2009-122664, and an optical functional film containing a (meth)acrylic resin having a glutaric anhydride unit as described in Japanese Patent Laid-Open No. 2009-139754.
  • a film containing a cyclic olefin resin as a film containing a cyclic olefin resin, a cyclic olefin resin film described in paragraph [0029] and thereafter of JP-A-2009-237376, and a cyclic olefin resin film containing an additive that reduces Rth described in JP-A-4881827 and JP-A-2008-063536 can be used.
  • the light transmission/absorption filter I can be obtained by irradiating the laminate I with ultraviolet light and exposing it using a mask.
  • the mask pattern is preferably such that the portions corresponding to the non-light-emitting portions of the OLED display element (portions from which display light is not emitted) become the above-mentioned second portions, and the portions corresponding to the light-emitting portions of the OLED display element (portions from which display light is emitted) become the above-mentioned first portions.
  • the light transmission-absorption filter I can be suitably obtained by irradiating the laminate I with ultraviolet light using a mask pattern that masks the portions corresponding to the non-light-emitting portions of the OLED display element and does not mask the portions corresponding to the light-emitting portions of the OLED display element.
  • the area ratio between the non-light-emitting portion of the OLED display element and the light-emitting portion of the OLED display element is as described above.
  • the conditions for ultraviolet irradiation can be adjusted as appropriate to obtain a light transmission-absorption filter I having a first region that includes a light-absorbency-eliminating region.
  • the pressure can be atmospheric pressure (101.33 kPa)
  • the temperature can be a mild temperature of 10 to 60°C
  • the lamp output can be 10 to 320 W/cm
  • the lamp used can be an air-cooled metal halide lamp, an ultra-high pressure mercury lamp, or the like.
  • the irradiation dose can be 200 to 5000 mJ/ cm2 .
  • the light transmission/absorption filter II can be obtained by laminating the laminate II and a laminate III obtained by irradiating the laminate pre-III with ultraviolet light and exposing it using a mask.
  • the mask pattern the area ratio between the non-light-emitting portions of the OLED display element and the light-emitting portions of the OLED display element, and the conditions for ultraviolet light irradiation
  • the descriptions relating to the mask pattern, the area ratio between the non-light-emitting portions of the OLED display element and the light-emitting portions of the OLED display element, and the conditions for ultraviolet light irradiation in the above-mentioned light-transmitting-absorbing filter I can be applied by replacing laminate I with laminate pre-III and light-transmitting-absorbing filter I with laminate III.
  • the method for laminating the laminate II and the laminate III is not particularly limited, and they may be laminated via a pressure-sensitive adhesive layer, or they may be attached to each other to form a laminate structure.
  • a pressure-sensitive adhesive layer the description of the pressure-sensitive adhesive layer described below can be applied.
  • the light transmission/absorption filter of the present invention may have the above-mentioned optically functional film.
  • the light transmission/absorption filter of the present invention may also have a layer containing an ultraviolet absorber.
  • the ultraviolet absorber any commonly used compound can be used without any particular limitations, and examples thereof include the ultraviolet absorbers in the ultraviolet absorbing layer described below.
  • the resin constituting the layer containing the ultraviolet absorber is also without any particular limitations, and examples thereof include the resins in the ultraviolet absorbing layer described below.
  • the content of the ultraviolet absorber in the layer containing the ultraviolet absorber is adjusted appropriately depending on the purpose.
  • Display element intermediate product In producing the OLED display element of the present invention including the light-transmitting-absorbing filter I, it is also preferable to use a display element intermediate including the laminate I.
  • the display element intermediate includes the laminate I
  • the other configurations of the display element intermediate can be any configuration of an OLED display element that is commonly used in display devices, without any particular limitations.
  • the laminate I and the OLED display element may be laminated so as to be in direct contact with each other, or may be bonded together via an adhesive layer.
  • the adhesive layer may be the same as the adhesive layer described below.
  • an optional layer such as a barrier film may be laminated via the adhesive layer.
  • the display element intermediate product may have a laminate structure in which either the wavelength-selective absorption layer or the light-absorbing and dissipating layer in the laminate I is closer to the OLED display element. From the viewpoint of being able to discolor the light-absorbing and dissipating layer with a small amount of ultraviolet light irradiation, it is preferable that the display element intermediate product have a laminate structure in which the wavelength-selective absorption layer in the laminate I is closer to the OLED display element than the light-absorbing and dissipating layer.
  • the OLED display element of the present invention includes the light-absorbing filter of the present invention, and preferably includes the above-mentioned light-absorbing filter I or II.
  • the OLED display element may use, without any particular limitation, the configuration of an OLED display element that is normally used in a display device, as the other configuration.
  • OLED display element including light-transmitting/absorbing filter I The display element intermediate is exposed to ultraviolet light through a mask, thereby obtaining the OLED display element of the present invention, in which the laminate I contained in the display element intermediate is converted into a light-transmitting/absorbing filter I.
  • the display element intermediate is an intermediate product as a precursor to the OLED display element of the present invention
  • the OLED display element of the present invention means a finished product as an OLED display element.
  • the OLED display element of the present invention has a configuration in which the first portion of the light transmission-absorption filter of the present invention is disposed on a light-emitting portion of the OLED display element, and the second portion of the light transmission-absorption filter of the present invention is disposed on a non-light-emitting portion of the OLED display element.
  • an OLED display element of the present invention including the above-mentioned light-transmitting-absorbing filter II can be obtained, for example, by previously producing the above-mentioned light-transmitting-absorbing filter II having first and second regions corresponding to the pattern of the light-emitting portions and non-light-emitting portions of the OLED display element, and then bonding this light-transmitting-absorbing filter II to the OLED display element or laminating it via another layer.
  • the above description of the lamination of the laminate I and the OLED display element can be applied as is to the lamination of the light transmitting/absorbing filter II and the OLED display element.
  • the layer structure may be such that either layer of the laminate II or the laminate III in the light-transmitting-absorbing filter II is closer to the OLED display element. Note that, as described below, from the viewpoint of easily realizing suppression of color shift due to viewing angle of display light, it is preferable that the laminate III be closer to the OLED display element than the laminate II.
  • an OLED display element including a light-transmitting-absorbing filter II by adjusting the distance between the laminate III in the light-transmitting-absorbing filter II and the OLED display element layer, it is possible to suppress the effect on the transmittance of display light (reduction in brightness) and, when applied to an OLED display device having a microcavity structure, to adjust the viewing angle dependence of the color of the display light. This is because, as the distance between the laminate III in the light-transmitting-absorbing filter II and the OLED display element layer increases, the proportion of light transmitted through the second portion in the total display light perceived by the viewer increases due to the effect of parallax.
  • the distance between the laminate III and the OLED display element layer may be, for example, 2 to 45 ⁇ m.
  • the distance between the laminate III and the OLED display element layer is preferably 5 to 35 ⁇ m, more preferably 10 to 30 ⁇ m, even more preferably 15 to 28 ⁇ m, and most preferably 20 to 25 ⁇ m.
  • the "distance between the laminate III and the OLED display element layer" is synonymous with the "distance d between the laminate III and the light emitting element layer" in the OLED display elements II-1 to II-3 described later.
  • an OLED display element including a light-transmitting/absorbing filter II from the viewpoint of simultaneously suppressing the color change of the display light due to the viewing angle and suppressing a decrease in brightness, the following OLED display elements II-1 to II-3 are preferred.
  • the following OLED display elements II-1 to II-3 a laminate II, a laminate III, and a light-emitting element layer are arranged in this order, and the elements are incorporated into an OLED display device so that the laminate II faces the viewer.
  • OLED display element II-1 An OLED display element, wherein a distance d between the laminate III and the light-emitting element layer, an average area S of each light-emitting element constituting the light-emitting element layer, and an average area Sf of a portion of the first light-transmitting/absorbing site located directly above each light-emitting element satisfy the relationships of the following formulas (1) and (2): Formula (1) 0.6 ⁇ d/ ⁇ S ⁇ 7.5 Formula (2) 0.7 ⁇ Sf/S ⁇ 1.5 (OLED display element II-2) an OLED display element, wherein a distance d between the laminate III and the light-emitting element layer, an average area S B of each blue light-emitting element constituting the light-emitting element layer, and an average area Sf B of a portion of the first light-transmitting and absorbing site located directly above each blue light-emitting element satisfy the relationships of the following formulas (3) and (4): Formula (3) 1.0 ⁇ d/ ⁇ S B ⁇ 7.0 Formula (4) 0.8 ⁇ Sf B /S
  • the unit of the distance d between the laminate III and the light emitting element layer is ⁇ m
  • the unit of each of the average areas S, Sf, S B , Sf B , S G and Sf G is ⁇ m 2 .
  • the "distance d between the laminate III and the light-emitting element layer” means the distance between the mask-exposed light-absorbing and dissipative layer in the laminate III and the light-emitting element layer, and is a value measured by observing a cross section of an element including the laminate III and the light-emitting element layer.
  • the method for observing the cross section is not particularly limited, and examples thereof include a method in which a cross section cut out with a microtome is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average area S B of each blue light-emitting element constituting the light-emitting element layer and the average area S G of each green light-emitting element constituting the light-emitting element layer are both values measured by observation with an optical microscope.
  • the average area S of each light-emitting element constituting the light-emitting element layer means the number average of the areas of each color light-emitting element, and is a value measured and calculated by dividing the sum of the areas of each color light-emitting element by the total number of light-emitting elements.
  • the sum of the areas of each color light-emitting element is measured by observation with an optical microscope.
  • the "average area Sf of the portions of the first light-transmitting and absorbing sites located directly above each light-emitting element" refers to the number average value of the areas of the first sites that overlap with the emitted light when light is emitted from the surface of each light-emitting element perpendicular to the surface.
  • the average areas Sf, Sf B , and Sf G are values measured by observation with an optical microscope.
  • the above formula (1) preferably satisfies 1.5 ⁇ d/ ⁇ S ⁇ 7.0, more preferably 2.5 ⁇ d/ ⁇ S ⁇ 6.0, and further preferably 3.5 ⁇ d/ ⁇ S ⁇ 5.7.
  • the above formula (2) preferably satisfies 0.8 ⁇ Sf/S ⁇ 1.3, and more preferably satisfies 0.9 ⁇ Sf/S ⁇ 1.1.
  • the above formula (3) preferably satisfies 1.5 ⁇ d/ ⁇ S B ⁇ 7.0, more preferably 2.5 ⁇ d/ ⁇ S B ⁇ 5.7, and further preferably 3.5 ⁇ d/ ⁇ S B ⁇ 5.5. In the above formula (4), it is preferable that 0.9 ⁇ Sf B /S B ⁇ 1.1.
  • the above formula (5) preferably satisfies 1.5 ⁇ d/ ⁇ SG ⁇ 7.0, more preferably 2.7 ⁇ d/ ⁇ SG ⁇ 6.7, and further preferably 4.0 ⁇ d/ ⁇ SG ⁇ 5.0.
  • the organic electroluminescence display device of the present invention (also referred to as an organic EL (electroluminescence) display device or OLED (organic light emitting diode) display device, and in the present invention, also abbreviated as an OLED display device) includes the light transmission/absorption filter of the present invention or the OLED display element of the present invention.
  • OLED display device of the present invention includes the light transmission-absorption filter of the present invention or the OLED display element of the present invention, the other components of a commonly used OLED display device can be used without any particular limitations.
  • the OLED display element of the present invention is incorporated into the OLED display device of the present invention so that the light transmission-absorption filter of the present invention is on the external light side. Furthermore, as described above, the light transmission-absorption filter of the present invention is incorporated into the OLED display device of the present invention so that the first region is disposed on the light-emitting portion of the OLED display element and the second region is disposed on the non-light-emitting portion of the OLED display element.
  • the area ratio between the non-light-emitting portion and the light-emitting portion of the OLED display element is usually 90/10 to 60/40.
  • Examples of the configuration of the OLED display device of the present invention are not particularly limited, but when it includes the light transmission-absorbing filter of the present invention, examples include a display device comprising, from the opposite side to external light, glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a pressure-sensitive adhesive layer, the light transmission-absorbing filter of the present invention, a pressure-sensitive adhesive layer, glass, a pressure-sensitive adhesive layer, and a surface film.
  • a display device comprising, from the opposite side to external light, glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a pressure-sensitive adhesive layer, the light transmission-absorbing filter of the present invention, a pressure-sensitive adhesive layer, glass, a pressure-sensitive adhesive layer, and a surface film.
  • examples include a display device comprising, from the opposite side to external light, glass, a layer including a TFT (thin film transistor), the OLED display element of the present invention, a barrier film, glass, a pressure-sensitive adhesive layer, and a surface film.
  • the OLED display element has a configuration in which an anode electrode, a light-emitting layer, and a cathode electrode are arranged in this order.
  • layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer are included between the anode electrode and the cathode electrode.
  • a resin film may be used.
  • the surface of the light transmission-absorption filter of the present invention or the OLED display element of the present invention facing external light may be bonded, via an adhesive layer, to glass, a barrier film, an optically functional film having an antireflection layer or the like, or a polarizing plate including a polarizer and a polarizing plate protective film.
  • the surface of the light transmission-absorption filter of the present invention or the OLED display element of the present invention facing the external light is preferably bonded, via an adhesive layer, to glass (substrate), a barrier film, or a layer including a TFT.
  • the above description of the pressure-sensitive adhesive layer shall be read as a description relating to the pressure-sensitive adhesive layer that the OLED display element of the present invention has on its outermost surface.
  • the descriptions relating to the pressure-sensitive adhesive layer and the forming method in the OLED display device described in [0239] to [0290] of WO 2021/132674 can be applied as is.
  • the pressure-sensitive adhesive composition described in WO 2021/132674 preferably contains an ultraviolet absorber described later in terms of the light resistance of the light transmission-absorption filter of the present invention and the light transmission-absorption filter contained in the OLED display element of the present invention.
  • the light transmission-absorption filter of the present invention or the OLED display element of the present invention may be bonded to an optically functional film via a pressure-sensitive adhesive layer on the surface facing the external light side.
  • the light transmission-absorption filter of the present invention or the OLED display element of the present invention is preferably bonded to glass (substrate) via a pressure-sensitive adhesive layer on the surface facing the external light side.
  • the method for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a method in which a pressure-sensitive adhesive composition is applied to the laminate I, the light transmission-absorption filter of the present invention (preferably light transmission-absorption filter I) or the OLED display element of the present invention by a conventional means such as a bar coater, followed by drying and curing; and a method in which the pressure-sensitive adhesive composition is first applied to the surface of a release substrate, dried, and then the pressure-sensitive adhesive layer is transferred to the laminate I, the light transmission-absorption filter of the present invention (preferably light transmission-absorption filter I) or the OLED display element of the present invention using the release substrate, followed by aging and curing.
  • the release substrate is not particularly limited, and any release substrate can be used, for example, the support film in the above-mentioned production methods of Laminate I, Laminate II, and Laminate pre-III.
  • the conditions for application, drying, aging and curing can be appropriately adjusted based on conventional methods.
  • the OLED display device of the present invention including the light transmission-absorption filter of the present invention or the OLED display element of the present invention, preferably has a layer (hereinafter also referred to as an "ultraviolet absorbing layer") that inhibits light absorption (ultraviolet absorption) of the compound that generates radicals upon ultraviolet irradiation, on the viewer side of the light transmission-absorption filter of the present invention or the OLED display element of the present invention.
  • an ultraviolet absorbing layer By providing the ultraviolet absorbing layer, it is possible to prevent fading of the light transmission-absorption filter of the present invention or the light transmission-absorption filter of the present invention included in the OLED display element of the present invention due to external light.
  • the ultraviolet absorbing layer used in the present invention will be described below.
  • the ultraviolet absorbing layer generally contains a resin and an ultraviolet absorbing agent.
  • ultraviolet absorbers preferably used in the present invention include hindered phenol compounds, benzophenone compounds such as hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds, and nickel complex salt compounds.
  • the hindered phenol compounds and benzotriazole compounds the hindered phenol compounds and benzotriazole compounds described in paragraph [0227] of WO 2023/234353 can also be suitably used in the present invention.
  • the amount of these ultraviolet absorbents added is preferably 0.1 to 30.0 parts by mass relative to 100 parts by mass of the resin constituting the ultraviolet absorbing layer.
  • the resin used in the ultraviolet absorbing layer may be any known resin, and is not particularly limited as long as it does not deviate from the spirit of the present invention.
  • the resin include cellulose acylate resin, acrylic resin, cycloolefin resin, polyester resin, and epoxy resin.
  • the location of the ultraviolet absorbing layer is not particularly limited as long as it is on the viewer side of the light transmission-absorption filter of the present invention or the display element of the present invention, and it can be installed at any position.
  • an ultraviolet absorber to a member such as a protective film of a polarizing plate or an antireflection film to give it the function of an ultraviolet absorbing layer.
  • an ultraviolet absorber can be added to the pressure-sensitive adhesive layer.
  • the materials used to prepare the laminate are as follows: ⁇ Polymer (resin)> (Resin 1) ARUFON UC-3920 (trade name) manufactured by Toagosei Co., Ltd., a carboxyl group-containing acrylic polymer, weight average molecular weight 15,500. (Resin 2) Adamantyl methacrylate-acrylic acid random copolymer, acrylic acid content 52 mol%, weight average molecular weight 46,300.
  • the acrylic acid portion of Resin 2 corresponds to Compound A having an acid group as defined in the present invention.
  • Resin 3 A benzyl methacrylate-methacrylic acid copolymer (manufactured by Fujikura Kasei Co., Ltd., Acribase FF-187 (trade name), benzyl methacrylate ratio 70%) was used as resin 3.
  • Resin 4 An amorphous reactive polymer having oxazoline groups pendant on a polystyrene main chain (Epocross RPS-1005 (trade name), manufactured by Nippon Shokubai Co., Ltd., proportion of oxazoline group-containing structural units: 3 mol%) was used as resin 4.
  • Resin 5 A cyclic polyolefin resin, Arton R5000 (trade name, manufactured by JSR Corporation, norbornene-based polymer, Tg: 135° C.), was used as resin 5.
  • the blending amount (unit: parts by mass) in the composition of each forming liquid described below is the blending amount of the resin itself excluding the solvent.
  • the resins 1 and 3 to 5 were used to form the wavelength selective absorption layer, and the resin 2 was used to form the light absorbing and disappearing layer.
  • Bu represents a butyl group.
  • Solvent Blue 35 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., anthraquinone dye, ⁇ max 652 nm) was used as dye H-1.
  • PD-311F (trade name, manufactured by Yamamoto Chemical Industries, Ltd., tetraazaporphyrin copper complex dye, ⁇ max 585 nm) was used as dye I-2.
  • FDB-002 (trade name, manufactured by Yamada Chemical Industry Co., Ltd., porphyrin dye, ⁇ max 432 nm) was used as dye J-1.
  • Adhesion improver 1 A fluorine-containing copolymer composed of the following components was used as adhesion improver 1, synthesized in the same manner as in the synthesis of the fluorine-containing copolymer (A-19-1) described in Synthesis Example 22 of Japanese Patent No. 6722602, except that 2-(perfluorohexyl)ethyl acrylate (C6FA) was changed to 25 parts by mass, monomer II-12 described in paragraph [0063] of Japanese Patent No. 6722602 was changed to 5 parts by mass, and acrylic acid (AA) was changed to 70 parts by mass.
  • C6FA 2-(perfluorohexyl)ethyl acrylate
  • Tuftec M-1913 (trade name, manufactured by Asahi Kasei Corporation, maleic anhydride-modified styrene/ethylene/butylene/styrene block copolymer resin)
  • Leveling Agent 1 A polymer surfactant composed of the following components was used as leveling agent 1.
  • the ratio of each component is a molar ratio
  • t-Bu means a tert-butyl group.
  • Base material 1 A polyethylene terephthalate film Lumirror XD-510P (trade name, film thickness 50 ⁇ m, manufactured by Toray Industries, Inc.) was used as the substrate 1.
  • Base material 11 Cellulose acylate film (manufactured by Fujifilm Corporation, product name: TG60UL, film thickness 60 ⁇ m)
  • Base material 21 Cellulose acylate film (manufactured by Fujifilm Corporation, product name: ZRD40SL, film thickness 40 ⁇ m)
  • ⁇ Laminate I Preparation of laminate including wavelength-selective absorption layer and light-absorbing and dissipating layer>>
  • Example 1 Preparation of Laminate No. 101 Having a Gas Barrier Layer] ⁇ 1.
  • Fabrication of wavelength-selective absorption layer> (1) Preparation of Wavelength-Selective Absorbing Layer Forming Solution 1 The components were mixed in the composition shown below to prepare wavelength-selective absorbing layer forming solution 1.
  • the resulting wavelength-selective absorption layer forming solution 1 was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • the resulting diffusion-preventing layer-forming solution A was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • the resulting light-absorbing, dissipative layer-forming solution Ba-1 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 ⁇ m, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 ⁇ m.
  • Laminate I The above-mentioned filtered light-absorbing and dissipating layer-forming solution Ba-1 was applied to the diffusion-preventing layer of the diffusion-preventing layer-attached substrate 3 using a bar coater so that the film thickness after drying would be 2.2 ⁇ m, and the coating was dried at 120° C. to form a light-absorbing and dissipating layer, thereby preparing Laminate No. 101.
  • Laminate No. 101 (also referred to as "Laminate No. 101 having a gas barrier layer").
  • Gas Barrier Layer-Forming Solution 1 Kuraray Exeval AQ-4105 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, with the components adjusted to the composition ratio shown below. The solution was then cooled to room temperature, and polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) was added to prepare Gas Barrier Layer-Forming Solution 1.
  • Kuraray Exeval AQ-4105 trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol
  • the solution was then cooled to room temperature, and polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) was added to prepare Gas Barrier Layer-Forming Solution 1.
  • the resulting gas barrier layer forming solution 1 was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • Laminates Nos. 102 to 104 and c201 to c202 Having Gas Barrier Layer Laminates Nos. 102 to 104 and c201 to c202 each having a gas barrier layer were prepared in the same manner as in the preparation of laminate No. 101 having a gas barrier layer, except that in the preparation of laminate No. 101 having a gas barrier layer, at least one of the amount of each dye added in the light-absorbing and disappearing layer and the amount of each dye added in the wavelength-selective absorption layer was changed to the value shown in Table 1. In producing laminates Nos.
  • the amount of resin 1 was adjusted in accordance with the change in the amount of dye blended, while keeping the mass of the wavelength-selective absorption layer constant, and the amount of resin 2 was adjusted in accordance with the change in the amount of dye blended, while keeping the mass of the light-absorbing and disappearing layer constant.
  • a laminate No. r301 having a gas barrier layer was prepared in the same manner as in the preparation of the laminate No. 101 having a gas barrier layer, except that in the preparation of the laminate No. 101 having a gas barrier layer, dyes A-321, 7-23, C-122, and H-1 were removed from the wavelength-selective absorption layer-forming solution, and further, dyes B-18 and D-7, and 4-methylquinoline were removed from the light-absorbing and disappearing layer-forming solution.
  • the blending amounts of the dye in the wavelength selective absorption layer and the light absorbing and dissipating layer refer to parts by mass of the dye in 100 parts by mass of the wavelength selective absorption layer and parts by mass of the dye in 100 parts by mass of the light absorbing and dissipating layer, respectively.
  • the unit of thickness of the wavelength selective absorption layer and the thickness of the light absorbing and disappearing layer is both ⁇ m.
  • the laminate having the gas barrier layer was irradiated with ultraviolet (UV) rays at an illuminance of 100 mW/cm 2 and an exposure dose of 2000 mJ/cm 2 from the gas barrier layer side (the side opposite to the substrate 1) using an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) on a hot plate at 45°C.
  • UV ultraviolet
  • the transmittance in the wavelength range of 380 to 780 nm was calculated using the absorption spectrum obtained from the absorbance Ab( ⁇ ) of the first and second regions.
  • the obtained transmittance in the wavelength range of 380 to 780 nm was multiplied by the photopic standard relative luminosity factor and summed (luminosity correction) to calculate the color (a * , b * ) of the transmitted light.
  • the reflectance spectrum of the OLED substrate was measured using an OLED display device from which anti-reflection layers, such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later).
  • anti-reflection layers such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later).
  • the reflectance at each wavelength of each pixel, which is the light-emitting portion, and the reflectance at each wavelength of the substrate, thin metal wires, and black bank (black partition wall), which are non-light-emitting portions were measured using a conventional microspectroscopy method.
  • the reflectance was calculated as the relative reflectance to the reflectance of a silver mirror with a protective film.
  • the simulation of the reflection spectrum was carried out for each part, divided into a light-emitting part and a non-light-emitting part.
  • the reflection spectrum R x ( ⁇ ) of the light-emitting section was calculated by the following formula using the reflection spectrum R x0 ( ⁇ ) of the light-emitting section of the OLED substrate measured by microspectroscopy, the transmission spectrum T 1 ( ⁇ ) of the first section, and the surface reflectance R S.
  • the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the first section, and specifically means the surface reflectance of the gas barrier layer.
  • R x ( ⁇ ) R x0 ( ⁇ ) x T 1 ( ⁇ ) 2 + R S (2) Reflectance of Non-Emitting Portion
  • the reflection spectrum R y ( ⁇ ) of the non-emitting portion was calculated by the following formula using the reflection spectrum R y0 ( ⁇ ) of the non-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 2 ( ⁇ ) of the second portion, and the surface reflectance R S.
  • the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the second portion, and specifically means the surface reflectance of the gas barrier layer.
  • R y ( ⁇ ) R y0 ( ⁇ ) ⁇ T 2 ( ⁇ ) 2 +R S (3) Average Reflectance
  • the reflectance spectrum of the entire display device was calculated as the sum of the reflectance spectrum R x ( ⁇ ) of the light-emitting portion and the reflectance spectrum R y ( ⁇ ) of the non-light-emitting portion calculated above, multiplied by the area ratio of each portion.
  • the resulting reflectance spectrum was then multiplied by the CIE standard illuminant D65 spectrum and the photopic standard relative luminosity factor to obtain the sum (luminosity correction), thereby calculating the luminosity-corrected reflectance Y (hereinafter simply referred to as "reflectance") and the color (a * , b * ) of the reflected light.
  • Nos. 101 to 104 are simulation results for the light transmission-absorption filter of the present invention, performed using the transmittance simulation results for the first and second regions obtained using the laminate Nos. 101 to 104 prepared above.
  • Nos. c201 and c202 are simulation results for a light transmission-absorption filter for comparison, performed using the transmittance simulation results for the first and second regions obtained using the laminate Nos. c201 and c202 prepared above.
  • the light transmission-absorption filters No. c201 and c202 do not satisfy the requirements of the present invention in that the signs of the values in the first region and the second region for a * and b * in the L*a * b * color space of transmitted light are not reversed.
  • the light transmission-absorption filter No. c201 had a high reflectance of 8.9%, failing to suppress external light reflection, while the light transmission-absorption filter No. c202 had a high a * value for reflected light, failing to adjust the reflected color to a neutral tone.
  • the light transmission-absorption filters Nos Nos.
  • 101 to 104 are light transmission-absorption filters that ensure the desired transmittance of display light when incorporated into a display device, have a reflectance as low as 6.7% or less, can achieve a high level of suppression of external light reflection, and furthermore, a * and b * of the reflected light are within the range of ⁇ 2.8 to 6.3, and a * and b * of the display light (first portion and second portion) are within the range of ⁇ 9.3 to 28.0, making it possible to adjust both the color of the reflected light and the color of the display light to a neutral color.
  • the resulting wavelength-selective absorption layer forming liquid 11 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 ⁇ m, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 ⁇ m.
  • wavelength-selective absorption layer forming liquid 12 Preparation of wavelength-selective absorption layer forming liquid 12> The components were mixed in the composition shown below to prepare a wavelength selective absorption layer forming solution 12. ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  • wavelength-selective absorption layer forming liquid 12 was filtered in the same manner as wavelength-selective absorption layer forming liquid 11.
  • gas barrier layer-forming liquid 2 Preparation of gas barrier layer-forming liquid 2> Kuraray Exeval AQ-4104 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, with the components adjusted to the composition ratio shown below. The solution was then cooled to room temperature, and Epomin P-1000 (trade name, manufactured by Nippon Shokubai Co., Ltd., 30% by mass solution of polyethyleneimine, weight average molecular weight approximately 70,000) was added to prepare gas barrier layer-forming solution 2.
  • Kuraray Exeval AQ-4104 trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol
  • the solution was then cooled to room temperature, and Epomin P-1000 (trade name, manufactured by Nippon Shokubai Co., Ltd., 30% by mass solution of poly
  • the resulting gas barrier layer-forming solution 2 was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • wavelength-selective absorption filter No. 501 with substrate>
  • the filtered wavelength-selective absorption layer-forming liquid 11 was applied to a substrate 11 using a bar coater so that the film thickness after drying would be 2.0 ⁇ m, and the applied film was dried at 130° C. to form a substrate-attached first wavelength-selective absorption layer 11.
  • the filtered gas-barrier layer-forming liquid 2 was applied to the first wavelength-selective absorption layer using a bar coater so that the film thickness after drying would be 0.4 ⁇ m, and the applied film was dried at 130° C. to form a gas-barrier layer 2.
  • the filtered wavelength-selective absorption layer-forming liquid 12 was applied to the gas-barrier layer 2 using a bar coater so that the film thickness after drying would be 2.0 ⁇ m, and the applied film was dried at 130° C. to form a substrate-attached wavelength-selective absorption filter No. 501 (laminate II).
  • the resulting diffusion-preventing layer-forming solution B was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • the resulting light-absorbing, dissipative layer-forming solution Ba-2 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 ⁇ m, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 ⁇ m.
  • filter paper #63, manufactured by Toyo Roshi Kaisha
  • a sintered metal filter product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation
  • Gas Barrier Layer-Forming Solution 3 Kuraray Exeval AQ-4104 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, and then the solution was cooled to room temperature, and polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) was added to prepare Gas Barrier Layer-Forming Solution 3.
  • Kuraray Exeval AQ-4104 trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol
  • polyethyleneimine manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000
  • the resulting gas barrier layer-forming solution 3 was then filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).
  • this laminate No. 701 was incorporated into a display device, the reflectance was as low as 6.0%, achieving a high level of suppression of external light reflection.
  • Laminate pre-III laminate pre-III having a gas barrier layer prepared above, and a laminate obtained by bonding the second wavelength-selective absorption layer 12 in the laminate II to the gas barrier layer in the laminate pre-III. Furthermore, the absorbance of the first portion was measured using, as a measurement sample, a laminate obtained by bonding together Laminate III obtained by subjecting the above-prepared light-absorbing and dissipating filter No. 601 (laminate pre-III) having a gas barrier layer to the following ultraviolet irradiation test without patterning, and wavelength-selective absorption filter No. 501 (laminate II) with a substrate.
  • a light-absorbing and dissipative filter No. 601 (laminate pre-III) having a gas barrier layer was irradiated with ultraviolet (UV) rays at an illuminance of 100 mW/cm 2 and an exposure dose of 2000 mJ/cm 2 from the gas barrier layer side (the side opposite to the substrate 21) using an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) on a hot plate at 45°C.
  • UV ultraviolet
  • the transmittance in the wavelength range of 380 to 780 nm was calculated using the absorption spectrum obtained from the absorbance Ab( ⁇ ) of the first and second regions.
  • the obtained transmittance in the wavelength range of 380 to 780 nm was multiplied by the photopic standard relative luminosity factor and summed (luminosity correction) to calculate the color (a * , b * ) of the transmitted light.
  • the reflectance spectrum of the OLED substrate was measured using an OLED display device from which anti-reflection layers, such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later).
  • anti-reflection layers such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later).
  • the reflectance at each wavelength of each pixel, which is the light-emitting portion, and the reflectance at each wavelength of the substrate, thin metal wires, and black bank (black partition wall), which are non-light-emitting portions were measured using a conventional microspectroscopy method.
  • the reflectance was calculated as the relative reflectance to the reflectance of a silver mirror with a protective film.
  • the simulation of the reflection spectrum was carried out for each part, divided into a light-emitting part and a non-light-emitting part.
  • the reflection spectrum R x ( ⁇ ) of the light-emitting portion was calculated by the following formula using the reflection spectrum R x0 ( ⁇ ) of the light-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 1 ( ⁇ ) of the first portion, and the surface reflectance R S.
  • the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the first portion, and specifically means the surface reflectance of the substrate 11.
  • R x ( ⁇ ) R x0 ( ⁇ ) x T 1 ( ⁇ ) 2 + R S (2) Reflectance of Non-Emitting Portion
  • the reflection spectrum R y ( ⁇ ) of the non-emitting portion was calculated by the following formula using the reflection spectrum R y0 ( ⁇ ) of the non-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 2 ( ⁇ ) of the second portion, and the surface reflectance R S.
  • the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the second portion, and specifically means the surface reflectance of the substrate 11.
  • R y ( ⁇ ) R y0 ( ⁇ ) ⁇ T 2 ( ⁇ ) 2 +R S (3) Average Reflectance
  • the reflectance spectrum of the entire display device was calculated as the sum of the reflectance spectrum R x ( ⁇ ) of the light-emitting portion and the reflectance spectrum R y ( ⁇ ) of the non-light-emitting portion calculated above, multiplied by the area ratio of each portion.
  • the resulting reflectance spectrum was then multiplied by the CIE standard illuminant D65 spectrum and the photopic standard relative luminosity factor to obtain the sum (luminosity correction), thereby calculating the luminosity-corrected reflectance Y (hereinafter simply referred to as "reflectance") and the color (a * , b * ) of the reflected light.
  • RO 60 The ratio of overlap between the first portion and the light emitted from the light-emitting portion relative to the area of the light-emitting portion when observed from infinity at a polar angle of 60° was defined as RO 60 , and the RO 60s for the B pixel, G pixel, and R pixel were defined as RO B60 , RO G60 , and RO R60 , respectively.
  • the emission spectrum E x60 ( ⁇ ) (x represents the B pixel (B), G pixel (G), or R pixel (G)) at a polar angle of 60° was determined for each of B, G, and R using the following formula, and the resulting emission spectra E x60 ( ⁇ ) for B, G, and R at a polar angle of 60° were summed in the same ratio as the B/G/R ratio during white display to calculate the luminosity-corrected luminance Y (hereinafter also simply referred to as "luminance”) and whiteness (x, y) at a polar angle of 60° when a light-absorbing filter II (light-absorbing disappearing layer) was used.
  • luminance luminosity-corrected luminance
  • E B60 ( ⁇ ) B 60 ( ⁇ ) x T 1 ( ⁇ ) x RO B60 + B 60 ( ⁇ ) x T 2 ( ⁇ ) x (1-RO B60 )
  • E G60 ( ⁇ ) G 60 ( ⁇ ) x T 1 ( ⁇ ) x RO G60 + G 60 ( ⁇ ) x T 2 ( ⁇ ) x (1-RO G60 )
  • E R60 ( ⁇ ) R 60 ( ⁇ ) x T 1 ( ⁇ ) x RO R60 + R 60 ( ⁇ ) x T 2 ( ⁇ ) x (1-RO R60 ) RO 60 was calculated geometrically from the distance between the light-emitting section and the light-absorbing and dissipative layer and the diameter of the light-emitting section and the first section when the sizes of the light-emitting section and the first section and their positions when viewed from the front are exactly the same (i.e., when "Sf/S" in the above formula (2) is 1).
  • the angle of the display light with a polar angle of 60° inside the display device was
  • the “distance” is the distance (distance d) in the film thickness direction between the light-emitting portion (light-emitting element layer) of the OLED substrate and the light-absorbing and dissipating layer.
  • the "B pixel distance ratio” is the value (d/ ⁇ S B ) obtained by dividing the distance d between the light-absorbing and disappearing layer in the first light-transmitting and absorbing portion and the light-emitting element layer by the square root of the average area S B of each blue light-emitting element that constitutes the light-emitting element layer
  • the “G pixel distance ratio” is the value (d/ ⁇ S G ) obtained by dividing the distance d between the light-absorbing and disappearing layer in the first light-transmitting and absorbing portion and the light-emitting element layer by the square root of the average area S G of each green light-emitting element that constitutes the light-emitting element layer.
  • the "distance d" used in calculating the "distance” and the “B pixel distance ratio” and “G pixel distance ratio” is shorter than the film thickness of the substrate 21 and diffusion-preventing layer of the laminate III obtained by mask-exposing the laminate pre-III.
  • the “relative luminance” is the luminance at a polar angle of 60° and an azimuth angle of 0°, and is a relative value when the light-absorbing filter II (light-absorbing disappearing layer) is used, with the value when the light-absorbing filter II (light-absorbing disappearing layer) is not used being taken as 100.
  • the "color change” is the distance ( ⁇ xy) between the whiteness at a polar angle of 0° and an azimuth angle of 0° when displaying white, and the whiteness at a polar angle of 60° and an azimuth angle of 0° when comparing the two whitenesses on an xy chromaticity diagram, and is a value calculated using the following formula.
  • x 0 and y 0 are respectively x and y on the xy chromaticity diagram of white at a polar angle of 0° and an azimuth angle of 0°
  • x 60 and y 60 are respectively x and y on the xy chromaticity diagram of white at a polar angle of 60° and an azimuth angle of 0°.
  • First section (first light transmitting/absorbing section) 2.
  • Second region (second light transmitting/absorbing region) 3: Wavelength-selective absorption layer exposed with a mask 4: Light-absorbing and decolorizable layer exposed with a mask 5: Light-absorbing disappearance portion 6: Light-absorbing portion 7: Light-emitting portion of display element 8: Non-light-emitting portion of display element 10: Light-transmitting and absorbing filter I

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Abstract

Provided are a light-transmitting absorption filter, an organic electroluminescence display element, and an organic electroluminescence display device. The light-transmitting absorption filter comprises a first light-transmitting absorption site and a second light-transmitting absorption site, wherein the transmittances T(460), T(530), and T(620) of the first light-transmitting absorption site at wavelengths of 460 nm, 530 nm, and 620 nm respectively satisfy the following relationships, and wherein a relationship is satisfied in which the sign of at least one value out of a* and b* in an L*a*b* color space of transmitted light is opposite between the first light-transmitting absorption site and the second light-transmitting absorption site. T(460) ≥ 30% T(530) ≥ 40% T(620) ≥ 30%

Description

光透過吸収フィルタ、有機エレクトロルミネッセンス表示素子及び有機エレクトロルミネッセンス表示装置Light-transmitting and absorbing filter, organic electroluminescent display element, and organic electroluminescent display device

 本発明は、光透過吸収フィルタ、有機エレクトロルミネッセンス表示素子及び有機エレクトロルミネッセンス表示装置に関する。 The present invention relates to a light-transmitting/absorbing filter, an organic electroluminescent display element, and an organic electroluminescent display device.

 画像表示装置としては、有機エレクトロルミネッセンス(OLED)表示装置、無機エレクトロルミネッセンス表示装置(無機EL表示装置)及び液晶表示装置等が近年用いられている。 In recent years, organic electroluminescence (OLED) display devices, inorganic electroluminescence display devices (inorganic EL display devices), and liquid crystal display devices have been used as image display devices.

 液晶表示装置は、消費電力の小さい省スペースの画像表示装置として年々その用途が広がっている。液晶表示装置は、画像を表示する液晶パネル自体は発光をしない非発光型素子であるため、液晶パネルの背面に配置され、液晶パネルに光を供給するバックライトユニットを備えている。
 OLED表示装置(「有機EL表示装置」とも称す。)は、OLED素子の自発光を利用して画像を表示する装置である。そのため、液晶表示装置及びプラズマ表示装置等の各種表示装置に比べて、高コントラスト比、高い色再現性、広い視野角、高速応答性、及び、薄型軽量化が可能であること等の利点を有する。これらの利点に加え、フレキシブル性の点からも、次世代の表示装置として、活発に研究開発が行われている。
 無機EL表示装置は、蛍光材料としてOLED表示装置におけるOLED素子に代えて無機EL素子の自発光を利用して画像を表示する装置である。近年の研究により、大画面化、及び、長寿命化などの面でOLED表示装置よりも優れた表示装置が実現可能として期待されている。
Liquid crystal display devices are becoming more and more popular as space-saving, low-power image display devices. Because the liquid crystal panel that displays images is a non-emissive element, a liquid crystal display device is equipped with a backlight unit that is placed behind the liquid crystal panel and supplies light to the liquid crystal panel.
OLED display devices (also referred to as "organic EL display devices") are devices that display images by utilizing the spontaneous emission of OLED elements. As a result, compared to various display devices such as liquid crystal display devices and plasma display devices, they have advantages such as a high contrast ratio, high color reproducibility, a wide viewing angle, fast response, and the possibility of being thin and lightweight. In addition to these advantages, OLED display devices are being actively researched and developed as next-generation display devices due to their flexibility.
Inorganic EL display devices are devices that display images by utilizing the spontaneous emission of inorganic EL elements instead of the OLED elements used in OLED display devices as fluorescent materials. Recent research has raised hopes that inorganic EL display devices will be superior to OLED display devices in terms of larger screens and longer life.

 画像表示装置の開発においては、光吸収フィルタを構成として組み込む技術が知られている。
 例えば、液晶表示装置では、バックライトユニット用の光源として白色発光ダイオード(LED)を用いた場合に、白色LEDから発せられる不要な波長の光を遮断するため、光吸収フィルタを設ける試みがなされている。また、OLED表示装置では、外光反射を抑制する観点から、光吸収フィルタを設ける試みがなされており、特許文献1には、極大吸収波長が異なる複数の色素を組み合わせることにより、表示光の透過率を低下させずに外光の反射を防止する方法が開示されている。
In the development of image display devices, a technique of incorporating a light absorbing filter as a component is known.
For example, in a liquid crystal display device, when a white light-emitting diode (LED) is used as a light source for a backlight unit, an attempt has been made to provide a light-absorbing filter to block light of unnecessary wavelengths emitted from the white LED. Also, in an OLED display device, an attempt has been made to provide a light-absorbing filter from the viewpoint of suppressing reflection of external light, and Patent Document 1 discloses a method of preventing reflection of external light without reducing the transmittance of display light by combining a plurality of dyes with different maximum absorption wavelengths.

 画像表示装置に組み込まれる光吸収フィルタの別の形態として、所望の部位については光吸収性を消失させることにより、光吸収効果を有する光吸収性部位と、光吸収性を消失させた部位(以下、単に「光吸収性消失部位」とも称す。)を併せ持つ光学フィルタの研究も進められている。一般に、OLED表示装置の非発光部(表示光が出射されない部位)には金属配線等が配置されているため、発光部(表示光が出射される部位)に対して反射率が高い場合が多い。画像表示装置に光学フィルタを組み込んで用いる際に、上記光吸収性部位をOLED表示装置の非発光部上に、また上記光吸収性消失部位をOLED表示装置の発光部上にそれぞれ配置することにより、表示光の透過率の低下を最小限にとどめて反射防止効果を向上させることができる。
 例えば、特許文献2には、樹脂と、酸基を有する化合物と、酸基を有する化合物と水素結合を形成し紫外光照射によりラジカルを生成する化合物と、波長400~700nmに主吸収波長帯域を有する染料とを含有する光吸収フィルタが記載されている。上記特許文献2に記載の光吸収フィルタによれば、紫外線照射による高い消色率を示し、かつ、紫外線照射による染料の分解に伴う新たな着色構造由来の吸収(以下、「二次的な吸収」とも称す。)もほとんど生じず、高い消色性が得られるとされる。また、特許文献3には、樹脂と、波長400~700nmに主吸収波長帯域を有する染料と、紫外線照射によりラジカルを生成する化合物とを含有し、上記染料が、一般式(i)~(iv)のいずれかで表されるアゾ系色素及び一般式(v)で表されるインドアニリン系色素のうちの少なくとも1種を含む、光吸収フィルタが記載されている。上記特許文献3に記載の光吸収フィルタによれば、室温で紫外線照射した場合でも優れた消色率を示し、かつ、紫外線照射による上記二次的な吸収もほとんど生じず、高い消色性が得られるとされる。
 また、特許文献4には、多色発光有機EL表示装置において、青色光の発光部、赤色光の発光部、及び非発光部上にマゼンタ色のカラーフィルタ(第1調光層)を配置し、緑色光の発光部上には上記マゼンタ色のカラーフィルタを配置せず、さらに青色光の発光部、赤色光の発光部、緑色光の発光部、及び非発光部上に赤色光と緑色光との中間の波長の光に対して選択的な吸収性を有する(具体的には透過率の最小値を示す波長が580~600nmの範囲に存在する)第1調光層を配置する構成が開示されている。
As another form of light-absorbing filter incorporated into an image display device, research is also being conducted on optical filters that have both light-absorbing portions with a light-absorbing effect and portions where light absorption has been eliminated (hereinafter simply referred to as "light-absorbency-eliminated portions") by eliminating the light-absorbency in desired portions. Generally, non-light-emitting portions (portions from which display light is not emitted) of OLED display devices have metal wiring or the like arranged therein, and therefore often have a higher reflectance than light-emitting portions (portions from which display light is emitted). When an optical filter is incorporated into an image display device and used, by arranging the light-absorbing portions on the non-light-emitting portions of the OLED display device and the light-absorbency-eliminated portions on the light-emitting portions of the OLED display device, it is possible to minimize the decrease in transmittance of display light and improve the anti-reflection effect.
For example, Patent Document 2 describes a light-absorbing filter containing a resin, a compound having an acid group, a compound that forms a hydrogen bond with the compound having an acid group and generates radicals upon irradiation with ultraviolet light, and a dye having a main absorption wavelength band in the range of 400 to 700 nm. The light-absorbing filter described in Patent Document 2 is said to exhibit a high decolorization rate upon ultraviolet irradiation, and to exhibit high decolorization performance with almost no absorption (hereinafter also referred to as "secondary absorption") resulting from a new colored structure associated with decomposition of the dye upon ultraviolet irradiation. Patent Document 3 also describes a light-absorbing filter containing a resin, a dye having a main absorption wavelength band in the range of 400 to 700 nm, and a compound that generates radicals upon ultraviolet irradiation, wherein the dye includes at least one of an azo dye represented by any one of general formulas (i) to (iv) and an indoaniline dye represented by general formula (v). The light-absorbing filter described in Patent Document 3 is said to exhibit an excellent decolorization rate even when irradiated with ultraviolet light at room temperature, and to exhibit almost no secondary absorption upon ultraviolet irradiation, thereby exhibiting high decolorization performance.
Furthermore, Patent Document 4 discloses a configuration in which, in a multicolor light-emitting organic EL display device, magenta color filters (first dimming layers) are arranged on blue light-emitting sections, red light-emitting sections, and non-light-emitting sections, and the magenta color filters are not arranged on green light-emitting sections, and further, first dimming layers that have selective absorption properties for light of wavelengths intermediate between red light and green light (specifically, the wavelength at which the transmittance is at a minimum exists in the range of 580 to 600 nm) are arranged on the blue light-emitting sections, red light-emitting sections, green light-emitting sections, and non-light-emitting sections.

国際公開第2021/066082号International Publication No. 2021/066082 国際公開第2023/068235号International Publication No. 2023/068235 国際公開第2023/234353号International Publication No. 2023/234353 国際公開第2010/150535号International Publication No. 2010/150535

 しかし、上記特許文献1に記載の光吸収フィルタでは、外光の反射を十分に抑制できるまで吸光度を高めると表示光の透過率が損なわれる問題があった。また、特許文献2及び3に記載の方法では表示装置中の発光部に起因する外光反射の抑制が不十分であり、改良が求められていた。
 また、マイクロキャビティ構造を有するOLED表示装置は、表示光の色純度を改善することができるものの、視野角依存性が高く、視野角により色味が大きく変化してしまうことが知られている。特許文献4に記載の多色発光有機EL表示装置は、視野角による色味変化に対しては一定の改良効果を示すものの、青色の外光反射の抑制が不十分となるため、染料を含有しない場合と比較して反射光の色味が変化してしまう(反射光の色味がニュートラルからずれる)問題があった。
However, the light-absorbing filter described in Patent Document 1 has a problem in that the transmittance of display light is impaired when the absorbance is increased to the point where reflection of external light can be sufficiently suppressed. Also, the methods described in Patent Documents 2 and 3 do not sufficiently suppress reflection of external light caused by light-emitting sections in display devices, and improvements have been desired.
Furthermore, although OLED display devices having a microcavity structure can improve the color purity of display light, they are known to have high viewing angle dependency, resulting in significant color changes depending on the viewing angle.The multicolor light-emitting organic EL display device described in Patent Document 4 shows a certain improvement effect in reducing color changes due to viewing angle, but has a problem in that it does not sufficiently suppress the reflection of blue external light, resulting in a change in the color of the reflected light compared to a display that does not contain a dye (the color of the reflected light deviates from neutral).

 すなわち、本発明は、表示装置に組み込んだ際に表示光の所望の透過率が担保される光透過吸収フィルタであって、表示装置に組み込んだ際には、外光反射が抑制され、しかも、染料を含有しない場合と比較した反射光の色味の変化が抑制(以下、「反射光の色味がニュートラルに調整」と称す。)され、染料を含有しない場合と比較した表示光の色味の変化が抑制(以下、「表示光の色味がニュートラルに調整」と称す。)された光透過吸収フィルタ、及びこの光透過吸収フィルタを含む有機エレクトロルミネッセンス表示素子、この光透過吸収フィルタ又は有機エレクトロルミネッセンス表示素子を備えた有機エレクトロルミネッセンス表示装置を提供することを課題とする。 In other words, the present invention aims to provide a light-transmitting-absorbing filter that, when incorporated into a display device, ensures the desired transmittance of display light; when incorporated into a display device, it suppresses external light reflection and also suppresses changes in the color of reflected light compared to when the filter does not contain a dye (hereinafter referred to as "the color of reflected light is adjusted to be neutral"), and suppresses changes in the color of display light compared to when the filter does not contain a dye (hereinafter referred to as "the color of display light is adjusted to be neutral"); an organic electroluminescent display element including this light-transmitting-absorbing filter; and an organic electroluminescent display device equipped with this light-transmitting-absorbing filter or organic electroluminescent display element.

 本発明者らは上記課題に鑑み鋭意検討した結果、特定の波長における透過率がいずれも特定の値以上を満たす第一の光透過吸収部位と、この第一の光透過吸収部位との間で色度が特定の関係を満たす第二の光透過吸収部位とを有する、所望の高い光透過性を示す光透過吸収フィルタの構成とすることにより、表示装置に組み込んだ際には、外光反射が抑制され、しかも、反射光の色味と表示光の色味を共にニュートラルに調整できることを見出した。本発明はこの知見に基づきさらに検討を重ね、完成されるに至ったものである。 In light of the above-mentioned problems, the inventors conducted extensive research and discovered that by configuring a light-transmitting/absorbing filter that exhibits the desired high light transmittance, having a first light-transmitting/absorbing section whose transmittance at specific wavelengths is equal to or greater than a specific value, and a second light-transmitting/absorbing section whose chromaticity satisfies a specific relationship with the first light-transmitting/absorbing section, it is possible to suppress external light reflection when incorporated into a display device, and further adjust the color of both the reflected light and the displayed light to be neutral. The present invention was completed after further research based on this finding.

 すなわち、上記の課題は以下の手段により解決された。
<1>
 第一の光透過吸収部位と第二の光透過吸収部位とを有し、
 上記第一の光透過吸収部位の、波長460nmにおける透過率T(460)、波長530nmにおける透過率T(530)及び波長620nmにおける透過率T(620)がそれぞれ下記関係を満たし、
 上記第一の光透過吸収部位と上記第二の光透過吸収部位との間で、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たす、光透過吸収フィルタ。
  T(460)≧30%
  T(530)≧40%
  T(620)≧30%
<2>
 上記の第一の光透過吸収部位の透過光のa及びbが下記関係を満たす、<1>に記載の光透過吸収フィルタ。
  -20.0≦a≦+20.0
  -20.0≦b≦+20.0
<3>
 光吸収透過特性が異なる2つ以上の層を含む、<1>又は<2>に記載の光透過吸収フィルタ。
<4>
 <1>~<3>のいずれか1つに記載の光透過吸収フィルタを含む、有機エレクトロルミネッセンス表示素子。
<5>
 上記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 上記有機エレクトロルミネッセンス表示素子が、上記積層体II、上記積層体III、及び発光素子層がこの順に配置されてなり、
 上記積層体IIIと上記発光素子層との距離dと、上記発光素子層を構成する各発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各発光素子の直上に位置する部分の平均面積Sfとが、下記式(1)及び(2)の関係を満たす、<4>に記載の有機エレクトロルミネッセンス表示素子。
    式(1)  0.6≦d/√S≦7.5
    式(2)  0.7≦Sf/S≦1.5
<6>
 上記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 上記有機エレクトロルミネッセンス表示素子が、上記積層体II、上記積層体III、及び発光素子層がこの順に配置されてなり、
 上記積層体IIIと上記発光素子層との距離dと、上記発光素子層を構成する各青色発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各青色発光素子の直上に位置する部分の平均面積Sfとが、下記式(3)及び(4)の関係を満たす、<4>又は<5>に記載の有機エレクトロルミネッセンス表示素子。
    式(3)  1.0≦d/√S≦7.0
    式(4)  0.8≦Sf/S≦1.2
<7>
 上記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 上記有機エレクトロルミネッセンス表示素子が、上記積層体II、上記積層体III、及び発光素子層がこの順に配置されてなり、
 上記積層体IIIと上記発光素子層との距離dと、上記発光素子層を構成する各緑色発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各緑色発光素子の直上に位置する部分の平均面積Sfとが、下記式(5)及び(6)の関係を満たす、<4>~<6>のいずれか1つに記載の有機エレクトロルミネッセンス表示素子。
    式(5)  1.0≦d/√S≦7.0
    式(6)  0.8≦Sf/S≦1.2
<8>
 <1>~<3>のいずれか1つに記載の光透過吸収フィルタ又は<4>~<7>のいずれか1つに記載の有機エレクトロルミネッセンス表示素子を含む、有機エレクトロルミネッセンス表示装置。
That is, the above problems were solved by the following means.
<1>
having a first light-transmitting-absorbing portion and a second light-transmitting-absorbing portion;
The transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm of the first light transmitting/absorbing site each satisfy the following relationships:
A light-transmitting-absorbing filter in which the first light-transmitting-absorbing portion and the second light-transmitting-absorbing portion satisfy a relationship in which the sign of at least one of the values a * and b * in the L * a * b * color space of the transmitted light is opposite.
T(460)≧30%
T(530)≧40%
T(620)≧30%
<2>
The light transmission-absorption filter according to <1>, wherein a * and b * of the transmitted light of the first light transmission-absorption site satisfy the following relationship:
−20.0≦a * ≦+20.0
−20.0≦b * ≦+20.0
<3>
The light transmission/absorption filter according to <1> or <2>, comprising two or more layers with different light absorption/transmission properties.
<4>
<1><2> An organic electroluminescence display element comprising the light-transmitting/absorbing filter according to any one of <1> to <2>.
<5>
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order;
The organic electroluminescent display element according to <4>, wherein a distance d between the laminate III and the light-emitting element layer, an average area S of each light-emitting element constituting the light-emitting element layer, and an average area Sf of the first light-transmitting/absorbing portion located directly above each light-emitting element satisfy the relationship of the following formulas (1) and (2):
Formula (1) 0.6≦d/√S≦7.5
Formula (2) 0.7≦Sf/S≦1.5
<6>
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order;
The organic electroluminescent display element according to <4> or <5>, wherein a distance d between the laminate III and the light-emitting element layer, an average area S B of each blue light-emitting element constituting the light-emitting element layer, and an average area Sf B of a portion of the first light-transmitting and absorbing site located directly above each blue light-emitting element satisfy the following formulas (3) and (4):
Formula (3) 1.0≦d/√S B ≦7.0
Formula (4) 0.8≦Sf B /S B ≦1.2
<7>
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order;
The organic electroluminescent display element according to any one of <4> to <6>, wherein a distance d between the laminate III and the light-emitting element layer, an average area S G of each green light-emitting element constituting the light-emitting element layer, and an average area Sf G of a portion of the first light-transmitting and absorbing site located directly above each green light-emitting element satisfy the relationships of the following formulas (5) and (6):
Formula (5) 1.0≦d/ √SG ≦7.0
Formula (6) 0.8≦Sf G /S G ≦1.2
<8>
An organic electroluminescence display device comprising the light transmission/absorption filter according to any one of <1> to <3> or the organic electroluminescence display element according to any one of <4> to <7>.

 本発明において、特定の符号又は式で表示された置換基若しくは連結基等(以下、置換基等という)が複数あるとき、又は、複数の置換基等を同時に規定するときには、特段の断りがない限り、それぞれの置換基等は互いに同一でも異なっていてもよい。このことは、置換基等の数の規定についても同様である。また、複数の置換基等が近接するとき(特に、隣接するとき)には、特段の断りがない限り、それらが互いに連結して環を形成していてもよい。また、特段の断りがない限り、環、例えば脂環、芳香族環、ヘテロ環は、更に縮環して縮合環を形成していてもよい。
 本発明において、特段の断りがない限り、二重結合については、分子内にE型及びZ型が存在する場合、そのいずれであっても、またこれらの混合物であってもよい。
 本発明において、化合物(錯体を含む。)の表示については、化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、本発明の効果を損なわない範囲で、構造の一部を変化させたものを含む意味である。更に、置換又は無置換を明記していない化合物については、本発明の効果を損なわない範囲で、任意の置換基を有していてもよい意味である。このことは、置換基及び連結基についても同様である。
 本発明において、物性等について、数値範囲を示して説明する場合、数値範囲の上限値及び下限値を別々に説明するときは、いずれかの上限値及び下限値を適宜に組み合わせて、特定の数値範囲とすることができる。一方、「~」を用いて表される数値範囲を複数設定して説明するときは、数値範囲を形成する上限値及び下限値は、特定の数値範囲として「~」の前後に記載された特定の上限値及び下限値の組み合わせに限定されず、各数値範囲の上限値と下限値とを適宜に組み合わせた数値範囲とすることができる。なお、本発明において「~」を用いて表される数値範囲は、「~」前後に記載される数値を下限値及び上限値として含む範囲を意味する。
 本発明において、組成物とは、成分濃度が一定である(各成分が均一に分散している)混合物に加えて、目的とする機能を損なわない範囲で成分濃度が変動している混合物を包含する。
 本発明において、積層体とは、各層が直接又は他の層を介して積層されている形態に加えて、各層が貼り合わされることによって積層構造を形成している形態を含む。
 本発明において、波長XX~YYnmに主吸収波長帯域を有するとは、極大吸収を示す波長(すなわち、極大吸収波長)が波長領域XX~YYnmに存在することを意味する。したがって、この極大吸収波長が上記波長領域内にあれば、この波長を含む吸収帯域全体が上記波長領域内にあってもよく、上記波長領域外まで広がっていてもよい。また、極大吸収波長が複数存在する場合、最も大きい吸光度を示す極大吸収波長(本発明において、「最大極大吸収波長」と称す。)が上記波長領域に存在していればよい。すなわち、最大極大吸収波長以外の極大吸収波長は、上記波長領域XX~YYnmの内外のいずれに存在していてもよい。
 本発明において、単に「樹脂」と称す場合には、エラストマーを含むものとする。
 本発明において、「(メタ)アクリレート」はアクリレート及びメタクリレートのいずれか一方又は両方を表し、「(メタ)アクリル酸」はアクリル酸及びメタクリル酸のいずれか一方又は両方を表し、「(メタ)アクリロイル」はアクリロイル及びメタクリロイルのいずれか一方又は両方を表す。
In the present invention, when there are multiple substituents or linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol or formula, or when multiple substituents, etc. are specified simultaneously, unless otherwise specified, the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. Furthermore, when multiple substituents, etc. are adjacent to each other (particularly when adjacent), they may be linked to each other to form a ring, unless otherwise specified. Furthermore, unless otherwise specified, rings, such as alicyclic rings, aromatic rings, and heterocyclic rings, may be further condensed to form a condensed ring.
In the present invention, unless otherwise specified, when double bonds exist in a molecule, they may be either E-type or Z-type, or a mixture thereof.
In the present invention, the expression "compound" (including complex) is used to mean not only the compound itself, but also its salts and ions. It also means that compounds with partially modified structures are included as long as the effects of the present invention are not impaired. Furthermore, compounds that are not specified as substituted or unsubstituted may have any substituent as long as the effects of the present invention are not impaired. The same applies to substituents and linking groups.
In the present invention, when describing physical properties and the like by showing a numerical range, if the upper and lower limits of the numerical range are described separately, any of the upper and lower limits can be appropriately combined to form a specific numerical range. On the other hand, when describing multiple numerical ranges expressed using "to", the upper and lower limits forming the numerical range are not limited to the combination of the specific upper and lower limits written before and after "to" as a specific numerical range, but can be a numerical range obtained by appropriately combining the upper and lower limits of each numerical range. Note that in the present invention, a numerical range expressed using "to" means a range that includes the numerical values written before and after "to" as the upper and lower limits.
In the present invention, the term "composition" includes not only a mixture in which the component concentrations are constant (each component is uniformly dispersed), but also a mixture in which the component concentrations vary within a range that does not impair the intended function.
In the present invention, the term "laminate" includes a form in which each layer is laminated directly or via another layer, as well as a form in which each layer is bonded to form a laminate structure.
In the present invention, having a main absorption wavelength band in the wavelength range of XX to YY nm means that the wavelength showing maximum absorption (i.e., the maximum absorption wavelength) is present in the wavelength range of XX to YY nm. Therefore, as long as this maximum absorption wavelength is within the above wavelength range, the entire absorption band including this wavelength may be within the above wavelength range, or may extend outside the above wavelength range. Furthermore, when there are multiple maximum absorption wavelengths, it is sufficient that the maximum absorption wavelength showing the greatest absorbance (referred to as the "maximum maximum absorption wavelength" in the present invention) is present in the above wavelength range. In other words, maximum absorption wavelengths other than the maximum maximum absorption wavelength may be present either inside or outside the above wavelength range of XX to YY nm.
In the present invention, when the term "resin" is simply mentioned, it includes elastomers.
In the present invention, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic acid" refers to either or both of acrylic acid and methacrylic acid, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl.

 本発明の光透過吸収フィルタは、表示装置に組み込んだ際に表示光の所望の透過率が担保される光透過吸収フィルタであって、表示装置に組み込んだ際には、外光反射が抑制され、しかも、反射光の色味と表示光の色味が共にニュートラルに調整されている。
 また、本発明の有機エレクトロルミネッセンス表示素子及び本発明の有機エレクトロルミネッセンス表示装置は、これらを構成する光透過吸収フィルタが表示光の所望の透過率が担保され、外光反射が抑制され、しかも、反射光の色味と表示光の色味が共にニュートラルに調整できる本発明の光透過吸収フィルタを備えている。
The light transmission-absorption filter of the present invention is a light transmission-absorption filter that ensures a desired transmittance of display light when incorporated into a display device, and when incorporated into a display device, it suppresses reflection of external light and also adjusts the color of both the reflected light and the display light to be neutral.
Furthermore, the organic electroluminescent display element of the present invention and the organic electroluminescent display device of the present invention are equipped with the light transmission-absorption filter constituting them, which ensures a desired transmittance of display light, suppresses reflection of external light, and can adjust the color of both the reflected light and the display light to be neutral.

図1は、本発明の光透過吸収フィルタの一実施形態である光透過吸収フィルタIの概略、及び発光素子との位置関係の概略を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing an outline of a light transmission-absorption filter I, which is one embodiment of the light transmission-absorption filter of the present invention, and an outline of the positional relationship with a light emitting element.

[光透過吸収フィルタ]
 本発明の光透過吸収フィルタは、第一の光透過吸収部位と第二の光透過吸収部位とを有し、
 上記第一の光透過吸収部位の、波長460nmにおける透過率T(460)、波長530nmにおける透過率T(530)及び波長620nmにおける透過率T(620)がそれぞれ後述の関係を満たし、
 上記第一の光透過吸収部位と上記第二の光透過吸収部位との間で、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たす、光透過吸収フィルタである。
[Light transmission absorption filter]
The light transmission-absorption filter of the present invention has a first light transmission-absorption region and a second light transmission-absorption region,
the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm of the first light transmitting/absorbing site each satisfy the following relationships,
This is a light-transmitting-absorbing filter in which the first light-transmitting-absorbing portion and the second light-transmitting-absorbing portion satisfy a relationship in which the sign of at least one of the values a * and b * in the L * a * b * color space of transmitted light is opposite.

 本発明の光透過吸収フィルタは、厚みを有するフィルム状であればよく、光透過吸収フィルタ単独で自立するフィルムであってもよく、基材フィルム等の上に配置された形態のフィルムであってもよい。フィルム状の本発明の光透過吸収フィルタを厚み方向に観察した際に、第一の透過部と第二の透過部とが存在していればよい。
 また、本発明の光透過吸収フィルタは、上記第一の光透過吸収部位(以下、単に「第一の部位」とも称す。)及び上記第二の光透過吸収部位(以下、単に「第二の部位」とも称す。)を有する限り、単層構造であってもよく、2層以上の複層構造であってもよい。2層以上の複層構造とすることにより、異なる光透過吸収特性を有する上記第一の部位及び上記第二の部位を実現することが容易になるため好ましい。2層以上の複層構造からなる本発明の光透過吸収フィルタとしては、光吸収透過特性が異なる2つ以上の層を含む構造が好ましく、例えば、後述の波長選択吸収層と光吸収消失性層とを含む積層体を紫外線照射によりマスク露光して得られる光透過吸収フィルタI、及び、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体と、波長選択吸収層を含む積層体とを含む光透過吸収フィルタIIが好ましく挙げられる。
 また、本発明の光透過吸収フィルタは、上記第一の部位及び上記第二の部位として規定される、異なる光透過吸収特性を有する光透過吸収部位を有していればよい。本発明の光透過吸収フィルタは、上記第一の部位を有機エレクトロルミネッセンス表示素子(OLED表示素子)の表示領域における発光部(本発明において、単に「発光部」とも称す。)上に配置し、上記第二の部位をOLED表示素子の表示領域における非発光部(基板、金属細線(金属配線)及びブラックバンク(黒隔壁)等。本発明において、単に「非発光部」とも称す。)上に配置して用いられる。本発明の効果を奏する限り、本発明の光透過吸収フィルタは、上記第一の部位及び上記第二の部位とは異なる光透過吸収特性を有するその他の光透過吸収部位(以下、「その他の部位」と称す。)をさらに有していてもよい。例えば、OLED表示素子が、表示領域と非表示領域とを有する場合において、表示領域上には上述の通りに第一の部位及び第二の部位が配置されるようにし、非表示領域(例えば、表示領域を囲う額縁領域、筐体等の固定部材で覆われる領域等)上にはその他の部位が配されるようにすることができる。その他の部位の光透過吸収特性については、OLED表示素子の非表示領域の構成にあわせて、適宜調整することができる。
 なお、本発明において、OLED表示素子の発光部とは、表示領域における表示光が出射される部位を意味し、OLED表示素子の非発光部とは、表示領域における表示光が出射されない部位を意味する。
 よって、本発明の光透過吸収フィルタが有する上記第一の部位と上記第二の部位とは、本発明の光透過吸収フィルタが組み込まれるOLED表示素子の発光部と非発光部の配置に沿った構成となる。
 また、本発明の光透過吸収フィルタが有する上記第一の部位は、本発明の光透過吸収フィルタが組み込まれるOLED表示素子の発光部の数に応じて、本発明の光透過吸収フィルタ中に、通常、複数個存在する。また、本発明の光透過吸収フィルタが有する上記第二の部位は、本発明の光透過吸収フィルタが組み込まれるOLED表示素子の非発光部の数に応じて、本発明の光透過吸収フィルタ中に、複数個存在し得る。
 このため、本発明の光透過吸収フィルタが有する、第一の部位に係る規定、第二の部位に係る規定、及び、第一の部位と第二の部位との関係に係る規定については、いずれの規定も、複数個存在する第一の部位、複数個存在し得る第二の部位の全てにおいて成り立つ。例えば、第一の部位と第二の部位とのa及び/又はbの符号が逆となる関係は、複数個存在する第一の部位のいずれにおいても、第二の部位との間で関係を満たす。
The light transmission-absorption filter of the present invention may be in the form of a film having a certain thickness, and may be a film that stands on its own, or may be a film that is disposed on a substrate film, etc. When the film-shaped light transmission-absorption filter of the present invention is observed in the thickness direction, it is sufficient that a first transmission portion and a second transmission portion are present.
Furthermore, the light transmission-absorption filter of the present invention may have a single-layer structure or a multi-layer structure of two or more layers, as long as it has the first light transmission-absorption region (hereinafter also simply referred to as the "first region") and the second light transmission-absorption region (hereinafter also simply referred to as the "second region"). A multi-layer structure of two or more layers is preferred because it makes it easier to realize the first region and the second region having different light transmission-absorption properties. As the light transmission-absorption filter of the present invention having a multi-layer structure of two or more layers, a structure including two or more layers with different light absorption-transmission properties is preferred. For example, preferred examples include light transmission-absorption filter I obtained by mask-exposing a laminate including a wavelength-selective absorption layer and a light-absorbing-disappearing layer described below with ultraviolet light irradiation, and light transmission-absorption filter II including a laminate obtained by mask-exposing a laminate including a light-absorbing-disappearing layer with ultraviolet light irradiation, and a laminate including a wavelength-selective absorption layer.
Furthermore, the light transmission-absorption filter of the present invention may have light transmission-absorption regions having different light transmission-absorption characteristics, defined as the first region and the second region. The light transmission-absorption filter of the present invention is used by arranging the first region on a light-emitting region (also simply referred to as a "light-emitting region" in the present invention) in the display region of an organic electroluminescence display element (OLED display element), and the second region on a non-light-emitting region (such as a substrate, thin metal wires (metal wiring), and a black bank (black partition wall); also simply referred to as a "non-light-emitting region" in the present invention) in the display region of the OLED display element. As long as the effects of the present invention are achieved, the light transmission-absorption filter of the present invention may further have other light transmission-absorption regions (hereinafter referred to as "other regions") having light transmission-absorption characteristics different from those of the first region and the second region. For example, when an OLED display element has a display area and a non-display area, the first and second areas may be arranged on the display area as described above, and other areas may be arranged on the non-display area (for example, a frame area surrounding the display area, an area covered by a fixing member such as a housing, etc.). The light transmission and absorption characteristics of the other areas may be adjusted as appropriate in accordance with the configuration of the non-display area of the OLED display element.
In the present invention, the light-emitting portion of the OLED display element means a portion in the display area from which display light is emitted, and the non-light-emitting portion of the OLED display element means a portion in the display area from which display light is not emitted.
Therefore, the first and second regions of the light transmission absorption filter of the present invention are configured in accordance with the arrangement of the light emitting portions and non-light emitting portions of the OLED display element into which the light transmission absorption filter of the present invention is incorporated.
Furthermore, the light transmission-absorption filter of the present invention usually has a plurality of the above-mentioned first regions in accordance with the number of light-emitting sections of the OLED display element into which the light transmission-absorption filter of the present invention is incorporated, and the light transmission-absorption filter of the present invention may have a plurality of the above-mentioned second regions in accordance with the number of non-light-emitting sections of the OLED display element into which the light transmission-absorption filter of the present invention is incorporated.
For this reason, the provisions relating to the first portion, the second portion, and the relationship between the first portion and the second portion of the light transmission/absorption filter of the present invention all hold true for all of the multiple first portions and the multiple second portions that may be present. For example, the relationship between the first portion and the second portion in which the signs of a * and/or b * are opposite satisfies the relationship with the second portion in any of the multiple first portions.

 本発明の光透過吸収フィルタは、上述の第一の部位と第二の部位とを有する構成により、表示装置に組み込んだ際に表示光の所望の透過率が担保される光透過吸収フィルタであって、表示装置に組み込んだ際には、外光反射が抑制され、しかも、反射光の色味と表示光の色味が共にニュートラルに調整されている。これは、以下の理由によるものと考えられる。
 すなわち、本発明の光透過吸収フィルタは、波長460nm、530nm及び620nmの各波長における透過率が後述の関係(波長460nm及び620nmにおいては30%以上、波長530nmにおいては40%以上)を満たすため、表示光の所望の透過率が担保されている。このように、OLED表示素子の発光波長領域の光(460nm、530nm及び620nmを中心とする光)の吸収が抑えられた結果、表示光の利用効率の低下が抑制されている。また、本発明の光透過吸収フィルタにおいて、上記第一の部位と第二の部位とは、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たす。このため、第一の部位の色度(a及びb)と第二の部位の色度(a及びb)とが相補的になるように調節された結果、本発明の光透過吸収フィルタにおける第一の部位をOLED表示素子の発光部上に配置し、第二の部位をOLED表示素子の非発光部上に配置することにより、本発明の光透過吸収フィルタを、外光反射が抑制され、しかも、反射光の色味をニュートラルに調整されたものとすることができる。
 なお、本発明の光透過吸収フィルタにおける第一の部位は、波長460nm、530nm及び620nmの各波長における透過率が後述の関係を満たし、いずれの透過率も少なくとも30%以上(波長530nmにおいては少なくとも40%以上)であるため、波長460nm、530nm又は620nmにおける透過率が30%未満であるR(赤)G(緑)B(青)のいずれのカラーフィルタとも異なる光透過性を示す部位である。
The light transmission-absorption filter of the present invention is a light transmission-absorption filter that, due to its configuration having the above-mentioned first and second sections, ensures a desired transmittance of display light when incorporated into a display device, and when incorporated into a display device, external light reflection is suppressed, and the color of both the reflected light and the color of the display light are adjusted to be neutral. This is thought to be due to the following reasons.
That is, the light transmission-absorption filter of the present invention has transmittances at wavelengths of 460 nm, 530 nm, and 620 nm that satisfy the relationships described below (30% or more at wavelengths of 460 nm and 620 nm, and 40% or more at wavelength 530 nm), thereby ensuring the desired transmittance of display light. As a result of suppressing absorption of light in the emission wavelength region of the OLED display element (light centered at 460 nm, 530 nm, and 620 nm), a decrease in the utilization efficiency of display light is suppressed. Furthermore, in the light transmission-absorption filter of the present invention, the first and second regions satisfy a relationship in which the signs of at least one of the values of a * and b * in the L * a * b * color space of transmitted light are opposite. Therefore, the chromaticity (a * and b * ) of the first region and the chromaticity (a * and b * ) of the second region are adjusted to be complementary, and by arranging the first region of the light-transmitting-absorbing filter of the present invention on the light-emitting portion of the OLED display element and the second region on the non-light-emitting portion of the OLED display element, the light-transmitting-absorbing filter of the present invention can be one in which external light reflection is suppressed and the color of the reflected light is adjusted to be neutral.
The first portion of the light transmission-absorption filter of the present invention has transmittances at wavelengths of 460 nm, 530 nm, and 620 nm that satisfy the relationships described below, and each transmittance is at least 30% or more (at least 40% or more at a wavelength of 530 nm). Therefore, the first portion is a portion that exhibits light transmittance different from that of any of the R (red), G (green), and B (blue) color filters, each of which has a transmittance of less than 30% at a wavelength of 460 nm, 530 nm, or 620 nm.

(第一の部位の特定の波長における透過率)
 本発明の光透過吸収フィルタにおける第一の部位は、波長460nmにおける透過率T(460)、波長530nmにおける透過率T(530)及び波長620nmにおける透過率T(620)がそれぞれ下記関係を満たす。
  T(460)≧30%
  T(530)≧40%
  T(620)≧30%
 このため、本発明の光透過吸収フィルタにおける第一の部位は、波長460nm、530nm又は620nmにおける透過率が30%未満となるR(赤)G(緑)B(青)のいずれのカラーフィルタとも異なる光透過性を示す部位である。
 波長460nmにおける透過率T(460)、波長530nmにおける透過率T(530)及び波長620nmにおける透過率T(620)の上限値は、特に制限はなく、それぞれ、例えば80%以下とすることができ、70%以下が好ましく、65%以下がより好ましく、60%以下が更に好ましい。
 すなわち、波長460nmにおける透過率T(460)及び波長620nmにおける透過率T(620)の範囲としては、それぞれ、30~80%とすることができ、30~70%が好ましく、30~65%がより好ましく、30~60%が更に好ましく、波長530nmにおける透過率T(530)の範囲としては、40~80%とすることができ、40~70%が好ましく、40~65%がより好ましく、40~60%が更に好ましい。
 上記第一の部位の波長460nmにおける透過率T(460)は、45%以上であることが好ましく、50%以上であることがより好ましい。すなわち、波長460nmにおける透過率T(460)の範囲としては、45~80%であることが好ましく、50~70%がより好ましく、50~65%が更に好ましく、50~60%が特に好ましい。
(Transmittance of the first portion at a specific wavelength)
In the first portion of the light transmission/absorption filter of the present invention, the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm each satisfy the following relationships:
T(460)≧30%
T(530)≧40%
T(620)≧30%
For this reason, the first portion of the light transmission-absorption filter of the present invention is a portion that exhibits light transmittance different from that of any of the R (red), G (green), and B (blue) color filters, in that the transmittance at wavelengths of 460 nm, 530 nm, or 620 nm is less than 30%.
The upper limit values of the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm are not particularly limited, and can be, for example, 80% or less, preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less.
That is, the range of the transmittance T(460) at a wavelength of 460 nm and the range of the transmittance T(620) at a wavelength of 620 nm can be 30 to 80%, preferably 30 to 70%, more preferably 30 to 65%, and even more preferably 30 to 60%, and the range of the transmittance T(530) at a wavelength of 530 nm can be 40 to 80%, preferably 40 to 70%, more preferably 40 to 65%, and even more preferably 40 to 60%.
The transmittance T(460) of the first portion at a wavelength of 460 nm is preferably 45% or more, and more preferably 50% or more. That is, the transmittance T(460) at a wavelength of 460 nm is preferably in the range of 45 to 80%, more preferably 50 to 70%, even more preferably 50 to 65%, and particularly preferably 50 to 60%.

(第一の部位と第二の部位とのa及び/又はbの符号の関係)
 本発明の光透過吸収フィルタにおける上記第一の部位と上記第二の部位との間で、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たすとは、具体的には、以下の(1)及び/又は(2)を満たすことを意味する。
(1)上記第一の部位のL色空間におけるaの値の符号と、上記第二の部位のL色空間におけるaの値の符号とが逆であり、一方が+(プラス)であり、他方が-(マイナス)である。
(2)上記第一の部位のL色空間におけるbの値の符号と、上記第二の部位のL色空間におけるbの値の符号とが逆であり、一方が+(プラス)であり、他方が-(マイナス)である。
 本発明の光透過吸収フィルタは、上記第一の部位と上記第二の部位との間で、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たすため、上記第一の部位と上記第二の部位とは、互いに色相が異なる部位と言える。
 なお、外光反射をより抑制できる観点から、本発明の光透過吸収フィルタにおける上記第一の部位と上記第二の部位との間で、透過光のL色空間におけるa及びbの両方の値の符号が逆となる関係を満たすこと、すなわち、上記の(1)及び(2)の両方を満たすことが好ましい。
 なお、L色空間とは、1976年にCIE(国際照明委員会)で規格化されたL色空間を意味する。また、透過光のL色空間におけるa及びbは、光透過吸収フィルタの波長380~780nmの範囲の透過率に明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより、第一の部位、第二の部位それぞれについて算出される値である。
 また、特段の断りのない限り、透過光のL色空間におけるa及びbとは、極角0°方位角0°の透過光のa及びbを意味する。
(Relationship between the signs of a * and/or b * in the first and second moieties)
In the light transmission/absorption filter of the present invention, the relationship in which the sign of at least one of the values of a * and b * in the L * a * b * color space of transmitted light is opposite between the first region and the second region specifically means that the following (1) and/or (2) is satisfied:
(1) The sign of the a * value in the L * a * b * color space of the first region is opposite to the sign of the a * value in the L * a * b * color space of the second region, one being + (plus) and the other being − (minus).
(2) The sign of the b * value in the L * a * b * color space of the first region is opposite to the sign of the b * value in the L * a * b * color space of the second region, one being + (plus) and the other being − (minus).
The light transmission-absorption filter of the present invention satisfies a relationship in which the sign of at least one of the values of a * and b * in the L * a * b * color space of transmitted light is opposite between the first region and the second region, and therefore the first region and the second region can be said to be regions with different hues.
From the viewpoint of further suppressing external light reflection, it is preferable that the light transmission/absorption filter of the present invention satisfy a relationship in which the signs of both the a * and b * values in the L * a * b * color space of the transmitted light between the first and second regions are opposite, i.e., that both of the above (1) and (2) are satisfied.
The L * a * b * color space refers to the L * a * b * color space standardized by the CIE (International Commission on Illumination) in 1976. In addition, a * and b * in the L * a * b * color space of transmitted light are values calculated for each of the first and second regions by multiplying the transmittance of the light-transmitting/absorbing filter in the wavelength range of 380 to 780 nm by the standard relative luminous efficiency for photopic vision and then summing (luminous efficiency correction).
Unless otherwise specified, a * and b * in the L * a * b * color space of transmitted light refer to a * and b * of transmitted light at a polar angle of 0° and an azimuthal angle of 0°.

 本発明の光透過吸収フィルタが有する第一の部位及び第二の部位について、上述の点以外の点について、以下、順に説明する。 Further details about the first and second sections of the light transmission/absorption filter of the present invention, other than those mentioned above, will be explained below.

<<第一の部位>>
 本発明の光透過吸収フィルタが有する上記第一の部位は、OLED表示素子の発光部上に配置されるようにして用いられる。
 表示素子の発光部と非発光部とは、1つの画素において通常10~30μm位の幅で配置されており、また、本発明の光透過吸収フィルタをOLED表示素子に適用する際には、通常、本発明の光透過吸収フィルタとOLED表示素子層との距離は、例えば、2~40μm程度に設定される。このような構成においては、表示光の色味については、第一の部位のa及びbを評価することにより表示光の色味の評価を代替することができる。
 上記第一の部位の透過光のa及びbは、通常、下記関係を満たすものであり、
  -30.0≦a≦+30.0
  -30.0≦b≦+30.0
 表示光の色味をよりニュートラルに調整する観点から、下記関係を満たすことが好ましく、
  -20.0≦a≦+20.0
  -20.0≦b≦+20.0
 下記関係を満たすことがより好ましく、
  -10.0≦a≦+10.0
  -10.0≦b≦+10.0
 下記関係を満たすことが更に好ましく、
  -8.0≦a≦+8.0
  -8.0≦b≦+8.0
 下記関係を満たすことが特に好ましい。
  -7.0≦a≦+7.0
  -7.0≦b≦+7.0
 なお、本段落の式中におけるa及びbは、上記の第一の部位の透過光のL色空間におけるa及びbとそれぞれ同義である。第一の部位の透過光のL色空間におけるa及びbが上記関係を満たすとは、a及びbがいずれも上記関係を満たすことを意味する。また、上記関係を満たすかどうかについては、小数第二位を四捨五入して得られたa及びbに基づき判断する。
<<First part>>
The first portion of the light transmission/absorption filter of the present invention is used by being disposed above the light-emitting portion of an OLED display element.
The light-emitting and non-light-emitting portions of the display element are typically arranged with a width of about 10 to 30 μm in one pixel, and when the light-transmitting and -absorbing filter of the present invention is applied to an OLED display element, the distance between the light-transmitting and -absorbing filter of the present invention and the OLED display element layer is typically set to, for example, about 2 to 40 μm. In such a configuration, the color of the display light can be evaluated by evaluating a * and b * of the first portion.
a * and b * of the transmitted light through the first portion usually satisfy the following relationship:
−30.0≦a * ≦+30.0
−30.0≦b * ≦+30.0
From the viewpoint of adjusting the color tone of the display light to be more neutral, it is preferable that the following relationship be satisfied:
−20.0≦a * ≦+20.0
−20.0≦b * ≦+20.0
It is more preferable that the following relationship is satisfied:
−10.0≦a * ≦+10.0
−10.0≦b * ≦+10.0
It is more preferable that the following relationship is satisfied:
−8.0≦a * ≦+8.0
−8.0≦b * ≦+8.0
It is particularly preferable that the following relationship is satisfied:
−7.0≦a * ≦+7.0
−7.0≦b * ≦+7.0
In addition, a * and b * in the formula in this paragraph are respectively synonymous with a * and b* in the L * a * b * color space of the transmitted light through the first portion. "A * and b * in the L * a * b * color space of the transmitted light through the first portion satisfy the above relationship " means that a * and b * both satisfy the above relationship. Furthermore, whether or not the above relationship is satisfied is determined based on a * and b * obtained by rounding off to one decimal place.

<<第二の部位>>
 本発明の光透過吸収フィルタが有する上記第二の部位は、OLED表示素子の非発光部上に配置されるようにして用いられる。そのため、上記第二の部位の透過率においては、上記第一の部位で規定されるような、特定の波長領域における透過率についての制限は特にない。
 本発明の光透過吸収フィルタを外光反射が抑制され、しかも、反射光の色味をニュートラルに調整されたものへと調整しやすい観点から、上記第二の部位の透過光のa及びbは下記関係を満たすことが好ましく、
  -30.0≦a≦+30.0
  -30.0≦b≦+30.0
 下記関係を満たすことがより好ましく、
  -25.0≦a≦+25.0
  -25.0≦b≦+25.0
 下記関係を満たすことが更に好ましい。
  -20.0≦a≦+20.0
  -20.0≦b≦+20.0
 なお、本段落の式中におけるa及びbは、上記の第二の部位の透過光のL色空間におけるa及びbとそれぞれ同義である。第二の部位の透過光のL色空間におけるa及びbが上記関係を満たすとは、a及びbがいずれも上記関係を満たすことを意味する。また、上記関係を満たすかどうかについては、小数第二位を四捨五入して得られたa及びbに基づき判断する。
<<Second part>>
The second portion of the light transmission-absorption filter of the present invention is disposed on a non-light-emitting portion of an OLED display element, and therefore the transmittance of the second portion is not particularly limited in a specific wavelength range, as is the transmittance of the first portion.
From the viewpoint of suppressing external light reflection in the light transmission/absorption filter of the present invention and easily adjusting the color of the reflected light to a neutral color, it is preferable that a * and b * of the transmitted light in the second region satisfy the following relationship:
−30.0≦a * ≦+30.0
−30.0≦b * ≦+30.0
It is more preferable that the following relationship is satisfied:
−25.0≦a * ≦+25.0
−25.0≦b * ≦+25.0
It is more preferable that the following relationship is satisfied:
−20.0≦a * ≦+20.0
−20.0≦b * ≦+20.0
In addition, a * and b * in the formula in this paragraph are respectively synonymous with a * and b* in the L * a * b * color space of the transmitted light through the second portion. "A * and b * in the L * a * b * color space of the transmitted light through the second portion satisfy the above relationship " means that a * and b * both satisfy the above relationship. Furthermore, whether or not the above relationship is satisfied is determined based on a * and b * obtained by rounding off to one decimal place.

 本発明の光透過吸収フィルタにおいて、上記第一の部位と上記第二の部位との面積比率は、本発明の光透過吸収フィルタを適用するOLED表示素子の発光部と非発光部との面積比率に対応する。すなわち、第二の部位(OLED表示素子の非発光部)と第一の部位(OLED表示素子の発光部)との面積比率は、通常、第二の部位(OLED表示素子の非発光部)/第一の部位(OLED表示素子の発光部)=90/10~60/40であり、外光反射が抑制され、反射色味及び表示色味が共にニュートラルに調整された光透過吸収フィルタとする観点からは、85/15~60/40が好ましい。 In the light transmission/absorption filter of the present invention, the area ratio between the first region and the second region corresponds to the area ratio between the light-emitting region and the non-light-emitting region of the OLED display element to which the light transmission/absorption filter of the present invention is applied. That is, the area ratio between the second region (non-light-emitting region of the OLED display element) and the first region (light-emitting region of the OLED display element) is typically second region (non-light-emitting region of the OLED display element)/first region (light-emitting region of the OLED display element) = 90/10 to 60/40, and from the perspective of obtaining a light transmission/absorption filter in which external light reflection is suppressed and both reflected and displayed colors are adjusted to be neutral, a ratio of 85/15 to 60/40 is preferred.

 本発明の光透過吸収フィルタが示す反射色味は、上記L色空間におけるa及びbの少なくとも一方が-5.0~5.0であることが好ましく、上記L色空間におけるa及びbの両方が-5.0~5.0であることがより好ましく、上記L色空間におけるa及びbの両方が-2.0~2.0であることが更に好ましい。
 また、本発明の光透過吸収フィルタが示す反射率は、8.0%以下であることが好ましく、7.5%以下であることがより好ましく、7.0%以下であることがさらに好ましい。下限値に特に制限はなく、4.0%以上であることが実際的である。
 なお、本発明の光透過吸収フィルタが示す反射光のL色空間におけるa及びb及び反射率は、後述の実施例に記載の方法により、発光部の反射スペクトル及び非発光部の反射スペクトルに対して、発光部と非発光部の面積比率を掛け合わせた和として算出し、得られた反射スペクトルにCIE標準光源D65スペクトルと明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより算出される値である。
With regard to the reflection color exhibited by the light transmission/absorption filter of the present invention, it is preferable that at least one of a * and b * in the L * a * b * color space is −5.0 to 5.0, more preferably both a * and b * in the L * a*b* color space are −5.0 to 5.0, and even more preferably both a * and b * in the L*a * b * color space are −2.0 to 2.0.
Furthermore, the reflectance exhibited by the light transmission/absorption filter of the present invention is preferably 8.0% or less, more preferably 7.5% or less, and even more preferably 7.0% or less. There is no particular lower limit, and a reflectance of 4.0% or more is practical.
The a * and b * and reflectance in the L * a * b * color space of the reflected light exhibited by the light transmission/absorption filter of the present invention are values calculated by the method described in the Examples below, as the sum of the reflection spectra of the light-emitting portions and the reflection spectra of the non-light-emitting portions multiplied by the area ratio of the light-emitting portions to the non-light-emitting portions, and then multiplying the resulting reflection spectra by the CIE standard illuminant D65 spectrum and the photopic standard relative luminous efficiency and taking the sum (luminous efficiency correction).

 本発明の光透過吸収フィルタの厚みは、特に制限されず、例えば、2~130μmとすることができる。後述の光透過吸収フィルタIは、2~80μmが好ましく、2~70μmがより好ましく、2~60μmがさらに好ましい。後述の光透過吸収フィルタIIは、5~120μmが好ましく、7~110μmがより好ましく、9~110μmがさらに好ましい。厚みは、後述の光吸収消失性層及び波長選択吸収層における膜厚の測定方法に基づき測定される値である。 The thickness of the light transmission/absorption filter of the present invention is not particularly limited and can be, for example, 2 to 130 μm. Light transmission/absorption filter I, described below, is preferably 2 to 80 μm, more preferably 2 to 70 μm, and even more preferably 2 to 60 μm. Light transmission/absorption filter II, described below, is preferably 5 to 120 μm, more preferably 7 to 110 μm, and even more preferably 9 to 110 μm. The thickness is a value measured based on the method for measuring the film thickness of the light-absorbing/dissipating layer and wavelength-selective absorption layer, described below.

 本発明の光透過吸収フィルタの好ましい形態の一つとして、以下に、波長選択吸収層と光吸収消失性層とを含む積層体(以下、「積層体I」とも称す。)を紫外線照射によりマスク露光して得られる光透過吸収フィルタ(以下、「光透過吸収フィルタI」とも称す。)について詳述する。
 また、本発明の光透過吸収フィルタの別の好ましい形態の一つとして、光吸収消失性層を含む積層体(以下、「積層体pre-III」とも称す)を紫外線照射によりマスク露光して得られた積層体(以下、「積層体III」とも称す)と、波長選択吸収層を含む積層体(以下、「積層体II」とも称す)とを含む光透過吸収フィルタ(以下、「光透過吸収フィルタII」とも称す。)についても詳述する。
 ただし、本発明の光透過吸収フィルタはこれらの形態に何ら限定されるものではない。
As one preferred embodiment of the light transmission-absorption filter of the present invention, a light transmission-absorption filter (hereinafter also referred to as “light transmission-absorption filter I”) obtained by mask-exposing a laminate including a wavelength-selective absorption layer and a light-absorbing-disappearing layer (hereinafter also referred to as “laminate I”) to ultraviolet light will be described in detail below.
Furthermore, as another preferred embodiment of the light transmission-absorption filter of the present invention, a light transmission-absorption filter (hereinafter also referred to as “light transmission-absorption filter II”) comprising a laminate (hereinafter also referred to as “laminate III”) obtained by mask-exposing a laminate (hereinafter also referred to as “laminate pre-III”) containing a light-absorbing and disappearing layer with ultraviolet light irradiation, and a laminate (hereinafter also referred to as “laminate II”) containing a wavelength-selective absorption layer will be described in detail.
However, the light transmission/absorption filter of the present invention is not limited to these forms at all.

[光透過吸収フィルタI]
 光透過吸収フィルタIは、波長選択吸収層と光吸収消失性層とを含む積層体Iを紫外線照射によりマスク露光して得られる光透過吸収フィルタである。
 上記波長選択吸収層は、紫外線照射によるマスク露光によらず、マスク露光前の積層体Iにおける波長選択吸収層とほとんど変わらない光吸収特性を有する層を意味する。
 一方で、上記光吸収消失性層は、紫外線照射により、光吸収消失性層に含有される染料が化学変化して消色可能な特性を有する層を意味する。よって、本発明の光透過吸収フィルタIにおける光吸収消失性層は、光吸収効果を有する光吸収性部位と、光吸収性を消失させた部位(光吸収性消失部位)とを、紫外線照射によるマスク露光のパターン(以下、「マスクパターン」とも称す。)に応じて有する。上記光吸収性部位は、所望の吸光度を示すことができる。
 すなわち、波長選択吸収層と光吸収消失性層とを含む積層体Iを紫外線照射によりマスク露光することによって、積層体Iのうちマスクしていた箇所は露光されずに、光吸収効果を有する光吸収性部位として存在し、マスクしていなかった箇所は露光され、マスクしていなかった箇所における光吸収消失性層は消色されて光吸収性消失部位となり、光吸収性の低い部位となる。
 その結果、上記光透過吸収フィルタIにおいては、波長選択吸収層とマスクしていなかった箇所の光吸収消失性層(光吸収性消失部位)とを含む部位が上述の第一の部位となり、波長選択吸収層とマスクしていた箇所の光吸収消失性層(光吸収性部位)とを含む部位が上述の第二の部位となる。
 特に、上記光吸収性消失部位は、後述する通り、上記光吸収消失性層が優れた消色率を示し、しかも、染料の分解に伴う二次的な吸収がほとんど生じない場合には、光透過吸収フィルタIにおける光吸収消失性層は無色に近い光学特性を示すことができ、上述の第一の部位は、波長選択吸収層に特有の光吸収特性を示すことができる。
 なお、光透過吸収フィルタIは、積層体Iにおける光吸収消失性層に相当する層が、紫外線照射によって形成された光吸収性消失部位を有することを除き、特段の断りのない限り、積層体Iの記載を好ましく適用することができる。
 積層体Iとしては、例えば、波長選択吸収層、後述の拡散阻害層、光吸収消失性層がこの順に配置された構成を含む積層体が好ましく挙げられる。
[Light transmission absorption filter I]
The light transmission/absorption filter I is a light transmission/absorption filter obtained by exposing a laminate I including a wavelength-selective absorption layer and a light-absorbing/disappearing layer to ultraviolet light using a mask.
The wavelength-selective absorption layer means a layer that has light absorption properties that are almost the same as those of the wavelength-selective absorption layer in the laminate I before exposure to ultraviolet light using a mask, regardless of the exposure to ultraviolet light using a mask.
On the other hand, the light-absorbing and dissipative layer refers to a layer that has the property of being discolorable due to a chemical change of the dye contained in the light-absorbing and dissipative layer when irradiated with ultraviolet light. Therefore, the light-absorbing and dissipative layer in the light-transmitting and absorbing filter I of the present invention has light-absorbing portions that have a light-absorbing effect and portions where the light-absorbency has been eliminated (light-absorbency-eliminating portions) according to the pattern of mask exposure by ultraviolet light irradiation (hereinafter also referred to as the "mask pattern"). The light-absorbing portions can exhibit the desired absorbance.
That is, by masking and exposing a laminate I containing a wavelength-selective absorption layer and a light-absorbing and dissipating layer with ultraviolet light irradiation, the masked portions of the laminate I are not exposed and exist as light-absorbing portions with a light-absorbing effect, while the unmasked portions are exposed, and the light-absorbing and dissipating layer in the unmasked portions is discolored to become light-absorbing and dissipating portions, resulting in portions with low light absorption.
As a result, in the light transmission absorption filter I, the region including the wavelength selection absorption layer and the light-absorbing and dissipating layer (light-absorbing and dissipating region) in the unmasked region becomes the first region, and the region including the wavelength selection absorption layer and the light-absorbing and dissipating layer (light-absorbing region) in the masked region becomes the second region.
In particular, as will be described later, when the light-absorbing and dissipating layer exhibits an excellent discoloration rate and there is almost no secondary absorption due to the decomposition of the dye, the light-absorbing and dissipating layer in light-transmitting and absorbing filter I can exhibit optical properties that are close to colorless, and the first portion can exhibit light-absorbing properties that are specific to the wavelength-selective absorption layer.
Unless otherwise specified, the description of laminate I can be preferably applied to light transmission-absorption filter I, except that the layer corresponding to the light-absorbing-disappearing layer in laminate I has a light-absorbing-disappearing site formed by ultraviolet irradiation.
As the laminate I, for example, a laminate including a configuration in which a wavelength selective absorption layer, a diffusion-preventing layer described below, and a light-absorbing and dissipating layer are arranged in this order can be mentioned.

[光透過吸収フィルタII]
 光透過吸収フィルタIIは、光吸収消失性層を含む積層体pre-IIIを紫外線照射によりマスク露光して得られた積層体IIIと、波長選択吸収層を含む積層体IIとを含む光透過吸収フィルタである。なお、積層体pre-IIIは波長選択吸収層を含まず、また、積層体IIは光吸収消失性層を含まない。
 上記波長選択吸収層は、上述の光透過吸収フィルタIにおける波長選択吸収層と同様に、紫外線照射によるマスク露光によらず、マスク露光前の積層体IIにおける波長選択吸収層とほとんど変わらない光吸収特性を有する層を意味する。
 一方で、上記光吸収消失性層は、上述の光透過吸収フィルタIにおける光吸収消失性層と同様に、紫外線照射により、光吸収消失性層に含有される染料が化学変化して消色可能な特性を有する層を意味する。よって、本発明の光透過吸収フィルタIIにおける光吸収消失性層は、光吸収効果を有する光吸収性部位と、光吸収性を消失させた部位(光吸収性消失部位)とを、紫外線照射によるマスク露光のパターン(以下、「マスクパターン」とも称す。)に応じて有する。上記光吸収性部位は、所望の吸光度を示すことができる。
 すなわち、光吸収消失性層を含む積層体pre-IIIを紫外線照射によりマスク露光することによって、積層体pre-IIIのうちマスクしていた箇所は露光されずに、光吸収効果を有する光吸収性部位として存在し、マスクしていなかった箇所は露光され、マスクしていなかった箇所における光吸収消失性層は消色されて光吸収性消失部位となり、光吸収性の低い部位として存在する、積層体IIIが得られる。
 その結果、上記光透過吸収フィルタIIにおいては、波長選択吸収層とマスクしていなかった箇所の光吸収消失性層(光吸収性消失部位)とを含む部位が上述の第一の部位となり、波長選択吸収層とマスクしていた箇所の光吸収消失性層(光吸収性部位)とを含む部位が上述の第二の部位となる。
 特に、上記光吸収性消失部位は、後述する通り、上記光吸収消失性層が優れた消色率を示し、しかも、染料の分解に伴う二次的な吸収がほとんど生じない場合には、光透過吸収フィルタIIにおける光吸収消失性層は無色に近い光学特性を示すことができ、上述の第一の部位は、波長選択吸収層に特有の光吸収特性を示すことができる。
 なお、光透過吸収フィルタIIにおける積層体IIIは、積層体pre-IIIにおける光吸収消失性層に相当する層が、紫外線照射によって形成された光吸収性消失部位を有することを除き、特段の断りのない限り、積層体pre-IIIの記載を好ましく適用することができる。
 積層体IIとしては、例えば、後述の第一波長選択吸収層、後述のガスバリア層、後述の第一波長選択吸収層がこの順に配置された構成を含む積層体が好ましく挙げられる。また、積層体pre-IIIとしては、例えば、後述の拡散阻害層、光吸収消失性層、後述のガスバリア層がこの順に配置された構成を含む積層体が好ましく挙げられる。
[Light transmission absorption filter II]
Light transmission-absorption filter II is a light transmission-absorption filter comprising laminate III obtained by mask-exposing laminate pre-III, which includes a light-absorbing and dissipating layer, to ultraviolet light, and laminate II, which includes a wavelength-selective and absorbent layer. Note that laminate pre-III does not include a wavelength-selective and absorbent layer, and laminate II does not include a light-absorbing and dissipating layer.
The wavelength-selective absorption layer, like the wavelength-selective absorption layer in the above-described light-transmitting-absorbing filter I, means a layer that has light absorption properties that are almost the same as those of the wavelength-selective absorption layer in the laminate II before mask exposure, regardless of whether or not it is subjected to mask exposure by ultraviolet irradiation.
On the other hand, the light-absorbing and dissipative layer refers to a layer that has the property of being discolorable due to a chemical change of the dye contained in the light-absorbing and dissipative layer when irradiated with ultraviolet light, similar to the light-absorbing and dissipative layer in the light-transmitting and absorbing filter I described above. Thus, the light-absorbing and dissipative layer in the light-transmitting and absorbing filter II of the present invention has light-absorbing portions that have a light-absorbing effect and portions where the light-absorbency has been eliminated (light-absorbency-eliminating portions) according to the pattern of mask exposure by ultraviolet irradiation (hereinafter also referred to as the "mask pattern"). The light-absorbing portions can exhibit the desired absorbance.
That is, by masking and exposing the laminate pre-III containing the light-absorbing and dissipating layer with ultraviolet light irradiation, the masked areas of the laminate pre-III are not exposed and exist as light-absorbing parts with a light-absorbing effect, while the unmasked areas are exposed, and the light-absorbing and dissipating layer in the unmasked areas is discolored to become light-absorbing and dissipating parts and exist as parts with low light absorption, resulting in the laminate III.
As a result, in the light transmission/absorption filter II, the region including the wavelength selection/absorption layer and the light-absorbing/disappearing layer (light-absorbing/disappearing region) in the unmasked region becomes the first region, and the region including the wavelength selection/absorption layer and the light-absorbing/disappearing layer (light-absorbing region) in the masked region becomes the second region.
In particular, as will be described later, when the light-absorbing and dissipating layer exhibits an excellent discoloration rate and there is almost no secondary absorption due to the decomposition of the dye, the light-absorbing and dissipating layer in the light-transmitting and absorbing filter II can exhibit optical properties that are close to colorless, and the first portion can exhibit light-absorbing properties that are specific to the wavelength-selective and absorbing layer.
Unless otherwise specified, the description of laminate pre-III can be preferably applied to laminate III in light transmission-absorption filter II, except that the layer corresponding to the light-absorbing and dissipating layer in laminate pre-III has a light-absorbing and dissipating site formed by ultraviolet irradiation.
A preferred example of the laminate II is a laminate including a configuration in which a first wavelength selective absorption layer (described later), a gas barrier layer (described later), and a first wavelength selective absorption layer (described later) are arranged in this order. A preferred example of the laminate pre-III is a laminate including a configuration in which a diffusion-preventing layer (described later), a light-absorbing and dissipating layer (described later), and a gas barrier layer (described later) are arranged in this order.

 光透過吸収フィルタIについて、本発明の光透過吸収フィルタにおける第一の部位及び第二の部位と発光素子であるOLED表示素子との位置関係を、図1を用いて以下に説明する。なお、上記の位置関係については、光透過吸収フィルタIに限定されず、光透過吸収フィルタII等の本発明の光透過吸収フィルタにおいても適用されるものである。
 具体的には、図1に示されるように、光透過吸収フィルタI(10)は、積層体I(図示せず)をマスク露光にすることにより得られ、マスク露光された波長選択吸収層3とマスク露光された光吸収消色性層4とを有する。マスク露光された光吸収消色性層4において、マスクしていなかった箇所は光吸収性消失部位5となり、マスクしていた箇所は光吸収性部位6となる。上記マスクパターンは、OLED表示素子の発光部7及び非発光部8の配置に対応するようにして施され、具体的には、OLED表示素子の発光部7の上部に位置する積層体Iの部位がマスクされ、OLED表示素子の非発光部8の上部に位置する積層体Iの部位がマスクされていないパターンである。この結果、光透過吸収フィルタI(10)は、OLED表示素子の発光部7の上部に対応する箇所には、マスク露光された波長選択吸収層3と光吸収性消失部位5とを含む第一の部位1を有し、OLED表示素子の非発光部8の上部に対応する箇所には、マスク露光された波長選択吸収層3と光吸収性部位6とを含む第二の部位2を有するフィルタとなる。
 なお、図1においては、マスク露光された光吸収消色性層4、マスク露光された波長選択吸収層3、及び、OLED表示素子の発光部7の順に配置して記載されているが、マスク露光された波長選択吸収層3、マスク露光された光吸収消色性層4、及び、OLED表示素子の発光部7の順に配置されていてもよい。このことは、光透過吸収フィルタII等の本発明の光透過吸収フィルタにおいても同様である。
Regarding light transmission-absorption filter I, the positional relationship between the first and second portions in the light transmission-absorption filter of the present invention and the OLED display element, which is a light-emitting element, will be explained below with reference to Fig. 1. Note that the above positional relationship is not limited to light transmission-absorption filter I, but is also applicable to light transmission-absorption filters of the present invention such as light transmission-absorption filter II.
1 , the light-transmitting-absorbing filter I (10) is obtained by mask-exposing the laminate I (not shown), and has a mask-exposed wavelength-selective-absorbing layer 3 and a mask-exposed light-absorbing and decolorizable layer 4. In the mask-exposed light-absorbing and decolorizable layer 4, the unmasked areas become light-absorbent loss areas 5, and the masked areas become light-absorbing areas 6. The mask pattern is applied so as to correspond to the arrangement of the light-emitting sections 7 and non-light-emitting sections 8 of the OLED display element, and specifically, the pattern is such that the areas of the laminate I located above the light-emitting sections 7 of the OLED display element are masked, and the areas of the laminate I located above the non-light-emitting sections 8 of the OLED display element are not masked. As a result, the light-transmitting-absorbing filter I (10) has a first region 1 including the masked wavelength-selective-absorbing layer 3 and the light-absorbency-disappearing region 5 at a location corresponding to the top of the light-emitting region 7 of the OLED display element, and a second region 2 including the masked wavelength-selective-absorbing layer 3 and the light-absorbent region 6 at a location corresponding to the top of the non-light-emitting region 8 of the OLED display element.
1, the mask-exposed light-absorbing and decolorizing layer 4, the mask-exposed wavelength-selective absorption layer 3, and the light-emitting portion 7 of the OLED display element are arranged in this order, but they may also be arranged in this order: the mask-exposed wavelength-selective absorption layer 3, the mask-exposed light-absorbing and decolorizing layer 4, and the light-emitting portion 7 of the OLED display element. This also applies to the light transmission and absorption filters of the present invention, such as light transmission and absorption filter II.

 以下、波長選択吸収層と光吸収消失性層とを含む積層体I、波長選択吸収層を含む積層体II、及び、光吸収消失性層を含む積層体pre-IIIについて説明する。 The following describes laminate I, which includes a wavelength-selective absorption layer and a light-absorbing and dissipating layer, laminate II, which includes a wavelength-selective absorption layer, and laminate pre-III, which includes a light-absorbing and dissipating layer.

[積層体I]
 積層体Iは、光吸収消失性層と波長選択吸収層とを含む積層体であり、具体的には、樹脂と、波長400~700nmに主吸収波長帯域を有する染料と、紫外線照射によりラジカルを生成する化合物とを含有する光吸収消失性層と、
 樹脂と、波長400~700nmに主吸収波長帯域を有する染料とを含有し、紫外線照射によりラジカルを生成する化合物を含有しない波長選択吸収層とを含む積層体であることが好ましい。
[積層体II]
 積層体IIは、波長選択吸収層を含む積層体であり、具体的には、樹脂と、波長400~700nmに主吸収波長帯域を有する染料とを含有し、紫外線照射によりラジカルを生成する化合物を含有しない波長選択吸収層を含む積層体であることが好ましい。ただし、積層体IIは光吸収消失性層を含まない。
[積層体pre-III]
 積層体pre-IIIは、光吸収消失性層を含む積層体であり、具体的には、樹脂と、波長400~700nmに主吸収波長帯域を有する染料と、紫外線照射によりラジカルを生成する化合物とを含有する光吸収消失性層を含む積層体であることが好ましい。ただし、積層体pre-IIIは波長選択吸収層を含まない。
[Laminate I]
The laminate I is a laminate including a light-absorbing and dissipating layer and a wavelength-selective and absorbing layer, specifically, a light-absorbing and dissipating layer containing a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light;
It is preferable that the laminate includes a wavelength selective absorption layer that contains a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and does not contain a compound that generates radicals when irradiated with ultraviolet light.
[Laminate II]
The laminate II is a laminate including a wavelength-selective absorption layer, and specifically, it is preferably a laminate including a wavelength-selective absorption layer that contains a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and does not contain a compound that generates radicals upon irradiation with ultraviolet light, however, the laminate II does not include a light-absorbing and disappearing layer.
[Laminate pre-III]
The laminate pre-III is a laminate including a light-absorbing and dissipating layer, and more specifically, it is preferably a laminate including a light-absorbing and dissipating layer containing a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light, however, the laminate pre-III does not include a wavelength-selective absorption layer.

 本発明において、特段の断りがない限り、積層体I及び積層体pre-IIIにおける光吸収消失性層を構成する成分(樹脂、染料、紫外線照射によりラジカルを生成する化合物、及び、その他の適宜含有していてもよい成分等)は、それぞれ、積層体I及び積層体pre-IIIにおける光吸収消失性層中に1種含有されていてもよく、2種以上含有されていてもよい。また、本発明において、積層体I及び積層体IIにおける波長選択吸収層を構成する成分(樹脂、染料、及び、その他の適宜含有していてもよい成分等)は、それぞれ、積層体I及び積層体IIにおける波長選択吸収層中に1種含有されていてもよく、2種以上含有されていてもよい。積層体Iを用いて作製される光透過吸収フィルタI及び積層体IIと積層体pre-IIIとを用いて作製される光透過吸収フィルタIIについても同義である。 In the present invention, unless otherwise specified, the components constituting the light-absorbing and dissipating layers in Laminate I and Laminate pre-III (such as resins, dyes, compounds that generate radicals upon UV irradiation, and other components that may be optionally contained) may each be contained in the light-absorbing and dissipating layers in Laminate I and Laminate pre-III, either singly or in combination of two or more. Furthermore, in the present invention, the components constituting the wavelength-selective absorption layers in Laminate I and Laminate II (such as resins, dyes, and other components that may be optionally contained) may each be contained in the wavelength-selective absorption layers in Laminate I and Laminate II, either singly or in combination of two or more. This also applies to a light-transmitting and absorbing filter I produced using Laminate I and a light-transmitting and absorbing filter II produced using Laminate II and Laminate pre-III.

 本発明において、染料が有する主吸収波長帯域とは、積層体Iの状態、積層体II及び積層体pre-IIIの各積層体について、又は積層体IIと積層体pre-IIIの積層体の状態で測定される染料の主吸収波長帯域である。具体的には、後述する実施例において、[第一、及び第二の部位の吸光度測定]に記載の条件により、積層体Iの状態、積層体II及び積層体pre-IIIの各積層体について、又は積層体IIと積層体pre-IIIの積層体の状態で測定される。
 積層体I、積層体II及び積層体pre-IIIの各積層体中において、上記「染料」は、同じ層(光吸収消失性層又は波長選択吸収層)中に含まれる上記樹脂中に分散(好ましくは溶解)することにより、積層体I、積層体II及び積層体pre-IIIを染料に由来する特定の吸収スペクトルを示すフィルタとするものである。この分散は、ランダム、規則的等いずれであってもよい。
In the present invention, the main absorption wavelength band of the dye refers to the main absorption wavelength band of the dye measured in the state of laminate I, for each of laminates II and pre-III, or for the laminate of laminates II and pre-III. Specifically, the measurement is performed in the state of laminate I, for each of laminates II and pre-III, or for the laminate of laminates II and pre-III under the conditions described in [Measurement of absorbance of first and second portions] in the Examples described later.
In each of the laminates I, II, and pre-III, the "dye" is dispersed (preferably dissolved) in the resin contained in the same layer (light-absorbing and dissipating layer or wavelength-selective and absorbing layer), thereby making the laminate I, II, and pre-III filters exhibiting a specific absorption spectrum derived from the dye. This dispersion may be random, regular, or the like.

 上記光吸収消失性層は、紫外線照射によりラジカルを生成する化合物が、樹脂中に分散(好ましくは溶解)することにより、紫外線照射された場合にはラジカルを生成し、生成したラジカルが染料と反応し、染料が化学変化することにより染料を褪色させ、消色することができる。
 また、積層体I及び積層体pre-IIIを構成する光吸収消失性層において、紫外線照射によりラジカルを生成する化合物として、後述するように、酸基を有する化合物Aと、化合物Aが含む酸基と水素結合を形成できる構造を有する化合物Bとを含有する場合、紫外線照射によるラジカル種の発生効率が、ベンゾフェノン化合物等の常用の光ラジカル発生剤を用いた場合と比較して向上される。このため、室温等の穏和な温度条件下で紫外線照射を行った場合にも十分なラジカル種が発生し、このラジカル種が直接または間接的に上記染料と反応し、染料が分解することによって、染料は褪色、消色する。
 また、積層体I及び積層体pre-IIIを構成する光吸収消失性層において、酸基を有する化合物Aが光吸収消失性層に含まれる樹脂を構成するポリマーと結合している場合には、紫外線照射により上記染料の近傍でラジカルが生成し、上記ラジカルが染料と反応しやすくなる効果を奏する。
 さらに、後述する「化合物Aが含む上記酸基と水素結合を形成できる構造を有する化合物B」は、化合物Aと水素結合を形成して樹脂中に分散(好ましくは溶解)され、または上記酸基を含む化合物Aが樹脂を構成するポリマーと結合している場合は樹脂中の化合物Aと水素結合を形成し、紫外線が照射された場合にラジカルを生成し、生成したラジカルが近傍の染料と反応する機構により、このラジカルが染料と反応しやすくなり、より効率的に染料を退色させ、消色することができる。
 以下に積層体I及び積層体pre-IIIを構成する光吸収消失性層について詳しく説明する。
The light-absorbing and dissipating layer has a compound that generates radicals when irradiated with ultraviolet light dispersed (preferably dissolved) in the resin, so that when irradiated with ultraviolet light, radicals are generated, and the generated radicals react with the dye, causing a chemical change in the dye, fading and decolorizing the dye.
Furthermore, when the light-absorbing and dissipative layers constituting the laminate I and laminate pre-III contain, as compounds that generate radicals upon ultraviolet irradiation, compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, as described below, the efficiency of generating radical species upon ultraviolet irradiation is improved compared to when a commonly used photoradical generator such as a benzophenone compound is used. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose, thereby fading and discoloring the dye.
Furthermore, in the light-absorbing and disappearing layers constituting the laminate I and laminate pre-III, when compound A having an acid group is bonded to a polymer constituting the resin contained in the light-absorbing and disappearing layer, radicals are generated in the vicinity of the dye upon irradiation with ultraviolet light, which has the effect of making the radicals more likely to react with the dye.
Furthermore, "compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A," which will be described later, forms a hydrogen bond with compound A and is dispersed (preferably dissolved) in the resin, or, when compound A containing the acid group is bonded to a polymer constituting the resin, forms a hydrogen bond with compound A in the resin, and when irradiated with ultraviolet light, generates a radical, and the generated radical reacts with a nearby dye, making the radical more likely to react with the dye, thereby enabling the dye to be faded and decolorized more efficiently.
The light-absorbing and dissipative layers constituting the laminate I and the laminate pre-III will be described in detail below.

<<光吸収消失性層>>
<波長400~700nmに主吸収波長帯域を有する染料>
 積層体I及び積層体pre-IIIを構成する光吸収消失性層に用いられる波長400~700nmに主吸収波長帯域を有する染料の具体例としては、例えば、スクアライン(squaraine、SQ)系、シアニン(cyanine、CY)系、ベンジリデン系、シンナミリデン系、アゾ系及びインドアニリン系の各色素(染料)が挙げられる。
<<Light-absorbing and dissipative layer>>
<Dyes Having a Main Absorption Wavelength Band in the Wavelength Range of 400 to 700 nm>
Specific examples of dyes having a main absorption wavelength band in the wavelength range of 400 to 700 nm and used in the light-absorbing and dissipative layers constituting the laminate I and laminate pre-III include squaraine (SQ), cyanine (CY), benzylidene, cinnamylidene, azo, and indoaniline coloring matter (dyes).

 上記光吸収消失性層は、これらの中でも、染料の分解に伴う二次的な着色構造が生成しにくい点から、後記一般式(i)~(iv)のいずれかで表されるアゾ系色素及び後記一般式(v)で表されるインドアニリン系色素のうちの少なくとも1種を含むことが好ましい。後記一般式(i)で表されるアゾ系色素は、およそ400~500nmの波長域に主吸収波長帯域を有する染料であり、後記一般式(ii)~(iv)のいずれかで表されるアゾ系色素は、およそ450~650nmの波長域に主吸収波長帯域を有する染料であり、後記一般式(v)で表されるインドアニリン系色素は、およそ580~700nmの波長域に主吸収波長帯域を有する染料である。上記光吸収消失性層がこのような構成を有する形態においては、紫外線照射をした場合に、上記光吸収消失性層は優れた消色性を示すことができる。 Among these, the light-absorbing and dissipative layer preferably contains at least one of an azo dye represented by any one of general formulas (i) to (iv) below and an indoaniline dye represented by general formula (v) below, because these dyes are less likely to produce secondary colored structures due to dye decomposition. The azo dye represented by general formula (i) below is a dye having a main absorption wavelength band in the wavelength range of approximately 400 to 500 nm, the azo dye represented by any one of general formulas (ii) to (iv) below is a dye having a main absorption wavelength band in the wavelength range of approximately 450 to 650 nm, and the indoaniline dye represented by general formula (v) below is a dye having a main absorption wavelength band in the wavelength range of approximately 580 to 700 nm. When the light-absorbing and dissipative layer has this configuration, it can exhibit excellent discoloration properties when irradiated with ultraviolet light.

 上記光吸収消失性層中に含有され得る下記一般式(i)で表されるアゾ系色素、下記一般式(ii)で表されるアゾ系色素、下記一般式(iii)で表されるアゾ系色素、下記一般式(iv)で表されるアゾ系色素及び下記一般式(v)で表されるインドアニリン系色素の各色素は、それぞれ、1種でもよく、2種以上であってもよい。
 上記光吸収消失性層は、後述の波長選択吸収層において記載する一般式(1)で表されるスクアライン系色素を含有していてもよい。
 上記光吸収消失性層はこれらの一般式(i)~(iv)のいずれかで表されるアゾ系色素、一般式(v)で表されるインドアニリン系色素及び後述の一般式(1)で表されるスクアライン系色素以外の染料を含有することもできる。後記一般式(i)~(iv)のいずれかで表されるアゾ系色素及び後記一般式(v)で表されるインドアニリン系色素の配合比を最適化することにより、後述の波長選択吸収層と組み合わせて、染料を含有しない場合と比較した反射光の色味の変化を抑制する(以下、「反射光の色味をよりニュートラルに調整する」とも称す。)ことができる。
The azo dye represented by the following general formula (i), the azo dye represented by the following general formula (ii), the azo dye represented by the following general formula (iii), the azo dye represented by the following general formula (iv), and the indoaniline dye represented by the following general formula (v), which can be contained in the light-absorbing and disappearing layer, may each be one type or two or more types.
The light-absorbing and disappearing layer may contain a squaraine dye represented by general formula (1) which will be described later in relation to the wavelength-selective absorption layer.
The light-absorbing and disappearing layer may also contain a dye other than the azo dye represented by any one of general formulas (i) to (iv), the indoaniline dye represented by general formula (v), and the squaraine dye represented by general formula (1) described below. By optimizing the blending ratio of the azo dye represented by any one of general formulas (i) to (iv) described below and the indoaniline dye represented by general formula (v) described below, in combination with a wavelength-selective absorption layer described below, it is possible to suppress a change in the color of reflected light compared to when no dye is contained (hereinafter, also referred to as "adjusting the color of reflected light to be more neutral").

 上記光吸収消失性層は、後述の波長選択吸収層に含有される各染料が有する主吸収波長帯域に対して、吸光度が低い波長領域に吸収を有するような染料を含むことが、外光反射の抑制及び輝度低下の抑制の両立をより実現しやすい観点から好ましい。
 具体的には、上記光吸収消失性層は、後述の波長選択吸収層に含有される各染料が有する主吸収波長帯域のいずれに対しても、5nm以上離れた主吸収波長帯域を有する染料を含有することが好ましい。
 上記光吸収消失性層中に含有される上記「染料」は、OLED表示装置に適用する形態においては、異なる波長域に主吸収波長帯域を有する下記染料E~Gの少なくとも1種を含むことが好ましい。
 染料E:波長430~480nmに主吸収波長帯域を有する染料
 染料F:波長500~590nmに主吸収波長帯域を有する染料
 染料G:波長600~660nmに主吸収波長帯域を有する染料
 なお、上記光吸収消失性層中に含有され得る上記の染料Eは、1種でもよく、2種以上であってもよい。上記光吸収消失性層中に含有され得る上記の染料F及びGについても、染料Eと同様に、各々独立に、1種でもよく、2種以上であってもよい。
 上記染料Eが主吸収波長帯域を有する波長範囲は、430~475nmが好ましく、430~470nmがより好ましく、430~465nmが更に好ましい。
 上記染料Fが主吸収波長帯域を有する波長範囲は、505~585nmが好ましく、510~580nmがより好ましく、515~580nmが更に好ましい。
 上記染料Gが主吸収波長帯域を有する波長範囲は、610~655nmが好ましく、610~650nmがより好ましく、610~640nmが更に好ましい。
 上記光吸収消失性層は上記染料E~G以外の染料を含有することもできる。
It is preferable that the light-absorbing and disappearing layer contains a dye that has absorption in a wavelength region with low absorbance compared to the main absorption wavelength band of each dye contained in the wavelength-selective absorption layer described below, from the viewpoint of more easily achieving both suppression of external light reflection and suppression of brightness reduction.
Specifically, the light-absorbing and dissipating layer preferably contains a dye having a main absorption wavelength band that is 5 nm or more away from any of the main absorption wavelength bands of the dyes contained in the wavelength-selective and absorbent layer described below.
In an embodiment applied to an OLED display device, the "dye" contained in the light-absorbing and dissipative layer preferably includes at least one of the following dyes E to G, which have main absorption wavelength bands in different wavelength regions.
Dye E: a dye having a main absorption wavelength band in a wavelength range of 430 to 480 nm Dye F: a dye having a main absorption wavelength band in a wavelength range of 500 to 590 nm Dye G: a dye having a main absorption wavelength band in a wavelength range of 600 to 660 nm The dye E that can be contained in the light-absorbing and disappearing layer may be one type or two or more types. As with dye E, the dyes F and G that can be contained in the light-absorbing and disappearing layer may each independently be one type or two or more types.
The wavelength range in which the dye E has its main absorption wavelength band is preferably 430 to 475 nm, more preferably 430 to 470 nm, and even more preferably 430 to 465 nm.
The wavelength range in which the dye F has its main absorption wavelength band is preferably 505 to 585 nm, more preferably 510 to 580 nm, and even more preferably 515 to 580 nm.
The wavelength range in which the dye G has a main absorption wavelength band is preferably 610 to 655 nm, more preferably 610 to 650 nm, and even more preferably 610 to 640 nm.
The light-absorbing and dissipative layer may contain dyes other than the dyes E to G.

 特に、後述の波長選択吸収層との組み合わせの観点からは、染料E、染料F及び染料Gは、少なくとも2種の組み合わせであることが好ましく、例えば、染料E及び染料Fを少なくとも含み、染料Gをさらに含んでいてもよい組み合わせが挙げられる。なかでも、後述の波長選択吸収層が後述の染料A~Dの全てを含有し、上記光吸収消失性層が上記染料E~Gのうちの少なくとも2種を含有することが、光透過吸収フィルタI及びIIの外光反射の抑制及び輝度低下の抑制をより高度に実現でき、また、得られた光透過吸収フィルタIないしIIを表示装置に適用した場合には、反射光の色味をニュートラルに調整できる観点から好ましい。
 後述の波長選択吸収層が含有し得る染料との関係においては、上記染料Eが有する主吸収波長帯域は、後述の染料Aが有する主吸収波長帯域に対して5~70nm(より好ましくは5~60nm)離れ、後述の染料Bが有する主吸収波長帯域に対して5~80nm(より好ましくは10~80nm)離れていることが好ましい。なお、波長選択吸収層を2層以上有する場合には、上記染料Eが有する主吸収波長帯域は、後述の染料Aが有する主吸収波長帯域に対して1~70nm(より好ましくは1~60nm)離れ、後述の染料Bが有する主吸収波長帯域に対して5~80nm(より好ましくは10~80nm)離れていることが好ましい。
 また、上記染料Fが有する主吸収波長帯域は、後述の染料Bが有する主吸収波長帯域に対して5~80nm(より好ましくは10~80nm)離れ、後述の染料Cが有する主吸収波長帯域に対して5~60nm(より好ましくは5~50nm)離れていることが好ましい。
 また、上記染料Gが有する主吸収波長帯域は、後述の染料Cが有する主吸収波長帯域に対して5~60nm(より好ましくは10~50nm)離れ、後述の染料Dが有する主吸収波長帯域に対して5~80nm(より好ましくは10~60nm)離れていることが好ましい。
In particular, from the viewpoint of combination with the wavelength-selective absorption layer described below, it is preferable that the dyes E, F, and G are a combination of at least two types, and examples include a combination that includes at least dyes E and F and may further include dye G. Among these, it is preferable that the wavelength-selective absorption layer described below contains all of the dyes A to D described below, and the light-absorbing and disappearing layer contains at least two types of dyes E to G, from the viewpoints that the suppression of external light reflection and the suppression of brightness reduction of the light transmission-absorption filters I and II can be more highly realized, and that when the obtained light transmission-absorption filters I or II are applied to a display device, the color of the reflected light can be adjusted to a neutral color.
In relation to the dyes that may be contained in the wavelength-selective absorption layer described below, the main absorption wavelength band of the dye E is preferably 5 to 70 nm (more preferably 5 to 60 nm) away from the main absorption wavelength band of the dye A described below, and 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below. When the wavelength-selective absorption layer has two or more layers, the main absorption wavelength band of the dye E is preferably 1 to 70 nm (more preferably 1 to 60 nm) away from the main absorption wavelength band of the dye A described below, and 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below.
Furthermore, the main absorption wavelength band of the dye F is preferably 5 to 80 nm (more preferably 10 to 80 nm) away from the main absorption wavelength band of the dye B described below, and is preferably 5 to 60 nm (more preferably 5 to 50 nm) away from the main absorption wavelength band of the dye C described below.
The main absorption wavelength band of the dye G is preferably 5 to 60 nm (more preferably 10 to 50 nm) away from the main absorption wavelength band of the dye C described below, and is preferably 5 to 80 nm (more preferably 10 to 60 nm) away from the main absorption wavelength band of the dye D described below.

 本発明において、以降の各一般式で表される色素において、カチオンは非局在化して存在しており、複数の互変異性体構造が存在する。そのため、本発明において、ある色素の少なくとも1つの互変異性体構造が各一般式に当てはまる場合、ある色素は各一般式で表される色素とする。したがって、特定の一般式で表される色素とは、その少なくとも1つの互変異性体構造を特定の一般式で表すことができる色素ということもできる。本発明において、一般式で表される色素は、その互変異性体構造の少なくとも1つがこの一般式に当てはまる限り、どのような互変異性体構造をとるものでもよい。 In the present invention, in the dyes represented by the following general formulas, the cation exists in a delocalized state, and multiple tautomeric structures exist. Therefore, in the present invention, if at least one tautomeric structure of a dye corresponds to one of the general formulas, the dye is considered to be a dye represented by that general formula. Therefore, a dye represented by a specific general formula can also be said to be a dye whose at least one tautomeric structure can be represented by that specific general formula. In the present invention, the dye represented by a general formula may have any tautomeric structure, as long as at least one of the tautomeric structures corresponds to that general formula.

(1-1)下記一般式(i)で表されるアゾ系色素。 (1-1) An azo dye represented by the following general formula (i):

 上記式中、R17及びR18は、各々独立に、水素原子、又は1価の置換基を示す。
 R19は、水素原子、脂肪族基、アリール基、ヘテロ環基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基、アリールスルホニル基、又はスルファモイル基を示す。
 Qはジアゾ成分残基を示す。
In the above formula, R 17 and R 18 each independently represent a hydrogen atom or a monovalent substituent.
R 19 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.
Q represents a residue of a diazo component.

 R17及びR18として採り得る1価の置換基としては、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、脂肪族基、アリール基、ヘテロ環基、シアノ基、カルボキシ基、カルバモイル基、脂肪族オキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、脂肪族オキシ基、アリールオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、アミノ基(-NH)、脂肪族アミノ基、アリールアミノ基、ヘテロ環アミノ基、アシルアミノ基、カルバモイルアミノ基、スルファモイルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族スルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、脂肪族チオ基、アリールチオ基、脂肪族スルホニル基、アリールスルホニル基、スルファモイル基、スルホ基、イミド基及びヘテロ環チオ基が挙げられる。これらのなかでも、主に溶解性付与の観点から、脂肪族基、アリール基、ヘテロ環基、シアノ基、カルバモイル基、脂肪族オキシカルボニル基、アリールオキシカルボニル基、アシル基、脂肪族オキシ基、アリールオキシ基、脂肪族アミノ基又はアリールアミノ基が好ましい。
 これらのR17及びR18として採り得る置換基は更に置換されていてもよい。
Examples of the monovalent substituent which may be taken as R 17 and R 18 include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an amino group (—NH 2 ), an aliphatic amino group, an arylamino group, a heterocyclic amino group, an acylamino group, a carbamoylamino group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, a nitro group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imido group, and a heterocyclic thio group. Among these, mainly from the viewpoint of imparting solubility, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an arylamino group is preferred.
These substituents that can be taken as R 17 and R 18 may be further substituted.

 R17~R19として採り得る脂肪族基は、さらに1価の置換基を有していてもよく、飽和であっても不飽和であってもよく、環状であってもよい。具体的には、例えば、アルキル基、置換アルキル基、アルケニル基、置換アルケニル基、アルキニル基、置換アルキニル基、アラルキル基及び置換アラルキル基等が挙げられる。脂肪族基の総炭素数は、1~30であることが好ましく、1~16であることがより好ましい。脂肪族基の具体例としては、例えば、メチル基、エチル基、ブチル基、イソプロピル基、t-ブチル基、ヒドロキシエチル基、メトキシエチル基、シアノエチル基、トリフルオロメチル基、3-スルホプロピル基、4-スルホブチル基、2-(2-ヒドロキシエトキシ)エチル基、2-(2-(アセチルオキシ)エトキシ)エチル基、シクロヘキシル基、ベンジル基、2-フェネチル基、ビニル基、及びアリル基等が挙げられる。
 なお、有していてもよい1価の置換基としては、R17及びR18として採り得る1価の置換基を挙げることができ、有していてもよい1価の置換基に係る以降の説明においても同様である。有していてもよい1価の置換基としては、例えば、アルコキシ基、アシルオキシ基、ヒドロキシ基等が好ましい。また、これらの置換基は、さらに置換基を有していてもよく、例えば、アルコキシ基、アシルオキシ基、ヒドロキシ基等が好ましく挙げられる。
The aliphatic groups that can be represented by R 17 to R 19 may further have a monovalent substituent, and may be saturated or unsaturated, or may be cyclic. Specific examples include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups. The total number of carbon atoms in the aliphatic group is preferably 1 to 30, and more preferably 1 to 16. Specific examples of the aliphatic group include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2-(2-(acetyloxy)ethoxy)ethyl group, a cyclohexyl group, a benzyl group, a 2-phenethyl group, a vinyl group, and an allyl group.
Examples of the monovalent substituent that may be present include the monovalent substituents that may be present as R 17 and R 18 , and the same applies to the following description of the monovalent substituent that may be present. Preferred examples of the monovalent substituent that may be present include an alkoxy group, an acyloxy group, and a hydroxy group. These substituents may further have a substituent, and preferred examples thereof include an alkoxy group, an acyloxy group, and a hydroxy group.

 R17~R19として採り得るアリール基は、さらに1価の置換基を有していてもよく、総炭素数は6~30のアリール基が好ましく、6~16のアリール基がより好ましい。具体的には、例えば、フェニル基、4-トリル基、4-メトキシフェニル基、2-クロロフェニル基、3-(3-スルホプロピルアミノ)フェニル基、4-スルファモイルフェニル基、4-(エトキシエチルスルファモイル)フェニル基及び3-(ジメチルカルバモイル)フェニル基等が挙げられる。 The aryl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and is preferably an aryl group having a total carbon number of 6 to 30, more preferably 6 to 16. Specific examples include a phenyl group, a 4-tolyl group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-(3-sulfopropylamino)phenyl group, a 4-sulfamoylphenyl group, a 4-(ethoxyethylsulfamoyl)phenyl group, and a 3-(dimethylcarbamoyl)phenyl group.

 R17~R19として採り得るヘテロ環基としては、飽和もしくは不飽和の脂肪族環基であってもよく、芳香族環基であってもよく、芳香族ヘテロ環基であることが好ましい。ヘテロ環基を構成する環構成原子として、窒素原子、イオウ原子、酸素原子等のヘテロ原子の少なくともいずれか1つを含むものが挙げられ、更に1価の置換基を有していてもよく、総炭素数1~30のヘテロ環基であることが好ましく、1~15のヘテロ環基であることがより好ましい。具体的には、例えば、2-ピリジル基、2-チエニル基、2-チアゾリル基、2-ベンゾチアゾリル基、2-ベンゾオキサゾリル基及び2-フリル基等が挙げられる。 The heterocyclic group that can be taken as R 17 to R 19 may be a saturated or unsaturated aliphatic ring group or an aromatic ring group, with an aromatic heterocyclic group being preferred. Examples of ring-constituting atoms that constitute the heterocyclic group include those containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and may further have a monovalent substituent. The heterocyclic group is preferably a heterocyclic group having a total of 1 to 30 carbon atoms, and more preferably a heterocyclic group having 1 to 15 carbon atoms. Specific examples include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.

 R17~R19として採り得るカルバモイル基としては、無置換のカルバモイル基(-CONH)に加え、脂肪族基、アリール基等で置換されたカルバモイル基を含む。
 R17~R19として採り得るカルバモイル基は、さらに1価の置換基を有していてもよく、総炭素数1~30のカルバモイル基が好ましく、炭素原子数1~16のカルバモイル基であることがより好ましい。具体的には、例えば、メチルカルバモイル基、ジメチルカルバモイル基、フェニルカルバモイル及びN-メチル-N-フェニルカルバモイル基等が挙げられる。
The carbamoyl groups that can be taken as R 17 to R 19 include unsubstituted carbamoyl groups (—CONH 2 ) as well as carbamoyl groups substituted with an aliphatic group, aryl group, or the like.
The carbamoyl groups which can be represented by R 17 to R 19 may further have a monovalent substituent, and are preferably carbamoyl groups having a total of 1 to 30 carbon atoms, and more preferably carbamoyl groups having 1 to 16 carbon atoms. Specific examples include methylcarbamoyl groups, dimethylcarbamoyl groups, phenylcarbamoyl groups, and N-methyl-N-phenylcarbamoyl groups.

 R17及びR18として採り得る脂肪族オキシカルボニル基における脂肪族基としては、R17~R19として採り得る脂肪族基の記載を適用することができる。
 R17及びR18として採り得る脂肪族オキシカルボニル基は、さらに1価の置換基を有していてもよく、飽和であっても不飽和であってもよく、環状であってもよく、総炭素数2~30の脂肪族オキシカルボニル基が好ましく、総炭素数2~16脂肪族オキシカルボニル基であることがより好ましい。具体的には、例えば、メトキシカルボニル基、エトキシカルボニル基及び2-メトキシエトキシカルボニル基等が挙げられる。
 R19として採り得るアルコキシカルボニル基は、さらに1価の置換基を有していてもよく、飽和であっても不飽和であってもよく、環状であってもよく、総炭素数2~30のアルコキシカルボニル基が好ましく、総炭素数2~16のアルコキシカルボニル基であることがより好ましい。具体的には、例えば、メトキシカルボニル基、エトキシカルボニル基及び2-メトキシエトキシカルボニル基等が挙げられる。
As the aliphatic group in the aliphatic oxycarbonyl group which can be taken as R 17 and R 18 , the descriptions of the aliphatic groups which can be taken as R 17 to R 19 can be applied.
The aliphatic oxycarbonyl group which can be represented by R 17 and R 18 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and is preferably an aliphatic oxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an aliphatic oxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.
The alkoxycarbonyl group that can be taken as R 19 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and is preferably an alkoxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an alkoxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.

 R17~R19として採り得るアリールオキシカルボニル基は、さらに1価の置換基を有していてもよく、総炭素数7~30のアリールオキシカルボニル基が好ましく、炭素原子数7~16のアリールオキシカルボニル基がより好ましい。具体的には、例えば、フェノキシカルボニル基、4-メチルフェノキシカルボニル基及び3-クロルフェノキシカルボニル基等が挙げられる。 The aryloxycarbonyl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and is preferably an aryloxycarbonyl group having a total of 7 to 30 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms. Specific examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

 R17~R19として採り得るアシル基には、脂肪族カルボニル基、アリールカルボニル基、及び、ヘテロ環カルボニル基が含まれ、総炭素数が1~30である態様が好ましく、総炭素数が1~16である態様がより好ましい。具体的には、例えば、アセチル基、メトキシアセチル基、チエノイル基及びベンゾイル基等が挙げられる。 The acyl group that can be taken as R 17 to R 19 includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably has a total of 1 to 30 carbon atoms, more preferably has a total of 1 to 16 carbon atoms. Specific examples include an acetyl group, a methoxyacetyl group, a thienoyl group, and a benzoyl group.

 R17及びR18として採り得る脂肪族スルホニル基における脂肪族基としては、R17~R19として採り得る脂肪族基の記載を適用することができる。
 R17及びR18として採り得る脂肪族スルホニル基は、さらに1価の置換基を有していてもよく、飽和であっても不飽和であってもよく、環状であってもよく、総炭素数1~30である態様が好ましく、総炭素数1~16である態様がより好ましい。具体的には、例えば、メタンスルホニル基、メトキシメタンスルホニル及びエトキシエタンスルホニル基等が挙げられる。
 R19として採り得るアルキルスルホニル基は、さらに1価の置換基を有していてもよく、飽和であっても不飽和であってもよく、環状であってもよく、総炭素数1~30である態様が好ましく、総炭素数1~16である態様がより好ましい。具体的には、例えば、メタンスルホニル基、メトキシメタンスルホニル及びエトキシエタンスルホニル基等が挙げられる。
As the aliphatic group in the aliphatic sulfonyl group which can be taken as R 17 and R 18 , the descriptions of the aliphatic groups which can be taken as R 17 to R 19 can be applied.
The aliphatic sulfonyl group which can be represented by R 17 and R 18 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.
The alkylsulfonyl group that can be taken as R 19 may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.

 R17~R19として採り得るアリールスルホニル基は、さらに1価の置換基を有していてもよく、総炭素数6~30である態様が好ましく、総炭素数6~18である態様がより好ましい。具体的には、例えば、ベンゼンスルホニル及びトルエンスルホニル基等が挙げられる。 The arylsulfonyl group which can be represented by R 17 to R 19 may further have a monovalent substituent, and preferably has a total of 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Specific examples include benzenesulfonyl and toluenesulfonyl groups.

 R17~R19として採り得るスルファモイル基としては、無置換のスルファモイル基(-SONH)に加え、脂肪族基、アリール基等で置換されたスルファモイル基を含む。
 R17~R19として採り得るスルファモイル基は、さらに1価の置換基を有していてもよく、総炭素数0~30である態様が好ましく、総炭素数0~16である態様がより好ましい。具体的には、例えば、無置換のスルファモイル基、ジメチルスルファモイル基及びジ-(2-ヒドロキシエチル)スルファモイル基等が挙げられる。
The sulfamoyl groups that can be taken as R 17 to R 19 include unsubstituted sulfamoyl groups (—SO 2 NH 2 ) as well as sulfamoyl groups substituted with an aliphatic group, aryl group, or the like.
The sulfamoyl group which can be taken as R 17 to R 19 may further have a monovalent substituent, and preferably has a total of 0 to 30 carbon atoms, more preferably 0 to 16 carbon atoms. Specific examples include an unsubstituted sulfamoyl group, a dimethylsulfamoyl group, and a di-(2-hydroxyethyl)sulfamoyl group.

 R17及びR18として採り得るイミド基は、さらに1価の置換基を有していてもよく、5~6員環のイミド基が好ましい。また、イミド基の総炭素数は4~30である態様が好ましく、4~20である態様がより好ましい。具体的には、例えば、コハク酸イミド及びフタル酸イミド基等が挙げられる。 The imido group which can be taken as R 17 and R 18 may further have a monovalent substituent, and is preferably a 5- or 6-membered ring imido group. The imido group preferably has a total of 4 to 30 carbon atoms, more preferably 4 to 20. Specific examples include succinimide and phthalimide groups.

 R17及びR18として採り得る脂肪族オキシ基、脂肪族アミノ基、脂肪族オキシカルボニルアミノ基、脂肪族スルホニルアミノ基及び脂肪族チオ基における脂肪族基としては、R17~R19として採り得る脂肪族基の記載を適用することができる。
 R17及びR18として採り得るアリールオキシ基、アリールアミノ基、アリールオキシカルボニルアミノ基、アリールスルホニルアミノ基及びアリールチオ基におけるアリール基としては、R17~R19として採り得るアリール基の記載を適用することができる。
 R17及びR18として採り得るアシルオキシ基及びアシルアミノ基におけるアシル基としては、R17~R19として採り得るアシル基の記載を適用することができる。
 R17及びR18として採り得るカルバモイルオキシ基及びカルバモイルアミノ基におけるカルバモイル基としては、R17~R19として採り得るカルバモイル基の記載を適用することができる。
 R17及びR18として採り得るヘテロ環オキシ基、ヘテロ環アミノ基及びヘテロ環チオ基におけるヘテロ環基としては、R17~R19として採り得るヘテロ環基の記載を適用することができる。
 R17及びR18として採り得るスルファモイルアミノ基におけるスルファモイル基としては、R17~R19として採り得るスルファモイル基の記載を適用することができる。
As the aliphatic group in the aliphatic oxy group, aliphatic amino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group and aliphatic thio group which can be taken as R 17 and R 18 , the descriptions of the aliphatic groups which can be taken as R 17 to R 19 can be applied.
As the aryl group in the aryloxy group, arylamino group, aryloxycarbonylamino group, arylsulfonylamino group and arylthio group which can be taken as R 17 and R 18 , the descriptions of the aryl group which can be taken as R 17 to R 19 can be applied.
As the acyl group in the acyloxy group and acylamino group which can be taken as R 17 and R 18 , the descriptions of the acyl groups which can be taken as R 17 to R 19 can be applied.
As the carbamoyl group in the carbamoyloxy group and carbamoylamino group which can be taken as R 17 and R 18 , the descriptions of the carbamoyl groups which can be taken as R 17 to R 19 can be applied.
As the heterocyclic group in the heterocyclic oxy group, heterocyclic amino group and heterocyclic thio group which can be taken as R 17 and R 18 , the descriptions of the heterocyclic groups which can be taken as R 17 to R 19 can be applied.
As for the sulfamoyl group in the sulfamoylamino group which can be taken as R 17 and R 18 , the description of the sulfamoyl group which can be taken as R 17 to R 19 can be applied.

 Qで表されるジアゾ成分残基とは、ジアゾ成分「Q-NH」の残基であることを意味する。特に、目標とする色再現性の点から、Qはアリール基又は芳香族ヘテロ環基であることが好ましい。
 Qとして採り得るアリール基を構成する芳香族炭化水素環は単環であっても縮合環であってもよく、単環であることが好ましい。総炭素数は6~30のアリール基が好ましく、6~16のアリール基がより好ましい。具体的には、フェニル基が好ましい。Qとして採り得るアリール基は置換基を有していてもよく、有していてもよい置換基としては、スルファモイル基(好ましくはアルキルスルファモイル基又はジアルキルスルファモイル基)、スルホニル基(好ましくはアルキルスルホニル基)、シアノ基が好ましく挙げられる。
The diazo component residue represented by Q means a residue of the diazo component "Q-NH 2 ". In particular, from the viewpoint of the target color reproducibility, Q is preferably an aryl group or an aromatic heterocyclic group.
The aromatic hydrocarbon ring constituting the aryl group that can be taken as Q may be a monocyclic ring or a fused ring, and is preferably a monocyclic ring. An aryl group having a total of 6 to 30 carbon atoms is preferred, and an aryl group having a total of 6 to 16 carbon atoms is more preferred. Specifically, a phenyl group is preferred. The aryl group that can be taken as Q may have a substituent, and preferred examples of the substituent that may be had include a sulfamoyl group (preferably an alkylsulfamoyl group or a dialkylsulfamoyl group), a sulfonyl group (preferably an alkylsulfonyl group), and a cyano group.

 Qとして採り得る芳香族ヘテロ環基としては、ヘテロ環基を構成する環構成原子として、窒素原子、イオウ原子、酸素原子等のヘテロ原子のうちの少なくともいずれか1つを含む芳香族環基であって、5~6員環により構成されることが好ましい。芳香族ヘテロ環基の炭素原子数としては、1~25が好ましく、1~15がより好ましい。芳香族ヘテロ環基を構成する芳香族ヘテロ環は単環であっても縮合環であってもよく、単環であることが好ましい。
 芳香族ヘテロ環基としては、具体的には、ピラゾール基、1,2,4-トリアゾール基、イソチアゾール基、ベンゾイソチアゾール基、チアゾール基、ベンゾチアゾール基、オキサゾール基、1,2,4-チアジアゾール基等が挙げられる。
The aromatic heterocyclic group that can be taken as Q is preferably an aromatic ring group containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom as a ring-constituting atom constituting the heterocyclic group, and is preferably constituted by a 5- or 6-membered ring. The number of carbon atoms in the aromatic heterocyclic group is preferably 1 to 25, more preferably 1 to 15. The aromatic heterocycle constituting the aromatic heterocyclic group may be a monocycle or a fused ring, and is preferably a monocycle.
Specific examples of the aromatic heterocyclic group include a pyrazole group, a 1,2,4-triazole group, an isothiazole group, a benzisothiazole group, a thiazole group, a benzothiazole group, an oxazole group, and a 1,2,4-thiadiazole group.

 上記一般式(i)で表されるアゾ系色素の例としては、例えば、国際公開第2023/234353号の段落[0042]に記載の一般式(i)で表されるアゾ系色素の具体例の記載をそのまま適用することができる。ただし、本発明はこれらに限定されるものではない。 As examples of azo dyes represented by the above general formula (i), the specific examples of azo dyes represented by general formula (i) described in paragraph [0042] of WO 2023/234353 can be applied as is. However, the present invention is not limited to these.

(1-2)下記一般式(ii)で表されるアゾ系色素。 (1-2) An azo dye represented by the following general formula (ii):

 上記式中、R21~R24、R26及びR27は、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルボキシ基、スルホ基、-OR108、-SR109、-NR110111、-S(=O)NR112113、-C(=O)NR114115、-NHC(=O)R116、-C(=O)OR117、-O(CHCHO)118、-O(CHCHS)119、-S(CHCHO)120、-S(CHCHS)121、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基又は複素環基を示す。
 R108~R121は水素原子、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基又は複素環基を示す。nは正の整数である。
 なお、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基及び複素環基は、ハロゲン原子、シアノ基、ニトロ基、カルボキシ基、スルホ基、-OR108、-SR109、-NR110111、-S(=O)NR112113、-C(=O)NR114115、-NHC(=O)R116、-C(=O)OR117、-O(CHCHO)118、-O(CHCHS)119、-S(CHCHO)120、-S(CHCHS)121、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基及び複素環基のうちの1つまたは2つ以上を置換基として有していてもよい。
In the above formula, R 21 to R 24 , R 26 and R 27 each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 108 , —SR 109 , —NR 110 R 111 , —S(═O) 2 NR 112 R 113 , —C(═O)NR 114 R 115 , —NHC(═O)R 116 , —C(═O)OR 117 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups.
R 108 to R 121 each represent a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group, and n is a positive integer.
The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 108 , —SR 109 , —NR 110 R 111 , —S(═O) 2 NR 112 R 113 , —C(═O)NR 114 R 115 , —NHC(═O)R 116 , —C(═O)OR 117 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 and —S(CH 2 CH 2 S) n R 121 The aryl group may have one or more substituents selected from the group consisting of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups.

 R21~R24、R26、R27及びR108~R121として採り得る非環式炭化水素基とは、非環式アルカンから1個の水素原子が取り除かれた非環式アルキル基を意味する。ただし、非環式アルキル基は置換基として環構造を有していてもよい。非環式アルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~12が更に好ましく、1~8が特に好ましく、なかでも1~6が好ましい。
 R21~R24、R26、R27及びR108~R121として採り得る単環式炭化水素基とは、単環式脂肪族炭化水素環(単環式シクロアルカン、単環式シクロアルケン及び単環式シクロアルキンのいずれでもよい。)又は単環式芳香族炭化水素環から1個の水素原子が取り除かれた基である、単環式シクロアルキル基、単環式シクロアルケニル基、単環式シクロアルキニル基又は単環式アリール基を意味する。
 単環式シクロアルキル基、単環式シクロアルケニル基及び単環式シクロアルキニル基の炭素数は、構造として可能な限り特に制限されないが、3~30がより好ましく、3~20がより好ましく、3~16が更に好ましい。単環式アリール基の炭素数は、6~30がより好ましく、6~20がより好ましく、6~16が更に好ましい。
 R21~R24、R26、R27及びR108~R121として採り得る縮合多環式炭化水素基とは、縮合多環式脂肪族炭化水素環(縮合多環式シクロアルカン、縮合多環式シクロアルケン及び縮合多環式シクロアルキンのいずれでもよい。)又は縮合多環式芳香族炭化水素環から1個の水素原子が取り除かれた基である、縮合多環式シクロアルキル基、縮合多環式シクロアルケニル基、縮合多環式シクロアルキニル基又は縮合多環式アリール基を意味する。
 縮合多環式シクロアルキル基、縮合多環式シクロアルケニル基及び縮合多環式シクロアルキニル基の炭素数は、構造として可能な限り特に制限されないが、8~30がより好ましく、8~20がより好ましい。縮合多環式アリール基の炭素数は、12~30がより好ましく、12~20がより好ましい。
 R21~R24、R26、R27及びR108~R121として採り得る複素環基としては、上述の一般式(i)におけるR17~R19として採り得るヘテロ環基の記載を適用することができる。
 nは、1~12の整数が好ましく、1~6の整数がより好ましく、1~3の整数が更に好ましい。
The acyclic hydrocarbon group which can be taken as R 21 to R 24 , R 26 , R 27 and R 108 to R 121 means an acyclic alkyl group in which one hydrogen atom has been removed from an acyclic alkane. However, the acyclic alkyl group may have a ring structure as a substituent. The number of carbon atoms in the acyclic alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 12, particularly preferably 1 to 8, and of these, 1 to 6 is preferred.
The monocyclic hydrocarbon group which may be taken as R 21 to R 24 , R 26 , R 27 and R to R 121 means a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a monocyclic cycloalkynyl group or a monocyclic aryl group, which is a group in which one hydrogen atom has been removed from a monocyclic aliphatic hydrocarbon ring (which may be any of a monocyclic cycloalkane, a monocyclic cycloalkene and a monocyclic cycloalkyne) or a monocyclic aromatic hydrocarbon ring.
The number of carbon atoms in the monocyclic cycloalkyl group, monocyclic cycloalkenyl group, and monocyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 16. The number of carbon atoms in the monocyclic aryl group is more preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 16.
The fused polycyclic hydrocarbon group which may be taken as R 21 to R 24 , R 26 , R 27 and R to R 121 means a fused polycyclic cycloalkyl group, a fused polycyclic cycloalkenyl group, a fused polycyclic cycloalkynyl group or a fused polycyclic aryl group, which is a group in which one hydrogen atom has been removed from a fused polycyclic aliphatic hydrocarbon ring (which may be any of a fused polycyclic cycloalkane, a fused polycyclic cycloalkene and a fused polycyclic cycloalkyne) or a fused polycyclic aromatic hydrocarbon ring.
The number of carbon atoms in the fused polycyclic cycloalkyl group, fused polycyclic cycloalkenyl group, and fused polycyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is preferably 8 to 30, and more preferably 8 to 20. The number of carbon atoms in the fused polycyclic aryl group is more preferably 12 to 30, and more preferably 12 to 20.
As the heterocyclic groups which can be taken as R 21 to R 24 , R 26 , R 27 and R 108 to R 121 , the descriptions of the heterocyclic groups which can be taken as R 17 to R 19 in the above general formula (i) can be applied.
n is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 3.

 一般式(ii)中の各置換基の具体的な基については、特段の断りのない限り、特開平5-257180号公報に記載の一般式[1]で表される化合物についてのR~R、R、R、R~R21に関する記載をそれぞれR21~R24、R26、R27、R108~R121にそのまま適用できる。 With regard to the specific groups of the respective substituents in general formula (ii), unless otherwise specified, the descriptions of R 1 to R 4 , R 6 , R 7 , and R 8 to R 21 in the compounds represented by general formula [1] described in JP-A-5-257180 can be applied as they are to R 21 to R 24 , R 26 , R 27 , and R 108 to R 121 , respectively.

 R21は、シアノ基、ニトロ基、-OR108、非環式炭化水素基(好ましくは、非環式アルキル基又は非環式アルケニル基)又は複素環基が好ましく、シアノ基又はニトロ基であるか、ハロゲン原子で置換された非環式アルキル基(好ましくはフッ素原子で置換されたアルキル基)であることがより好ましく、シアノ基が更に好ましい。
 R22は、水素原子、シアノ基、非環式炭化水素基(好ましくは非環式アルキル基)又は単環式炭化水素基が好ましく、水素原子、アルキル基又はアリール基がより好ましく、アルキル基又はアリール基が更に好ましい。
 なお、R21及びR22の少なくとも一方は、シアノ基又はニトロ基であるか、ハロゲン原子、シアノ基又はニトロ基で置換された非環式アルキル基であることが好ましい。
 R23は、水素原子、-OR108、-SR109、-NR110111、-C(=O)NR114115、-NHC(=O)R116、-O(CHCHO)118、-O(CHCHS)119、-S(CHCHO)120、-S(CHCHS)121又は非環式炭化水素基(好ましくは非環式アルキル基)が好ましく、水素原子、-OR108、-SR109、-NR110111、-NHC(=O)R116又は非環式アルキル基がより好ましく、-NHC(=O)R116が更に好ましい。ここで、R108~R111、R116、R118~R121は非環式アルキル基が好ましい。
 R24及びR27は、水素原子が好ましい。
 R26は、水素原子、-OR108、-SR109、-NR110111、-NHC(=O)R116、-O(CHCHO)118、-O(CHCHS)119、-S(CHCHO)120、-S(CHCHS)121又は非環式炭化水素基(好ましくは非環式アルキル基)が好ましく、水素原子、-OR108又は-SR109がより好ましく、水素原子が更に好ましい。ここで、R108~R111、R116、R118~R121は非環式アルキル基が好ましい。
 R24及びR26に対してオルト位に位置する-NR110111において、R110は、非環式アルキル基が好ましく、R111は、非環式アルキル基が好ましく、無置換の非環式アルキル基、又は、-OR108、単環式炭化水素基もしくは縮合多環式炭化水素基を置換基として有する非環式アルキル基がより好ましい。ここで、R108は水素原子又は非環式アルキル基が好ましい。
R 21 is preferably a cyano group, a nitro group, —OR 108 , an acyclic hydrocarbon group (preferably an acyclic alkyl group or an acyclic alkenyl group) or a heterocyclic group, more preferably a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom (preferably an alkyl group substituted with a fluorine atom), and still more preferably a cyano group.
R 22 is preferably a hydrogen atom, a cyano group, an acyclic hydrocarbon group (preferably an acyclic alkyl group) or a monocyclic hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably an alkyl group or an aryl group.
At least one of R 21 and R 22 is preferably a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom, a cyano group, or a nitro group.
R 23 is preferably a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —C(═O)NR 114 R 115 , —NHC(═O)R 116 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), and a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —NHC(═O)R 116 or an acyclic alkyl group is more preferred, and —NHC(═O)R 116 is even more preferred. Here, R 108 to R 111 , R 116 and R 118 to R 121 are preferably acyclic alkyl groups.
R 24 and R 27 are preferably hydrogen atoms.
R 26 is preferably a hydrogen atom, —OR 108 , —SR 109 , —NR 110 R 111 , —NHC(═O)R 116 , —O(CH 2 CH 2 O) n R 118 , —O(CH 2 CH 2 S) n R 119 , —S(CH 2 CH 2 O) n R 120 , —S(CH 2 CH 2 S) n R 121 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), more preferably a hydrogen atom, —OR 108 or —SR 109 , and even more preferably a hydrogen atom. Here, R 108 to R 111 , R 116 , and R 118 to R 121 are preferably acyclic alkyl groups.
In —NR 110 R 111 located at the ortho position relative to R 24 and R 26 , R 110 is preferably an acyclic alkyl group, and R 111 is preferably an acyclic alkyl group, more preferably an unsubstituted acyclic alkyl group, or an acyclic alkyl group having —OR 108 , a monocyclic hydrocarbon group, or a fused polycyclic hydrocarbon group as a substituent, wherein R 108 is preferably a hydrogen atom or an acyclic alkyl group.

 一般式(ii)で表される色素の具体例としては、後述の実施例で使用する化合物の他に、特開平5-257180号公報の段落[0023]~[0034]に記載の化合物、並びに、特開2013-129712号公報の段落[0050]及び[0052]に記載の化合物、段落[0055]に記載の化合物D-18、段落[0056]に記載の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。 Specific examples of dyes represented by general formula (ii) include the compounds used in the examples described below, as well as the compounds described in paragraphs [0023] to [0034] of JP-A No. 5-257180, the compounds described in paragraphs [0050] and [0052] of JP-A No. 2013-129712, compound D-18 described in paragraph [0055], and the compound described in paragraph [0056]. However, the present invention is not limited to these.

(1-3)下記一般式(iii)で表されるアゾ系色素。 (1-3) An azo dye represented by the following general formula (iii):

 上記式中、R31は、水素原子、アルキル基、アルコキシ基、シアノ基、カルボニル基(アルキルオキシカルボニル基又はアリールオキシカルボニル基が好ましい)、芳香族基又は複素環基を示す。
 R32は、水素原子、アルキル基、アルコキシ基、シアノ基、ニトロ基、カルボニル基(アルキルオキシカルボニル基又はアリールオキシカルボニル基が好ましい)、芳香族基又は複素環基を示す。
 R34及びR35は、各々独立に、水素原子、アルキル基又は芳香族基を示す。
 R37は、水素原子、アルキル基、アルコキシ基、シアノ基、カルボニル基(アルキルオキシカルボニル基又はアリールオキシカルボニル基が好ましい)、アシルアミノ基又は芳香族基を示す。
 R34とR35が互いに結合して環を形成していてもよい。
In the above formula, R 31 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group, or a heterocyclic group.
R 32 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group or a heterocyclic group.
R 34 and R 35 each independently represent a hydrogen atom, an alkyl group, or an aromatic group.
R 37 represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an acylamino group or an aromatic group.
R 34 and R 35 may be bonded to each other to form a ring.

 一般式(iii)中の各置換基の定義及び好ましい範囲については、特段の断りのない限り、特開2013-129712号公報に記載の一般式(1)に関するR及びRに関する記載をそれぞれR31及びR32に、特開2013-129712号公報に記載の一般式(3)に関するR、R及びRに関する記載をそれぞれR34、R35及びR37に、そのまま適用できる。
 なお、本発明では、R37は、特開2013-129712号公報に記載の一般式(3)に関するRが採り得る水素原子、アルキル基、アルコキシ基、シアノ基、カルボニル基及び芳香族基に加えて、以下のアシルアミノ基を採り得る。
 R37として採り得るアシルアミノ基の炭素数は、1~12が好ましく、1~6がより好ましい。
 本発明においては、R31、R32及びR37として採り得るアルキル基の炭素数は、1~20がより好ましく、1~12が更に好ましく、1~6が特に好ましい。
 R31、R32及びR37として採り得るアルコキシ基の炭素数は、1~20がより好ましく、1~12が更に好ましく、1~6が特に好ましい。
 R31、R32及びR37として採り得るアルキルオキシカルボニル基の炭素数は、2~30が好ましく、2~20がより好ましく、2~12が更に好ましく、2~7が特に好ましい。
 R34及びR35として採り得るアルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~12が更に好ましい。
Regarding the definition and preferred range of each substituent in general formula (iii), unless otherwise specified, the descriptions regarding R 1 and R 2 in general formula (1) described in JP-A-2013-129712 can be applied directly to R 31 and R 32 , respectively, and the descriptions regarding R 4 , R 5 and R 7 in general formula (3) described in JP-A-2013-129712 can be applied directly to R 34 , R 35 and R 37 , respectively.
In the present invention, R 37 may be the following acylamino group in addition to the hydrogen atom, alkyl group, alkoxy group, cyano group, carbonyl group, and aromatic group that R 7 in the general formula (3) described in JP-A-2013-129712 can be.
The acylamino group that can be taken as R 37 preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
In the present invention, the alkyl group which can be taken as R 31 , R 32 and R 37 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The alkoxy group which can be represented by R 31 , R 32 and R 37 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The alkyloxycarbonyl group which can be represented by R 31 , R 32 and R 37 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 7 carbon atoms.
The alkyl group that can be taken as R 34 and R 35 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.

 R31は、アルキル基又はアリール基が好ましく、アルキル基がより好ましい。
 R32は、アルキル基又はシアノ基が好ましく、シアノ基がより好ましい。
 R34及びR35は、水素原子又はアルキル基が好ましく、アルキル基がより好ましい。
 R37は、水素原子、アルキル基、アシルアミノ基又は芳香族基が好ましく、水素原子又はアルキル基がより好ましく、アルキル基が更に好ましい。
R 31 is preferably an alkyl group or an aryl group, more preferably an alkyl group.
R 32 is preferably an alkyl group or a cyano group, more preferably a cyano group.
R 34 and R 35 are preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.
R 37 is preferably a hydrogen atom, an alkyl group, an acylamino group or an aromatic group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group.

 一般式(iii)で表される色素の具体例としては、例えば、国際公開第2023/234353号の段落[0056]~[0058]に記載の一般式(iii)で表されるアゾ系色素の具体例の記載をそのまま適用することができる。ただし、本発明はこれらに限定されるものではない。 Specific examples of dyes represented by general formula (iii) include the specific examples of azo dyes represented by general formula (iii) described in paragraphs [0056] to [0058] of WO 2023/234353. However, the present invention is not limited to these examples.

(1-4)下記一般式(iv)で表されるアゾ系色素。 (1-4) An azo dye represented by the following general formula (iv):

 上記式中、R41~R44、R46及びR47は、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルボキシ基、スルホ基、-OR208、-SR209、-NR210211、-S(=O)NR212213、-C(=O)NR214215、-NHC(=O)R216、-C(=O)OR217、-O(CHCHO)218、-O(CHCHS)219、-S(CHCHO)220、-S(CHCHS)221、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基又は複素環基を示す。
 R208~R221は水素原子、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基又は複素環基を示す。nは正の整数である。
 なお、非環式炭化水素基、単環式炭化水素基、縮合多環式炭化水素基及び複素環基は、ハロゲン原子、シアノ基、ニトロ基、カルボキシ基、スルホ基、-OR208、-SR209、-NR210211、-S(=O)NR212213、-C(=O)NR214215、-NHC(=O)R216、-C(=O)OR217、-O(CHCHO)218、-O(CHCHS)219、-S(CHCHO)220及び-S(CHCHS)221のうちの1つまたは2つ以上を置換基として有していてもよい。
In the above formula, R 41 to R 44 , R 46 and R 47 each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, —OR 208 , —SR 209 , —NR 210 R 211 , —S(═O) 2 NR 212 R 213 , —C(═O)NR 214 R 215 , —NHC(═O)R 216 , —C(═O)OR 217 , —O(CH 2 CH 2 O) n R 218 , —O(CH 2 CH 2 S) n R 219 , —S(CH 2 CH 2 O) n R 220 , —S(CH 2 CH 2 S) n R 221 , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups.
R 208 to R 221 each represent a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group, and n is a positive integer.
The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR 208 , -SR 209 , -NR 210 R 211 , -S(═O) 2 NR 212 R 213 , -C(═O)NR 214 R 215 , -NHC(═O)R 216 , -C(═O)OR 217 , -O(CH 2 CH 2 O) n R 218 , -O(CH 2 CH 2 S) n R 219 , -S(CH 2 CH 2 O) n R 220 and -S(CH 2 CH 2 S) n R 221 as a substituent.

 一般式(iv)におけるR41~R44、R46、R47、R208~R221及びnについては、特段の断りのない限り、上述の一般式(ii)におけるR21~R24、R26、R27、R108~R121及びnの記載を、それぞれそのまま適用することができる。
 R43は、水素原子、-OR208、-SR209、-NR210211、-NHC(=O)R216、-O(CHCHO)218、-O(CHCHS)219、-S(CHCHO)220、-S(CHCHS)221又は非環式炭化水素基(好ましくは非環式アルキル基)が好ましく、水素原子、-OR208、-SR209、-NR210211、-NHC(=O)R216又は非環式アルキル基がより好ましく、-NHC(=O)R216又は非環式アルキル基が更に好ましい。ここで、R208~R211、R216、R218~R221は非環式アルキル基が好ましい。
 R44及びR46に対してオルト位に位置する-NR210211において、R210は、非環式アルキル基が好ましく、R211は、非環式アルキル基が好ましく、無置換の非環式アルキル基(非環式アルキル基で置換された非環式アルキル基を含む)、又は、-OR208、単環式炭化水素基もしくは縮合多環式炭化水素基を置換基として有する非環式アルキル基がより好ましい。ここで、R208は水素原子又は非環式アルキル基が好ましい。
 なお、一般式(iv)におけるR44及び/又はR46は、ベンゼン環上のR44及びR46に対してオルト位に位置する-NR210211におけるR210及び/又はR211と結合して環を形成していてもよい。形成していてもよい環は5又は6員環が好ましく、飽和でも不飽和でもよく、飽和6員環であることが好ましい。形成していてもよい環は、さらに置換基を有していてもよく、例えば、アルキル基を有することが好ましい。
 なかでも、環を形成している形態としては、R46と、ベンゼン環上のR44及びR46に対してオルト位に位置する-NR210211におけるR211とが結合して、飽和6員環を形成していることが好ましい。
Unless otherwise specified, the descriptions of R 21 to R 24 , R 26 , R 27 , R 108 to R 121 and n in the general formula (ii) above can be applied as they are to R 41 to R 44 , R 46 , R 47 , R 208 to R 221 and n in the general formula (iv), respectively.
R 43 is preferably a hydrogen atom, —OR 208 , —SR 209 , —NR 210 R 211 , —NHC(═O)R 216 , —O(CH 2 CH 2 O) n R 218 , —O(CH 2 CH 2 S) n R 219 , —S(CH 2 CH 2 O) n R 220 , —S(CH 2 CH 2 S) n R 221 or an acyclic hydrocarbon group (preferably an acyclic alkyl group), more preferably a hydrogen atom, —OR 208 , —SR 209 , —NR 210 R 211 , —NHC(═O)R 216 or an acyclic alkyl group, and even more preferably —NHC(═O)R 216 or an acyclic alkyl group. Here, R 208 to R 211 , R 216 and R 218 to R 221 are preferably acyclic alkyl groups.
In —NR 210 R 211 located at the ortho position relative to R 44 and R 46 , R 210 is preferably an acyclic alkyl group, and R 211 is preferably an acyclic alkyl group, more preferably an unsubstituted acyclic alkyl group (including an acyclic alkyl group substituted with an acyclic alkyl group), or an acyclic alkyl group having —OR 208 , a monocyclic hydrocarbon group or a fused polycyclic hydrocarbon group as a substituent. Here, R 208 is preferably a hydrogen atom or an acyclic alkyl group.
In general formula (iv), R 44 and/or R 46 may be bonded to R 210 and/or R 211 in -NR 210 R 211 located at the ortho position relative to R 44 and R 46 on the benzene ring to form a ring. The ring that may be formed is preferably a 5- or 6-membered ring, and may be saturated or unsaturated, with a saturated 6-membered ring being preferred. The ring that may be formed may further have a substituent, and preferably has, for example, an alkyl group.
In particular, the ring is preferably formed by bonding R 46 to R 211 in —NR 210 R 211 located at the ortho position relative to R 44 and R 46 on the benzene ring to form a saturated 6-membered ring.

 一般式(iv)で表される色素の具体例としては、後述の実施例で使用する化合物の他に、特開2013-129712号公報の段落[0053]に記載の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。 Specific examples of the dye represented by general formula (iv) include the compounds used in the examples described below, as well as the compounds described in paragraph [0053] of JP-A-2013-129712. However, the present invention is not limited to these.

(1-5)下記一般式(v)で表されるインドアニリン系色素。 (1-5) An indoaniline dye represented by the following general formula (v):

 上記式中、Qは、少なくとも1個の窒素原子を含み、結合する炭素原子とともに5~7員の含窒素複素環を形成するのに必要な原子群を示す。
 R51はアシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基又はスルホニル基を示し、R52は水素原子又はアルキル基を示し、R53~R57は水素原子、アルキル基、アルコキシ基、アシルアミノ基、アルキルスルホニルアミノ基又はハロゲン原子を示し、R58及びR59は水素原子、アルキル基又はアリール基を示す。
 R51とR53が、R54とR55および/またはR55とR59が、あるいはR58とR59が、それぞれ互いに結合して環を形成していてもよい。すなわち、R51とR53が互いに結合して環を形成していてもよく、R54とR55および/またはR55とR59が互いに結合して環を形成していてもよく、あるいはR58とR59が互いに結合して環を形成していてもよいことを意味する。
In the above formula, Q 1 represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which it is attached, including at least one nitrogen atom.
R 51 represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group or a sulfonyl group, R 52 represents a hydrogen atom or an alkyl group, R 53 to R 57 represent a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group or a halogen atom, and R 58 and R 59 represent a hydrogen atom, an alkyl group or an aryl group.
R51 and R53 , R54 and R55 and/or R55 and R59 , or R58 and R59 may be bonded to each other to form a ring. That is, R51 and R53 may be bonded to each other to form a ring, R54 and R55 and/or R55 and R59 may be bonded to each other to form a ring, or R58 and R59 may be bonded to each other to form a ring.

 一般式(v)中の各置換基の定義及び好ましい範囲については、特段の断りのない限り、特開平2-92686号公報に記載の一般式(I)に関するR~R、R、R及びQに関する記載をそれぞれR51~R56、R58、R59及びQにそのまま適用できる。
 なお、本発明では、R53~R56は、特開平2-92686号公報に記載の一般式(I)に関するR~Rが採り得る水素原子、アルキル基、アルコキシ基及びハロゲン原子に加えて、以下のアシルアミノ基及びアルキルスルホニルアミノ基を採り得る。
 R53~R57として採り得るアシルアミノ基の炭素数は、1~12が好ましく、1~6がより好ましい。
 R53~R57として採り得るアルキルスルホニルアミノ基の炭素数は、1~12が好ましく、1~6がより好ましい。
 R57として採り得るアルキル基、アルコキシ基及びハロゲン原子については、R53~R56として採り得るアルキル基、アルコキシ基及びハロゲン原子の記載をそのまま適用することができる。
With regard to the definition and preferred range of each substituent in general formula (v), unless otherwise specified, the descriptions of R 1 to R 6 , R 8 , R 9 and Q 1 in general formula (I) described in JP-A-2-92686 can be directly applied to R 51 to R 56 , R 58 , R 59 and Q 1 , respectively.
In the present invention, R 53 to R 56 can be the following acylamino group and alkylsulfonylamino group in addition to the hydrogen atom, alkyl group, alkoxy group and halogen atom that R 3 to R 6 in general formula (I) described in JP-A-2-92686 can be.
The acylamino group represented by R 53 to R 57 preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
The alkylsulfonylamino group represented by R 53 to R 57 preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms.
With regard to the alkyl group, alkoxy group and halogen atom that can be taken as R 57 , the descriptions of the alkyl group, alkoxy group and halogen atom that can be taken as R 53 to R 56 can be applied as they are.

 Qは好ましくは-NR16C(=O)-Q-で表される。Qは、-NR16C(=O)-Q-が結合する炭素原子及び-NR16C(=O)-とともに5~7員の含窒素複素環を形成するのに必要な原子群を示し、例えば、2価のアミノ基、エーテル結合、チオエーテル結合、アルキレン結合、エチレン結合、イミノ結合、スルホニル結合、カルボニル結合、アリーレン結合もしくは2価のヘテロ環基、又は、これらを複数組み合わせた基が挙げられる。R16は、水素原子、アルキル基、アリール基又は複素環基を示し、水素原子が好ましい。R16の各置換基の定義及び好ましい範囲についても、特開平2-92686号公報に記載の一般式(I)に関するR16に関する記載をそれぞれそのまま適用できる。
 R51は、炭素数2~7のアシル基又は炭素数2~7のアルコキシカルボニル基が好ましい。
 R52は水素原子が好ましく、R53~R56は水素原子が好ましい。
 R57はアルコキシ基、アシルアミノ基又はアルキルスルホニルアミノ基が好ましく、アルコキシ基又はアシルアミノ基がより好ましい。
 R58及びR59は炭素数1~6のアルキル基が好ましい。
Q 1 is preferably represented by -NR 16 C(=O)-Q 2 -. Q 2 represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which -NR 16 C(=O)-Q 2 - is bonded and -NR 16 C(=O)-, and examples thereof include a divalent amino group, an ether bond, a thioether bond, an alkylene bond, an ethylene bond, an imino bond, a sulfonyl bond, a carbonyl bond, an arylene bond, or a divalent heterocyclic group, or a group combining two or more of these. R 16 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a hydrogen atom is preferred. With regard to the definition and preferred range of each substituent of R 16 , the descriptions regarding R 16 in relation to general formula (I) described in JP-A-2-92686 can be applied as is.
R 51 is preferably an acyl group having 2 to 7 carbon atoms or an alkoxycarbonyl group having 2 to 7 carbon atoms.
R 52 is preferably a hydrogen atom, and R 53 to R 56 are preferably hydrogen atoms.
R 57 is preferably an alkoxy group, an acylamino group or an alkylsulfonylamino group, more preferably an alkoxy group or an acylamino group.
R 58 and R 59 are preferably alkyl groups having 1 to 6 carbon atoms.

 なかでも上記一般式(v)で表されるインドアニリン系色素は、下記一般式(v-a)で表されることが好ましい。 Among these, the indoaniline dye represented by the above general formula (v) is preferably represented by the following general formula (va):

 上記式中、R51、R53、R57~R59及びQは上記一般式(v)におけるR51、R53、R57~R59及びQと同義である。
 Qは、-CR1112CR1314-、-CR1112-又は-NR11-が好ましく、-CR1112CR1314-がより好ましい。
 R11~R14は水素原子又は炭素数1~4のアルキル基を示し、R11及びR12が水素原子であってR13及びR14が炭素数1~4のアルキル基であることが好ましい。
 なお、-CR1112CR1314-は、R11及びR12が結合する炭素原子の側で、>C=Oに結合することが好ましい。
In the above formula, R 51 , R 53 , R 57 to R 59 and Q 2 have the same meanings as R 51 , R 53 , R 57 to R 59 and Q 2 in the above general formula (v).
Q 2 is preferably —CR 11 R 12 CR 13 R 14 —, —CR 11 R 12 — or —NR 11 —, and more preferably —CR 11 R 12 CR 13 R 14 —.
R 11 to R 14 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and it is preferred that R 11 and R 12 are hydrogen atoms and R 13 and R 14 are alkyl groups having 1 to 4 carbon atoms.
It is preferable that —CR 11 R 12 CR 13 R 14 — is bonded to >C═O on the side of the carbon atom to which R 11 and R 12 are bonded.

 一般式(v)で表される色素の具体例としては、後述の実施例で使用する化合物の他に、特開平2-92686号公報の5~6頁に記載のNo.1~51の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。 Specific examples of dyes represented by general formula (v) include the compounds used in the examples described below, as well as compounds No. 1 to 51 listed on pages 5 and 6 of JP-A No. 2-92686. However, the present invention is not limited to these.

 上記光吸収消失性層における上記染料の合計含有量は、0.10~50質量%が好ましく、0.15~40質量%がより好ましく、0.20~30質量%が更に好ましく、0.25~15質量%が特に好ましく、とりわけ0.30~15質量%が好ましい。 The total content of the dyes in the light-absorbing and dissipative layer is preferably 0.10 to 50% by mass, more preferably 0.15 to 40% by mass, even more preferably 0.20 to 30% by mass, particularly preferably 0.25 to 15% by mass, and especially preferably 0.30 to 15% by mass.

 上記光吸収消失性層中における上記一般式(i)で表されるアゾ系色素の含有量は、0.01~30質量%が好ましく、0.1~10質量%がより好ましい。上記光吸収消失性層中における、上記一般式(ii)で表されるアゾ系色素、上記一般式(iii)で表されるアゾ系色素、上記一般式(iv)で表されるアゾ系色素、及び、上記一般式(v)で表されるインドアニリン系色素の各色素の含有量についても、上記一般式(i)で表されるアゾ系色素の含有量と同様に、それぞれ、0.01~30質量%が好ましく、0.1~10質量%がより好ましい。なお、上記光吸収消失性層において、上記染料の全てが上記一般式(i)~(iv)のうちのいずれかで表されるアゾ系色素及び上記一般式(v)で表されるインドアニリン系色素のうちの少なくとも1種で構成されていてもよい。 The content of the azo dye represented by general formula (i) in the light-absorbing and dissipating layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass. Similarly to the content of the azo dye represented by general formula (i), the content of the azo dye represented by general formula (ii), the azo dye represented by general formula (iii), the azo dye represented by general formula (iv), and the indoaniline dye represented by general formula (v) in the light-absorbing and dissipating layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass. In addition, all of the dyes in the light-absorbing and dissipating layer may be composed of at least one of the azo dyes represented by any of general formulas (i) to (iv) and the indoaniline dye represented by general formula (v).

<紫外線照射によりラジカルを生成する化合物>
 上記光吸収消失性層は、紫外線照射によりラジカルを生成する化合物(本発明において、単に「ラジカル発生剤」とも称す。)を含む。
 上記ラジカル発生剤は、紫外線照射によりラジカルを生成する化合物であって、上記染料を消色する機能を有する化合物であれば、特に限定されず、例えば、後述の化合物Bと併用してもよい光ラジカル発生剤をラジカル発生剤として使用することができる。
<Compounds that generate radicals upon exposure to ultraviolet light>
The light-absorbing and dissipative layer contains a compound that generates radicals upon irradiation with ultraviolet light (also simply referred to as a "radical generator" in the present invention).
The radical generator is not particularly limited as long as it is a compound that generates radicals when irradiated with ultraviolet light and has the function of decolorizing the dye. For example, a photoradical generator that may be used in combination with compound B described below can be used as the radical generator.

 上記ラジカル発生剤は、2種以上の化合物の組み合わせであって、上記光吸収消失性層中において2種以上の化合物が錯体形成等の相互作用をした結果、紫外線照射によりラジカルを生成する組み合わせも好ましく挙げられる。組み合わせる化合物の種類は、紫外線照射によりラジカルを生成する機構において、異なる機能を示す化合物を2種以上用いればよく、2種であることが好ましい。このような組み合わせとしては、酸基を有する化合物Aと、化合物Aが含む酸基と水素結合を形成できる構造を有する化合物Bとの組み合わせが好ましく挙げられる。
 上記光吸収消失性層が、酸基を有する化合物Aと、化合物Aが含む酸基と水素結合を形成できる構造を有する化合物Bとを含有する場合、紫外線照射によるラジカル種の発生効率が、上記光ラジカル発生剤を用いた場合と比較して向上される。このため、室温等の穏和な温度条件下で紫外線照射を行った場合にも十分なラジカル種が発生し、このラジカル種が直接または間接的に上記染料と反応し、染料が分解することによって、染料は褪色、消色する。特に、上記光吸収消失性層中に含有され得る前述の一般式(i)~(iv)のうちのいずれかで表されるアゾ系色素、前述の一般式(v)で表されるインドアニリン系色素、並びに、後述の一般式(1)で表されるスクアライン系色素は、染料の分解に伴う二次的な吸収をほとんど生じることなく、消色される。
 以下、酸基を有する化合物Aと、化合物Aが含む酸基と水素結合を形成できる構造を有する化合物Bについて詳述する。
The radical generator may be a combination of two or more compounds, and the two or more compounds may form a complex or other interaction in the light-absorbing/disappearing layer to generate radicals upon ultraviolet irradiation. The types of compounds to be combined may be two or more compounds that exhibit different functions in the mechanism of generating radicals upon ultraviolet irradiation, and two types are preferred. A preferred example of such a combination is a combination of a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A.
When the light-absorbing and dissipating layer contains compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, the efficiency of generating radical species upon ultraviolet irradiation is improved compared to when the above-mentioned photoradical generator is used. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose and fade or disappear. In particular, the azo dye represented by any of the above general formulas (i) to (iv), the indoaniline dye represented by the above general formula (v), and the squaraine dye represented by the below-mentioned general formula (1), which can be contained in the light-absorbing and dissipating layer, are discolored with almost no secondary absorption associated with dye decomposition.
Compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A will be described in detail below.

(1)酸基を有する化合物A
 上記光吸収消失性層は、上記ラジカル発生剤として、酸基を有する化合物A(本発明において、単に「化合物A」とも称す。)を、後述の化合物Aが含む酸基と水素結合を形成できる構造を有する化合物Bと共に含むことが好ましい。
 化合物Aが含む酸基としては、pKaが12以下のプロトン解離性基が好ましい。酸基としては、具体的には、カルボキシ基、スルホンアミド基、ホスホン酸基(-P(=O)(OH))、リン酸基(-OP(=O)(OH))、スルホ基、フェノール性水酸基、及びスルホニルイミド基等が挙げられ、カルボキシ基が好ましい。なお、pKaは25℃の水における酸解離定数(Ka)の負の常用対数(-logKa)を意味し、後述の化合物BにおけるpKaにおいて、水/メタノール=50/50(体積比)の混合溶媒を水に変更する以外は同様にして算出することができる。
 化合物Aは、低分子化合物であっても、高分子化合物(以下「ポリマー」ともいう。)であってもよく、ポリマーであることが好ましい。
 化合物Aがポリマーであるとは、すなわち、上記光吸収消失性層に含有される樹脂を構成するポリマーに化合物Aが化学結合していることを意味する。
 化合物Aが低分子化合物である場合、化合物Aの分子量は、5000未満であり、2000以下が好ましく、1000以下がより好ましく、500以下がさらに好ましく、400以下が特に好ましい。下限値に特に制限はないが、100以上が実際的であり、200以上が好ましい。すなわち、100以上5000未満が実際的であり、200~2000が好ましく、200~1000がより好ましく、200~500が更に好ましく、200~400が特に好ましい。
 化合物Aがポリマーである場合、化合物Aの重量平均分子量の下限値は、5000以上であり、光透過吸収フィルタIの物理特性の観点から、10000以上が好ましく、15000以上がより好ましい。上限値としては特に制限されないが、溶剤に対する溶解性の観点から、50万以下が好ましく、20万以下がより好ましく、15万以下がさらに好ましい。すなわち、5000~50万が実際的であり、10000~20万が好ましく、15000~15万がより好ましい。
(1) Compound A having an acid group
The light-absorbing and disappearing layer preferably contains, as the radical generator, a compound A having an acid group (also simply referred to as "compound A" in the present invention), together with a compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, which will be described later.
The acid group contained in compound A is preferably a proton dissociative group having a pKa of 12 or less. Specific examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group (-P(=O)(OH) 2 ), a phosphate group (-OP(=O)(OH) 2 ), a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group, with a carboxy group being preferred. Note that pKa means the negative common logarithm (-log Ka) of the acid dissociation constant (Ka) in water at 25°C, and can be calculated in the same manner as in the pKa of compound B described below, except that the 50/50 (volume ratio) mixed solvent of water/methanol is changed to water.
Compound A may be a low molecular weight compound or a high molecular weight compound (hereinafter also referred to as a "polymer"), and is preferably a polymer.
The compound A being a polymer means that the compound A is chemically bonded to a polymer that constitutes the resin contained in the light-absorbing and dissipating layer.
When compound A is a low molecular weight compound, the molecular weight of compound A is less than 5,000, preferably 2,000 or less, more preferably 1,000 or less, even more preferably 500 or less, and particularly preferably 400 or less. There is no particular restriction on the lower limit, but a practical value is 100 or more, and preferably 200 or more. That is, a practical value is 100 or more and less than 5,000, and a range of 200 to 2,000 is preferred, more preferably 200 to 1,000, even more preferably 200 to 500, and particularly preferably 200 to 400.
When compound A is a polymer, the lower limit of the weight-average molecular weight of compound A is 5,000 or more, and from the viewpoint of the physical properties of the light transmission/absorption filter I, it is preferably 10,000 or more, and more preferably 15,000 or more. The upper limit is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 500,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less. That is, a range of 5,000 to 500,000 is practical, with 10,000 to 200,000 being preferred, and 15,000 to 150,000 being more preferred.

 また、化合物Aが含む酸基の一部又は全部は、積層体I及び積層体pre-IIIを構成する光吸収消失性層中でアニオン化していてもよく、アニオン化していなくてもよく、本発明において、アニオン化した酸基も、アニオン化していない酸基も共に含めて、酸基と称する。つまり、化合物Aは積層体I及び積層体pre-III中で、アニオン化していてもアニオン化していなくてもよい。 Furthermore, some or all of the acid groups contained in Compound A may or may not be anionized in the light-absorbing and dissipative layers that constitute Laminate I and Laminate pre-III, and in the present invention, both anionized and non-anionized acid groups are referred to as acid groups. In other words, Compound A may or may not be anionized in Laminate I and Laminate pre-III.

 化合物Aとしては、光吸収消失性層の製膜性に優れる点で、カルボキシ基を有する化合物であることが好ましい。
 上記のカルボキシ基を有する化合物としては、カルボキシ基を含むモノマー(以下「カルボキシ基含有モノマー」ともいう。)又はカルボキシ基を含むポリマー(以下「カルボキシ基含有ポリマー」ともいう。)であることが好ましく、光吸収消失性層の製膜性の観点から、カルボキシ基含有ポリマーであることがより好ましい。
Compound A is preferably a compound having a carboxy group, in view of excellent film-forming properties of the light-absorbing and disappearing layer.
The compound having a carboxy group is preferably a monomer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing monomer") or a polymer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing polymer"), and from the viewpoint of film-forming properties of the light-absorbing and disappearing layer, it is more preferably a carboxy group-containing polymer.

 なお、カルボキシ基含有モノマー及びカルボキシ基含有ポリマーが有するカルボキシ基(-COOH)の一部又は全部は、積層体I及び積層体pre-III中でアニオン化していてもアニオン化していなくてもよく、アニオン化したカルボキシ基(-COO)も、アニオン化していないカルボキシ基も共に含めて、カルボキシ基と称する。
 つまり、カルボキシ基含有ポリマーは積層体I及び積層体pre-IIIを構成する光吸収消失性層中で、アニオン化していてもアニオン化していなくてもよく、アニオン化したカルボキシ基含有ポリマーも、アニオン化していないカルボキシ基含有ポリマーも共に含めてカルボキシ基含有ポリマーと称する。
Some or all of the carboxy groups (—COOH) possessed by the carboxy group-containing monomer and the carboxy group-containing polymer may or may not be anionized in the laminate I and the laminate pre-III, and the term “carboxy group” includes both anionized carboxy groups (—COO ) and non-anionized carboxy groups.
In other words, the carboxyl group-containing polymer in the light-absorbing and dissipative layer constituting the laminate I and laminate pre-III may be anionized or not, and both anionized and not anionized carboxyl group-containing polymers are referred to as the carboxyl group-containing polymer.

 上記光吸収消失性層中の化合物Aの含有量は、1質量%以上が好ましく、25質量%以上がより好ましく、30質量%以上が更に好ましく、45質量%以上が特に好ましく、とりわけ50質量%以上が好ましい。化合物Aの含有量の上限値は、100質量%未満が好ましく、99質量%以下がより好ましく、97質量%以下が更に好ましい。すなわち、1質量%以上100質量%未満が好ましく、25~99質量%がより好ましく、30~97質量%が更に好ましく、45~97質量%が特に好ましく、とりわけ50~97質量%が好ましい。
 なかでも、化合物Aがポリマーである場合、上記光吸収消失性層中の化合物Aの含有量は50質量%以上100質量%未満が好ましく、60質量%以上100質量%未満がより好ましく、70質量%以上100質量%未満がさらに好ましい。上限値は99質量%以下であることも好ましく、97質量%以下がより好ましく、95質量%以下が更に好ましく、90質量%以下が特に好ましい。
 化合物Aは、一種単独で使用してもよく、二種以上を併用してもよい。
The content of compound A in the light-absorbing and disappearing layer is preferably 1% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 45% by mass or more, and especially preferably 50% by mass or more. The upper limit of the content of compound A is preferably less than 100% by mass, more preferably 99% by mass or less, and even more preferably 97% by mass or less. That is, the content is preferably 1% by mass or more but less than 100% by mass, more preferably 25 to 99% by mass, more preferably 30 to 97% by mass, particularly preferably 45 to 97% by mass, and especially preferably 50 to 97% by mass.
In particular, when compound A is a polymer, the content of compound A in the light-absorbing and dissipating layer is preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass or more and less than 100% by mass, and even more preferably 70% by mass or more and less than 100% by mass. The upper limit is also preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass or less.
The compound A may be used alone or in combination of two or more kinds.

(カルボキシ基含有モノマー)
 カルボキシ基含有モノマーとしては、カルボキシ基を含み、且つ、エチレン性不飽和基を1つ以上(例えば1~15個)含む重合性化合物が挙げられる。
 エチレン性不飽和基としては、例えば、(メタ)アクリロイル基、ビニル基、及びスチリル基が挙げられ、(メタ)アクリロイル基が好ましい。
 なお、エチレン性不飽和基が(メタ)アクリロイル基である場合、(メタ)アクリロイル基におけるカルボニル結合とカルボキシ基におけるカルボニル結合とが1つのカルボニル結合を共有していてもよい。
 カルボキシ基含有モノマーとしては、製膜性により優れる観点から、カルボキシ基を含む2官能以上のモノマーが好ましい。なお、2官能以上のモノマーとは、一分子中にエチレン性不飽和基を2つ以上(例えば2~15個)有する重合性化合物を意味する。
 カルボキシ基含有モノマーが含むカルボキシ基の数は1個以上であればよく、例えば、1~8個が好ましく、1~4個がより好ましく、1~2個が更に好ましい。
 カルボキシ基含有モノマーは、酸基として、カルボキシ基以外の酸基を更に有してもよい。カルボキシ基以外の酸基としては、例えば、フェノール性水酸基、リン酸基、及びスルホン酸基が挙げられる。
(Carboxy group-containing monomer)
The carboxy group-containing monomer may be a polymerizable compound that contains a carboxy group and one or more (for example, 1 to 15) ethylenically unsaturated groups.
Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred.
When the ethylenically unsaturated group is a (meth)acryloyl group, the carbonyl bond in the (meth)acryloyl group and the carbonyl bond in the carboxy group may share one carbonyl bond.
From the viewpoint of superior film-forming properties, the carboxyl group-containing monomer is preferably a difunctional or higher functional monomer containing a carboxyl group. Note that the difunctional or higher functional monomer refers to a polymerizable compound having two or more (e.g., 2 to 15) ethylenically unsaturated groups in one molecule.
The number of carboxy groups contained in the carboxy group-containing monomer may be one or more, and for example, 1 to 8 is preferred, 1 to 4 is more preferred, and 1 or 2 is even more preferred.
The carboxyl group-containing monomer may further have an acid group other than a carboxyl group, such as a phenolic hydroxyl group, a phosphoric acid group, or a sulfonic acid group.

 カルボキシ基を含む2官能以上のモノマーは特に制限されず、公知の化合物の中から適宜選択できる。
 カルボキシ基を含む2官能以上のモノマーとしては、例えば、商品名で、アロニックスM-520、及びアロニックスM-510(いずれも東亞合成社製)等が挙げられる。
The di- or higher functional monomer containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of bifunctional or higher functional monomers containing a carboxy group include trade names such as Aronix M-520 and Aronix M-510 (both manufactured by Toagosei Co., Ltd.).

 また、カルボキシ基を含む2官能以上のモノマーとしては、例えば、カルボキシ基を有する3~4官能の重合性化合物(ペンタエリスリトールトリアクリレート及びペンタエリスリトールテトラアクリレート[PETA]骨格にカルボキシ基を導入した化合物(酸価=80~120mgKOH/g))、及びカルボキシ基を有する5~6官能の重合性化合物(ジペンタエリスリトールペンタアクリレート及びジペンタエリスリトールヘキサアクリレート[DPHA]骨格にカルボキシ基を導入した化合物(酸価=25~70mgKOH/g))等も挙げられる。なお、上述のカルボキシ基を含む3官能以上のモノマーを使用する場合、製膜性がより優れる観点から、カルボキシ基を含む2官能以上のモノマーを併用することも好ましい。 Furthermore, examples of difunctional or higher functional monomers containing a carboxy group include trifunctional or tetrafunctional polymerizable compounds containing a carboxy group (compounds in which a carboxy group has been introduced into a pentaerythritol triacrylate or pentaerythritol tetraacrylate [PETA] skeleton (acid value = 80 to 120 mg KOH/g)), and pentafunctional or hexafunctional polymerizable compounds containing a carboxy group (compounds in which a carboxy group has been introduced into a dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate [DPHA] skeleton (acid value = 25 to 70 mg KOH/g)). When using the above-mentioned trifunctional or higher functional monomers containing a carboxy group, it is also preferable to use them in combination with difunctional or higher functional monomers containing a carboxy group, from the perspective of achieving better film-forming properties.

 カルボキシ基を含む2官能以上のモノマー、酸基を含む2官能以上のモノマーとしては、特開2004-239942号公報の段落0025~0030に記載の酸基を有する重合性化合物も挙げられる。この公報の内容は本明細書に組み込まれる。 Examples of difunctional or higher functional monomers containing a carboxy group and difunctional or higher functional monomers containing an acid group include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP 2004-239942 A. The contents of this publication are incorporated herein by reference.

(カルボキシ基含有ポリマー)
 カルボキシ基含有ポリマーは、酸基として、カルボキシ基以外の酸基を更に有してもよい。カルボキシ基以外の酸基としては、例えば、フェノール性水酸基、リン酸基、及びスルホン酸基が挙げられる。
 カルボキシ基含有ポリマーが共重合体である場合、ポリマーの構造はランダムポリマーでもよく、ブロック等の規則性ポリマーであってもよい。
(Carboxy group-containing polymer)
The carboxyl group-containing polymer may further have an acid group other than a carboxyl group, such as a phenolic hydroxyl group, a phosphoric acid group, or a sulfonic acid group.
When the carboxy group-containing polymer is a copolymer, the structure of the polymer may be a random polymer or a regular polymer such as a block polymer.

≪カルボキシ基を有する構成単位≫
 カルボキシ基含有ポリマーは、カルボキシ基を有する構成単位を有することが好ましい。
 カルボキシ基を有する構成単位としては、例えば、(メタ)アクリル酸、クロトン酸、イタコン酸、マレイン酸、又は、フマル酸に由来する構成単位が挙げられる。なかでも、染料の消色性に優れる点から(メタ)アクリル酸に由来する構成単位が好ましい。
<Structural Unit Having a Carboxy Group>
The carboxy group-containing polymer preferably has a structural unit having a carboxy group.
Examples of structural units having a carboxy group include structural units derived from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, or fumaric acid. Among these, structural units derived from (meth)acrylic acid are preferred because of their excellent decolorization properties.

 カルボキシ基含有ポリマー中、カルボキシ基を有する構成単位の含有量は、カルボキシ基含有ポリマーの全構成単位の合計を100モル%とした際に、1~100モル%が好ましく、3~65モル%がより好ましく、5~60モル%が更に好ましく、10~60モル%が特に好ましく、なかでも20~55モル%が好ましい。
 カルボキシ基を有する構成単位は、一種単独で使用してもよく、二種以上を併用してもよい。
The content of the structural unit having a carboxy group in the carboxy group-containing polymer is preferably 1 to 100 mol%, more preferably 3 to 65 mol%, still more preferably 5 to 60 mol%, particularly preferably 10 to 60 mol%, and of these, 20 to 55 mol% is preferred, when the total of all structural units of the carboxy group-containing polymer is taken as 100 mol%.
The structural unit having a carboxy group may be used alone or in combination of two or more types.

≪芳香環を有する構成単位≫
 カルボキシ基含有ポリマーは、上述の構成単位以外に、芳香環(好ましくは芳香族炭化水素環)を有する構成単位を有することも好ましい。例えば、芳香環を有する(メタ)アクリレート(具体的には、ベンジル(メタ)アクリレート、フェネチル(メタ)アクリレート、又は、フェノキシエチル(メタ)アクリレート等)に由来する構成単位が挙げられる。
<Structural units having aromatic rings>
In addition to the above-mentioned structural units, the carboxyl group-containing polymer preferably also contains a structural unit having an aromatic ring (preferably an aromatic hydrocarbon ring), such as a structural unit derived from a (meth)acrylate having an aromatic ring (specifically, benzyl (meth)acrylate, phenethyl (meth)acrylate, or phenoxyethyl (meth)acrylate).

 カルボキシ基含有ポリマー中、芳香環を有する構成単位の含有量は、カルボキシ基含有ポリマーの全構成単位の合計を100モル%とした際に、0~97モル%が好ましく、0~95モル%がより好ましく、0~90モル%が更に好ましい。
 芳香環を有する構成単位は、一種単独で使用してもよく、二種以上を併用してもよい。
The content of the structural unit having an aromatic ring in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units of the carboxy group-containing polymer is 100 mol %.
The aromatic ring-containing structural unit may be used alone or in combination of two or more types.

≪脂環式構造を有する構成単位≫
 カルボキシ基含有ポリマーは、上述の構成単位以外に、脂環式構造を有する構成単位を有することも好ましい。
 脂環式構造としては、例えば、トリシクロ[5.2.1.02,6]デカン環構造(テトラヒドロジシクロペンタジエンとも称す。1価の基はジシクロペンタニル)、トリシクロ[5.2.1.02,6]デカン-3-エン環構造(5,6-ジヒドロジシクロペンタジエンとも称す。1価の基はジシクロペンテニル)、イソボルナン環構造(1価の基はイソボルニル)、アダマンタン環構造(1価の基はアダマンチル)、及びシクロヘキサン環構造(1価の基はシクロヘキシル)が挙げられる。
 脂環式構造を有する構成単位としては、例えば、脂環式構造を有する(メタ)アクリレート(具体的には、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、メチルアダマンチル(メタ)アクリレート、又は、シクロヘキシル(メタ)アクリレート等)に由来する構成単位が挙げられる。
<Structural Unit Having Alicyclic Structure>
In addition to the above-mentioned structural units, the carboxyl group-containing polymer also preferably has a structural unit having an alicyclic structure.
Examples of alicyclic structures include a tricyclo[5.2.1.0 2,6 ]decane ring structure (also called tetrahydrodicyclopentadiene; the monovalent group is dicyclopentanyl), a tricyclo[5.2.1.0 2,6 ]decane-3-ene ring structure (also called 5,6-dihydrodicyclopentadiene; the monovalent group is dicyclopentenyl), an isobornane ring structure (the monovalent group is isobornyl), an adamantane ring structure (the monovalent group is adamantyl), and a cyclohexane ring structure (the monovalent group is cyclohexyl).
Examples of structural units having an alicyclic structure include structural units derived from (meth)acrylates having an alicyclic structure (specifically, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, methyl adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.).

 カルボキシ基含有ポリマー中、脂環式構造を有する構成単位の含有量は、カルボキシ基含有ポリマーの全構成単位の合計を100モル%とした際に、0~97モル%が好ましく、0~95モル%がより好ましく、0~90モル%が更に好ましい。
 脂環式構造を有する構成単位は、一種単独で使用してもよく、二種以上を併用してもよい。
The content of the structural unit having an alicyclic structure in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units in the carboxy group-containing polymer is 100 mol %.
The structural unit having an alicyclic structure may be used alone or in combination of two or more types.

≪その他の構成単位≫
 カルボキシ基含有ポリマーは、上述の構成単位以外に、その他の構成単位を有していてもよい。
 上記その他の構成単位としては、例えば、メチル(メタ)アクリレートに由来する構成単位が挙げられる。
 カルボキシ基含有ポリマー中、その他の構成単位の含有量は、カルボキシ基含有ポリマーの全構成単位の合計を100モル%とした際に、0~70モル%が好ましく、0~50モル%がより好ましく、0~20モル%が更に好ましい。
 その他の構成単位は、一種単独で使用してもよく、二種以上を併用してもよい。
Other structural units
The carboxyl group-containing polymer may have other structural units in addition to the structural units described above.
Examples of the other structural units include structural units derived from methyl (meth)acrylate.
The content of other structural units in the carboxy group-containing polymer is preferably 0 to 70 mol %, more preferably 0 to 50 mol %, and even more preferably 0 to 20 mol %, when the total of all structural units of the carboxy group-containing polymer is 100 mol %.
The other structural units may be used alone or in combination of two or more.

(2)化合物B
 上記光吸収消失性層は、上記ラジカル発生剤として、上述の化合物Aと共に、化合物A中が含む酸基と水素結合を形成できる構造を有する化合物B(本発明において、単に「化合物B」とも称す。)を含むことが好ましい。
 化合物Bとしては、紫外線を吸収し励起状態になることにより塩基性が増大する構造を有する化合物が好ましい。化合物Bの塩基性が励起状態で増大することにより化合物Aが含む酸基が化合物Bとより強く相互作用した錯体を形成することができ、ラジカルの発生効率を高めることが可能となる。
 化合物Bが有する、化合物Aが含む酸基と水素結合を形成できる構造とは、化合物Bの全体構造であってもよく、化合物Bの一部分を構成する部分構造であってもよい。
 化合物Bは、高分子化合物(分子量5000以上の化合物を意味する。)でも低分子化合物(分子量5000未満の化合物を意味する。)でもよく、低分子化合物であることが好ましい。
 低分子化合物である化合物Bの分子量は、5000未満であり、1000未満が好ましく、500以下がより好ましく、350以下がさらに好ましい。下限値に特に制限はないが、65以上が好ましく、75以上がより好ましい。低分子化合物である化合物Bの分子量の好ましい範囲としては、例えば、65以上5000未満であり、65以上1000未満が好ましく、65~500がより好ましく、さらに好ましくは75~350が挙げられる。
(2) Compound B
The light-absorbing and disappearing layer preferably contains, as the radical generator, together with the compound A, a compound B (also simply referred to as "compound B" in the present invention) having a structure capable of forming a hydrogen bond with an acid group contained in the compound A.
Compound B is preferably a compound having a structure that increases its basicity by absorbing ultraviolet light and becoming excited. The increased basicity of compound B in the excited state allows the acid group contained in compound A to form a complex with compound B through stronger interaction, thereby increasing the efficiency of radical generation.
The structure of compound B that can form a hydrogen bond with the acid group contained in compound A may be the entire structure of compound B or a partial structure that constitutes a part of compound B.
Compound B may be a high molecular weight compound (meaning a compound having a molecular weight of 5000 or more) or a low molecular weight compound (meaning a compound having a molecular weight of less than 5000), and is preferably a low molecular weight compound.
The molecular weight of compound B, which is a low molecular weight compound, is less than 5,000, preferably less than 1,000, more preferably 500 or less, and even more preferably 350 or less. There is no particular restriction on the lower limit, but it is preferably 65 or more, and more preferably 75 or more. A preferred range for the molecular weight of compound B, which is a low molecular weight compound, is, for example, 65 or more and less than 5,000, preferably 65 or more and less than 1,000, more preferably 65 to 500, and even more preferably 75 to 350.

 紫外線に対するモル吸光係数が大きい点から化合物Bは芳香族化合物であることが好ましい。
 ここで、芳香族化合物とは、芳香環を1個以上有する化合物である。
 上記芳香環は、化合物B中に1個のみ存在していてもよく、複数存在していてもよい。複数存在する場合、例えば、上記芳香環が樹脂を構成するポリマーの側鎖等に存在していてもよい。
 上記芳香環は、芳香族炭化水素環及び芳香族ヘテロ環のいずれでもよい。芳香族ヘテロ環(複素芳香環とも称す。)である場合、環員原子(環構成原子)としてヘテロ原子(窒素原子、酸素原子又は硫黄原子等の少なくとも1種)を1つ以上(例えば1~4つ)有する化合物であり、環員原子として窒素原子を1つ以上(例えば1~4つ)有することが好ましい。
 なお、無置換の芳香族炭化水素は、化合物Aが含む酸基と水素結合を形成できる構造を有しないため、紫外線照射によりラジカルを生成する機能を有さず、化合物Bに該当しない。また、樹脂を構成するポリマーの側鎖に無置換の芳香族炭化水素環が結合した形態における無置換の芳香族炭化水素環は、化合物Aが含む酸基と水素結合を形成できる構造を有しないため、紫外線照射によりラジカルを生成する機能を有さず、化合物Bに該当しない。
 上記芳香環の環員原子数は、5~15が好ましい。
Compound B is preferably an aromatic compound because it has a large molar absorption coefficient for ultraviolet light.
Here, the aromatic compound is a compound having one or more aromatic rings.
Only one or more aromatic rings may be present in compound B. When more than one aromatic ring is present, the aromatic ring may be present, for example, in a side chain of a polymer constituting the resin.
The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic hetero ring. When the aromatic hetero ring (also referred to as a heteroaromatic ring) is used, it is a compound having one or more (e.g., 1 to 4) heteroatoms (at least one of nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms (ring-constituting atoms), and preferably has one or more (e.g., 1 to 4) nitrogen atoms as ring member atoms.
Note that unsubstituted aromatic hydrocarbons do not have a structure capable of forming a hydrogen bond with the acid group contained in compound A, and therefore do not have the function of generating radicals upon ultraviolet irradiation, and do not fall under compound B. Furthermore, unsubstituted aromatic hydrocarbon rings in a form in which an unsubstituted aromatic hydrocarbon ring is bonded to a side chain of a polymer constituting a resin do not have a structure capable of forming a hydrogen bond with the acid group contained in compound A, and therefore do not have the function of generating radicals upon ultraviolet irradiation, and do not fall under compound B.
The aromatic ring preferably has 5 to 15 ring atoms.

 上記芳香環としては、例えば、ピリジン環、ピラジン環、ピリミジン環、及びトリアジン環のような単環の芳香環;キノリン環、イソキノリン環、キノキサリン環、及びキナゾリン環のような2環が縮環した芳香環;アクリジン環、フェナントリジン環、フェナントロリン環、及びフェナジン環のような3環が縮環した芳香環が挙げられる。 Examples of the aromatic ring include monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; aromatic rings formed by condensing two rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring; and aromatic rings formed by condensing three rings such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.

 上記芳香環は1つ以上(例えば1~5個)の置換基を有していてもよく、上記置換基としては、アルキル基、アリール基、ハロゲン原子、アシル基、アルコキシカルボニル基、アリールカルボニル基、カルバモイル基、ヒドロキシ基、シアノ基、及びニトロ基が挙げられる。また、上記芳香環が2つ以上の置換基を有する場合、複数の置換基が互いに結合して非芳香環を形成していてもよい。
 なお、複数の芳香環(例えば、2~5つの芳香環)が、単結合、カルボニル結合、及び、多重結合(例えば、置換基を有してもよいビニレン基、-C≡C-、-N=N-等)から選択される構造で結合した一連の芳香環構造を形成している場合、上記一連の芳香環構造全体で1つの特定構造とみなす。
 上記の複数の芳香環が、単結合、カルボニル結合、及び、多重結合から選択される構造で結合した一連の芳香環構造は、上述の無置換の芳香族炭化水素環には該当せず、樹脂を構成するポリマーの側鎖に無置換の芳香族炭化水素環が結合した形態における無置換の芳香族炭化水素環にも該当しない。
 また、上記一連の芳香環構造を構成する複数の芳香環のうちの1つ以上が上記複素芳香環であることが好ましい。
The aromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. When the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring.
In addition, when a series of aromatic ring structures is formed by a plurality of aromatic rings (for example, 2 to 5 aromatic rings) being bonded via a structure selected from a single bond, a carbonyl bond, and a multiple bond (for example, a vinylene group which may have a substituent, -C≡C-, -N=N-, etc.), the series of aromatic ring structures as a whole is regarded as one specific structure.
The series of aromatic ring structures in which the above-mentioned multiple aromatic rings are bonded via a structure selected from a single bond, a carbonyl bond, and a multiple bond does not fall under the above-mentioned unsubstituted aromatic hydrocarbon ring, nor does it fall under the unsubstituted aromatic hydrocarbon ring in a form in which an unsubstituted aromatic hydrocarbon ring is bonded to a side chain of a polymer constituting the resin.
It is also preferred that one or more of the aromatic rings constituting the series of aromatic ring structures be the heteroaromatic ring.

 化合物Bの具体例としては、ピリジン化合物(ピリジン及びピリジン誘導体)、ピラジン化合物(ピラジン及びピラジン誘導体)、ピリミジン化合物(ピリミジン及びピリミジン誘導体)、並びに、トリアジン化合物(トリアジン及びトリアジン誘導体)等の単環の芳香族化合物;キノリン化合物(キノリン及びキノリン誘導体)、イソキノリン化合物(イソキノリン及びイソキノリン誘導体)、キノキサリン化合物(キノキサリン及びキノキサリン誘導体)、並びに、キナゾリン化合物(キナゾリン及びキナゾリン誘導体)等の2環が縮合して芳香環を形成している化合物;アクリジン化合物(アクリジン及びアクリジン誘導体)、フェナントリジン化合物(フェナントリジン及びフェナントリジン誘導体)、フェナントロリン化合物(フェナントロリン及びフェナントロリン誘導体)、並びに、フェナジン化合物(フェナジン及びフェナジン誘導体)等の3環以上が縮合して芳香環を形成している化合物が挙げられる。これらの化合物Bの具体例において、化合物とは、化合物そのもののほか、本発明の効果を損なわない範囲で、構造の一部を変化させた無置換の化合物を含め、置換基を有する化合物(「誘導体」と称す。)を含む意味で使用する。
 これらの化合物Bは、前述の化合物Aと錯体を形成し、紫外線の照射により以下の機構により2分子のラジカルを生成するものと推定している。
1)紫外線を吸収することにより励起状態の化合物Bが生成する。
2)励起状態の化合物Bから基底状態の化合物Aに正孔が移動する(励起状態の化合物Bの二つの半占軌道のうちのエネルギーが低い側の軌道に化合物Aの電子が移動する)。
3)化合物Aから化合物Bにプロトンが移動することによって、化合物Bに水素ラジカルが負荷したラジカルと、化合物Aから水素ラジカルが脱離したラジカルとが生成する。
 化合物Aがカルボキシ基を有する化合物である場合には、さらに以下の反応が起こり、光脱炭酸反応によりラジカルが生成する。
4)化合物Aから水素ラジカルが脱離したラジカルから二酸化炭素が脱離する。
Specific examples of compound B include monocyclic aromatic compounds such as pyridine compounds (pyridine and pyridine derivatives), pyrazine compounds (pyrazine and pyrazine derivatives), pyrimidine compounds (pyrimidine and pyrimidine derivatives), and triazine compounds (triazine and triazine derivatives); compounds in which two rings are fused to form an aromatic ring, such as quinoline compounds (quinoline and quinoline derivatives), isoquinoline compounds (isoquinoline and isoquinoline derivatives), quinoxaline compounds (quinoxaline and quinoxaline derivatives), and quinazoline compounds (quinazoline and quinazoline derivatives); and compounds in which three or more rings are fused to form an aromatic ring, such as acridine compounds (acridine and acridine derivatives), phenanthridine compounds (phenanthridine and phenanthridine derivatives), phenanthroline compounds (phenanthroline and phenanthroline derivatives), and phenazine compounds (phenazine and phenazine derivatives). In these specific examples of compound B, the term "compound" is used to mean not only the compound itself, but also a compound having a substituent (referred to as a "derivative"), including an unsubstituted compound whose structure is partially modified within a range that does not impair the effects of the present invention.
It is presumed that these compounds B form complexes with the aforementioned compound A, and when irradiated with ultraviolet light, generate two radical molecules through the following mechanism.
1) Compound B is generated in an excited state by absorbing ultraviolet light.
2) A hole moves from compound B in the excited state to compound A in the ground state (an electron from compound A moves to the lower energy orbital of the two half-occupied orbitals of compound B in the excited state).
3) A proton is transferred from compound A to compound B, generating a radical in which a hydrogen radical is added to compound B and a radical in which a hydrogen radical is released from compound A.
When compound A is a compound having a carboxy group, the following reaction further occurs, and a radical is generated by a photodecarboxylation reaction.
4) Carbon dioxide is released from the radical resulting from the release of a hydrogen radical from compound A.

 なかでも、化合物Bは、キノリン化合物(キノリン及びキノリン誘導体)、並びに、イソキノリン化合物(イソキノリン及びイソキノリン誘導体)のうちの1種以上であることが好ましい。
 これらの化合物が有していてもよい置換基としては、アルキル基、アリール基、ハロゲン原子、アシル基、アルコキシカルボニル基、アリールカルボニル基、カルバモイル基、ヒドロキシ基、シアノ基、又はニトロ基が好ましい。
Among these, compound B is preferably at least one of quinoline compounds (quinoline and quinoline derivatives) and isoquinoline compounds (isoquinoline and isoquinoline derivatives).
The substituents which these compounds may have are preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group.

 化合物Bがポリマーである場合、上記特定構造がポリマー主鎖と単結合又は連結基を介して結合しているポリマーでもよい。
 ポリマーである化合物Bは、例えば、複素芳香環を有する単量体(具体的には、ビニル基を有する複素芳香環、及び/又は、複素芳香環を有する(メタ)アクリレート単量体)を重合することにより得られる。必要に応じて他の単量体と共重合してもよい。
When compound B is a polymer, it may be a polymer in which the specific structure is bonded to the polymer main chain via a single bond or a linking group.
Compound B, which is a polymer, can be obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a heteroaromatic ring having a vinyl group and/or a (meth)acrylate monomer having a heteroaromatic ring). If necessary, it may be copolymerized with other monomers.

 化合物Bの具体例としては、例えば、キノリン、2-メチルキノリン、4-メチルキノリン、2,4-ジメチルキノリン、2-メチル-4-フェニルキノリン、イソキノリン、1-メチルイソキノリン、3-メチルイソキノリン、1-フェニルイソキノリンが挙げられる。 Specific examples of compound B include quinoline, 2-methylquinoline, 4-methylquinoline, 2,4-dimethylquinoline, 2-methyl-4-phenylquinoline, isoquinoline, 1-methylisoquinoline, 3-methylisoquinoline, and 1-phenylisoquinoline.

 紫外線照射部位の消色性と紫外線未照射部位の染料の耐久性を両立させる観点から化合物Bの含有量は、光吸収消失性層の全質量に対して、0.1~50質量%が好ましく、2.0~40質量%がより好ましく、4~35質量%がさらに好ましく、8~30質量%が特に好ましい。
 また、化合物Bの塩基性の尺度であるpKaH(共役酸のpKa)は、同じく紫外線照射部位の消色性と紫外線未照射部位の染料の耐久性を両立させる観点から、2.0~7.0が好ましく、3.0~6.0がより好ましく、4.3~5.5がさらに好ましい。
 本発明において、pKaは25℃の水/メタノール=50/50(体積比)の混合溶媒における酸解離定数(Ka)の負の常用対数(-logKa)を意味する。pKaは、測定用サンプル(化合物Bの共役酸)の水/メタノール=50/50(体積比)の混合溶液に対して0.01mоl/Lの水酸化ナトリウム水溶液を滴下し、半当量点までに滴下した水酸化ナトリウム水溶液の量を読み取ることで算出できる。
 化合物Bは、一種単独で使用してもよく、二種以上を併用してもよい。
From the viewpoint of achieving both the decolorization property in the ultraviolet irradiated portion and the durability of the dye in the ultraviolet non-irradiated portion, the content of Compound B is preferably from 0.1 to 50 mass %, more preferably from 2.0 to 40 mass %, still more preferably from 4 to 35 mass %, and particularly preferably from 8 to 30 mass %, relative to the total mass of the light-absorbing and disappearing layer.
Similarly, from the viewpoint of achieving both the decolorization property of the ultraviolet irradiated portion and the durability of the dye in the ultraviolet non-irradiated portion, the pKaH (pKa of the conjugate acid) which is a measure of the basicity of compound B is preferably 2.0 to 7.0, more preferably 3.0 to 6.0, and still more preferably 4.3 to 5.5.
In the present invention, pKa means the negative common logarithm (−logKa) of the acid dissociation constant (Ka) in a mixed solvent of water/methanol = 50/50 (volume ratio) at 25° C. The pKa can be calculated by adding 0.01 mol/L of aqueous sodium hydroxide solution dropwise to a mixed solution of water/methanol = 50/50 (volume ratio) of a measurement sample (conjugate acid of compound B) and reading the amount of aqueous sodium hydroxide added dropwise up to the half-equivalent point.
The compound B may be used alone or in combination of two or more.

<樹脂>
 上記光吸収消失性層に含まれる樹脂は、上記の染料を分散(好ましくは溶解)することができ、紫外線照射によりラジカルを生成する化合物(好ましくは、化合物Aが含む酸基と水素結合した化合物Bを含むラジカル発生剤)から生じるラジカルによる染料の消色作用を発現することができ、所望の光透過性(波長400~800nmの可視領域において、光透過率が80%以上であることが好ましい。)を有する限り、特に限定されるものではない。
<Resin>
The resin contained in the light-absorbing and disappearing layer is not particularly limited as long as it can disperse (preferably dissolve) the dye, can exhibit the dye decolorizing action by radicals generated from a compound that generates radicals upon ultraviolet irradiation (preferably a radical generator containing compound B hydrogen-bonded with an acid group contained in compound A), and has the desired light transmittance (a light transmittance of 80% or more is preferred in the visible region of wavelengths of 400 to 800 nm).

 上記樹脂を構成するポリマーとして、さまざまなポリマーが使用可能であり、紫外線照射による樹脂の分子量低下がおこりにくい観点から側鎖に芳香環あるいは脂環式構造を有するポリマーが好ましく、芳香環あるいは脂環式構造を有する構成単位を含む(メタ)アクリルポリマー等の連鎖重合ポリマーがより好ましい。なかでも、消色率をより向上させることができ、また、耐熱性及び耐光性についてもより向上させることができる観点から、脂環式構造を有する構成単位を含む(メタ)アクリルポリマーがさらに好ましい。
 ここで、(メタ)アクリルポリマーは、(メタ)アクリル酸に由来する構成単位及び(メタ)アクリル酸エステルに由来する構成単位の少なくとも一方を含むポリマーを指す。なお、ポリマーが(メタ)アクリル酸に由来する構成単位を含む場合、(メタ)アクリル酸に由来する構成単位は上述の化合物Aにおける酸基としてカルボキシ基を有する構成単位となり、上述の、樹脂を構成するポリマーに上述の化合物Aが化学結合しているポリマーに相当する。
 また、本発明において、「主鎖」とは、高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは、主鎖から枝分かれしている原子団を表す。
As the polymer constituting the resin, various polymers can be used, and from the viewpoint of preventing the molecular weight of the resin from decreasing due to ultraviolet irradiation, a polymer having an aromatic ring or an alicyclic structure in the side chain is preferred, and a chain polymerization polymer such as a (meth)acrylic polymer containing a structural unit having an aromatic ring or an alicyclic structure is more preferred. Among them, from the viewpoint of further improving the decolorization rate and further improving the heat resistance and light resistance, a (meth)acrylic polymer containing a structural unit having an alicyclic structure is even more preferred.
Here, the (meth)acrylic polymer refers to a polymer containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid ester. When the polymer contains a structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylic acid becomes a structural unit having a carboxy group as the acid group in the above-mentioned compound A, and corresponds to the above-mentioned polymer in which the above-mentioned compound A is chemically bonded to the polymer constituting the resin.
In the present invention, the term "main chain" refers to the relatively longest bond chain in the molecule of a polymer compound, and the term "side chain" refers to an atomic group branching off from the main chain.

 芳香環を有する構成単位を導くモノマーとしては、ベンジルアクリレート、ベンジルメタクリレート、ナフチルアクリレート、ナフチルメタクリレート、ナフチルメチルアクリレート及びナフチルメチルメタクリレート等の芳香環を有する(メタ)アクリレートが挙げられる。ポリマーが(メタ)アクリル酸に由来する構成単位を含有しない場合、芳香環を有する構成単位の含有量は、ポリマーの全質量に対し、5~100質量%であることが好ましく、10~100質量%であることがより好ましく、20~100質量%であることが更に好ましい。 Monomers that derive structural units having an aromatic ring include (meth)acrylates having an aromatic ring, such as benzyl acrylate, benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, naphthyl methyl acrylate, and naphthyl methyl methacrylate. When the polymer does not contain structural units derived from (meth)acrylic acid, the content of structural units having an aromatic ring is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass, relative to the total mass of the polymer.

 脂環式構造を有する構成単位を導くモノマーとしては、ジシクロペンタニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート及びアダマンチル(メタ)アクリレート等が挙げられる。
 上記ポリマーが脂環式構造を有する構成単位を含む場合、脂環式構造を有する構成単位の含有量は、ポリマーの全質量に対し、1~90質量%であることが好ましく、5~90質量%であることがより好ましく、5~80質量%であることがさらに好ましい。
Examples of monomers that lead to structural units having an alicyclic structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
When the polymer contains a structural unit having an alicyclic structure, the content of the structural unit having an alicyclic structure is preferably 1 to 90 mass%, more preferably 5 to 90 mass%, and even more preferably 5 to 80 mass%, relative to the total mass of the polymer.

 また、上記光吸収消失性層においては、上記樹脂を構成するポリマーが、酸基を有する化合物Aと結合した構成単位を含んでいてもよい。酸基を有する化合物Aと結合した構成単位としては、上述の化合物Aにおけるカルボキシ基を有する構成単位に係る記載を適用することができ、(メタ)アクリル酸に由来する構成単位が好ましい。酸基を有する化合物Aと結合した構成単位(好ましくは(メタ)アクリル酸に由来する構成単位)の含有量は、ポリマーの全質量に対し、1~70質量%であることが好ましく、1~60質量%であることがより好ましい。さらに好ましくは、上述の化合物Aにおけるカルボキシ基含有ポリマーにおけるカルボキシ基を有する構成単位の含有量の記載を適用する。
 上記樹脂を構成するポリマーが、酸基を有する化合物Aと結合した構成単位を含む場合には、酸基を有する化合物Aと結合した構成単位の含有量、芳香環を有する構成単位の含有量及び脂環式構造を有する構成単位の含有量について、上述の化合物Aのカルボキシ基含有ポリマーにおけるカルボキシ基を有する構成単位の含有量、芳香環を有する構成単位の含有量及び脂環式構造を有する構成単位の含有量に係る記載を適用する。
Furthermore, in the light-absorbing and disappearing layer, the polymer constituting the resin may contain a structural unit bonded to a compound A having an acid group. The structural unit bonded to a compound A having an acid group can be the same as the structural unit having a carboxy group in the compound A described above, and a structural unit derived from (meth)acrylic acid is preferred. The content of the structural unit bonded to a compound A having an acid group (preferably a structural unit derived from (meth)acrylic acid) is preferably 1 to 70% by mass, more preferably 1 to 60% by mass, relative to the total mass of the polymer. More preferably, the content of the structural unit having a carboxy group in the carboxy group-containing polymer in the compound A described above is applied.
When the polymer constituting the resin contains a structural unit bonded to a compound A having an acid group, the contents of structural units having an aromatic ring and structural units having an alicyclic structure in the carboxy group-containing polymer of compound A described above apply to the contents of structural units bonded to a compound A having an acid group, the content of structural units having an aromatic ring and the content of structural units having an alicyclic structure.

 上記樹脂を構成するポリマーはガラス転移温度の調節等の観点から、炭素数1~14のアルキル基を有する構成単位を含んでいてもよい。炭素数1~14のアルキル基を有する構成単位としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-エチルブチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソノニル(メタ)アクリレート、ラウリル(メタ)アクリレート及びテトラデシル(メタ)アクリレート等のアルキル(メタ)アクリレート由来の構成単位が挙げられる。本発明では、炭素数1~14のアルキル基を有する構成単位を単独で用いてもよく、2種以上を組み合わせて用いてもよい。炭素数1~14のアルキル基を有する構成単位の含有量は、樹脂を構成するポリマーの全質量に対し、0~95質量%含まれることが好ましい。 The polymer constituting the resin may contain a structural unit having an alkyl group having 1 to 14 carbon atoms, from the perspective of adjusting the glass transition temperature, etc. Examples of structural units having an alkyl group having 1 to 14 carbon atoms include structural units derived from alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate. In the present invention, structural units having an alkyl group having 1 to 14 carbon atoms may be used alone, or two or more types may be used in combination. The content of structural units having an alkyl group having 1 to 14 carbon atoms is preferably 0 to 95% by mass relative to the total mass of the polymers that make up the resin.

 上記樹脂を構成するポリマーの重量平均分子量(Mw)は、1万以上であることが好ましく、1万~20万であることがより好ましく、1.5万~15万であることが更に好ましい。 The weight-average molecular weight (Mw) of the polymer that constitutes the resin is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.

 次に積層体I及び積層体IIを構成する波長選択吸収層について詳しく説明する。 Next, we will explain in detail the wavelength-selective absorption layers that make up Laminate I and Laminate II.

<<波長選択吸収層>>
 積層体I及び積層体IIを構成する波長選択吸収層は、樹脂と、波長400~700nmに主吸収波長帯域を有する染料とを含有し、紫外線照射によりラジカルを生成する化合物を含有しない。なお、上記「染料」は、460nm、530nm及び620nmのいずれの波長にも主吸収波長帯域を有しないことが好ましく、450~470nm、520nm超え540nm以下、610nm超え630nm以下のいずれの波長領域にも主吸収波長帯域を有しないことがより好ましい。
 上記波長選択吸収層中において、上記「染料」は、上記樹脂中に分散(好ましくは溶解)することにより、波長選択吸収層を染料に由来する特定の吸収スペクトルを示す層とするものである。
<<Wavelength-selective absorption layer>>
The wavelength-selective absorption layers constituting the laminates I and II contain a resin and a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and do not contain a compound that generates radicals upon ultraviolet irradiation. The dye preferably does not have a main absorption wavelength band at any of the wavelengths of 460 nm, 530 nm, and 620 nm, and more preferably does not have a main absorption wavelength band at any of the wavelength ranges of 450 to 470 nm, more than 520 nm but not more than 540 nm, or more than 610 nm but not more than 630 nm.
In the wavelength selective absorption layer, the "dye" is dispersed (preferably dissolved) in the resin, thereby making the wavelength selective absorption layer a layer exhibiting a specific absorption spectrum derived from the dye.

<染料>
 上記波長選択吸収層中に含有される上記「染料」は、異なる波長域に主吸収波長帯域を有する下記染料A~Dの少なくとも1種を含むことが好ましい。
 染料A:波長390~435nmに主吸収波長帯域を有する染料
 染料B:波長480~520nmに主吸収波長帯域を有する染料
 染料C:波長560~610nmに主吸収波長帯域を有する染料
 染料D:波長640~780nmに主吸収波長帯域を有する染料
 なお、上記波長選択吸収層中に含有され得る上記の染料Aは、1種でもよく、2種以上であってもよい。上記波長選択吸収層中に含有され得る上記の染料B~Dについても、染料Aと同様に、各々独立に、1種でもよく、2種以上であってもよい。
 上記波長選択吸収層は上記染料A~D以外の染料を含有することもできる。
<Dye>
The "dye" contained in the wavelength selective absorption layer preferably includes at least one of the following dyes A to D, each of which has a main absorption wavelength band in a different wavelength region.
Dye A: a dye having a main absorption wavelength band in a wavelength range of 390 to 435 nm Dye B: a dye having a main absorption wavelength band in a wavelength range of 480 to 520 nm Dye C: a dye having a main absorption wavelength band in a wavelength range of 560 to 610 nm Dye D: a dye having a main absorption wavelength band in a wavelength range of 640 to 780 nm The dye A that can be contained in the wavelength selective absorption layer may be one type or two or more types. As with dye A, the dyes B to D that can be contained in the wavelength selective absorption layer may each independently be one type or two or more types.
The wavelength selective absorption layer may contain dyes other than the dyes A to D.

 上記波長選択吸収層の形態は、波長選択吸収層中の染料が吸収スペクトルを示し、上述の光吸収消失性層との組み合わせにより、得られる光透過吸収フィルタI及びIIにおいて外光反射の抑制及び輝度低下の抑制の両立を実現することができればよく、好ましくは、さらに、表示画像本来の色味に影響しにくいものであればよい。上記波長選択吸収層の一形態としては、染料(好ましくは、染料A~Dの少なくとも1種)が樹脂中に分散(好ましくは溶解)した形態が挙げられる。この分散は、ランダム、規則的等いずれであってもよい。 The wavelength-selective absorption layer may take any form so long as the dye in the wavelength-selective absorption layer exhibits an absorption spectrum, and in combination with the light-absorbing and dissipative layer described above, the resulting light-transmitting and absorbing filters I and II are able to simultaneously suppress external light reflection and brightness reduction, and preferably are also not likely to affect the original color of the displayed image. One form of the wavelength-selective absorption layer is one in which a dye (preferably at least one of dyes A to D) is dispersed (preferably dissolved) in a resin. This dispersion may be random, regular, or otherwise.

 上記染料A~Dは、上記波長選択吸収層において、OLED表示装置の発光源として使用される、B(Blue、460nm)、G(Green、530nm)及びR(Red、620nm)と重複しない波長域である、390~435nm、480~520nm、560~610nm及び640~780nmに、それぞれ主吸収波長帯域を有する。そのため、これらの染料A~Dの少なくとも1種を含有することにより、上記波長選択吸収層は、OLED表示素子から発せられる光の色再現域を損なうことなく、表示装置の発光部における外光の反射を抑制することができる。 In the wavelength-selective absorption layer, the dyes A to D have their main absorption wavelength bands in the wavelength ranges of 390 to 435 nm, 480 to 520 nm, 560 to 610 nm, and 640 to 780 nm, respectively, which do not overlap with the wavelength ranges of B (Blue, 460 nm), G (Green, 530 nm), and R (Red, 620 nm) used as light sources in OLED display devices. Therefore, by containing at least one of these dyes A to D, the wavelength-selective absorption layer can suppress reflection of external light in the light-emitting section of the display device without compromising the color reproduction range of light emitted from the OLED display element.

 特に、上記発光源の出射スペクトルとの間に負の相関関係を有する吸収スペクトルを示す波長選択吸収層とし、OLED表示装置の画像本来の色味を引き出す観点からは、上記波長選択吸収層中に含有され得る染料A、染料B、染料C及び染料Dは、少なくとも2種の組み合わせであることが好ましく、少なくとも3種の組み合わせであることがより好ましく、4種全てを含有することがさらに好ましい。
 上記のように波長選択吸収層中に2種以上の染料A~Dを含有させる場合、染料分解時に発生したラジカルの連鎖移動等により、染料の混合による耐光性の低下という問題も生じてしまうことがある。このような問題に対しても、積層体I及び積層体II、並びに、積層体Iをマスク露光して得られる光透過吸収フィルタI及び積層体IIと積層体IIIとを含む光透過吸収フィルタII中における波長選択吸収層は、後述する特定のガスバリア層を設けたり、複数の染料を2層の波長選択吸収層に分けて有することにより、染料の混合に伴う耐光性の低下を上回る、優れたレベルの耐光性を示すことができる。
In particular, from the viewpoint of providing a wavelength selective absorption layer that exhibits an absorption spectrum that has a negative correlation with the emission spectrum of the light source and bringing out the original color of an image of an OLED display device, the dyes A, B, C, and Dye D that can be contained in the wavelength selective absorption layer are preferably a combination of at least two types, more preferably a combination of at least three types, and even more preferably a combination of all four types.
When two or more types of dyes A to D are contained in the wavelength-selective absorption layer as described above, a problem of reduced lightfastness due to mixing of the dyes may occur due to chain transfer of radicals generated during dye decomposition, etc. To address this problem, the wavelength-selective absorption layer in the laminate I and laminate II, as well as the light-transmission-absorption filter I obtained by mask-exposing the laminate I, and the light-transmission-absorption filter II including the laminate II and laminate III, can exhibit an excellent level of lightfastness that overcomes the reduced lightfastness that accompanies mixing of the dyes by providing a specific gas barrier layer as described below or by having multiple dyes separated into two wavelength-selective absorption layers.

 なかでも、OLED表示装置の画像本来の色味をより引き出す観点からは、上記波長選択吸収層は、前述の4種の染料A~Dの全てを含有し、かつ、下記関係式(I)~(VI)を満たすことが好ましい。このような構成を有する波長選択吸収層と前述の光吸収消失性層とを有する積層体Iから得られる光透過吸収フィルタI及びこのような構成を有する波長選択吸収層を含む積層体IIと積層体IIIから得られる光透過吸収フィルタIIは、外光反射の抑制及び輝度低下の抑制を充足に加えて、OLED表示装置の画像本来の色味をより優れたレベルで保持することができる。
 関係式(I)    Ab(450)/Ab(430)<1.0
 関係式(II)   Ab(450)/Ab(500)<1.0
 関係式(III)  Ab(540)/Ab(500)<1.0
 関係式(IV)   Ab(540)/Ab(600)<1.0
 関係式(V)    Ab(630)/Ab(600)≦0.5
 関係式(VI)   Ab(630)/Ab(700)<1.0
In particular, from the viewpoint of further bringing out the original color of an image of an OLED display device, it is preferable that the wavelength-selective-absorption layer contains all of the four dyes A to D and satisfies the following relational formulas (I) to (VI): Light-transmission-absorption filter I obtained from laminate I having a wavelength-selective-absorption layer with such a configuration and the above-mentioned light-absorbing-disappearing layer, and light-transmission-absorption filter II obtained from laminate II and laminate III including a wavelength-selective-absorption layer with such a configuration, can not only satisfactorily suppress external light reflection and brightness reduction, but also maintain the original color of an image of an OLED display device at an excellent level.
Relationship (I): Ab(450)/Ab(430)<1.0
Relational formula (II): Ab(450)/Ab(500)<1.0
Relational formula (III): Ab(540)/Ab(500)<1.0
Relationship (IV): Ab(540)/Ab(600)<1.0
Relational formula (V) Ab(630)/Ab(600)≦0.5
Relationship (VI): Ab(630)/Ab(700)<1.0

 上記関係式(I)~(VI)で規定する範囲において、好ましい範囲は下記の通りである。
 関係式(I)におけるAb(450)/Ab(430)の上限値は、0.90以下が好ましく、0.85以下がより好ましく、0.80以下がさらに好ましく、0.60以下が特に好ましい。下限値に特に制限はないが、0.05以上が実際的であり、0.10以上が好ましく、0.20以上がより好ましい。
 関係式(II)におけるAb(450)/Ab(500)の上限値は、0.90以下が好ましく、0.80以下がより好ましく、0.75以下がさらに好ましく、0.65以下が特に好ましく、なかでも0.60以下が好ましく、0.50以下が最も好ましい。下限値に特に制限はないが、0.05以上が実際的であり、0.10以上が好ましく、0.20以上がより好ましい。
 関係式(III)におけるAb(540)/Ab(500)の上限値は、0.90以下が好ましく、0.80以下がより好ましく、0.75以下がさらに好ましく、0.70以下が特に好ましく、なかでも0.50以下が好ましく、0.20以下が最も好ましい。下限値に特に制限はないが、0.01以上が実際的であり、0.02以上が好ましく、0.05以上がより好ましい。
 関係式(IV)におけるAb(540)/Ab(600)の上限値は、0.90以下が好ましく、0.85以下がより好ましく、0.80以下がさらに好ましく、0.70以下が特に好ましく、なかでも0.50以下が好ましく、0.25以下が最も好ましい。下限値に特に制限はないが、0.01以上が実際的であり、0.02以上が好ましく、0.05以上がより好ましい。
 関係式(V)におけるAb(630)/Ab(600)の上限値は、0.40以下が好ましく、0.30以下がより好ましく、0.20以下がさらに好ましく、0.15以下が特に好ましい。下限値に特に制限はないが、0.01以上が実際的であり、0.02以上が好ましく、0.05以上がより好ましい。
 関係式(VI)におけるAb(630)/Ab(700)の上限値は、0.95以下が好ましく、0.90以下がより好ましく、0.80以下がさらに好ましく、0.75以下が特に好ましい。下限値に特に制限はないが、0.01以上が実際的であり、0.03以上が好ましく、0.10以上がより好ましく、0.40以上がさらに好ましく、0.50以上が特に好ましい。
Among the ranges defined by the above relational expressions (I) to (VI), the preferred ranges are as follows:
The upper limit of Ab(450)/Ab(430) in the relational formula (I) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, and particularly preferably 0.60 or less. There is no particular restriction on the lower limit, but a practical value is 0.05 or more, preferably 0.10 or more, and more preferably 0.20 or more.
The upper limit of Ab(450)/Ab(500) in the relational formula (II) is preferably 0.90 or less, more preferably 0.80 or less, even more preferably 0.75 or less, particularly preferably 0.65 or less, and among these, 0.60 or less is preferable, and 0.50 or less is most preferable. There is no particular restriction on the lower limit, but a practical value is 0.05 or more, preferably 0.10 or more, and more preferably 0.20 or more.
The upper limit of Ab(540)/Ab(500) in the relational formula (III) is preferably 0.90 or less, more preferably 0.80 or less, even more preferably 0.75 or less, particularly preferably 0.70 or less, and among these, 0.50 or less is preferable, and 0.20 or less is most preferable. There is no particular restriction on the lower limit, but a practical value is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.
The upper limit of Ab(540)/Ab(600) in the relational formula (IV) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, particularly preferably 0.70 or less, and among these, 0.50 or less is preferable, and 0.25 or less is most preferable. There is no particular restriction on the lower limit, but a practical value is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.
The upper limit of Ab(630)/Ab(600) in the relational formula (V) is preferably 0.40 or less, more preferably 0.30 or less, even more preferably 0.20 or less, and particularly preferably 0.15 or less. There is no particular restriction on the lower limit, but a practical value is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.
The upper limit of Ab(630)/Ab(700) in the relational formula (VI) is preferably 0.95 or less, more preferably 0.90 or less, even more preferably 0.80 or less, and particularly preferably 0.75 or less. There is no particular restriction on the lower limit, but a practical value is 0.01 or more, preferably 0.03 or more, more preferably 0.10 or more, even more preferably 0.40 or more, and particularly preferably 0.50 or more.

 関係式(I)~(VI)が、それぞれ上記好ましい範囲を満たすことにより、光透過吸収フィルタIないしIIを設けることによる色味変化を小さくすることができ、OLED表示装置の画像本来の色味をより引き出すことができる。そのため、染料A~Dは、主吸収波長帯域における吸収波形が先鋭であることが好ましい。
 例えば、染料Bが後述の一般式(1)で表されるスクアライン系色素である場合、上記波長選択吸収層は、関係式(II)及び(III)が上記好ましい範囲を満たすことができ、OLED表示装置の画像本来の色味をより優れたレベルで保持することができる。これは、ヒトの錐状体の緑色視物質の吸収極大(534nm)付近の波長における吸光度が低いためと考えられる。
 また、染料Cが後述の一般式(1)で表されるスクアライン系色素である場合、上記波長選択吸収層は、関係式(I)~(IV)が上記好ましい範囲を満たすことができ、OLED表示装置の画像本来の色味をより優れたレベルで保持することができる。これも、上記と同じくヒトの錐状体の緑色視物質の吸収極大(534nm)付近の波長における吸光度が低いためと考えられる。
 特に、関係式(V)を満たすことは、OLED表示装置の画像本来の色味に影響を与えない点で重要である。関係式(V)により、aの変化を抑制することができ、この結果、上記の色味を優れたレベルで保持できると考えられる。
When the relational expressions (I) to (VI) each satisfy the above-mentioned preferred ranges, the change in color caused by the provision of the light-transmitting-absorbing filters I and II can be reduced, and the original color of the image of the OLED display device can be further enhanced. For this reason, it is preferable that the dyes A to D have a sharp absorption waveform in the main absorption wavelength band.
For example, when dye B is a squaraine dye represented by general formula (1) described below, the wavelength selective absorption layer can satisfy the above-mentioned preferred ranges for relational formulas (II) and (III), and can maintain the original color of the image of the OLED display device at a superior level. This is thought to be due to the low absorbance at wavelengths around the absorption maximum (534 nm) of the green visual pigment in human cones.
Furthermore, when dye C is a squaraine dye represented by general formula (1) described below, the wavelength selective absorption layer can satisfy the above-mentioned preferable ranges of relational formulas (I) to (IV), and can maintain the original color of the image of the OLED display device at a superior level. This is also thought to be due to the low absorbance at wavelengths around the absorption maximum (534 nm) of the green visual pigment in human cones, as described above.
In particular, satisfying the relational expression (V) is important in that it does not affect the original color of the image of the OLED display device. It is believed that the change in a * can be suppressed by satisfying the relational expression (V), and as a result, the above-mentioned color can be maintained at an excellent level.

 積層体I及び積層体IIが有する波長選択吸収層は、1層であってもよく、上述の染料の混合に伴う耐光性の低下を抑制する観点から、2層であってもよい。波長選択吸収層が第一波長選択吸収層と第二波長選択吸収層の2層構成である場合には、第一波長選択吸収層に含まれる染料が第二波長選択吸収層に含まれる染料とは異なる波長域に主吸収波長帯域を有することが好ましい。なお、第一波長選択吸収層に含まれる染料が第二波長選択吸収層に含まれる染料とは異なる波長域に主吸収波長帯域を有するとは、第一波長選択吸収層に含まれる染料が有する最大極大吸収波長と、第二波長選択吸収層に含まれる染料の有する最大極大吸収波長とが、いずれの染料間においても50nm以上離れていることを意味する。
 なかでも、積層体I及び積層体IIが、第一波長選択吸収層側が外光側(視認者側)になり、第二波長選択吸収層側が表示装置側になるようにして表示装置に配置して使用される場合において、第一波長選択吸収層が、第一波長選択吸収層及び第二波長選択吸収層に含まれる染料のうち、最も短波長側に主吸収波長帯域を有する染料(以下、「最短波長染料」と称する)を含有することが好ましい。外光側に位置する第一波長選択吸収層が最短波長染料を含有する場合には、最短波長染料の光励起による最短波長染料以外の染料の光分解をより効果的に抑制することができ、優れた耐光性を示すことができる。
The wavelength-selective absorption layer of Laminate I and Laminate II may be a single layer, or may be a two-layer structure from the viewpoint of suppressing a decrease in light resistance due to the mixing of the above-mentioned dyes. When the wavelength-selective absorption layer has a two-layer structure consisting of a first wavelength-selective absorption layer and a second wavelength-selective absorption layer, it is preferable that the dye contained in the first wavelength-selective absorption layer has a main absorption wavelength band in a wavelength range different from that of the dye contained in the second wavelength-selective absorption layer. Note that, "the dye contained in the first wavelength-selective absorption layer has a main absorption wavelength band in a wavelength range different from that of the dye contained in the second wavelength-selective absorption layer" means that the maximum absorption maximum wavelength of the dye contained in the first wavelength-selective absorption layer and the maximum absorption maximum wavelength of the dye contained in the second wavelength-selective absorption layer are separated by 50 nm or more.
In particular, when the laminate I and the laminate II are used by being arranged in a display device such that the first-wavelength-selective-absorption layer side faces the external light side (the viewer side) and the second-wavelength-selective-absorption layer side faces the display device, it is preferable that the first-wavelength-selective-absorption layer contains a dye having a main absorption wavelength band on the shortest wavelength side (hereinafter referred to as "shortest-wavelength dye") among the dyes contained in the first-wavelength-selective-absorption layer and the second-wavelength-selective-absorption layer. When the first-wavelength-selective-absorption layer located on the external light side contains the shortest-wavelength dye, photodecomposition of dyes other than the shortest-wavelength dye due to photoexcitation of the shortest-wavelength dye can be more effectively suppressed, and excellent lightfastness can be exhibited.

 第一波長選択吸収層に含有される染料と第二波長選択吸収層に含有される染料との組み合わせについては、本発明の光透過吸収フィルタを表示装置に適用した場合に、輝度低下の抑制と反射色味の影響の抑制とを両立できるものが好ましい。
 第一波長選択吸収層と第二波長選択吸収層には、それぞれ、異なる波長域に主吸収波長帯域を有する少なくとも1種の染料を含有していることが好ましい。第一波長選択吸収層は、主吸収波長帯域の異なる2種以上の染料を含有していてもよく、第二波長選択吸収層は、主吸収波長帯域の異なる2種以上の染料を含有していてもよい。なお、第一波長選択吸収層及び第二波長選択吸収層のうちの少なくとも一方が、主吸収波長帯域の異なる2種以上の染料を含有する場合にも、第一波長選択吸収層に含まれる染料と第二波長選択吸収層に含まれる染料とは、いずれの染料同士においても、異なる波長域に主吸収波長帯域を有する関係を満たすことが好ましい。
 第一波長選択吸収層が、主吸収波長帯域の異なる2種以上の染料を含有するとは、第一波長選択吸収層に含まれる2種以上の染料が有する最大極大吸収波長が、第一波長選択吸収層に含まれるいずれの染料間においても50nm以上離れていることを意味する。
 また、第二波長選択吸収層が、主吸収波長帯域の異なる2種以上の染料を含有するとは、第二波長選択吸収層に含まれる2種以上の染料が有する最大極大吸収波長が、第二波長選択吸収層に含まれるいずれの染料間においても50nm以上離れていることを意味する。
 このうち、最短波長染料は、第一波長選択吸収層に含まれていることが上述の通り好ましく、最短波長染料は、前述の染料Aであることが好ましい。
A combination of the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer is preferably one that can both suppress a decrease in brightness and suppress the influence of reflected color when the light transmission and absorption filter of the present invention is applied to a display device.
The first wavelength selective absorption layer and the second wavelength selective absorption layer preferably contain at least one dye having a main absorption wavelength band in a different wavelength region. The first wavelength selective absorption layer may contain two or more dyes having different main absorption wavelength bands, and the second wavelength selective absorption layer may contain two or more dyes having different main absorption wavelength bands. Note that even when at least one of the first wavelength selective absorption layer and the second wavelength selective absorption layer contains two or more dyes having different main absorption wavelength bands, it is preferable that the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer have main absorption wavelength bands in different wavelength regions.
The first wavelength selective absorption layer containing two or more dyes having different main absorption wavelength bands means that the maximum absorption maximum wavelengths of the two or more dyes contained in the first wavelength selective absorption layer are different from each other by 50 nm or more.
Furthermore, the second wavelength selective absorption layer containing two or more dyes having different main absorption wavelength bands means that the maximum absorption maximum wavelengths of the two or more dyes contained in the second wavelength selective absorption layer are different from each other by 50 nm or more.
Of these, the shortest wavelength dye is preferably contained in the first wavelength selective absorption layer as described above, and the shortest wavelength dye is preferably dye A described above.

 第一波長選択吸収層及び第二波長選択吸収層中に含有される上記「染料」は、それぞれ、上述の「染料」に係る記載を適用することができ、上記染料A~Dの少なくとも1種を含むことが好ましい。2層以上の波長選択吸収層中に含有され得る上記染料A~Dは、各々独立に、1種でもよく、2種以上であってもよい。
 なかでも、第一波長選択吸収層が含有する染料と第二波長選択吸収層が含有する染料とをあわせることにより、上記染料A~Dの全てを含有する構成となることが好ましい。このような構成としては、例えば、第一波長選択吸収層が上記染料A及びCを含み、第二波長選択吸収層が上記染料B及びDを含む構成が好ましく挙げられる。
 また、上述の関係式(I)~(VI)については、第一波長選択吸収層及び第二波長選択吸収層単独では上述の関係式(I)~(VI)の全てを満たさず、第一波長選択吸収層及び第二波長選択吸収層を含む波長選択吸収層全体として、上述の関係式(I)~(VI)の全てを満たすことが好ましい。
The above-mentioned descriptions relating to "dye" can be applied to the "dye" contained in the first wavelength selective absorption layer and the second wavelength selective absorption layer, and it is preferable that the "dye" contains at least one of the dyes A to D. The dyes A to D that can be contained in two or more wavelength selective absorption layers may each independently be one type or two or more types.
In particular, it is preferable that the dye contained in the first wavelength selective absorption layer and the dye contained in the second wavelength selective absorption layer are combined to form a configuration containing all of the dyes A to D. For example, a preferred example of such a configuration is a configuration in which the first wavelength selective absorption layer contains the dyes A and C, and the second wavelength selective absorption layer contains the dyes B and D.
Furthermore, with regard to the above-mentioned relational expressions (I) to (VI), it is preferable that the first wavelength selective absorption layer and the second wavelength selective absorption layer do not satisfy all of the above-mentioned relational expressions (I) to (VI) individually, and that the wavelength selective absorption layer as a whole including the first wavelength selective absorption layer and the second wavelength selective absorption layer satisfies all of the above-mentioned relational expressions (I) to (VI).

(染料A)
 染料Aは、積層体I及び積層体II中で波長390~435nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
 なお、染料Aが主吸収波長帯域を有する波長範囲は、395~435nmが好ましく、400~435nmがより好ましく、405~435nmが更に好ましい。
 染料Aの具体例としては、例えば、ポルフィリン系、スクアライン系、シアニン(cyanine、CY)系、ピロールメチン系、インドアニリン系の各色素(染料)が挙げられる。
(Dye A)
There are no particular limitations on the dye A, so long as it has a main absorption wavelength band in the wavelength range of 390 to 435 nm in the laminate I and laminate II, and various dyes can be used.
The wavelength range in which dye A has its main absorption wavelength band is preferably 395 to 435 nm, more preferably 400 to 435 nm, and even more preferably 405 to 435 nm.
Specific examples of dye A include porphyrin-based, squaraine-based, cyanine (CY)-based, pyrrolmethine-based, and indoaniline-based pigments (dyes).

 上記染料Aとしては、主吸収波長帯域における吸収波形が先鋭である点から、下記一般式(A1)で表される色素が好ましい。 As the dye A, a dye represented by the following general formula (A1) is preferred because it has a sharp absorption waveform in the main absorption wavelength band.

 式(A1)中、R及びRは、各々独立に、アルキル基又はアリール基を示し、R~Rは、各々独立に、水素原子又は置換基を示し、RとRは互いに結合して6員環を形成していてもよい。 In formula (A1), R1 and R2 each independently represent an alkyl group or an aryl group, R3 to R6 each independently represent a hydrogen atom or a substituent, and R5 and R6 may be bonded to each other to form a 6-membered ring.

 一般式(A1)中の各置換基の定義及び好ましい範囲については、特段の断りのない限り、国際公開第2022/138925号の段落[0022]~[0056]に記載の一般式(A1)で表される色素の各置換基に関する記載をそれぞれそのまま適用することができる。 Unless otherwise specified, the definitions and preferred ranges of each substituent in general formula (A1) can be directly applied to the descriptions of each substituent in the dye represented by general formula (A1) in paragraphs [0022] to [0056] of WO 2022/138925.

 また、耐熱性及び耐光性の点からは、式(A1)中のR及びRがいずれもアリール基であることも好ましい。
 R及びRが各々独立にアリール基を表す場合、R、R及びRは、各々独立に、水素原子、アルキル基又はアリール基であって、かつ、R及びRの少なくとも一方は水素原子であることが好ましい。中でも、耐熱性及び耐光性の観点から、Rが水素原子を表し、R及びRが各々独立にアルキル基又はアリール基を表す場合がより好ましく、Rが水素原子を表し、R及びRが各々独立にアルキル基を表す場合が更に好ましく、Rが水素原子を表し、R及びRが各々独立にアルキル基を表し、かつ、R及びRが互いに結合して環を形成してピロール環に縮合し、ピロール環と共にインドール環を形成している場合が特に好ましい。即ち、上記一般式(A1)で表される色素は、下記一般式(A2)で表される色素であることが特に好ましい。
From the viewpoint of heat resistance and light resistance, it is also preferable that R 1 and R 2 in formula (A1) are both aryl groups.
When R1 and R2 each independently represent an aryl group, it is preferable that R3 , R5 , and R6 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R3 and R6 is a hydrogen atom. Among these, from the viewpoint of heat resistance and light fastness, it is more preferable that R3 represents a hydrogen atom, and R5 and R6 each independently represent an alkyl group or an aryl group, even more preferable that R3 represents a hydrogen atom, and R5 and R6 each independently represent an alkyl group, and it is particularly preferable that R3 represents a hydrogen atom, R5 and R6 each independently represent an alkyl group, and R5 and R6 are bonded to each other to form a ring that is condensed with a pyrrole ring and forms an indole ring together with the pyrrole ring. That is, it is particularly preferable that the dye represented by the above general formula (A1) is a dye represented by the following general formula (A2):

 式(A2)中、R~Rは、一般式(A1)中のR~Rとそれぞれ同義であり、好ましい態様も同様である。 In formula (A2), R 1 to R 4 have the same meanings as R 1 to R 4 in general formula (A1), respectively, and the preferred embodiments are also the same.

 式(A2)において、R15は、置換基を示す。R15として採り得る置換基としては、上述の国際公開第2022/138925号に記載の一般式(A1)で表される色素に係る記載における置換基群Aに含まれる置換基を挙げることができる。R15としては、アルキル基、アリール基、ハロゲン原子、アシル基又はアルコキシカルボニル基が好ましい。
 R15として採り得るアルキル基及びアリール基は、R、R及びRとして採り得るアルキル基及びアリール基とそれぞれ同義であり、好ましい態様もそれぞれ同様である。
 R15として採り得るハロゲン原子としては、例えば、塩素原子、臭素原子及びヨウ素原子が挙げられる。
 R15として採り得るアシル基としては、例えば、アセチル基、プロピオニル基及びブチロイル基が挙げられる。
 R15として採り得るアミノ基としては、Rにおける置換アリール基が有し得るアミノ基の記載を適用することができる。また、アミノ基の窒素原子上のアルキル基が結合して環を形成した、5~7員環の含窒素複素環基も好ましい。
 R15として採り得るアルコキシカルボニル基としては、炭素数2~5のアルコキシカルボニル基が好ましく、例えば、メトキシカルボニル、エトキシカルボニル、ノルマルプロポキシカルボニル及びイソプロポキシカルボニルが挙げられる。
In formula (A2), R 15 represents a substituent. Examples of the substituent that can be adopted as R 15 include the substituents included in the substituent group A in the description of the dye represented by general formula (A1) described in the above-mentioned WO 2022/138925. R 15 is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, or an alkoxycarbonyl group.
The alkyl group and aryl group which can be taken as R 15 have the same meanings as the alkyl group and aryl group which can be taken as R 3 , R 5 and R 6 , respectively, and the preferred embodiments are also the same.
Examples of halogen atoms that can be taken as R 15 include a chlorine atom, a bromine atom, and an iodine atom.
Examples of acyl groups that can be taken as R 15 include an acetyl group, a propionyl group, and a butyroyl group.
The amino group that can be taken as R 15 can be the same as the amino group that can be possessed by the substituted aryl group in R 4. Also preferred is a 5- to 7-membered nitrogen-containing heterocyclic group in which the alkyl group on the nitrogen atom of the amino group is bonded to form a ring.
The alkoxycarbonyl group that can be taken as R 15 is preferably an alkoxycarbonyl group having 2 to 5 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl, and isopropoxycarbonyl.

 nは、0~4の整数である。nは特に制限されないが、例えば、0又は1が好ましい。 n is an integer from 0 to 4. There are no particular restrictions on n, but it is preferably 0 or 1, for example.

 一般式(A1)で表される色素の具体例としては、国際公開第2022/138925号の[0063]~[0065]に記載の化合物及び下記化合物(E-42)が挙げられる。但し、本発明は、これらに限定されるものではない。 Specific examples of dyes represented by general formula (A1) include the compounds described in paragraphs [0063] to [0065] of WO 2022/138925 and the following compound (E-42). However, the present invention is not limited to these.

 また、上記染料Aとしては、下記一般式(B)で表される染料も好ましく挙げられる。なお、下記一般式(B)で表される染料としては、国際公開第2023/100715号の段落[0016]~[0097]に記載の一般式(1)、(3)又は(6)で表される化合物及び具体例の記載をそのまま適用することができる。また、後述の実施例で使用する染料A-321も、上記染料Aとして好ましい。 Furthermore, dyes represented by the following general formula (B) are also preferred as dyes A. The compounds and specific examples represented by general formula (1), (3), or (6) described in paragraphs [0016] to [0097] of WO 2023/100715 can be applied as they are to dyes represented by the following general formula (B). Dye A-321, used in the examples described below, is also preferred as dye A.

 上記式(B)中、Qは下記式(Q-1)で表される基を示す。
 Qは、=O、=S、=NRq1又は=CRq2q3を示し、Rq1~Rq3は、水素原子又は置換基を示し、Rq2とRq3は互いに結合して環を形成してもよい。ただし、Rq2とRq3が結合して環を形成している場合、=CRq2q3はQと同一の構造ではない。
 R及びRは、水素原子又は置換基を示す。
 X~Xは、各々独立して-S-、-NRX1-又は-SO-を示し、RX1は水素原子又はアルキル基を示す。
In the above formula (B), Q1 represents a group represented by the following formula (Q-1).
Q2 represents =O, =S, =NR q1 or =CR q2 R q3 , R q1 to R q3 represent a hydrogen atom or a substituent, and R q2 and R q3 may be bonded to each other to form a ring, provided that when R q2 and R q3 are bonded to form a ring, =CR q2 R q3 does not have the same structure as Q1 .
R 1 and R 2 each represent a hydrogen atom or a substituent.
X 1 to X 4 each independently represent —S—, —NR X1 — or —SO 2 —, where R X1 represents a hydrogen atom or an alkyl group.

 上記式(Q-1)中、*は結合手を示し、R101及びR102は、水素原子、アルキル基、アラルキル基、アリール基、複素環基又はエチレン性不飽和結合を有する重合性基を含む基を示す。
 ただし、R101及びR102のいずれか一方が水素原子である場合、他方はアルキル基、アラルキル基、アリール基、複素環基又はエチレン性不飽和結合を有する重合性基を含む基であり、
 R101及びR102のいずれか一方がメチル基である場合、他方は水素原子、炭素数2以上のアルキル基、アラルキル基、アリール基、複素環基又はエチレン性不飽和結合を有する重合性基を含む基を示し、
 R101及びR102のいずれか一方がフェニル基である場合、他方は水素原子、アルキル基、アラルキル基、置換基を有するアリール基、複素環基又はエチレン性不飽和結合を有する重合性基を含む基を示す。
In the above formula (Q-1), * represents a bond, and R 101 and R 102 represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
provided that when either R 101 or R 102 is a hydrogen atom, the other is an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond;
When one of R 101 and R 102 is a methyl group, the other represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond,
When either R 101 or R 102 is a phenyl group, the other represents a hydrogen atom, an alkyl group, an aralkyl group, a substituted aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.

 一般式(B)中の各置換基の定義及び好ましい範囲については、特段の断りのない限り、国際公開第2023/100715号に記載の一般式(1)で表される化合物の各置換基に関する記載をそれぞれそのまま適用することができる。
 なかでも、本発明においては、上記一般式(B)で表される染料は、下記置換基の組み合わせからなる染料であることが好ましい。
 R101及びR102は、アルキル基又はアラルキル基であることが好ましく、炭素数2以上のアルキル基であることがより好ましい。
 Qは、=CRq2q3であって、Rq2とRq3は互いに結合してシクロプロパン環、シクロブタン環、シクロペンタン環又はシクロヘキサン環を形成していることが好ましく、シクロブタン間を形成していることがより好ましい。これらのRq2とRq3が互いに結合して形成される環は、1つ又は2つの=Oで置換されていることが好ましく、さらに置換ベンゼン環と縮合していてもよく、好ましい。
 R及びRは、-OC(=O)-Y11、-O-Y11又は-OC(=O)NRy11であることが好ましく、-OC(=O)-Y11であることがより好ましい。Y11はアルキル基が好ましく、分岐アルキル基がより好ましい。Ry11は水素原子又はアルキル基が好ましく、アルキル基がより好ましい。
 X~Xは、-S-であることが好ましい。
With regard to the definition and preferred range of each substituent in the general formula (B), unless otherwise specified, the descriptions regarding each substituent of the compound represented by the general formula (1) described in WO 2023/100715 can be applied as they are.
In particular, in the present invention, the dye represented by the above general formula (B) is preferably a dye having a combination of the following substituents.
R 101 and R 102 are preferably an alkyl group or an aralkyl group, and more preferably an alkyl group having 2 or more carbon atoms.
Q2 is =CR q2 R q3 , and R q2 and R q3 are preferably bonded to each other to form a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, more preferably a cyclobutane ring. The ring formed by bonding R q2 and R q3 to each other is preferably substituted with one or two =O groups, and may further be fused with a substituted benzene ring, which is preferable.
R 1 and R 2 are preferably —OC(═O)—Y 11 , —O—Y 11 or —OC(═O)NR y11 , and more preferably —OC(═O)—Y 11. Y 11 is preferably an alkyl group, and more preferably a branched alkyl group. R y11 is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
X 1 to X 4 are preferably —S—.

 また、上記染料Aとしては、銅、マグネシウム、亜鉛、コバルト、チタン、鉄、バナジウム又は酸化バナジウムを中心金属として含む、下記一般式(7)で表されるポルフィリン系色素も好ましく挙げられる。 Furthermore, preferred examples of the dye A include porphyrin dyes represented by the following general formula (7), which contain copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide as a central metal.

 上記式中、X~Xは、水素原子、ハロゲン原子、アルキル基、アルコキシ基、置換あるいは無置換のエテニル基、置換あるいは無置換のエチニル基、アリール基、アリールオキシ基、アリールオキシカルボニル基、アルキルチオ基、アリールチオ基又はアシル基を示す。
 なお、X~Xのうちの隣接する基は互いに結合して、置換している炭素原子と共に芳香環を形成していてもよい。
 R18~R21は、アリール基を示す。
 Mは、銅、マグネシウム、亜鉛、コバルト、チタン、鉄、バナジウム又は酸化バナジウムを示す。
 なお、上記式中において、紙面上、Mの上下に位置する窒素原子は、非共有電子対によってMに配位していることを示す。
In the above formula, X 1 to X 8 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted ethynyl group, an aryl group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or an acyl group.
Adjacent groups among X 1 to X 8 may be bonded to each other to form an aromatic ring together with the carbon atoms that substitute for them.
R 18 to R 21 each represent an aryl group.
M represents copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide.
In the above formula, the nitrogen atoms located above and below M on the paper indicate that they are coordinated to M via an unshared electron pair.

 X~Xとして採り得るハロゲン原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アリールオキシカルボニル基、アルキルチオ基、アリールチオ基及びアシル基については、前述の一般式(i)中のR17及びR18として採り得る置換基におけるハロゲン原子、アルキル基、アルコキシ基(脂肪族オキシ基における脂肪族基がアルキル基である形態として記載)、アリール基、アリールオキシ基、アリールオキシカルボニル基、アルキルチオ基(脂肪族チオ基における脂肪族基がアルキル基である形態として記載)、アリールチオ基及びアシル基の記載を適用することができる。
 X~Xとして採り得るアルキル基は置換基を有していてもよく、置換基で置換されたアルキル基としては、例えば、アラルキル基、ハロゲノアルキル基、アルコキシアルキル基、アリールオキシアルキル基、アラルキルオキシアルキル基、ハロゲノアルコキシアルキル基が挙げられる。これらの置換基で置換されたアルキル基における置換基(アリール基、ハロゲン原子、アルコキシ基、アリールオキシ基、アラルキルオキシ基、ハロゲノアルコキシ基)についても、前述の一般式(i)中のR17及びR18として採り得る置換基における対応する置換基又は前述の一般式(i)中のR17及びR18として採り得る置換基における対応する複数の置換基を組合わせてなる置換基の記載を適用することができる。
 X~Xとして採り得るアルコキシ基は置換基を有していてもよく、置換基で置換されたアルコキシ基としては、例えば、アラルキルオキシ基、ハロゲノアルコキシ基が挙げられる。これらの置換基で置換されたアルコキシ基における置換基(アリール基、ハロゲン原子)についても、前述の一般式(i)中のR17及びR18として採り得る置換基における対応する置換基の記載を適用することができる。
 X~Xとして採り得る置換エテニル基及び置換エチニル基が有し得る置換基としては、前述の一般式(P)中のR~Rとして採り得る置換基における置換基を適用することができる。
 R18~R21として採り得るアリール基については、前述の一般式(i)中のR17及びR18として採り得る置換基におけるアリール基の記載を適用することができる。
With regard to the halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, aryloxycarbonyl group, alkylthio group, arylthio group and acyl group which can be taken as X 1 to X 8 , the descriptions of the halogen atom, alkyl group, alkoxy group (described as a form in which the aliphatic group in an aliphatic oxy group is an alkyl group), aryl group, aryloxy group, aryloxycarbonyl group, alkylthio group (described as a form in which the aliphatic group in an aliphatic thio group is an alkyl group), arylthio group and acyl group in the substituents which can be taken as R 17 and R 18 in the above-mentioned general formula (i) can be applied.
The alkyl groups that can be taken as X 1 to X 8 may have a substituent, and examples of the alkyl group substituted with a substituent include an aralkyl group, a halogenoalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an aralkyloxyalkyl group, and a halogenoalkoxyalkyl group. With regard to the substituents in the alkyl groups substituted with these substituents (aryl group, halogen atom, alkoxy group, aryloxy group, aralkyloxy group, halogenoalkoxy group), the descriptions of the corresponding substituents in the substituents that can be taken as R 17 and R 18 in the above general formula (i) or the substituents formed by combining multiple corresponding substituents in the substituents that can be taken as R 17 and R 18 in the above general formula (i) can also be applied.
The alkoxy groups that can be taken as X 1 to X 8 may have a substituent, and examples of the alkoxy group substituted with a substituent include an aralkyloxy group and a halogenoalkoxy group. The same descriptions of the corresponding substituents in the substituents that can be taken as R 17 and R 18 in the general formula (i) above can also be applied to the substituents (aryl group, halogen atom) in the alkoxy group substituted with these substituents.
As the substituents which the substituted ethenyl group and substituted ethynyl group which can be taken as X 1 to X 8 can have, the substituents which can be taken as R 1 to R 6 in the above-mentioned general formula (P) can be applied.
The aryl groups that can be taken as R 18 to R 21 can be the same as those described above for the aryl groups in the substituents that can be taken as R 17 and R 18 in the general formula (i).

 中でも、X~Xは、水素原子、ハロゲン原子、炭素数1~10の直鎖アルキル基、炭素数3~10の分岐アルキル基、又は炭素数3~10の環状アルキル基であることが好ましい。 Among these, X 1 to X 8 are preferably a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms.

 また、一般式(7)で表されるポルフィリン系色素は、市販のものも何ら制限なく使用することができ、例えば、東京化成工業社、山田化学工業社等が販売する、染料Aとしての主吸収波長帯域を満たすポルフィリン化合物を使用することができる。例えば、後述の実施例で使用するFDB-002(商品名、山田化学工業社製)は、一般式(7)で表されるポルフィリン系色素に該当する。 Furthermore, commercially available porphyrin dyes represented by general formula (7) can be used without any restrictions. For example, porphyrin compounds that satisfy the main absorption wavelength band of dye A, sold by Tokyo Chemical Industry Co., Ltd., Yamada Chemical Co., Ltd., etc., can be used. For example, FDB-002 (trade name, manufactured by Yamada Chemical Co., Ltd.) used in the examples described below corresponds to a porphyrin dye represented by general formula (7).

 染料Aとしては、上記一般式(A1)で表される色素、上記一般式(7)で表されるポルフィリン系色素及び上記一般式(B)で表される色素の他に、特開平5-53241号公報の段落0012~0067に記載の化合物、及び、特許第2707371号公報の段落0011~0076に記載の化合物も、好ましく使用することができる。 As dye A, in addition to the dye represented by the above general formula (A1), the porphyrin dye represented by the above general formula (7), and the dye represented by the above general formula (B), the compounds described in paragraphs 0012 to 0067 of JP-A No. 5-53241 and the compounds described in paragraphs 0011 to 0076 of Japanese Patent No. 2707371 can also be preferably used.

(染料B、染料C)
 染料Bは、積層体I及び積層体II中で波長480~520nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
 また、染料Cは、積層体I及び積層体II中で波長560~610nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
 なお、染料Bが主吸収波長帯域を有する波長範囲は、485~520nmが好ましく、490~520nmがより好ましく、490~515nmが更に好ましい。
 なお、染料Cが主吸収波長帯域を有する波長範囲は、580~615nmが好ましく、580~610nmがより好ましく、580~610nmが更に好ましい。
(Dye B, Dye C)
There are no particular limitations on the dye B, so long as it has a main absorption wavelength band in the wavelength range of 480 to 520 nm in the laminate I and laminate II, and various dyes can be used.
Furthermore, dye C is not particularly limited as long as it has a main absorption wavelength band in the wavelength range of 560 to 610 nm in the laminate I and laminate II, and various dyes can be used.
The wavelength range in which dye B has its main absorption wavelength band is preferably 485 to 520 nm, more preferably 490 to 520 nm, and even more preferably 490 to 515 nm.
The wavelength range in which dye C has its main absorption wavelength band is preferably 580 to 615 nm, more preferably 580 to 610 nm, and even more preferably 580 to 610 nm.

 染料Bの具体例としては、例えば、ピロールメチン(pyrrole methine、PM)系、ローダミン(rhodamine、RH)系、ボロンジピロメテン(boron dipyrromethene、BODIPY)系及びスクアライン(squaraine、SQ)系の各色素(染料)が挙げられる。
 染料Cの具体例としては、例えば、テトラアザポルフィリン(tetraaza porphyrin、TAP)系、スクアライン系及びシアニン(cyanine、CY)系の各色素(染料)が挙げられる。
Specific examples of dye B include pyrrole methine (PM)-based, rhodamine (RH)-based, boron dipyrromethene (BODIPY)-based, and squaraine (SQ)-based pigments (dyes).
Specific examples of dye C include tetraazaporphyrin (TAP)-based, squaraine-based, and cyanine (CY)-based pigments (dyes).

 これらの中でも、上記の染料B及び染料Cとしては、主吸収波長帯域における吸収波形が先鋭である点から、スクアライン系色素が好ましく、下記一般式(1)で表されるスクアライン系色素がより好ましい。染料B及び染料Cとして上記の通り吸収波形が先鋭な色素を使用することにより、上述の関係式(I)及び(II)を好ましいレベルで満たすことができ、OLED表示装置の画像本来の色味をより優れたレベルで保持することができる。
 すなわち、上記波長選択吸収層は、上記色味変化の抑制の観点から、染料B及び染料Cの少なくとも一方がスクアライン系色素(好ましくは、下記一般式(1)で表されるスクアライン系色素)であることが好ましく、染料B及び染料Cの両方がスクアライン系色素(好ましくは、下記一般式(1)で表されるスクアライン系色素)であることがより好ましい。
Among these, squaraine dyes are preferred as dye B and dye C because they have sharp absorption waveforms in the main absorption wavelength band, and squaraine dyes represented by the following general formula (1) are more preferred. By using dyes with sharp absorption waveforms as dye B and dye C, the above-mentioned relational expressions (I) and (II) can be satisfied at a preferred level, and the original color of the image of the OLED display device can be maintained at an excellent level.
That is, from the viewpoint of suppressing the color change, it is preferable that at least one of dye B and dye C in the wavelength selective absorption layer is a squaraine dye (preferably, a squaraine dye represented by the following general formula (1)), and it is more preferable that both dye B and dye C are squaraine dyes (preferably, squaraine dyes represented by the following general formula (1)).

 一般式(1)中、A及びBは、各々独立して、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、又は-CH=Gを示す。Gは置換基を有していてもよい複素環基を示す。 In general formula (1), A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G. G represents a heterocyclic group which may have a substituent.

 一般式(1)中の各置換基の定義及び好ましい範囲については、特段の断りのない限り、国際公開第2021/221122号の段落[0073]~[0095]、[0099]及び[0100]に記載の一般式(1)で表される色素の各置換基に関する記載をそれぞれそのまま適用することができる。 Unless otherwise specified, the definitions and preferred ranges of each substituent in general formula (1) can be directly applied to the descriptions of each substituent in the dye represented by general formula (1) in paragraphs [0073] to [0095], [0099], and [0100] of WO 2021/221122.

 上記一般式(1)で表される色素の好ましい1実施形態として、下記一般式(2)で表される色素が挙げられる。 A preferred embodiment of the dye represented by the above general formula (1) is a dye represented by the following general formula (2):

 一般式(2)中、Aは、一般式(1)中のAと同様である。中でも、含窒素5員環である複素環基が好ましい。 In the general formula (2), A 1 is the same as A in the general formula (1). Among them, a nitrogen-containing five-membered heterocyclic group is preferred.

 一般式(2)において、R及びRは、各々独立に、水素原子又は置換基を示す。RとRはそれぞれ同一であっても異なっていてもよく、また互いに結合して環を形成してもよい。
 R及びRとして採りうる置換基としては、特に制限はないが、例えば、アルキル基(メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t-ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、トリフルオロメチル基等)、シクロアルキル基(シクロペンチル基、シクロヘキシル基等)、アルケニル基(ビニル基、アリル基等)、アルキニル基(エチニル基、プロパルギル基等)、アリール基(フェニル基、ナフチル基等)、ヘテロアリール基(フリル基、チエニル基、ピリジル基、ピリダジル基、ピリミジル基、ピラジル基、トリアジル基、イミダゾリル基、ピラゾリル基、チアゾリル基、ベンゾイミダゾリル基、ベンゾオキサゾリル基、キナゾリル基、フタラジル基等)、ヘテロ環基(複素環基とも呼び、例えば、ピロリジル基、イミダゾリジル基、モルホリル基、オキサゾリジル基等)、アルコキシ基(メトキシ基、エトキシ基、プロピルオキシ基等)、シクロアルコキシ基(シクロペンチルオキシ基、シクロヘキシルオキシ基等)、アリールオキシ基(フェノキシ基、ナフチルオキシ基等)、ヘテロアリールオキシ基(芳香族ヘテロ環オキシ基)、アルキルチオ基(メチルチオ基、エチルチオ基、プロピルチオ基等)、シクロアルキルチオ基(シクロペンチルチオ基、シクロヘキシルチオ基等)、アリールチオ基(フェニルチオ基、ナフチルチオ基等)、ヘテロアリールチオ基(芳香族ヘテロ環チオ基)、アルコキシカルボニル基(メチルオキシカルボニル基、エチルオキシカルボニル基、ブチルオキシカルボニル基、オクチルオキシカルボニル基等)、アリールオキシカルボニル基(フェニルオキシカルボニル基、ナフチルオキシカルボニル基等)、ホスホリル基(ジメトキシホスホニル、ジフェニルホスホリル)、スルファモイル基(アミノスルホニル基、メチルアミノスルホニル基、ジメチルアミノスルホニル基、ブチルアミノスルホニル基、シクロヘキシルアミノスルホニル基、オクチルアミノスルホニル基、フェニルアミノスルホニル基、2-ピリジルアミノスルホニル基等)、アシル基(アセチル基、エチルカルボニル基、プロピルカルボニル基、シクロヘキシルカルボニル基、オクチルカルボニル基、2-エチルヘキシルカルボニル基、フェニルカルボニル基、ナフチルカルボニル基、ピリジルカルボニル基等)、アシルオキシ基(アセチルオキシ基、エチルカルボニルオキシ基、ブチルカルボニルオキシ基、オクチルカルボニルオキシ基、フェニルカルボニルオキシ基等)、アミド基(メチルカルボニルアミノ基、エチルカルボニルアミノ基、ジメチルカルボニルアミノ基、プロピルカルボニルアミノ基、ペンチルカルボニルアミノ基、シクロヘキシルカルボニルアミノ基、2-エチルヘキシルカルボニルアミノ基、オクチルカルボニルアミノ基、ドデシルカルボニルアミノ基、フェニルカルボニルアミノ基、ナフチルカルボニルアミノ基等)、スルホニルアミド基(メチルスルホニルアミノ基、オクチルスルホニルアミノ基、2-エチルヘキシルスルホニルアミノ基、トリフルオロメチルスルホニルアミノ基等)、カルバモイル基(アミノカルボニル基、メチルアミノカルボニル基、ジメチルアミノカルボニル基、プロピルアミノカルボニル基、ペンチルアミノカルボニル基、シクロヘキシルアミノカルボニル基、オクチルアミノカルボニル基、2-エチルヘキシルアミノカルボニル基、ドデシルアミノカルボニル基、フェニルアミノカルボニル基、ナフチルアミノカルボニル基、2-ピリジルアミノカルボニル基等)、ウレイド基(メチルウレイド基、エチルウレイド基、ペンチルウレイド基、シクロヘキシルウレイド基、オクチルウレイド基、ドデシルウレイド基、フェニルウレイド基、ナフチルウレイド基、2-ピリジルアミノウレイド基等)、アルキルスルホニル基(メチルスルホニル基、エチルスルホニル基、ブチルスルホニル基、シクロヘキシルスルホニル基、2-エチルヘキシルスルホニル基等)、アリールスルホニル基(フェニルスルホニル基、ナフチルスルホニル基、2-ピリジルスルホニル基等)、アミノ基(アミノ基、エチルアミノ基、ジメチルアミノ基、ブチルアミノ基、ジブチルアミノ基、シクロペンチルアミノ基、2-エチルヘキシルアミノ基、ドデシルアミノ基、アニリノ基、ナフチルアミノ基、2-ピリジルアミノ基等)、アルキルスルホニルオキシ基(メタンスルホニルオキシ)、シアノ基、ニトロ基、ハロゲン原子(フッ素原子、塩素原子、臭素原子等)、ヒドロキシ基等が挙げられる。
 中でも、アルキル基、アルケニル基、アリール基又はヘテロアリール基が好ましく、アルキル基、アリール基又はヘテロアリール基がより好ましく、アルキル基がさらに好ましい。
In general formula (2), R1 and R2 each independently represent a hydrogen atom or a substituent. R1 and R2 may be the same or different, and may be bonded to each other to form a ring.
The substituents that can be taken as R1 and R2 are not particularly limited, and examples thereof include alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.), heteroaryl groups (furyl, thienyl, pyridyl, pyridyl, etc.), a pyridyl group, a pyrimidyl group, a pyrazyl group, a triazyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a quinazolyl group, a phthalazyl group, etc.), a heterocyclic group (also called a heterocyclic group, for example, a pyrrolidyl group, an imidazolidyl group, a morpholyl group, an oxazolidyl group, etc.), an alkoxy group (a methoxy group, an ethoxy group, a propyloxy group, etc.), a cycloalkoxy group (a cyclopentyloxy group, a cyclohexyloxy group, etc.), an aryloxy group (a phenoxy group, a naphthyloxy group, etc.), a heteroaryl group arylthio groups (aromatic heterocyclic oxy groups), alkylthio groups (methylthio, ethylthio, propylthio, etc.), cycloalkylthio groups (cyclopentylthio, cyclohexylthio, etc.), arylthio groups (phenylthio, naphthylthio, etc.), heteroarylthio groups (aromatic heterocyclic thio groups), alkoxycarbonyl groups (methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl groups (phenyloxycarbonyl, naphthylthio, etc.), a hydroxycarbonyl group, etc.), a phosphoryl group (dimethoxyphosphonyl, diphenylphosphoryl), a sulfamoyl group (aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), an acyl group (acetyl group, ethylcarbonyl group, propylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group, etc.), amido group (methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecyl carbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), sulfonylamide group (methylsulfonylamino group, octylsulfonylamino group, 2-ethylhexylsulfonylamino group, trifluoromethylsulfonylamino group, etc.), carbamoyl group (aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, an aminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc.), an ureido group (a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, an octylureido group, a dodecylureido group, a phenylureido group, a naphthylureido group, a 2-pyridylaminoureido group, etc.), an alkylsulfonyl group (a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl ... group, etc.), arylsulfonyl groups (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino groups (amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), alkylsulfonyloxy groups (methanesulfonyloxy), cyano group, nitro group, halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, etc.
Among these, an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group is preferred, an alkyl group, an aryl group, or a heteroaryl group is more preferred, and an alkyl group is even more preferred.

 R及びRとして採りうる置換基はさらに置換基を有していてもよい。さらに有していてもよい置換基としては、R及びRとして採りうる上記置換基、及び、前述の一般式(1)におけるA、B及びGが有してもよい置換基X(国際公開第2021/221122号の段落[0079]~[0095]に記載の置換基X)が挙げられる。また、RとRとは互いに結合して環を形成してもよく、R又はRと、B又はBが有する置換基とは結合して環を形成してもよい。
 このとき形成される環としてはヘテロ環又はヘテロアリール環が好ましく、形成される環の大きさは特に制限されないが、5員環又は6員環であることが好ましい。また、形成される環の数は特に限定されず、1個であってもよく、2個以上であってもよい。2個以上の環が形成される形態としては、例えば、RとBが有する置換基、及び、RとBが有する置換基とがそれぞれ結合して2個の環を形成する形態が挙げられる。
The substituents that can be taken as R 1 and R 2 may further have a substituent. Examples of the substituents that may further have include the above-mentioned substituents that can be taken as R 1 and R 2 , and the substituent X that A, B, and G in the above-mentioned general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122). In addition, R 1 and R 2 may be bonded to each other to form a ring, and R 1 or R 2 and the substituents that B 2 or B 3 have may be bonded to form a ring.
The ring formed in this case is preferably a heterocycle or heteroaryl ring, and the size of the ring formed is not particularly limited, but is preferably a 5-membered or 6-membered ring. The number of rings formed is also not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include a form in which the substituents carried by R1 and B2 , and the substituents carried by R2 and B3, are bonded to each other to form two rings.

 一般式(2)において、B、B、B及びBは、各々独立に、炭素原子又は窒素原子を示す。B、B、B及びBを含む環は芳香環である。B~Bのうち、少なくとも2つ以上は炭素原子であることが好ましく、B~Bの全てが炭素原子であることがより好ましい。
 B~Bとして採りうる炭素原子は、水素原子又は置換基を有する。B~Bとして採りうる炭素原子のうち、置換基を有する炭素原子の数は、特に制限されないが、0、1又は2であることが好ましく、1であることがより好ましい。特に、B及びBが炭素原子であって、少なくとも一方が置換基を有することが好ましい。
 B~Bとして採りうる炭素原子が有する置換基としては、特に制限されず、R及びRとして採りうる上記置換基が挙げられる。中でも、好ましくは、アルキル基、アルコキシ基、アルコキシカルボニル基、アリール基、アシル基、アミド基、スルホニルアミド基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、アミノ基、シアノ基、ニトロ基、ハロゲン原子又はヒドロキシ基であり、より好ましくは、アルキル基、アルコキシ基、アルコキシカルボニル基、アリール基、アシル基、アミド基、スルホニルアミド基、カルバモイル基、アミノ基、シアノ基、ニトロ基、ハロゲン原子又はヒドロキシ基である。
 B~Bとして採り得る炭素原子が有する置換基は、さらに置換基を有していてもよい。このさらに有していてもよい置換基としては、前述の一般式(2)におけるR及びRがさらに有してもよい置換基、及び、前述の一般式(1)におけるA、B及びGが有してもよい置換基X(国際公開第2021/221122号の段落[0079]~[0095]に記載の置換基X)が挙げられる。
In general formula (2), B 1 , B 2 , B 3 and B 4 each independently represent a carbon atom or a nitrogen atom. A ring including B 1 , B 2 , B 3 and B 4 is an aromatic ring. It is preferred that at least two of B 1 to B 4 are carbon atoms, and it is more preferred that all of B 1 to B 4 are carbon atoms.
The carbon atoms which can be taken as B 1 to B 4 have a hydrogen atom or a substituent. Of the carbon atoms which can be taken as B 1 to B 4 , the number of carbon atoms which have a substituent is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1. In particular, it is preferable that B 1 and B 4 are carbon atoms and at least one of them has a substituent.
The substituents that the carbon atoms that can be taken as B 1 to B 4 have are not particularly limited, and examples include the above-mentioned substituents that can be taken as R 1 and R 2. Among these, preferred are alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amido groups, sulfonylamido groups, carbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups, and more preferred are alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amido groups, sulfonylamido groups, carbamoyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups.
The substituents possessed by the carbon atoms that can be taken as B 1 to B 4 may further have a substituent. Examples of the substituents that may further be possessed include the substituents that may be further possessed by R 1 and R 2 in the general formula (2) described above, and the substituent X that may be possessed by A, B, and G in the general formula (1) described above (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).

 B及びBとして採りうる炭素原子が有する置換基としては、アルキル基、アルコキシ基、ヒドロキシ基、アミド基、スルホニルアミド基又はカルバモイル基がさらに好ましく、特に好ましくは、アルキル基、アルコキシ基、ヒドロキシ基、アミド基又はスルホニルアミド基が挙げられ、最も好ましくは、ヒドロキシ基、アミド基又はスルホニルアミド基である。
 B及びBとして採りうる炭素原子が有する置換基としては、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アミノ基、シアノ基、ニトロ基又はハロゲン原子がさらに好ましく、いずれか一方の置換基が電子吸引性基(例えば、アルコキシカルボニル基、アシル基、シアノ基、ニトロ基又はハロゲン原子)であることが特に好ましい。
The substituents that can be taken by the carbon atoms represented by B1 and B4 are more preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, a sulfonylamido group, or a carbamoyl group, particularly preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, or a sulfonylamido group, and most preferably a hydroxy group, an amide group, or a sulfonylamido group.
The substituents that the carbon atoms that can be taken as B2 and B3 have are more preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an amino group, a cyano group, a nitro group, or a halogen atom, and it is particularly preferred that either one of the substituents is an electron-withdrawing group (for example, an alkoxycarbonyl group, an acyl group, a cyano group, a nitro group, or a halogen atom).

 上記一般式(2)で表される色素は、下記一般式(3)、一般式(4)及び一般式(5)のいずれかで表される色素であることが好ましい。 The dye represented by the above general formula (2) is preferably a dye represented by any of the following general formulas (3), (4), and (5):

 一般式(3)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(2)におけるR及びRと同義であり、好ましい範囲も同じである。
 一般式(3)において、B~Bは、各々独立に、炭素原子又は窒素原子を示し、上記一般式(2)におけるB~Bと同義であり、好ましい範囲も同じである。
In formula (3), R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
In formula (3), B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.

 一般式(3)において、R及びRは、各々独立に、水素原子又は置換基を示す。R及びRとして採りうる置換基としては、特に制限されず、上記R及びRとして採りうる置換基と同じものを挙げることができる。
 ただし、Rとして採りうる置換基は、アルキル基、アルコキシ基、アミノ基、アミド基、スルホニルアミド基、シアノ基、ニトロ基、アリール基、ヘテロアリール基、ヘテロ環基、アルコキシカルボニル基、カルバモイル基又はハロゲン原子が好ましく、アルキル基、アリール基又はアミノ基がより好ましく、アルキル基がさらに好ましい。
 Rとして採りうる置換基としては、アルキル基、アリール基、ヘテロアリール基、ヘテロ環基、アルコキシ基、アルコキシカルボニル基、アシル基、アシルオキシ基、アミド基、カルバモイル基、アミノ基又はシアノ基が好ましく、アルキル基、アルコキシカルボニル基、アシル基、カルバモイル基又はアリール基がより好ましく、アルキル基がさらに好ましい。
In general formula (3), R3 and R4 each independently represent a hydrogen atom or a substituent. The substituents that can be taken as R3 and R4 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
However, the substituent that can be taken as R3 is preferably an alkyl group, an alkoxy group, an amino group, an amido group, a sulfonylamido group, a cyano group, a nitro group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom, more preferably an alkyl group, an aryl group, or an amino group, and still more preferably an alkyl group.
The substituent that can be taken as R4 is preferably an alkyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a carbamoyl group, an amino group, or a cyano group, more preferably an alkyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or an aryl group, and still more preferably an alkyl group.

 R及びRとして採りうるアルキル基は、直鎖状、分岐状及び環状のいずれであってもよいが、直鎖状又は分岐状が好ましい。アルキル基の炭素数は、1~12が好ましく、1~8がより好ましい。アルキル基の例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、t-ブチル基、2-エチルヘキシル基、シクロヘキシル基が好ましく、メチル基、t-ブチル基がより好ましい。 The alkyl group that can be taken as R3 and R4 may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 8. Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group, and more preferably a methyl group or a t-butyl group.

 一般式(4)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(2)におけるR及びRと同義であり、好ましい範囲も同じである。
 一般式(4)において、B~Bは、各々独立に、炭素原子又は窒素原子を示し、上記一般式(2)におけるB~Bと同義であり、好ましい範囲も同じである。
In formula (4), R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
In formula (4), B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.

 一般式(4)において、R及びRは、各々独立に、水素原子又は置換基を示す。R及びRとして採りうる置換基としては、特に制限されず、上記R及びRとして採りうる置換基と同じものを挙げることができる。
 ただし、Rとして採りうる置換基は、アルキル基、アルコキシ基、アリールオキシ基、アミノ基、シアノ基、アリール基、ヘテロアリール基、ヘテロ環基、アシル基、アシルオキシ基、アミド基、スルホニルアミド基、ウレイド基又はカルバモイル基が好ましく、アルキル基、アルコキシ基、アシル基、アミド基又はアミノ基がより好ましく、アルキル基がさらに好ましい。
 Rとして採りうるアルキル基は、一般式(3)におけるRとして採りうるアルキル基と同義であり、好ましい範囲も同じである。
In general formula (4), R5 and R6 each independently represent a hydrogen atom or a substituent. The substituents that can be taken as R5 and R6 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
However, the substituent that can be taken as R5 is preferably an alkyl group, an alkoxy group, an aryloxy group, an amino group, a cyano group, an aryl group, a heteroaryl group, a heterocyclic group, an acyl group, an acyloxy group, an amido group, a sulfonylamido group, a ureido group, or a carbamoyl group, more preferably an alkyl group, an alkoxy group, an acyl group, an amido group, or an amino group, and still more preferably an alkyl group.
The alkyl group that can be taken as R5 has the same meaning as the alkyl group that can be taken as R3 in general formula (3), and the preferred range is also the same.

 一般式(4)において、Rとして採りうる置換基は、アルキル基、アルケニル基、アリール基、ヘテロアリール基、ヘテロ環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシル基、アシルオキシ基、アミド基、スルホニルアミド基、アルキルスルホニル基、アリールスルホニル基、カルバモイル基、アミノ基、シアノ基、ニトロ基又はハロゲン原子が好ましく、アルキル基、アリール基、ヘテロアリール基又はヘテロ環基がより好ましく、アルキル基又はアリール基がさらに好ましい。
 Rとして採りうるアルキル基は、一般式(3)におけるRとして採りうるアルキル基と同義であり、好ましい範囲も同じである。
 Rとして採りうるアリール基は、炭素数6~12のアリール基が好ましく、フェニル基がより好ましい。このアリール基は置換基を有していてもよく、このような置換基としては、以下の置換基群Bに含まれる基が挙げられ、特に、炭素数1~10のアルキル基、スルホニル基、アミノ基、アシルアミノ基、スルホニルアミノ基等が好ましい。これらの置換基は、さらに置換基を有していてもよい。具体的に、置換基はアルキルスルホニルアミノ基が好ましい。
In general formula (4), the substituent that can be taken as R6 is preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a sulfonylamido group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an amino group, a cyano group, a nitro group, or a halogen atom, more preferably an alkyl group, an aryl group, a heteroaryl group, or a heterocyclic group, and still more preferably an alkyl group or an aryl group.
The alkyl group that can be taken as R6 has the same meaning as the alkyl group that can be taken as R4 in general formula (3), and the preferred range is also the same.
The aryl group that can be taken as R6 is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. This aryl group may have a substituent, and examples of such a substituent include groups included in the following substituent group B, with alkyl groups having 1 to 10 carbon atoms, sulfonyl groups, amino groups, acylamino groups, sulfonylamino groups, and the like being particularly preferred. These substituents may further have a substituent. Specifically, the substituent is preferably an alkylsulfonylamino group.

 - 置換基群B -
 ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アミノオキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、スルホニルアミノ基(アルキル若しくはアリールスルホニルアミノ基を含む)、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキル若しくはアリールスルフィニル基、スルホニル基(アルキル若しくはアリールスルホニル基を含む)、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基等。
- Substituent group B -
Examples of such groups include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an aminooxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a sulfonylamino group (including an alkyl or arylsulfonylamino group), a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, a sulfonyl group (including an alkyl or arylsulfonyl group), an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

 一般式(5)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(2)におけるR及びRと同義であり、好ましい範囲も同じである。
 一般式(5)において、B~Bは、各々独立に、炭素原子又は窒素原子を示し、上記一般式(2)におけるB~Bと同義であり、好ましい範囲も同じである。
In formula (5), R 1 and R 2 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 1 and R 2 in formula (2) above, and the preferred ranges are also the same.
In formula (5), B 1 to B 4 each independently represent a carbon atom or a nitrogen atom, and have the same meaning as B 1 to B 4 in formula (2) above, and the preferred ranges are also the same.

 一般式(5)において、R及びRは、各々独立に、水素原子又は置換基を示す。R及びRとして採りうる置換基としては、特に制限されず、上記R及びRとして採りうる置換基と同じものを挙げることができる。
 ただし、Rとして採りうる置換基の、好ましい範囲、より好ましい範囲及びさらに好ましい範囲は、一般式(4)におけるRとして採りうる置換基と同じである。Rとして採りうるアルキル基は、上記Rとして採りうるアルキル基と同義であり、好ましい範囲も同じである。
In general formula (5), R7 and R8 each independently represent a hydrogen atom or a substituent. The substituents that can be taken as R7 and R8 are not particularly limited, and examples thereof include the same substituents that can be taken as the above-mentioned R1 and R2 .
However, the preferred range, more preferred range, and even more preferred range of the substituent that can be taken as R7 are the same as the substituent that can be taken as R5 in general formula (4). The alkyl group that can be taken as R5 has the same definition as the alkyl group that can be taken as the above-mentioned R3 , and the preferred range is also the same.

 一般式(5)において、Rとして採りうる置換基の、好ましい範囲、より好ましい範囲及びさらに好ましい範囲は、一般式(4)におけるRとして採りうる置換基と同じである。Rとして採りうるアルキル基及びアリール基の好ましい範囲は、上記一般式(4)におけるRとして採りうるアルキル基及びアリール基と同義であり、好ましい範囲も同じである。 In general formula (5), the preferred range, more preferred range, and even more preferred range of the substituent that can be taken as R8 are the same as the substituent that can be taken as R6 in general formula (4). The preferred range of the alkyl group and aryl group that can be taken as R8 are the same as the alkyl group and aryl group that can be taken as R6 in general formula (4) above, and the preferred ranges are also the same.

 上記スクアライン系色素としては、一般式(1)~(5)のいずれかで表されるスクアライン色素であれば、特に制限なく使用することができる。その例として、例えば、特開2006-160618号公報、国際公開第2004/005981号、国際公開第2004/007447号、Dyes and Pigment,2001,49,p.161-179、国際公開第2008/090757号、国際公開第2005/121098号、特開2008-275726号公報に記載の化合物を挙げられる。 The squaraine dye can be any squaraine dye represented by any of the general formulas (1) to (5) and is not particularly limited. Examples include the compounds described in JP-A-2006-160618, WO-2004/005981, WO-2004/007447, Dyes and Pigment, 2001, 49, pp. 161-179, WO-2008/090757, WO-2005/121098, and JP-A-2008-275726.

 一般式(1)~(5)のいずれかで表される色素の具体例としては、国際公開第2021/221122号の段落[0119]~[0122]に記載の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。
 また、上記具体例の他に、一般式(3)~(5)のいずれかで表される色素の具体例としては、国際公開第2021/221122号の段落[0124]~[0132]に記載の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。
Specific examples of the dyes represented by any of the general formulas (1) to (5) include the compounds described in paragraphs [0119] to [0122] of WO 2021/221122. However, the present invention is not limited to these.
In addition to the above specific examples, specific examples of the dyes represented by any of the general formulas (3) to (5) include the compounds described in paragraphs [0124] to [0132] of WO 2021/221122. However, the present invention is not limited to these.

 上記一般式(1)で表される色素の好ましい1実施形態として、下記一般式(6)で表される色素が挙げられる。 A preferred embodiment of the dye represented by the above general formula (1) is a dye represented by the following general formula (6):

 一般式(6)中、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(3)におけるR及びRと同義であり、好ましいものも同じである。
 一般式(6)中、Aは、一般式(1)中のAと同様である。中でも、含窒素5員環である複素環基が好ましい。
In the general formula (6), R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meanings and preferred values as R3 and R4 in the general formula (3) above.
In the general formula (6), A2 is the same as A in the general formula (1). Among them, a nitrogen-containing five-membered heterocyclic group is preferred.

 上記一般式(6)で表される色素は、下記一般式(7)、一般式(8)及び一般式(9)のいずれかで表される色素であることが好ましい。 The dye represented by the above general formula (6) is preferably a dye represented by any of the following general formulas (7), (8), and (9):

 一般式(7)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(3)におけるR及びRと同義であり、好ましい範囲も同じである。2つのR及び2つRは、それぞれ、同一でも異なっていてもよい。 In general formula (7), R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meanings and preferred ranges as R3 and R4 in general formula (3). Two R3s and two R4s may be the same or different.

 一般式(8)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(3)におけるRと同義であり、好ましい範囲も同じである。
 一般式(8)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(4)におけるR及びRと同義であり、好ましい範囲も同じである。
In formula (8), R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meaning as R3 in formula (3) above, and the preferred range is also the same.
In formula (8), R5 and R6 each independently represent a hydrogen atom or a substituent, and have the same meanings as R5 and R6 in formula (4) above, and the preferred ranges are also the same.

 一般式(9)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(3)におけるRと同義であり、好ましい範囲も同じである。
 一般式(9)において、R及びRは、各々独立に、水素原子又は置換基を示し、上記一般式(5)におけるR及びRと同義であり、好ましい範囲も同じである。
In formula (9), R3 and R4 each independently represent a hydrogen atom or a substituent, and have the same meaning as R3 in formula (3) above, and the preferred range is also the same.
In formula (9), R 7 and R 8 each independently represent a hydrogen atom or a substituent, and have the same meanings as R 7 and R 8 in formula (5) above, and the preferred ranges are also the same.

 本発明においては、染料Bとしてスクアライン系色素を用いる場合、スクアライン系色素としては、一般式(6)~(9)のいずれかで表されるスクアライン系色素であれば、特に制限なく使用することができる。その例として、例えば特開2002-97383号公報及び特開2015-68945号公報に記載の化合物を挙げることができる。
 一般式(6)~(9)のいずれかで表されるスクアライン系色素の具体例としては、国際公開第2021/221122号の[0145]~[0148]に記載の化合物が挙げられる。ただし、本発明はこれらに限定されるものではない。
In the present invention, when a squaraine dye is used as dye B, any squaraine dye represented by any of general formulas (6) to (9) can be used without any particular limitation. Examples of squaraine dyes include the compounds described in JP-A-2002-97383 and JP-A-2015-68945.
Specific examples of the squaraine dyes represented by any of general formulas (6) to (9) include the compounds described in paragraphs [0145] to [0148] of WO 2021/221122. However, the present invention is not limited to these.

(消光剤内蔵型色素)
 上記一般式(1)で表されるスクアライン系色素は、連結基を介して、共有結合により消光剤部が色素に連結されてなる、消光剤内蔵型色素であってもよい。上記消光剤内蔵型色素も、染料B及びCの少なくとも一方の色素として好ましく用いることができる。すなわち、上記消光剤内蔵型色素は、主吸収波長帯域を有する波長に応じて、染料B又は染料Cとして計上する。
 上記消光剤部としては、例えば、上述の置換基X(国際公開第2021/221122号の段落[0079]~[0095]に記載の置換基X)におけるフェロセニル基が挙げられる。また、国際公開第2019/066043号の段落[0199]~[0212]および段落[0234]~[0310]に記載の消光剤化合物における消光剤部を挙げることができる。
(dye with built-in quencher)
The squaraine dye represented by the general formula (1) may be a quencher-containing dye in which a quencher moiety is covalently linked to the dye via a linking group. The quencher-containing dye can also be preferably used as at least one of dyes B and C. That is, the quencher-containing dye is counted as dye B or dye C depending on the wavelength of its main absorption wavelength band.
Examples of the quencher moiety include the ferrocenyl group in the above-mentioned substituent X (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122). Further examples include the quencher moiety in the quencher compound described in paragraphs [0199] to [0212] and paragraphs [0234] to [0310] of WO 2019/066043.

 一般式(1)で表されるスクアライン系色素のうち、消光剤内蔵型色素に該当する色素の具体例としては、国際公開第2021/221122号の[0151]~[0167]に記載の化合物並びに下記化合物(C-121)及び(C-122)が挙げられる。ただし、本発明はこれらに限定されるものではない。 Specific examples of squaraine dyes represented by general formula (1) that fall under the category of dyes with built-in quenchers include the compounds described in paragraphs [0151] to [0167] of WO 2021/221122 and the following compounds (C-121) and (C-122). However, the present invention is not limited to these.

 下記一般式(8)で表されるテトラアザポルフィリン系色素も上記染料Cとして好ましい。 Tetraazaporphyrin dyes represented by the following general formula (8) are also preferred as dye C.

 式(8)中、Y~Yは各々独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、カルボキシ基、スルホン酸基、炭素数1~20の直鎖、分岐あるいは環状のアルキル基、炭素数1~20の直鎖、分岐あるいは環状のアルコキシ基、炭素数6~20のアリールオキシ基、炭素数1~20のモノアルキルアミノ基、炭素数2~20のジアルキルアミノ基、炭素数7~20のジアルキルアミノ基、炭素数7~20のアラルキル基、炭素数6~20のアリール基、ヘテロアリール基、炭素数6~20のアルキルチオ基、炭素数6~20のアリールチオ基を表し、連結基を介して芳香族環を除く環を形成しても良い。Mは2個の水素原子、2価の金属原子、2価の1置換金属原子、3価の置換金属原子、4価の置換金属原子、又は酸化金属原子を表す。 In formula (8), Y 1 to Y 8 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms, and may form a ring other than an aromatic ring via a linking group. M represents two hydrogen atoms, a divalent metal atom, a divalent mono-substituted metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom.

 一般式(8)で表されるテトラアザポルフィリン系色素は、市販のものを何ら制限なく使用することができ、例えば、東京化成工業株式会社、山田化学工業株式会社、山本化成株式会社等が市販するテトラアザポルフィリン系色素を使用できる。 The tetraazaporphyrin dye represented by general formula (8) can be any commercially available product and can be used without any restrictions. For example, tetraazaporphyrin dyes commercially available from Tokyo Chemical Industry Co., Ltd., Yamada Chemical Industry Co., Ltd., Yamamoto Chemical Industry Co., Ltd., etc. can be used.

(染料D)
 染料Dは、積層体I及び積層体II中で波長640~780nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
 なお、染料Dが主吸収波長帯域を有する波長範囲は、640~750nmが好ましく、645~700nmがより好ましい。
 染料Dの具体例としては、例えば、ポルフィリン系、スクアライン系、シアニン(cyanine、CY)系、インドアニリン系、アントラキノン系の各色素(染料)が挙げられる。
 スクアライン系色素としては、下記一般式(1)で表されるスクアライン系色素が好ましく挙げられる。
(Dye D)
There are no particular limitations on the dye D, so long as it has a main absorption wavelength band in the wavelength range of 640 to 780 nm in the laminate I and laminate II, and various dyes can be used.
The wavelength range in which dye D has its main absorption wavelength band is preferably 640 to 750 nm, and more preferably 645 to 700 nm.
Specific examples of the dye D include porphyrin-based, squaraine-based, cyanine (CY)-based, indoaniline-based, and anthraquinone-based pigments (dyes).
Preferred examples of the squaraine dye include squaraine dyes represented by the following general formula (1).

(一般式(1)表される色素) (Dye represented by general formula (1))

 一般式(1)中、A及びBが採りうる態様については、前述の染料B、染料Cにおいて記載する一般式(1)におけるA及びBの通りである。 In general formula (1), the possible forms that A and B can take are the same as those for A and B in general formula (1) described above for dye B and dye C.

 染料Dが一般式(1)で表される色素である場合、下記一般式(14)で表される色素であることが好ましい。 When dye D is a dye represented by general formula (1), it is preferably a dye represented by the following general formula (14):

 一般式(14)において、R及びRは、前述した一般式(2)におけるR及びRと同義である。また、R41及びR42も、前述した一般式(2)におけるR及びRと同義である。
 R、R、R41及びR42は、中でも、アルキル基、アルケニル基、アリール基又はヘテロアリール基が好ましく、アルキル基、アリール基又はヘテロアリール基がより好ましく、アルキル基又はアリール基がさらに好ましい。
 R、R、R41及びR42はさらに置換基を有していてもよい。さらに有していてもよい置換基としては、前述の一般式(2)におけるR及びRがさらに有してもよい置換基、及び、前述の一般式(1)におけるA、B及びGが有してもよい置換基X(国際公開第2021/221122号の段落[0079]~[0095]に記載の置換基X)が挙げられる。
In general formula (14), R1 and R2 have the same meanings as R1 and R2 in general formula (2). R41 and R42 also have the same meanings as R1 and R2 in general formula (2).
Among these, R 1 , R 2 , R 41 and R 42 are preferably an alkyl group, an alkenyl group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and further preferably an alkyl group or an aryl group.
R 1 , R 2 , R 41 and R 42 may further have a substituent. Examples of the substituent that may be further substituted include the substituent that R 1 and R 2 in the general formula (2) may have, and the substituent X that A, B and G in the general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).

 一般式(14)におけるB、B、BおよびBは、それぞれ、前述した一般式(2)におけるB、B、BおよびBと同義である。また、一般式(14)におけるB、B、BおよびBは、それぞれ、前述した一般式(2)におけるB、B、BおよびBと同義である。
 B、B、B、B、B、B、BおよびBとして採り得る炭素原子が有する置換基は、さらに置換基を有していてもよい。このさらに有していてもよい置換基としては、前述の一般式(1)におけるA、B及びGが有してもよい置換基X(国際公開第2021/221122号の段落[0079]~[0095]に記載の置換基X)が挙げられる。
B1 , B2 , B3 and B4 in general formula (14) are respectively defined as B1 , B2 , B3 and B4 in general formula (2) described above. Also, B5 , B6 , B7 and B8 in general formula (14) are respectively defined as B1 , B2 , B3 and B4 in general formula (2) described above.
The substituents on the carbon atoms that can be taken as B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , and B 8 may further have a substituent. Examples of the substituents that may further have include the substituent X that A, B, and G in the general formula (1) may have (the substituent X described in paragraphs [0079] to [0095] of WO 2021/221122).

 一般式(14)において、RとRとは互いに結合して環を形成してもよく、R又はRと、B又はBが有する置換基とは結合して環を形成してもよい。また、R41とR42とは互いに結合して環を形成してもよく、R41又はR42と、B又はBが有する置換基とは結合して環を形成してもよい。
 上記において、形成される環としてはヘテロ環又はヘテロアリール環が好ましく、形成される環の大きさは特に制限されないが、5員環又は6員環であることが好ましい。また、形成される環の数は特に限定されず、1個であってもよく、2個以上であってもよい。2個以上の環が形成される形態としては、例えば、RとBが有する置換基、及び、RとBが有する置換基とがそれぞれ結合して2個の環を形成する形態が挙げられる。
In general formula (14), R1 and R2 may be bonded to each other to form a ring, and R1 or R2 may be bonded to a substituent carried by B2 or B3 to form a ring. In addition, R41 and R42 may be bonded to each other to form a ring, and R41 or R42 may be bonded to a substituent carried by B6 or B7 to form a ring.
In the above, the ring formed is preferably a heterocycle or heteroaryl ring, and the size of the ring formed is not particularly limited, but is preferably a 5-membered or 6-membered ring. The number of rings formed is also not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include a form in which the substituents carried by R1 and B2 , and the substituents carried by R2 and B3, are bonded to each other to form two rings.

 染料Dの具体例としての一般式(1)で表される色素としては、国際公開第2023/228799号の[0097]~[0099]に記載の化合物が挙げられる。但し、本発明は、これらに限定されるものではない。 Specific examples of dye D represented by general formula (1) include the compounds described in paragraphs [0097] to [0099] of WO 2023/228799. However, the present invention is not limited to these.

 上記染料Dとしては、輝度低下の抑制と、表示画像の本来的な色味への反射色味の影響の抑制の両立をより高いレベルで実現できる観点から、アントラキノン系色素が好ましく、下記一般式(20)で表されるアントラキノン系色素がより好ましい。 As the dye D, an anthraquinone dye is preferred, and an anthraquinone dye represented by the following general formula (20) is more preferred, from the viewpoint of achieving a higher level of both suppression of brightness reduction and suppression of the influence of reflected color on the original color of the displayed image.

 上記式中、Aは、ヒドロキシ基又は-NH-R62を示す。
 R61及びR62は、水素原子、炭素数1~10の脂肪族炭化水素基、炭素数3~10の脂環式炭化水素基又は下記式(20b)で表される基を示す。
In the above formula, A represents a hydroxy group or —NH—R 62 .
R 61 and R 62 each represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group represented by the following formula (20b).

 上記式中、R63は、炭素数1~6のアルキル基、ハロゲン原子、-SOH、-COH、-CO64、-NHCOR64、-SO64又は-SONR6465を示す。
 R64は、炭素数1~10の飽和炭化水素基を示す。
 R65は、水素原子又は炭素数1~10の飽和炭化水素基を示す。
 rは、0~5の整数である。
 X61は、単結合又は炭素数1~6のアルカンジイル基を示す。
 *は結合手を示す。
In the above formula, R 63 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, —SO 3 H, —CO 2 H, —CO 2 R 64 , —NHCOR 64 , —SO 3 R 64 or —SO 2 NR 64 R 65 .
R 64 represents a saturated hydrocarbon group having 1 to 10 carbon atoms.
R 65 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
r is an integer from 0 to 5.
X 61 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
* indicates a bond.

 R61及びR62として採り得る炭素数1~10の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、イソプロピル基、イソブチル基、sec-ブチル基、tert-ブチル基、イソペンチル基、ネオペンチル基及び2-エチルヘキシル基が挙げられる。
 R61及びR62として採り得る炭素数3~10の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基及びトリシクロデシル基が挙げられる。
 R61及びR62として採り得る炭素数1~10の脂肪族炭化水素基及び炭素数3~10の脂環式炭化水素基は置換基を有していてもよく、有していてもよい置換基としては、例えば、ヒドロキシ基及びハロゲン原子が挙げられる。
Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which can be taken as R 61 and R 62 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms that can be taken as R 61 and R 62 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
The aliphatic hydrocarbon group having 1 to 10 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms which can be taken as R 61 and R 62 may have a substituent, and examples of the substituent that may be had include a hydroxy group and a halogen atom.

 R63として採り得る炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、sec-ブチル基、tert-ブチル基、イソペンチル基及びネオペンチル基が挙げられる。
 R63として採り得る-SOH及び-COHは、それぞれ水素イオンが解離してイオン構造を取っていてもよく、塩構造を取っていてもよい。すなわち、「-COH」はカルボン酸イオン又はその塩の基を、「-SOH」はスルホン酸イオン又はその塩の基を、それぞれ含む意味で使用する。塩としては、例えば、ナトリウムおよびカリウムなどのアルカリ金属との塩;カルシウムおよびマグネシウムなどのアルカリ土類金属との塩;アンモニウム塩;などが挙げられる。
Examples of the alkyl group having 1 to 6 carbon atoms that can be taken as R 63 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a neopentyl group.
The —SO 3 H and —CO 2 H that can be taken as R 63 may each have an ionic structure in which a hydrogen ion is dissociated, or may each have a salt structure. That is, “—CO 2 H” is used to mean a carboxylate ion or a salt group thereof, and “—SO 3 H” is used to mean a sulfonate ion or a salt group thereof. Examples of salts include salts with alkali metals such as sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; ammonium salts; and the like.

 R64及びR65として採り得る炭素数1~10の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖アルキル基;イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、2-エチルヘキシル基等の分岐アルキル基;シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基等の飽和脂環式炭化水素基が挙げられる。
 R64及びR65として採り得る炭素数1~10の飽和炭化水素基に含まれる水素原子の少なくとも1つは、ハロゲン原子、ヒドロキシ基又はアミノ基で置き換えられていてもよい。
Examples of saturated hydrocarbon groups having 1 to 10 carbon atoms that can be taken as R 64 and R 65 include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and saturated alicyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.
At least one hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms which can be taken as R 64 and R 65 may be substituted with a halogen atom, a hydroxy group or an amino group.

 -CO64としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、tert-ブトキシカルボニル基、ヘキシルオキシカルボニル基及びイコシルオキシカルボニル基が挙げられる。 Examples of —CO 2 R 64 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

 -NHCOR64としては、例えば、N-アセチルアミノ基、N-プロパノイルアミノ基、N-ブチリルアミノ基、N-イソブチリルアミノ基及びN-ピバロイルアミノ基が挙げられる。 Examples of —NHCOR 64 include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group, and an N-pivaloylamino group.

 -SO64としては、例えば、メトキシスルホニル基、エトキシスルホニル基、プロポキシスルホニル基、tert-ブトキシスルホニル基、ヘキシルオキシスルホニル基及びイコシルオキシスルホニルル基が挙げられる。 Examples of —SO 3 R 64 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

 -SONR6465としては、例えば、N-メチルスルファモイル基、N-エチルスルファモイル基、N-プロピルスルファモイル基、N-イソプロピルスルファモイル基、N-ブチルスルファモイル基、N-イソブチルスルファモイル基、N-sec-ブチルスルファモイル基、N-tert-ブチルスルファモイル基、N-ペンチルスルファモイル基、N-(1-エチルプロピル)スルファモイル基、N-(1,1-ジメチルプロピル)スルファモイル基、N-(1,2-ジメチルプロピル)スルファモイル基、N-(2,2-ジメチルプロピル)スルファモイル基、N-(1-メチルブチル)スルファモイル基、N-(2-メチルブチル)スルファモイル基、N-(3-メチルブチル)スルファモイル基、N-シクロペンチルスルファモイル基、N-シクロヘキシルスルファモイル基、N-ヘキシルスルファモイル基、N-(1,3-ジメチルブチル)スルファモイル基、N-(3,3-ジメチルブチル)スルファモイル基、N-ヘプチルスルファモイル基、N-(1-メチルヘキシル)スルファモイル基、N-(1,4-ジメチルペンチル)スルファモイル基、N-オクチルスルファモイル基、N-(2-エチルヘキシル)スルファモイル基、N-(1,5-ジメチル)ヘキシルスルファモイル基、N-(1,1,2,2-テトラメチルブチル)スルファモイル基、N-(5-アミノペンチル)スルファモイル基等のN-1置換スルファモイル基;
N,N-ジメチルスルファモイル基、N-エチル-N-メチルスルファモイル基、N,N-ジエチルスルファモイル基、N-プロピル-N-メチルスルファモイル基、N-イソプロピル-N-メチルスルファモイル基、N-tert-ブチル-N-メチルスルファモイル基、N-ブチル-N-エチルスルファモイル基、N,N-ビス(1-メチルプロピル)スルファモイル基、N-ヘプチル-N-メチルスルファモイル基等のN,N-2置換スルファモイル基等が挙げられる。
Examples of —SO 2 NR 64 R 65 include an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-isopropylsulfamoyl group, an N-butylsulfamoyl group, an N-isobutylsulfamoyl group, an N-sec-butylsulfamoyl group, an N-tert-butylsulfamoyl group, an N-pentylsulfamoyl group, an N-(1-ethylpropyl)sulfamoyl group, an N-(1,1-dimethylpropyl)sulfamoyl group, an N-(1,2-dimethylpropyl)sulfamoyl group, an N-(2,2-dimethylpropyl)sulfamoyl group, an N-(1-methylbutyl)sulfamoyl group, an N-(2-methylbutyl)sulfamoyl group, an N-(3-methylbutyl)sulfamoyl group, an N-(4-methylbutyl)sulfamoyl group, an N-(5-methylbutyl)sulfamoyl group, an N-(6-methylbutyl)sulfamoyl group, an N-(7-methylbutyl)sulfamoyl group, an N-(8-methylbutyl)sulfamoyl group, an N-(9-methylbutyl)sulfamoyl group, an N-(1 ... N-1-substituted sulfamoyl groups such as an N-(1-methylhexyl)sulfamoyl group, an N-(1,4-dimethylpentyl)sulfamoyl group, an N-octylsulfamoyl group, an N-(2-ethylhexyl)sulfamoyl group, an N-(1,5-dimethyl)hexylsulfamoyl group, an N-(1,1,2,2-tetramethylbutyl)sulfamoyl group, or an N-(5-aminopentyl)sulfamoyl group;
Examples of the sulfamoyl group include N,N-disubstituted sulfamoyl groups such as N,N-dimethylsulfamoyl group, N-ethyl-N-methylsulfamoyl group, N,N-diethylsulfamoyl group, N-propyl-N-methylsulfamoyl group, N-isopropyl-N-methylsulfamoyl group, N-tert-butyl-N-methylsulfamoyl group, N-butyl-N-ethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, and N-heptyl-N-methylsulfamoyl group.

 X61として採り得る炭素数1~6のアルカンジイル基としては、例えば、メチレン基、エチレン基、プロパン-1,3-ジイル基、プロパン-1,2-ジイル基、ブタン-1,4-ジイル基、ペンタン-1,5-ジイル基、ヘキサン-1,6-ジイル基、エタン-1,1-ジイル基、ブタン-1,3-ジイル基、2-メチルプロパン-1,3-ジイル基、2-メチルプロパン-1,2-ジイル基、ペンタン-1,4-ジイル基及び2-メチルブタン-1,4-ジイル基が挙げられる。 Examples of the alkanediyl group having 1 to 6 carbon atoms that can be taken as X 61 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.

 上記一般式(20)で表されるアントラキノン系色素としては、例えば、以下に示す例示化合物(2-1)~(2-14)が挙げられる。ただし、本発明はこれらに限定されるものではない。 Examples of the anthraquinone dye represented by the above general formula (20) include the following exemplary compounds (2-1) to (2-14). However, the present invention is not limited to these.

 上記一般式(20)で表されるアントラキノン系色素としては、なかでも、C.I.(Colour Index International)ソルベントブルー35(上記例示化合物(2-4))、C.I.ソルベントブルー36(上記例示化合物(2-3))、C.I.ソルベントブルー45(上記例示化合物(2-14))、C.I.アシッドブルー80(上記例示化合物(2-11))、C.I.ソルベントブルー104(上記例示化合物(2-12))及びC.I.ソルベントブルー122(上記例示化合物(2-13))が好ましい。 Among the anthraquinone dyes represented by the general formula (20) above, C.I. (Colour Index International) Solvent Blue 35 (exemplified compound (2-4) above), C.I. Solvent Blue 36 (exemplified compound (2-3) above), C.I. Solvent Blue 45 (exemplified compound (2-14) above), C.I. Acid Blue 80 (exemplified compound (2-11) above), C.I. Solvent Blue 104 (exemplified compound (2-12) above), and C.I. Solvent Blue 122 (exemplified compound (2-13) above) are particularly preferred.

 また、前述の光吸収消失性層における一般式(v)で表されるインドアニリン系色素も上記波長選択吸収層の染料Dとして好ましく用いることができる。 Furthermore, the indoaniline dye represented by general formula (v) in the light-absorbing and dissipating layer described above can also be preferably used as dye D in the wavelength-selective absorption layer.

 上記波長選択吸収層中における上記染料(好ましくは上記染料A~D)の合計含有量は、0.10~50質量%が好ましく、0.15~50質量%がより好ましく、0.20~40質量%が更に好ましく、0.25~40質量%が特に好ましく、とりわけ0.30~35質量%が好ましい。
 積層体I及び積層体IIが上述の第一波長選択吸収層と第二波長選択吸収層とを有する場合、上記波長選択吸収層中における上記染料(好ましくは上記染料A~D)の合計含有量に係る記載については、第一波長選択吸収層及び第二波長選択吸収層のそれぞれについて適用するものとする。
The total content of the dyes (preferably the dyes A to D) in the wavelength selective absorption layer is preferably 0.10 to 50 mass%, more preferably 0.15 to 50 mass%, still more preferably 0.20 to 40 mass%, particularly preferably 0.25 to 40 mass%, and particularly preferably 0.30 to 35 mass%.
When the laminate I and the laminate II have the above-mentioned first wavelength-selective absorption layer and second wavelength-selective absorption layer, the description regarding the total content of the dyes (preferably the dyes A to D) in the wavelength-selective absorption layer applies to each of the first wavelength-selective absorption layer and the second wavelength-selective absorption layer.

 上記波長選択吸収層中に含有され得る染料A~Dそれぞれの含有量としては、好ましくは以下の通りである。
 波長選択吸収層中における染料Aの含有量は、0.05~50質量%が好ましく、0.2~40質量%がより好ましい。波長選択吸収層中における染料Bの含有量は、0.01~30質量%が好ましく、0.1~15質量%がより好ましい。波長選択吸収層中における染料Cの含有量は、0.01~30質量%が好ましく、0.1~10質量%がより好ましい。波長選択吸収層中における染料Dの含有量は、0.05~45質量%が好ましく、0.1~30質量%がより好ましい。
 積層体I及び積層体IIが上述の第一波長選択吸収層と第二波長選択吸収層とを有する場合、上記波長選択吸収層中に含有され得る染料A~Dそれぞれの含有量に係る記載については、第一波長選択吸収層及び第二波長選択吸収層のそれぞれについて適用するものとする。
The content of each of the dyes A to D that can be contained in the wavelength selective absorption layer is preferably as follows.
The content of dye A in the wavelength selective absorption layer is preferably 0.05 to 50% by mass, and more preferably 0.2 to 40% by mass. The content of dye B in the wavelength selective absorption layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass. The content of dye C in the wavelength selective absorption layer is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass. The content of dye D in the wavelength selective absorption layer is preferably 0.05 to 45% by mass, and more preferably 0.1 to 30% by mass.
When the laminate I and the laminate II have the above-mentioned first wavelength selective absorption layer and second wavelength selective absorption layer, the description regarding the contents of each of the dyes A to D that can be contained in the wavelength selective absorption layer applies to each of the first wavelength selective absorption layer and the second wavelength selective absorption layer.

 上記波長選択吸収層が4種の染料A~Dを全て含有する場合、波長選択吸収層中における各染料A~Dの含有割合は、質量比で、染料A:染料B:染料C:染料D=1~50:0.1~10:1:0.1~20が好ましく、1~40:0.2~10:1:0.2~15がより好ましい。
 積層体I及び積層体IIが上述の第一波長選択吸収層と第二波長選択吸収層とを有する場合、上記波長選択吸収層中における各染料A~Dの含有割合に係る記載については、第一波長選択吸収層及び第二波長選択吸収層に含まれる染料全体としての各染料A~Dの含有割合に適用するものとする。
When the wavelength selective absorption layer contains all of the four dyes A to D, the content ratio of the dyes A to D in the wavelength selective absorption layer is, in mass ratio, preferably dye A:dye B:dye C:dye D=1-50:0.1-10:1:0.1-20, and more preferably 1-40:0.2-10:1:0.2-15.
When the laminate I and the laminate II have the above-mentioned first wavelength selective absorption layer and second wavelength selective absorption layer, the description regarding the content ratio of each of the dyes A to D in the wavelength selective absorption layer applies to the content ratio of each of the dyes A to D as a whole of the dyes contained in the first wavelength selective absorption layer and the second wavelength selective absorption layer.

 なお、染料B及びCの少なくとも一方が上記消光剤内蔵型色素である場合、上記消光剤内蔵型色素の含有量は、反射防止効果の点から、波長選択吸収層100質量%に対し、0.1~45質量%であることが好ましい。 If at least one of dyes B and C is a dye containing a quencher, the content of the dye containing a quencher is preferably 0.1 to 45% by mass relative to 100% by mass of the wavelength-selective absorption layer, in terms of anti-reflection effect.

<樹脂>
 上記波長選択吸収層に含まれる樹脂(以下、「マトリックス樹脂」とも称す。)は、上記染料を分散(好ましくは溶解)することができる限り、特に限定されるものではない。なかでも、外光反射の抑制及び輝度低下の抑制を充足することができ、しかも、OLED表示装置の画像本来の色味を優れたレベルで保持することができる樹脂が、好ましい。
 染料B及びCの少なくとも一方が上述の一般式(1)で表されるスクアライン系色素である場合には、上記マトリックス樹脂は、このスクアライン系色素がより先鋭な吸収を示すことが可能な、低極性マトリックス樹脂であることが好ましい。上記スクアライン系色素がより先鋭な吸収を示すことにより、上述の関係式(I)~(VI)を好ましいレベルで満たすことができ、OLED表示装置の画像本来の色味をより優れたレベルで保持することができる。ここで、低極性とは、下記関係式Iで定義されるfd値が0.50以上であることが好ましい。
      関係式I:fd=δd/(δd+δp+δh)
 関係式Iにおいて、δd、δp及びδhは、それぞれ、Hoy法により算出される溶解度パラメータδtに対する、London分散力に対応する項、双極子間力に対応する項、及び、水素結合力に対応する項を示す。具体的な算出方法については、後述の通りである。すなわち、fdはδdとδpとδhの和に対するδdの比率を示す。
 fd値を0.50以上とすることにより、より先鋭な吸収波形が得られやすくなる。
 また、波長選択吸収層がマトリックス樹脂を2種以上含む場合、fd値は、下記のようにして算出する。
   fd=Σ(w・fd
 ここで、wはi番目のマトリックス樹脂の質量分率、fdはi番目のマトリックス樹脂のfd値を示す。
<Resin>
The resin contained in the wavelength selective absorption layer (hereinafter also referred to as "matrix resin") is not particularly limited as long as it can disperse (preferably dissolve) the dye. Among them, a resin that can satisfactorily suppress external light reflection and brightness reduction and can also maintain the original color of the image of the OLED display device at an excellent level is preferred.
When at least one of dyes B and C is a squaraine dye represented by the general formula (1), the matrix resin is preferably a low-polarity matrix resin that allows the squaraine dye to exhibit a sharper absorption peak. The sharper absorption peak of the squaraine dye satisfies the above-mentioned relational expressions (I) to (VI) to a preferred level, thereby enabling the original color of images produced by OLED display devices to be maintained at a superior level. Here, low polarity preferably refers to an fd value defined by the following relational expression I of 0.50 or greater.
Relational expression I: fd=δd/(δd+δp+δh)
In Relational Formula I, δd, δp, and δh represent the terms corresponding to the London dispersion force, the dipole-dipole force, and the hydrogen bonding force, respectively, relative to the solubility parameter δt calculated by the Hoy method. Specific calculation methods are described below. That is, fd represents the ratio of δd to the sum of δd, δp, and δh.
By setting the fd value to 0.50 or more, it becomes easier to obtain a sharper absorption waveform.
When the wavelength selective absorption layer contains two or more types of matrix resins, the fd value is calculated as follows.
fd=Σ( wi・fd i )
Here, wi represents the mass fraction of the i-th matrix resin, and fd i represents the fd value of the i-th matrix resin.

 - London分散力に対応する項δd -
 London分散力に対応する項δdは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy (1985,1989)」欄に記載のAmorphous Polymersについて求められるδdをいうものとし、上記文献の上記の欄の記載に従って算出される。
-Term δd corresponding to London dispersion force-
The term δd corresponding to the London dispersion force refers to the δd determined for Amorphous Polymers described in the section "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature "Properties of Polymers 3rd , Elsevier, (1990)," and is calculated according to the description in the above section of the literature.

 - 双極子間力に対応する項δp -
 双極子間力に対応する項δpは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy(1985,1989)」欄に記載のAmorphous Polymersについて求められるδpをいうものとし、上記文献の上記の欄の記載に従って算出される。
- term corresponding to dipole-dipole force δp -
The term δp corresponding to the dipole-dipole force refers to the δp determined for the amorphous polymers described in the section "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature "Properties of Polymers 3rd , Elsevier, (1990)," and is calculated according to the description in the above section of the literature.

 - 水素結合力に対応する項δh -
 水素結合力に対応する項δhは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy(1985,1989)」欄に記載のAmorphous Polymersについて求められるδhをいうものとし、上記文献の上記の欄の記載に従って算出される。
- term corresponding to hydrogen bonding force δh -
The term δh corresponding to the hydrogen bonding strength refers to the δh determined for the Amorphous Polymers described in the literature "Properties of Polymers 3rd , Elsevier, (1990)" on pages 214 to 220, in the section "2) Method of Hoy (1985, 1989)," and is calculated according to the description in the above section of the literature.

 また、上記マトリックス樹脂が一定の疎水性を示す樹脂であると、上記波長選択吸収層の含水率を、例えば0.5%以下といった低含水率にすることができ、波長選択吸収層を含む積層体I(ただし、光吸収消失性層を除く。)及び積層体IIの耐光性を向上させる点から好ましい。
 なお、樹脂とは、ポリマーに加えて任意の慣用成分を含んでいてもよい。ただし、上記マトリックス樹脂のfdは、マトリックス樹脂を構成するポリマーについての算出値である。
Furthermore, if the matrix resin is a resin exhibiting a certain degree of hydrophobicity, the moisture content of the wavelength-selective absorption layer can be set to a low moisture content of, for example, 0.5% or less, which is preferable from the viewpoint of improving the light resistance of the laminate I (excluding the light-absorbing and disappearing layer) and the laminate II containing the wavelength-selective absorption layer.
The resin may contain any conventional component in addition to the polymer, but the fd of the matrix resin is a calculated value for the polymer that constitutes the matrix resin.

 上記マトリックス樹脂の好ましい例としては、例えば、ポリスチレン樹脂及び環状ポリオレフィン樹脂が挙げられ、ポリスチレン樹脂がより好ましい。通常、ポリスチレン樹脂の上記fd値は0.45~0.60であり、環状ポリオレフィン樹脂の上記fd値は0.45~0.70である。上述のようにfd値は0.50以上のものを用いることが好ましい。
 また、例えば、これらの好ましい樹脂に加えて、後述する伸長性樹脂成分及び剥離性制御樹脂成分等の波長選択吸収層に機能性を付与する樹脂成分を用いることも好ましい。すなわち、本発明においてマトリックス樹脂とは、上述の樹脂の他に、伸長性樹脂成分及び剥離性制御樹脂成分を含む意味で使用する。
 上記マトリックス樹脂が、ポリスチレン樹脂を含むことが、色素の吸収波形の先鋭化の点から好ましい。
Preferred examples of the matrix resin include polystyrene resin and cyclic polyolefin resin, with polystyrene resin being more preferred. Typically, the fd value of polystyrene resin is 0.45 to 0.60, and the fd value of cyclic polyolefin resin is 0.45 to 0.70. As mentioned above, it is preferable to use a resin with an fd value of 0.50 or more.
In addition to these preferred resins, it is also preferable to use resin components that impart functionality to the wavelength-selective absorption layer, such as an extensible resin component and a release property-controlling resin component, which will be described later. That is, in the present invention, the term "matrix resin" is used to mean not only the resins described above, but also the extensible resin component and the release property-controlling resin component.
The matrix resin preferably contains a polystyrene resin in order to sharpen the absorption waveform of the dye.

(ポリスチレン樹脂)
 上記ポリスチレン樹脂に含まれるポリスチレンとしては、スチレン成分を含むポリマーを意味する。ポリスチレンはスチレン成分を50質量%以上含むことが好ましい。上記波長選択吸収層は、ポリスチレンを、1種含有してもよいし、2種以上を含有してもよい。ここで、スチレン成分とは、その構造中にスチレン骨格を有する単量体由来の構造単位である。
 ポリスチレンは、光弾性係数及び吸湿性を波長選択吸収層として好ましい範囲の値へ制御する点から、スチレン成分を70質量%以上含むことがより好ましく、85質量%以上含むことがさらに好ましい。また、ポリスチレンはスチレン成分のみから構成されていることも好ましい。
 上記ポリスチレン樹脂として、国際公開第2023/228799号の[0106]~[0110]に記載のポリスチレン樹脂の記載をそのまま適用することができる。
(Polystyrene resin)
The polystyrene contained in the polystyrene resin refers to a polymer containing a styrene component. The polystyrene preferably contains 50% by mass or more of the styrene component. The wavelength selective absorption layer may contain one type of polystyrene or two or more types of polystyrene. Here, the styrene component is a structural unit derived from a monomer having a styrene skeleton in its structure.
In order to control the photoelastic coefficient and hygroscopicity within the ranges preferred for the wavelength selective absorption layer, the polystyrene preferably contains 70% by mass or more, and more preferably 85% by mass or more, of a styrene component. It is also preferable that the polystyrene is composed only of a styrene component.
As the polystyrene resin, the description of the polystyrene resin described in [0106] to [0110] of WO 2023/228799 can be applied as is.

 上記波長選択吸収層は、上記ポリスチレン樹脂に加えてポリフェニレンエーテル樹脂を含有することも好ましい。ポリスチレン樹脂とポリフェニレンエーテル樹脂とを併せて含有することにより波長選択吸収層の靭性を向上させ、高温高湿等の過酷な環境下においてもクラック等の欠陥の発生を抑制することができる。
 上記ポリフェニレンエーテル樹脂としては、旭化成社製のザイロンS201A、同S202A、同S203A(いずれも商品名)等を好ましく用いることができる。また、あらかじめポリスチレン樹脂とポリフェニレンエーテル樹脂を混合した樹脂を用いてもよい。ポリスチレン樹脂とポリフェニレンエーテル樹脂との混合樹脂としては、例えば、旭化成社製のザイロン1002H、同1000H、同600H、同500H、同400H、同300H、同200H(いずれも商品名)等を好ましく用いることができる。
 上記波長選択吸収層において、ポリスチレン樹脂とポリフェニレンエーテル樹脂とを含有する場合、両者の質量比は、ポリスチレン樹脂/ポリフェニレンエーテル樹脂で、99/1~50/50が好ましく、98/2~60/40がより好ましく、95/5~70/30がさらに好ましい。ポリフェニレンエーテル樹脂の配合比率を上記好ましい範囲とすることにより、波長選択吸収層は十分な靱性を有し、また溶液製膜をした場合には溶剤を適度に揮散させることができる。
The wavelength selective absorption layer preferably contains a polyphenylene ether resin in addition to the polystyrene resin. By containing both the polystyrene resin and the polyphenylene ether resin, the toughness of the wavelength selective absorption layer can be improved and the occurrence of defects such as cracks can be suppressed even in harsh environments such as high temperature and high humidity.
As the polyphenylene ether resin, Zylon S201A, S202A, S203A (all trade names) manufactured by Asahi Kasei Corporation can be preferably used. Alternatively, a resin prepared by pre-mixing polystyrene resin and polyphenylene ether resin can be used. As a mixed resin of polystyrene resin and polyphenylene ether resin, for example, Zylon 1002H, 1000H, 600H, 500H, 400H, 300H, 200H (all trade names) manufactured by Asahi Kasei Corporation can be preferably used.
When the wavelength selective absorption layer contains a polystyrene resin and a polyphenylene ether resin, the mass ratio of the two, polystyrene resin/polyphenylene ether resin, is preferably 99/1 to 50/50, more preferably 98/2 to 60/40, and even more preferably 95/5 to 70/30. By setting the blending ratio of the polyphenylene ether resin within the above preferred range, the wavelength selective absorption layer has sufficient toughness, and when solution casting is performed, the solvent can be appropriately evaporated.

(環状ポリオレフィン樹脂)
 上記環状ポリオレフィン樹脂(ポリシクロオレフィン樹脂とも称される。)に含まれる環状ポリオレフィンを形成する環状オレフィン化合物としては、炭素-炭素二重結合を含む環構造を持つ化合物であれば特に制限されず、例えば、ノルボルネン化合物、ノルボルネン化合物以外の、単環の環状オレフィン化合物、環状共役ジエン化合物及びビニル脂環式炭化水素化合物等が挙げられる。
 環状ポリオレフィンとしては、例えば、(1)ノルボルネン化合物に由来する構造単位を含む重合体、(2)ノルボルネン化合物以外の、単環の環状オレフィン化合物に由来する構造単位を含む重合体、(3)環状共役ジエン化合物に由来する構造単位を含む重合体、(4)ビニル脂環式炭化水素化合物に由来する構造単位を含む重合体、及び、(1)~(4)の各化合物に由来する構造単位を含む重合体の水素化物等が挙げられる。
 本発明において、ノルボルネン化合物に由来する構造単位を含む重合体、及び、単環の環状オレフィン化合物に由来する構造単位を含む重合体には、各化合物の開環重合体を含む。
 上記環状ポリオレフィン樹脂として、国際公開第2023/228799号の[0112]~[0125]に記載の環状ポリオレフィン樹脂の記載をそのまま適用することができる。
(Cyclic polyolefin resin)
The cyclic olefin compound forming the cyclic polyolefin contained in the cyclic polyolefin resin (also referred to as polycycloolefin resin) is not particularly limited as long as it is a compound having a ring structure containing a carbon-carbon double bond, and examples thereof include norbornene compounds, monocyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, and vinyl alicyclic hydrocarbon compounds.
Examples of cyclic polyolefins include (1) polymers containing structural units derived from norbornene compounds, (2) polymers containing structural units derived from monocyclic olefin compounds other than norbornene compounds, (3) polymers containing structural units derived from cyclic conjugated diene compounds, (4) polymers containing structural units derived from vinyl alicyclic hydrocarbon compounds, and hydrogenated polymers containing structural units derived from each of the compounds (1) to (4).
In the present invention, the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic olefin compound include ring-opened polymers of each compound.
As the cyclic polyolefin resin, the description of the cyclic polyolefin resin described in paragraphs [0112] to [0125] of WO 2023/228799 can be applied as is.

 また、上述の光吸収消失性層の項に記載の樹脂も上記波長選択吸収層の樹脂として好ましく使用することができる。また、前述の光吸収消失性層の項に記載の樹脂において記載する各構成単位(芳香環を有する構成単位、脂環式構造を有する構成単位、炭素数1~14のアルキル基を有する構成単位)については、前述の記載に加えて以下の記載も適用することができ、さらに、後述の極性基を有する構成単位を有することもできる。 The resins described above in the section on the light-absorbing and dissipating layer can also be preferably used as the resin for the wavelength-selective absorption layer. Furthermore, the following descriptions can also be applied to the various structural units described in the resins described above in the section on the light-absorbing and dissipating layer (structural units having an aromatic ring, structural units having an alicyclic structure, structural units having an alkyl group with 1 to 14 carbon atoms), in addition to the above descriptions, and they can also contain structural units having a polar group, as described below.

≪芳香環を有する構成単位≫
 上記波長選択吸収層の樹脂を構成するポリマーは、芳香環を有する構成単位を有するポリマーを含むことも好ましい。
 前述の光吸収消失性層の項に記載の芳香環を有する構成単位を導くモノマーに由来する構成単位の他、例えば、芳香環と炭素-炭素二重結合とを有する連鎖重合系モノマーに由来する構成単位が挙げられ、スチレン;α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、3,5-ジメチルスチレン、2,4-ジメチルスチレン、o-エチルスチレン、p-エチルスチレン及びtert-ブチルスチレン等のアルキルスチレン;ヒドロキシスチレン、tert-ブトキシスチレン、ビニル安息香酸、o-クロロスチレン及びp-クロロスチレン等のスチレンのベンゼン核に水酸基、アルコキシ基、カルボキシ基及びハロゲン原子などが導入された置換スチレン等に由来する構成単位が好ましい。
 芳香環を有する構成単位を有するポリマー中、芳香環を有する構成単位の含有量は、芳香環を有する構成単位を有するポリマーの全構成単位の合計を100モル%とした際に、5~100モル%が好ましく、10~100モル%がより好ましく、20~100モル%が更に好ましい。
 芳香環を有する構成単位は、1種単独で使用してもよく、2種以上を併用してもよい。
<Structural units having aromatic rings>
The polymer constituting the resin of the wavelength selective absorption layer preferably contains a polymer having a structural unit with an aromatic ring.
In addition to the structural units derived from monomers that lead to structural units having an aromatic ring as described in the section on the light-absorbing and dissipative layer above, examples include structural units derived from chain polymerization monomers having an aromatic ring and a carbon-carbon double bond, and preferred structural units are those derived from styrene; alkylstyrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, and tert-butylstyrene; and substituted styrenes in which a hydroxyl group, alkoxy group, carboxy group, halogen atom, or the like has been introduced into the benzene nucleus of styrene, such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene.
In the polymer having a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 to 100 mol %, more preferably 10 to 100 mol %, and even more preferably 20 to 100 mol %, when the total of all structural units of the polymer having a structural unit having an aromatic ring is taken as 100 mol %.
The aromatic ring-containing structural unit may be used alone or in combination of two or more types.

≪脂環式構造を有する構成単位≫
 上記波長選択吸収層の樹脂を構成するポリマーは、脂環式構造を有する構成単位を有するポリマーを含むことも好ましい。
 前述の光吸収消失性層の項に記載の芳香環を有する構成単位を導くモノマーに由来する構成単位の他、ジシクロペンテニル(メタ)アクリレートに由来する構成単位が好ましい。
 脂環式構造を有する構成単位を有するポリマー中、脂環式構造を有する構成単位の含有量は、脂環式構造を有する構成単位を有するポリマーの全構成単位の合計を100モル%とした際に、1~90モル%が好ましく、5~90%がより好ましく、10~80モル%が更に好ましく、20~80モル%が特に好ましく、とりわけ25~80モル%が好ましい。
 脂環式構造を有する構成単位は、1種単独で使用してもよく、2種以上を併用してもよい。
<Structural Unit Having Alicyclic Structure>
The polymer constituting the resin of the wavelength selective absorption layer preferably contains a polymer having a structural unit with an alicyclic structure.
In addition to the structural units derived from monomers that lead to structural units having an aromatic ring as described above in the section on the light-absorbing and dissipating layer, structural units derived from dicyclopentenyl (meth)acrylate are preferred.
In the polymer having a structural unit having an alicyclic structure, the content of the structural unit having an alicyclic structure is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 80 mol%, particularly preferably 20 to 80 mol%, and especially preferably 25 to 80 mol%, when the total of all structural units of the polymer having a structural unit having an alicyclic structure is taken as 100 mol%.
The structural unit having an alicyclic structure may be used alone or in combination of two or more types.

≪炭素数1~14のアルキル基を有する構成単位≫
 上記波長選択吸収層の樹脂を構成するポリマーはガラス転移温度の調節等の観点から、炭素数1~14のアルキル基を有する構成単位を含んでいてもよい。炭素数1~14のアルキル基を有する構成単位としては、前述の光吸収消失性層の項に記載の炭素数1~14のアルキル基を有する構成単位が好ましい。本発明では、炭素数1~14のアルキル基を有する構成単位を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
 上記波長選択吸収層の樹脂を構成するポリマー中、炭素数1~14のアルキル基を有する構成単位の含有量は、ポリマーの全構成単位の合計を100モル%とした際に、0~95モル%であることが好ましく、0~70モル%がより好ましく、0~50モル%が更に好ましく、0~20モル%が特に好ましい。
<Structural Unit Having an Alkyl Group Having 1 to 14 Carbon Atoms>
The polymer constituting the resin of the wavelength selective absorption layer may contain a structural unit having an alkyl group having 1 to 14 carbon atoms from the viewpoint of adjusting the glass transition temperature, etc. As the structural unit having an alkyl group having 1 to 14 carbon atoms, the structural unit having an alkyl group having 1 to 14 carbon atoms described in the section on the light-absorbing and disappearing layer above is preferred. In the present invention, the structural unit having an alkyl group having 1 to 14 carbon atoms may be used alone, or two or more types may be used in combination.
In the polymer constituting the resin of the wavelength selective absorption layer, the content of the structural unit having an alkyl group having 1 to 14 carbon atoms is preferably 0 to 95 mol %, more preferably 0 to 70 mol %, still more preferably 0 to 50 mol %, and particularly preferably 0 to 20 mol %, when the total of all structural units of the polymer is 100 mol %.

≪極性基を有する構成単位≫
 上記波長選択吸収層の樹脂を構成するポリマーは、極性基を有するポリマーを含んでいてもよい。極性基を有するポリマーが有する極性基としては、カルボキシ基、ヒドロキシ基(フェノール性水酸基を含む。)、オキサゾリン環基等の含窒素芳香環基、アミド基等が挙げられ、カルボキシ基又はオキサゾリン環基が好ましい。
 極性基を有するポリマーは、極性基を有する構成単位を含むことが好ましく、例えば、極性基と炭素-炭素二重結合とを有する連鎖重合系モノマーに由来する構成単位が挙げられ、(メタ)アクリル酸、クロトン酸、イタコン酸、マレイン、フマル酸、4-ビニルピリジン、4-ビニルピロリドン、2-イソプロペニル-2-オキサゾリン又は4-ビニルフェノール等に由来する構成単位が好ましい。
<Structural Unit Having a Polar Group>
The polymer constituting the resin of the wavelength selective absorption layer may contain a polymer having a polar group. Examples of the polar group contained in the polymer having a polar group include a carboxy group, a hydroxy group (including a phenolic hydroxy group), a nitrogen-containing aromatic ring group such as an oxazoline ring group, an amide group, etc., and the carboxy group or the oxazoline ring group is preferred.
The polymer having a polar group preferably contains a structural unit having a polar group, and examples thereof include a structural unit derived from a chain polymerization monomer having a polar group and a carbon-carbon double bond, and preferred are structural units derived from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 4-vinylpyridine, 4-vinylpyrrolidone, 2-isopropenyl-2-oxazoline, 4-vinylphenol, or the like.

 極性基を有するポリマー中、極性基を有する構成単位の含有量は、極性基を有するポリマーの全構成単位の合計を100モル%とした際に、0.5~95モル%であることが好ましく、1.0~70モル%がより好ましく、1.5~50モル%が更に好ましく、2.0~45モル%が特に好ましい。 In the polymer having a polar group, the content of the structural unit having a polar group is preferably 0.5 to 95 mol%, more preferably 1.0 to 70 mol%, even more preferably 1.5 to 50 mol%, and particularly preferably 2.0 to 45 mol%, when the total of all structural units of the polymer having a polar group is taken as 100 mol%.

 なかでも、積層体I及び積層体IIが上述の第一波長選択吸収層と第二波長選択吸収層とを有する場合には、第一波長選択吸収層及び第二波長選択吸収層のうちの少なくとも1層における樹脂が、極性基を有するポリマーを含有することが優れた層間密着性を示す観点から好ましい。
 極性基を有するポリマーとしては、上述の極性基を有する構成単位と、上述の芳香環を有する構成単位、脂環式構造を有する構成単位及び炭素数1~14のアルキル基を有する構成単位のうちの少なくとも1種とを有するポリマーが挙げられ、カルボキシ基、ヒドロキシ基(フェノール性水酸基を含む。)、オキサゾリン環基等の含窒素芳香環基、アミド基のうちの少なくとも1種の極性基を有する構成単位と、上述の芳香環を有する構成単位及び脂環式構造を有する構成単位のうちの少なくとも1種とを有するポリマーが好ましく、カルボキシ基及びオキサゾリン環基うちの少なくとも1種の極性基を有する構成単位と、上述の芳香環を有する構成単位とを有するポリマーがより好ましい。
 オキサゾリン環基を有するポリマーとしては、オキサゾリン環基を有する油溶性ポリマーが好ましく、オキサゾリン環基を含有するスチレン系油溶性コポリマーがより好ましい。
 上記オキサゾリン環基を有するポリマーとしては、市販品を用いてもよく、例えば、日本触媒社製のエポクロスRPS-1005(商品名)等を挙げられる。
In particular, when the laminate I and the laminate II have the above-mentioned first wavelength-selective absorption layer and second wavelength-selective absorption layer, it is preferable that the resin in at least one of the first wavelength-selective absorption layer and the second wavelength-selective absorption layer contains a polymer having a polar group, from the viewpoint of exhibiting excellent interlayer adhesion.
Examples of polymers having a polar group include polymers having a structural unit having the above-mentioned polar group and at least one of the above-mentioned structural units having an aromatic ring, structural units having an alicyclic structure, and structural units having an alkyl group having 1 to 14 carbon atoms. Polymers having a structural unit having at least one polar group selected from a carboxy group, a hydroxy group (including a phenolic hydroxy group), a nitrogen-containing aromatic ring group such as an oxazoline ring group, and an amide group, and at least one of the above-mentioned structural units having an aromatic ring and structural units having an alicyclic structure are preferred, and polymers having a structural unit having at least one polar group selected from a carboxy group and an oxazoline ring group, and the above-mentioned structural unit having an aromatic ring are more preferred.
As the polymer having an oxazoline ring group, an oil-soluble polymer having an oxazoline ring group is preferred, and an oil-soluble styrene copolymer containing an oxazoline ring group is more preferred.
As the polymer having an oxazoline ring group, a commercially available product may be used, for example, EPOCROS RPS-1005 (trade name) manufactured by Nippon Shokubai Co., Ltd.

 上記波長選択吸収層の樹脂を構成するポリマーの重量平均分子量(Mw)は、1万以上であることが好ましく、1万~20万であることがより好ましく、1.5万~15万であることが更に好ましい。
 なお、本発明において、ポリマーの重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)によってポリスチレン換算の分子量として計測することができる。
 具体的には、GPC装置HLC-8220(商品名、東ソー社製)を用い、溶離液としてテトラヒドロフランを用い、カラムはG3000HXL+G2000HXL(いずれも商品名、東ソー社製)を用い、23℃で流量は1mL/minで、RI(示差屈折率)で検出できる。
The weight average molecular weight (Mw) of the polymer constituting the resin of the wavelength selective absorption layer is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.
In the present invention, the weight average molecular weight of the polymer can be measured as a molecular weight converted into polystyrene by gel permeation chromatography (GPC).
Specifically, a GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation) is used, tetrahydrofuran is used as an eluent, and G3000HXL+G2000HXL columns (both trade names, manufactured by Tosoh Corporation) are used, and detection can be performed by RI (differential refractive index) at 23°C and a flow rate of 1 mL/min.

 上記波長選択吸収層は、上記マトリックス樹脂を5質量%以上含むことが好ましく、20質量%以上含むことがより好ましく、50質量%以上含むことがさらに好ましく、70質量%以上含むことが特に好ましく、80質量%以上含むことが最も好ましい。
 上記波長選択吸収層中の上記マトリックス樹脂の含有量は、通常は99.90質量%以下であり、99.85質量%以下が好ましい。
The wavelength selective absorption layer preferably contains 5% by mass or more of the matrix resin, more preferably 20% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more.
The content of the matrix resin in the wavelength selective absorption layer is usually 99.90% by mass or less, and preferably 99.85% by mass or less.

(伸長性樹脂成分)
 上記波長選択吸収層は、樹脂成分として伸長性を示す成分(伸長性樹脂成分とも称す。)を適宜選んで含むことができる。具体的には、アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)、スチレン-ブタジエン樹脂(SB樹脂)、イソプレン樹脂、ブタジエン樹脂、ポリエーテル-ウレタン樹脂及びシリコーン樹脂等を挙げることができる。また、これらの樹脂をさらに、適宜水素添加してもよい。
 上記伸長性樹脂成分としては、ABS樹脂又はSB樹脂を用いることが好ましく、SB樹脂を用いることがより好ましい。
(Extensible resin component)
The wavelength-selective absorption layer can contain an appropriately selected resin component exhibiting extensibility (also referred to as an extensible resin component). Specific examples include acrylonitrile-butadiene-styrene resin (ABS resin), styrene-butadiene resin (SB resin), isoprene resin, butadiene resin, polyether-urethane resin, and silicone resin. Furthermore, these resins may be further hydrogenated as appropriate.
As the extensible resin component, it is preferable to use an ABS resin or an SB resin, and it is more preferable to use an SB resin.

 上記SB樹脂は、例えば、市販されているものが使用できる。このような市販品として、TR2000、TR2003、TR2250(以上、商品名、JSR社製)、クリアレン210M、220M、730V(以上、商品名、デンカ社製)、アサフレックス800S、805、810、825、830、840(以上、商品名、旭化成社製)、エポレックスSB2400、SB2610、SB2710(以上、商品名、住友化学社製)等を挙げることができる。 The above-mentioned SB resin can be, for example, a commercially available product. Examples of such commercially available products include TR2000, TR2003, and TR2250 (all trade names, manufactured by JSR Corporation), Clearen 210M, 220M, and 730V (all trade names, manufactured by Denka Company Limited), Asaflex 800S, 805, 810, 825, 830, and 840 (all trade names, manufactured by Asahi Kasei Corporation), and Eporex SB2400, SB2610, and SB2710 (all trade names, manufactured by Sumitomo Chemical Co., Ltd.).

 上記波長選択吸収層は、伸長性樹脂成分を、マトリックス樹脂中、15~95質量%含むことが好ましく、20~50質量%含むことがより好ましく、25~45質量%含むことがさらに好ましい。 The wavelength-selective absorption layer preferably contains 15 to 95% by mass of the extensible resin component in the matrix resin, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.

 上記伸長性樹脂成分としては、伸長性樹脂成分を単独で用いて、厚さ30μm、幅10mmの形態の試料を作製し、25℃での破断伸度をJIS 7127に基づき計測した際に、破断伸度が10%以上を示すものが好ましく、20%以上を示すものがより好ましい。 When the extensible resin component is used alone to prepare a sample 30 μm thick and 10 mm wide, and the breaking elongation at 25°C is measured in accordance with JIS 7127, it is preferable that the extensible resin component exhibits a breaking elongation of 10% or more, and more preferably 20% or more.

<密着改良剤>
 上記波長選択吸収層に隣接する層としてガスバリア層を有する場合、上記波長選択吸収層は、ガスバリア層との密着性を向上するために密着改良剤を含有することが好ましい。密着改良剤は、ガスバリア層との密着性が得られれば特に構造は限定されない。
 例えば、ガスバリア層が形成材料としてポリビニルアルコールを含む場合、密着改良剤は、ポリビニルアルコールの水酸基と結合する構造を有することが好ましく、ボロン酸含有基を有するポリマーがより好ましく、ボロン酸含有基を有する構成単位を含むポリマーがさらに好ましい。
 ボロン酸含有基を有するポリマーとしては、具体的には特許第6722602号公報の段落[0022]~[0083]に記載の共重合体(a)の記載をそのまま適用することができる。
 なお、ボロン酸含有基とは、-B(OH)で表される基に限定されず、特許第6722602号公報の段落[0025]に記載の一般式(II)で表される構成単位における-B(OR11)(OR12)で表される基(なお、R11とR12とは連結していてもよい)を意味するものである。
 上記波長選択吸収層にボロン酸含有基を有するポリマーが含有される場合、波長選択吸収層に含有されるボロン酸含有ポリマーは、波長選択吸収層中においてガスバリア層との界面に偏在し、ボロン酸含有基における-B-OHがガスバリア層中の-OH基等の親水性基との間でボロン酸エステル等の化学結合等を形成することにより、密着性を向上させることができる。
 なお、ボロン酸含有ポリマーは、上記波長選択吸収層における透明樹脂を構成するポリマーには含めないものとする。
 ここで、上記波長選択吸収層のガスバリア層との界面において、ボロン酸含有基が存在していること、又はボロン酸含有基がガスバリア層中の-OH基等の親水性基との間でボロン酸エステル等の化学結合等を形成していることについては、例えば、飛行時間型二次イオン質量分析法(TOF-SIMS)により確認することができる。なお、TOF-SIMSは、日本表面科学会編「表面分析技術選書 2次イオン質量分析法」丸善株式会社(1999年発行)に記載されている方法を採用することができる。具体的には、ボロン酸含有基、又はボロン酸含有基がガスバリア層中の-OH基等の親水性基との間で形成しているボロン酸エステル等の化学結合由来のフラグメントが検出されることになる。
 本発明において、「波長選択吸収層がボロン酸含有基を有するポリマーを更に含有する」とは、波長選択吸収層がボロン酸含有基を有するポリマーを含む形態の他、ボロン酸含有基を有するポリマーのボロン酸含有基がガスバリア層中の-OH基等の親水性基との間で化学結合を形成するために使用されている形態を含む。
<Adhesion improver>
When a gas barrier layer is provided adjacent to the wavelength selective absorption layer, the wavelength selective absorption layer preferably contains an adhesion improver to improve adhesion to the gas barrier layer. The structure of the adhesion improver is not particularly limited as long as adhesion to the gas barrier layer is obtained.
For example, when the gas barrier layer contains polyvinyl alcohol as a forming material, the adhesion improver preferably has a structure that bonds with the hydroxyl group of the polyvinyl alcohol, more preferably a polymer having a boronic acid-containing group, and even more preferably a polymer containing a structural unit having a boronic acid-containing group.
As the polymer having a boronic acid-containing group, the description of the copolymer (a) in paragraphs [0022] to [0083] of Japanese Patent No. 6722602 can be applied as is.
The boronic acid-containing group is not limited to a group represented by -B(OH) 2 , but also refers to a group represented by -B( OR11 )( OR12 ) ( R11 and R12 may be linked together) in the structural unit represented by general formula (II) described in paragraph [0025] of Japanese Patent No. 6722602.
When the wavelength selective absorption layer contains a polymer having a boronic acid-containing group, the boronic acid-containing polymer contained in the wavelength selective absorption layer is unevenly distributed in the wavelength selective absorption layer at the interface with the gas barrier layer, and —B—OH in the boronic acid-containing group forms a chemical bond such as a boronic acid ester with a hydrophilic group such as an —OH group in the gas barrier layer, thereby improving adhesion.
The boronic acid-containing polymer is not included in the polymer constituting the transparent resin in the wavelength selective absorption layer.
Here, the presence of a boronic acid-containing group at the interface between the wavelength selective absorption layer and the gas barrier layer, or the formation of a chemical bond such as a boronic acid ester between the boronic acid-containing group and a hydrophilic group such as an —OH group in the gas barrier layer, can be confirmed by, for example, time-of-flight secondary ion mass spectrometry (TOF-SIMS). For TOF-SIMS, the method described in "Surface Analysis Technology Selection: Secondary Ion Mass Spectrometry" edited by the Japan Surface Science Society and published by Maruzen Co., Ltd. (1999) can be employed. Specifically, fragments derived from the boronic acid-containing group or the chemical bond such as a boronic acid ester formed between the boronic acid-containing group and a hydrophilic group such as an —OH group in the gas barrier layer are detected.
In the present invention, the phrase "the wavelength selective absorption layer further contains a polymer having a boronic acid-containing group" includes an embodiment in which the wavelength selective absorption layer contains a polymer having a boronic acid-containing group, as well as an embodiment in which the boronic acid-containing group of the polymer having the boronic acid-containing group is used to form a chemical bond with a hydrophilic group such as an —OH group in the gas barrier layer.

 また、旭化成ケミカルズ社製「タフテックMシリーズ」、三井化学社製「アドマーシリーズ」、同「ユニストールシリーズ」、三洋化成社製「ユーメックスシリーズ」、東洋紡社製「ハードレンシリーズ」等の酸変性樹脂も上記波長選択吸収層に添加する密着改良剤として好ましく用いることができる。 Furthermore, acid-modified resins such as the "Tuftec M series" manufactured by Asahi Kasei Chemicals Corporation, the "Admer series" and "Unistall series" manufactured by Mitsui Chemicals, Inc., the "Umex series" manufactured by Sanyo Chemical Industries, Ltd., and the "Hardlen series" manufactured by Toyobo Co., Ltd. can also be preferably used as adhesion improvers to be added to the wavelength-selective absorption layer.

 上記波長選択吸収層中における密着改良剤の含有量は、例えば、0.1~15質量%が好ましく、0.3~13質量%がより好ましく、0.5~10質量%がさらに好ましい。 The content of the adhesion improver in the wavelength selective absorption layer is, for example, preferably 0.1 to 15% by mass, more preferably 0.3 to 13% by mass, and even more preferably 0.5 to 10% by mass.

<その他の成分>
 本発明の光吸収消失性層及び波長選択吸収層は、前述の各成分(染料、樹脂、光吸収消失性層においてはさらにラジカル発生剤)に加え、レベリング剤(界面活性剤)等を含んでもよい。
<Other ingredients>
The light-absorbing and dissipating layer and wavelength-selective and absorbing layer of the present invention may contain a leveling agent (surfactant) and the like in addition to the above-mentioned components (dye, resin, and in the light-absorbing and dissipating layer, further a radical generator).

(レベリング剤)
 上記光吸収消失性層及び波長選択吸収層は、それぞれ、レベリング剤(界面活性剤)を適宜含有することができる。レベリング剤としては、常用の化合物を使用することができ、特に含フッ素界面活性剤が好ましい。具体的には、例えば、特開2001-330725号公報明細書中の段落番号[0028]~[0056]記載の化合物が挙げられる。また、市販品としては、DIC社製のメガファックF(商品名)シリーズを使用することもできる。
 上記光吸収消失性層又は波長選択吸収層中のレベリング剤の含有量は目的に応じて適宜に調整される。
(Leveling agent)
The light-absorbing and dissipating layer and the wavelength-selective absorption layer may each appropriately contain a leveling agent (surfactant). Commonly used compounds may be used as the leveling agent, with fluorine-containing surfactants being particularly preferred. Specific examples include the compounds described in paragraphs [0028] to [0056] of JP-A No. 2001-330725. Furthermore, commercially available products such as the Megafac F (trade name) series manufactured by DIC Corporation may also be used.
The content of the leveling agent in the light-absorbing and disappearing layer or the wavelength-selective absorbing layer is adjusted appropriately depending on the purpose.

 上記光吸収消失性層および波長選択吸収層は、上記各成分に加え、それぞれ、低分子可塑剤、オリゴマー系可塑剤、レタデーション調整剤、紫外線吸収剤、劣化防止剤、剥離促進剤、赤外線吸収剤、酸化防止剤、フィラー及び相溶化剤等を含有してもよい。 In addition to the above components, the light-absorbing and dissipating layer and the wavelength-selective absorbing layer may each contain low-molecular-weight plasticizers, oligomeric plasticizers, retardation adjusters, ultraviolet absorbers, anti-degradants, peel promoters, infrared absorbers, antioxidants, fillers, compatibilizers, etc.

(マット剤)
 積層体I、及び、積層体IIと積層体pre-IIIの積層体の表面には、滑り性付与及びブロッキング防止のために微粒子を添加してもよい。この微粒子としては、疎水基で表面が被覆され、二次粒子の態様をとっているシリカ(二酸化ケイ素,SiO)が好ましく用いられる。なお、微粒子には、シリカとともに、あるいはシリカに代えて、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、タルク、クレイ、焼成カオリン、焼成珪酸カルシウム、水和珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム及び燐酸カルシウムなどの微粒子を用いてもよい。市販の微粒子としては、R972及びNX90S(いずれも日本アエロジル社製、商品名)などが挙げられる。
(Matte agent)
Fine particles may be added to the surfaces of the laminate I, and the laminates II and pre-III to impart slip properties and prevent blocking. As the fine particles, silica (silicon dioxide, SiO 2 ) whose surface is coated with hydrophobic groups and takes the form of secondary particles is preferably used. In addition to or instead of silica, fine particles such as titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate may also be used. Examples of commercially available fine particles include R972 and NX90S (both manufactured by Nippon Aerosil Co., Ltd.).

 この微粒子はいわゆるマット剤として機能し、微粒子添加により積層体I、及び、積層体IIと積層体pre-IIIの積層体の表面に微小な凹凸が形成され、この凹凸により、積層体I同士、積層体IIと積層体pre-IIIの積層体同士、あるいは積層体Iとその他のフィルム、積層体IIと積層体pre-IIIの積層体とその他のフィルム等が重なっても互いに貼り付かず、滑り性が確保される。
 積層体I、及び、積層体IIと積層体pre-IIIの積層体が微粒子としてのマット剤を含有する場合、フィルタ表面から微粒子が突出した突起による微小凹凸は、高さ30nm以上の突起が10個/mm以上存在すると、特に滑り性、ブロッキング性の改善効果が大きい。
These microparticles function as a so-called matting agent, and the addition of the microparticles creates minute irregularities on the surface of laminate I and the laminate of laminate II and laminate pre-III. These irregularities prevent laminate I from sticking together, laminate II and laminate pre-III from sticking together, or laminate I from sticking to other films, or laminate II from sticking to other films, even when they are overlapped, ensuring smoothness.
When the laminate I and the laminate of the laminate II and the laminate pre-III contain a matting agent as fine particles, the minute irregularities caused by protrusions of fine particles protruding from the filter surface have a particularly large effect of improving slip properties and anti-blocking properties when the number of protrusions having a height of 30 nm or more is 104 / mm2 or more.

 積層体I、及び、積層体IIと積層体pre-IIIの積層体の表層に微粒子を付与する方法としては、重層流延及び塗布などによる手段が挙げられる。
 積層体I、及び、積層体IIと積層体pre-IIIの積層体中のマット剤の含有量は目的に応じて適宜に調整される。
 なお、積層体Iの表面に添加(表層に付与とも称す。)されたマット剤(微粒子)は、積層体Iを用いて得られる光透過吸収フィルタIの表面にもそのまま存在し、光透過吸収フィルタI同士、あるいは光透過吸収フィルタIとその他のフィルム等が重なった場合に互いに貼り付くことを防止することができる。このことは、積層体IIと積層体pre-IIIの積層体についても同様であり、光透過吸収フィルタII同士、あるいは光透過吸収フィルタIIとその他のフィルム等が重なった場合に互いに貼り付くことを防止することができる。
 なお、マット剤は、本発明の光透過吸収フィルタの表層に付与することも、積層体I、及び、積層体IIと積層体pre-IIIの積層体と同様の観点から好ましい。
Methods for applying fine particles to the surface layer of the laminate I, and the laminates of the laminate II and laminate pre-III include means such as multilayer casting and coating.
The content of the matting agent in the laminate I, and the laminate of the laminate II and the laminate pre-III is adjusted appropriately depending on the purpose.
The matting agent (fine particles) added to the surface of laminate I (also referred to as being applied to the surface layer) also remains present on the surface of the light transmission-absorption filter I obtained using laminate I, and can prevent light transmission-absorption filters I from sticking to each other, or light transmission-absorption filter I and other films, etc., when they are overlapped. The same is true for laminates II and laminate pre-III, and can prevent light transmission-absorption filters II from sticking to each other, or light transmission-absorption filter II and other films, etc., when they are overlapped.
It is also preferable to apply a matting agent to the surface layer of the light transmission/absorption filter of the present invention from the same viewpoint as in the case of the laminate I, and the laminate of the laminate II and the laminate pre-III.

<積層体I、積層体II、積層体pre-IIIの製造方法>
(光吸収消失性層及び波長選択吸収層の製造方法)
 積層体I及び積層体pre-IIIにおける光吸収消失性層並びに積層体I及び積層体IIにおける波長選択吸収層は、常法により、溶液製膜法、溶融押出し法、又は、基材フィルム(支持体フィルム)上に任意の方法でコーティング層を形成する方法(コーティング法)で作製することができ、適宜延伸を組み合わせることもできる。上記の光吸収消失性層及び波長選択吸収層は、好ましくはコーティング法により作製される。
 上記の溶液製膜法及び溶融押出し法としては、国際公開第2021/132674号の[0197]~[0203]における溶液製膜法及び溶融押出し法の記載を、「光吸収フィルタ」を「光吸収消失性層」又は「波長選択吸収層」に読み替える以外はそのまま適用することができる。
<Methods of manufacturing laminate I, laminate II, and laminate pre-III>
(Method for producing the light-absorbing and dissipating layer and the wavelength-selective absorption layer)
The light-absorbing and dissipating layer in the laminate I and laminate pre-III and the wavelength-selective and absorbing layer in the laminate I and laminate II can be produced by a conventional method such as a solution film-forming method, a melt extrusion method, or a method of forming a coating layer on a substrate film (support film) by any method (coating method), and stretching can also be combined as appropriate. The light-absorbing and dissipating layer and the wavelength-selective and absorbing layer are preferably produced by a coating method.
As the solution casting method and melt extrusion method, the descriptions of the solution casting method and melt extrusion method in paragraphs [0197] to [0203] of WO 2021/132674 can be applied as they are, except that "light-absorbing filter" is read as "light-absorbing disappearing layer" or "wavelength-selective absorption layer".

(コーティング法)
 コーティング法では、支持体フィルムに光吸収消失性層又は波長選択吸収層の材料の溶液を塗布し、コーティング層を形成する。支持体フィルム表面には、コーティング層との接着性を制御するため、適宜、離型剤等を予め塗布しておいてもよい。また、支持体フィルムには、任意の樹脂層を介してコーティング層を形成してもよい。コーティング層は、後工程で接着層を介して他の部材と貼り合わせた後、支持体フィルムを剥離して用いることができる。接着層を構成する接着剤については、任意の接着剤を適宜使用することができる。なお、支持体フィルム上に、光吸収消失性層又は波長選択吸収層の材料の溶液を塗布した状態又はコーティング層が積層された状態で、適宜支持体フィルムごと延伸することができる。
(Coating method)
In the coating method, a solution of the material for the light-absorbing and disappearing layer or the wavelength-selective absorption layer is applied to a support film to form a coating layer. A release agent or the like may be applied in advance to the surface of the support film as appropriate to control adhesion to the coating layer. The coating layer may also be formed on the support film via an optional resin layer. The coating layer can be used by laminating it to another member via an adhesive layer in a subsequent process and then peeling off the support film. Any adhesive can be used as the adhesive constituting the adhesive layer. The support film can be stretched together with the solution of the material for the light-absorbing and disappearing layer or the wavelength-selective absorption layer, or with the coating layer laminated on the support film.

 光吸収消失性層又は波長選択吸収層の材料の溶液に用いられる溶媒は、光吸収消失性層又は波長選択吸収層の材料を溶解又は分散可能であること、塗布工程、乾燥工程において均一な面状となり易いこと、液保存性が確保できること、適度な飽和蒸気圧を有すること、等の観点で適宜選択することができる。 The solvent used in the solution of the material for the light-absorbing and dissipating layer or wavelength-selective absorption layer can be selected appropriately based on factors such as whether the solvent can dissolve or disperse the material for the light-absorbing and dissipating layer or wavelength-selective absorption layer, whether it can easily form a uniform surface during the coating and drying processes, whether the liquid can be stored, and whether it has an appropriate saturated vapor pressure.

-光吸収消失性層又は波長選択吸収層を構成する成分の添加-
 光吸収消失性層の材料に上記染料、上記ラジカル発生剤を添加するタイミングは、製膜される時点で添加されていれば特に限定されない。例えば、上記マトリックス樹脂を構成するポリマーの合成時点で添加してもよいし、光吸収消失性層の材料のコーティング液調製時に光吸収消失性層の材料と混合してもよい。なお、ラジカル発生剤が化合物Aと化合物Bとの組み合わせを含み、化合物Aが上記樹脂を構成するポリマーと結合している場合には、化合物Aは樹脂を構成するポリマーの添加時に添加される。
 波長選択吸収層の材料に上記染料を添加するタイミングは、製膜される時点で添加されていれば特に限定されない。例えば、上記樹脂を構成するポリマーの合成時点で添加してもよいし、波長選択吸収層の材料のコーティング液調製時に波長選択吸収層の材料と混合してもよい。
- Addition of components constituting the light-absorbing and dissipating layer or the wavelength-selective absorption layer -
The timing of adding the dye and the radical generator to the material of the light-absorbing and disappearing layer is not particularly limited as long as they are added at the time of film formation. For example, they may be added at the time of synthesis of the polymer constituting the matrix resin, or they may be mixed with the material of the light-absorbing and disappearing layer when preparing a coating solution for the material of the light-absorbing and disappearing layer. Note that when the radical generator contains a combination of compound A and compound B, and compound A is bonded to the polymer constituting the resin, compound A is added when the polymer constituting the resin is added.
The timing of adding the dye to the material for the wavelength selective absorption layer is not particularly limited as long as it is added at the time of film formation. For example, the dye may be added at the time of synthesis of the polymer constituting the resin, or may be mixed with the material for the wavelength selective absorption layer when preparing a coating solution for the material for the wavelength selective absorption layer.

-支持体フィルム-
 光吸収消失性層又は波長選択吸収層を、コーティング法等で形成させるために用いられる支持体フィルムは、膜厚が2~100μmであることが好ましく、5~100μmであることがより好ましく、10~75μmがさらに好ましく、15~65μmが特に好ましい。膜厚が上記好ましい下限値以上であると、十分な機械強度を確保しやすく、カール、シワ、座屈等の故障が生じにくい。また、膜厚が上記好ましい上限値以下であると、光吸収消失性層又は波長選択吸収層と支持体フィルムとの複層フィルム、更には光吸収消失性層と波長選択吸収層と支持体フィルムとを含む複層フィルムを、例えば長尺のロール形態で保管する場合に、複層フィルムにかかる面圧を適正な範囲に調整しやすく、接着の故障が生じにくい。
- Support film -
The support film used to form the light-absorbing and disappearing layer or wavelength-selective absorption layer by a coating method or the like preferably has a film thickness of 2 to 100 μm, more preferably 5 to 100 μm, even more preferably 10 to 75 μm, and particularly preferably 15 to 65 μm. When the film thickness is equal to or greater than the above-mentioned preferable lower limit, sufficient mechanical strength is easily ensured, and defects such as curling, wrinkling, and buckling are unlikely to occur. Furthermore, when the film thickness is equal to or less than the above-mentioned preferable upper limit, when a multilayer film comprising a light-absorbing and disappearing layer or wavelength-selective absorption layer and a support film, or even a multilayer film comprising a light-absorbing and disappearing layer, a wavelength-selective absorption layer, and a support film, is stored, for example, in a long roll form, the surface pressure applied to the multilayer film is easily adjusted to an appropriate range, and adhesion defects are unlikely to occur.

 支持体フィルムの表面エネルギーは、特に限定されることはないが、光吸収消失性層又は波長選択吸収層の材料及びコーティング溶液の表面エネルギーと、支持体フィルムの光吸収消失性層又は波長選択吸収層を形成させる側の表面の表面エネルギーとの関係性を調整することによって、積層体I、積層体IIないし積層体pre-IIIと支持体フィルムとの間の接着力を調整することができる。表面エネルギー差を小さくすれば、接着力が上昇する傾向があり、表面エネルギー差を大きくすれば、接着力が低下する傾向があり、適宜設定することができる。 The surface energy of the support film is not particularly limited, but the adhesive strength between Laminate I, Laminate II or Laminate pre-III and the support film can be adjusted by adjusting the relationship between the surface energy of the material and coating solution of the light-absorbing and dissipating layer or wavelength-selective absorption layer and the surface energy of the surface of the support film on which the light-absorbing and dissipating layer or wavelength-selective absorption layer is to be formed. Reducing the difference in surface energy tends to increase adhesive strength, while increasing the difference in surface energy tends to decrease adhesive strength, and these can be set appropriately.

 また、支持体フィルムの表面凹凸は、特に限定されることはないが、積層体I、積層体IIないし積層体pre-IIIにおける支持体フィルムとは反対側表面の表面エネルギー、硬度、表面凹凸と、支持体フィルムの積層体I、積層体IIないし積層体pre-IIIを形成させる側とは反対側の表面の表面エネルギー、硬度との関係性に応じて、例えば積層体I、積層体IIないし積層体pre-IIIと支持体フィルムとの複層フィルムを長尺のロール形態で保管する場合の接着故障を防ぐ目的で調整することができる。表面凹凸を大きくすれば、接着故障を抑制する傾向にあり、表面凹凸を小さくすれば、積層体I、積層体IIないし積層体pre-IIIの表面凹凸が減少し、積層体I、積層体IIないし積層体pre-IIIのヘイズが小さくなる傾向にあり、適宜設定することができる。 Furthermore, the surface roughness of the support film is not particularly limited, but can be adjusted, for example, for the purpose of preventing adhesion failure when a multilayer film of Laminate I, Laminate II, or Laminate pre-III and a support film is stored in the form of a long roll, depending on the relationship between the surface energy, hardness, and surface roughness of the surface of Laminate I, Laminate II, or Laminate pre-III opposite the support film and the surface energy and hardness of the surface of the support film opposite the side on which Laminate I, Laminate II, or Laminate pre-III is formed. Increasing the surface roughness tends to suppress adhesion failure, while decreasing the surface roughness tends to reduce the surface roughness of Laminate I, Laminate II, or Laminate pre-III and the haze of Laminate I, Laminate II, or Laminate pre-III, and can be set appropriately.

 このような支持体フィルムとしては、任意の素材及びフィルムを適宜使用することができる。具体的な材料として、ポリエステル系ポリマー(ポリエチレンテレフタレート系を含む)、オレフィン系ポリマー、シクロオレフィン系ポリマー、(メタ)アクリル系ポリマー、セルロース系ポリマー、ポリアミド系ポリマー等を挙げることができる。また、支持体フィルムの表面性を調整する目的で、適宜表面処理を行うことが出来る。表面エネルギーを低下させるには、例えば、コロナ処理、常温プラズマ処理、鹸化処理等を行うことができ、表面エネルギーを上昇させるには、シリコーン処理、フッ素処理、オレフィン処理等を行うことができる。 Any suitable material or film can be used as such a support film. Specific materials include polyester polymers (including polyethylene terephthalate), olefin polymers, cycloolefin polymers, (meth)acrylic polymers, cellulose polymers, and polyamide polymers. Furthermore, the support film can be subjected to appropriate surface treatments to adjust its surface properties. For example, corona treatment, room temperature plasma treatment, and saponification treatment can be used to reduce surface energy, while silicone treatment, fluorine treatment, and olefin treatment can be used to increase surface energy.

(拡散阻害層)
 積層体Iは、波長選択吸収層、拡散阻害層及び光吸収消失性層がこの順に直接接するようにして配置されていることが好ましい。
 上記拡散阻害層は、波長選択吸収層と光吸収消失性層との間に設けることにより、波長選択吸収層中に含有される染料等の成分が光吸収消失性層中へ拡散することを抑制する効果を有し、光吸収消失性層中に含有される染料及びラジカル発生剤等の成分が波長選択吸収層中へ拡散することを抑制する効果を有するものであればよい。
 波長選択吸収層中の成分の光吸収消失性層への拡散は、波長選択吸収層の光吸収消失性層上への形成時、および光吸収消失性層上への波長選択吸収層の形成時のいずれの状態においても起こりうる。光吸収消失性層中の成分の波長選択吸収層への拡散は、光吸収消失性層の波長選択吸収層上への形成時、および波長選択吸収層上への光吸収消失性層の形成時のいずれの状態においても起こりうる。
 積層体Iは、波長選択吸収層と光吸収消失性層との間に拡散阻害層を設けることによって、上述のように、波長選択吸収層中の成分の波長選択吸収層への拡散及び光吸収消失性層中の成分の波長選択吸収層への拡散を抑制することができる。これによって、積層体Iへの紫外線照射による光吸収消失性層中の染料の褪色、消色反応を、光吸収消失性層中における、紫外線照射によりラジカルを生成する化合物による染料の褪色、消色反応として行うことができる。拡散阻害層を設けることによって、積層体Iを用いて得られる光透過吸収フィルタIを、波長選択吸収層と光吸収消失性層とにそれぞれ由来する所望の光吸収特性をより実現することが可能となる。
(Diffusion-preventing layer)
In the laminate I, the wavelength selective absorption layer, the diffusion-preventing layer, and the light absorbing and dissipating layer are preferably arranged in this order so as to be in direct contact with each other.
The diffusion-inhibiting layer is provided between the wavelength-selective absorption layer and the light-absorbing and dissipating layer, and has the effect of inhibiting components such as dyes contained in the wavelength-selective absorption layer from diffusing into the light-absorbing and dissipating layer, and may be any layer as long as it has the effect of inhibiting components such as dyes and radical generators contained in the light-absorbing and dissipating layer from diffusing into the wavelength-selective absorption layer.
Diffusion of the components in the wavelength-selective absorption layer into the light-absorbing and dissipating layer can occur either when the wavelength-selective absorption layer is formed on the light-absorbing and dissipating layer, or when the wavelength-selective absorption layer is formed on the light-absorbing and dissipating layer. Diffusion of the components in the light-absorbing and dissipating layer into the wavelength-selective absorption layer can occur either when the light-absorbing and dissipating layer is formed on the wavelength-selective absorption layer, or when the light-absorbing and dissipating layer is formed on the wavelength-selective absorption layer.
By providing a diffusion-preventing layer between the wavelength-selective absorption layer and the light-absorbing and dissipating layer, the laminate I can suppress the diffusion of components in the wavelength-selective absorption layer into the wavelength-selective absorption layer and the diffusion of components in the light-absorbing and dissipating layer into the wavelength-selective absorption layer, as described above. This allows the fading and decolorization reaction of the dye in the light-absorbing and dissipating layer due to ultraviolet irradiation of the laminate I to occur as a fading and decolorization reaction of the dye in the light-absorbing and dissipating layer caused by a compound in the light-absorbing and dissipating layer that generates radicals upon ultraviolet irradiation. The provision of the diffusion-preventing layer makes it possible for the light transmission and absorption filter I obtained using the laminate I to more effectively achieve the desired light absorption characteristics derived from the wavelength-selective absorption layer and the light-absorbing and dissipating layer, respectively.

 波長選択吸収層、拡散阻害層及び光吸収消失性層がこの順に直接接するようにして積層されてなる形態においては、波長選択吸収層の拡散阻害層上への形成時又は波長選択吸収層の拡散阻害層上への形成時において、光吸収消失性層又は波長選択吸収層を形成するための塗布液中の溶剤(溶媒)により拡散阻害層が膨潤し、拡散阻害層中の自由体積が増大することの影響が大きいと考えられる。この観点から、積層体Iにおいて、波長選択吸収層と光吸収消失性層との間に設ける拡散阻害層を構成する樹脂は、拡散阻害層上へ波長選択吸収層又は光吸収消失性層を形成する時に使用される溶剤に対する親和性が低いことが好ましい。例えば、拡散阻害層上へ光吸収消失性層を形成する時には、光吸収消失性層中に含まれる染料、紫外線照射によりラジカルを生成する化合物等の成分が有機溶剤(非水系溶剤)に溶解する素材(材料)である場合、拡散阻害層を構成する樹脂は有機溶剤に対する親和性が低い樹脂、すなわち水溶性樹脂であることが好ましい。また、拡散阻害層上へ波長選択吸収層を形成する時には、波長選択吸収層中に含まれる染料等の成分が有機溶剤(非水系溶剤)に溶解する素材(材料)である場合、拡散阻害層を構成する樹脂は有機溶剤に対する親和性が低い樹脂、すなわち水溶性樹脂であることが好ましい。
 波長選択吸収層又は光吸収消失性層の形成時に使用される溶剤と拡散阻害層を構成する樹脂との親和性は、Hoy法により算出される溶解度パラメータδtにより評価することができる。溶解度パラメータδtは例えば、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy (1985,1989)」欄に記載の方法によって算出することができる。
 本発明において、波長選択吸収層又は光吸収消失性層の形成時に使用される溶剤のδt値と拡散阻害層を構成する樹脂のδt値の差の絶対値は、1.0以上が好ましく、2.0以上がより好ましく、3.0以上がさらに好ましく、4.0以上が特に好ましい。波長選択吸収層又は光吸収消失性層の形成時に使用される溶剤のδt値と拡散阻害層を構成する樹脂のδt値の差の絶対値が上記好ましい値以上となるように調整することにより、波長選択吸収層又は光吸収消失性層を形成する液を拡散阻害層上に塗布した際に、波長選択吸収層又は光吸収消失性層を形成する液に含有される溶剤が、拡散阻害層を透過することが抑制され、拡散阻害層の下側に位置する層(拡散阻害層上に波長選択吸収層を設ける場合には拡散阻害層の下側に位置する光吸収消失性層、拡散阻害層上に光吸収消失性層を設ける場合には拡散阻害層の下側に位置する波長選択吸収層)の膨潤が効果的に抑制されるため好ましい。波長選択吸収層又は光吸収消失性層の形成時に使用される溶剤のδt値と拡散阻害層を構成する樹脂のδt値の差の絶対値の上限値は、20.0以下が実際的であり、波長選択吸収層又は光吸収消失性層の形成時に使用される溶剤のδt値と拡散阻害層を構成する樹脂のδt値の差の絶対値としては、1.0~20.0が好ましく、2.0~20.0がより好ましく、3.0~20.0がさらに好ましく、4.0~20.0が特に好ましい。
 なお、波長選択吸収層又は光吸収消失性層の形成時に2種類以上の溶剤を使用する場合、溶剤のδt値とは各溶剤のδt値の重量平均値を意味する。また、拡散阻害層が2種類以上の樹脂で構成されている場合、樹脂のδt値とは各樹脂の重量平均値を意味する。
In a configuration in which the wavelength-selective absorption layer, the diffusion-preventing layer, and the light-absorbing/dissipating layer are laminated in this order in direct contact with each other, it is believed that when the wavelength-selective absorption layer is formed on the diffusion-preventing layer or when the wavelength-selective absorption layer is formed on the diffusion-preventing layer, the diffusion-preventing layer swells due to the solvent (solvent) in the coating solution for forming the light-absorbing/dissipating layer, and the free volume in the diffusion-preventing layer increases. From this perspective, in the laminate I, it is preferable that the resin constituting the diffusion-preventing layer provided between the wavelength-selective absorption layer and the light-absorbing/dissipating layer has low affinity for the solvent used when forming the wavelength-selective absorption layer or the light-absorbing/dissipating layer on the diffusion-preventing layer. For example, when forming the light-absorbing/dissipating layer on the diffusion-preventing layer, if the components contained in the light-absorbing/dissipating layer, such as dyes and compounds that generate radicals upon ultraviolet irradiation, are materials that dissolve in organic solvents (non-aqueous solvents), it is preferable that the resin constituting the diffusion-preventing layer be a resin with low affinity for organic solvents, i.e., a water-soluble resin. Furthermore, when forming a wavelength-selective absorption layer on a diffusion-preventing layer, if the components such as dyes contained in the wavelength-selective absorption layer are materials that dissolve in organic solvents (non-aqueous solvents), it is preferable that the resin constituting the diffusion-preventing layer be a resin with low affinity for organic solvents, i.e., a water-soluble resin.
The affinity between the solvent used in forming the wavelength-selective absorption layer or the light-absorbing/dissipating layer and the resin constituting the diffusion-preventing layer can be evaluated by the solubility parameter δt calculated by the Hoy method. The solubility parameter δt can be calculated, for example, by the method described in "2) Method of Hoy (1985, 1989)" on pages 214-220 of the literature "Properties of Polymers 3rd , Elsevier, (1990)."
In the present invention, the absolute value of the difference between the δt value of the solvent used when forming wavelength selective absorption layer or light absorbing and dissipating layer and the δt value of the resin that constitutes diffusion-inhibiting layer is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 3.0 or more, particularly preferably 4.0 or more.By adjusting the absolute value of the difference between the δt value of the solvent used when forming wavelength selective absorption layer or light absorbing and dissipating layer and the δt value of the resin that constitutes diffusion-inhibiting layer to be above the above-mentioned preferred value or more, when the solution that forms wavelength selective absorption layer or light absorbing and dissipating layer is applied on the diffusion-inhibiting layer, the solvent contained in the solution that forms wavelength selective absorption layer or light absorbing and dissipating layer is prevented from penetrating the diffusion-inhibiting layer, and the swelling of the layer located below the diffusion-inhibiting layer (when the wavelength selective absorption layer is provided on the diffusion-inhibiting layer, the light absorbing and dissipating layer located below the diffusion-inhibiting layer, when the light absorbing and dissipating layer is provided on the diffusion-inhibiting layer) is effectively suppressed, so it is preferable. The upper limit of the absolute value of the difference between the δt value of the solvent used when forming the wavelength-selective absorption layer or the light-absorbing and disappearing layer and the δt value of the resin constituting the diffusion-preventing layer is practically 20.0 or less, and the absolute value of the difference between the δt value of the solvent used when forming the wavelength-selective absorption layer or the light-absorbing and disappearing layer and the δt value of the resin constituting the diffusion-preventing layer is preferably 1.0 to 20.0, more preferably 2.0 to 20.0, even more preferably 3.0 to 20.0, and particularly preferably 4.0 to 20.0.
When two or more solvents are used in forming the wavelength-selective absorption layer or the light-absorbing/disappearing layer, the δt value of the solvent means the weight average of the δt values of the respective solvents. When the diffusion-preventing layer is composed of two or more resins, the δt value of the resin means the weight average of the respective resins.

(樹脂)
 上記拡散阻害層を構成する樹脂としては、水溶性樹脂が好ましい。水溶性樹脂は、熱硬化性樹脂、熱可塑性樹脂のいずれであってもよく、熱可塑性樹脂である場合には、結晶性であっても、非晶性であってもよい。
 例えば、水溶性樹脂としては、ポリビニルアルコール、ポリビニルピリジン、(メタ)アクリル樹脂、ポリウレタン、ポリエステル、エポキシ樹脂、セルロース樹脂等を好ましく用いることができる。これらの水溶性樹脂は、少なくとも1部が変性されていてもよい。
 上記ポリビニルアルコールは、変性されていてもよく、変性されていなくてもよい。変性ポリビニルアルコールとしては、例えば、アセトアセチル基、カルボキシ等の基を導入した変性ポリビニルアルコールが挙げられる。
 上記ポリビニルアルコールのけん化度は、有機溶剤のバリア性(透過抑制性能)をより高める観点から、60.0モル%以上が好ましく、80.0モル%以上がより好ましく、90.0モル%以上がさらに好ましい。上限値に特に制限はないが、99.99モル%以下が実際的である。上記ポリビニルアルコールのけん化度は、JIS K 6726 (1994)に記載の方法に基づき算出される値である。
 上記(メタ)アクリル系樹脂としては、(メタ)アクリル酸に由来する構成単位及び(メタ)アクリル酸エステルに由来する構成単位の少なくとも一方を含む樹脂であればよく、(メタ)アクリル酸に由来する構成単位を含む樹脂が好ましい。(メタ)アクリル系樹脂を構成する全構成単位に占める(メタ)アクリル酸に由来する構成単位の割合は、70~100モル%が好ましく、80~100モル%がより好ましく、90~100モル%が更に好ましい。
 なかでも、結晶部が溶剤分子の透過を効果的に抑制することができる点、および染料層で使用される有機溶剤による膨潤が生じにくい点から、上記拡散阻害層を構成する樹脂は、ポリビニルアルコール及び(メタ)アクリル系樹脂の少なくとも1種を用いることが好ましく、ポリビニルアルコール及びポリ(メタ)アクリル酸の少なくとも1種を用いることがより好ましい。
 さらに、積層体Iを構成する各層間の密着性を優れたものとできる観点から、上記拡散阻害層を構成する樹脂は、ポリ(メタ)アクリル酸であることが更に好ましい。
 上記拡散阻害層を構成する樹脂の重量平均分子量(Mw)は、1万以上であることが好ましく、1万~20万であることがより好ましく、1.5万~15万であることが更に好ましい。
 上記拡散阻害層中における樹脂(好ましくは水溶性樹脂)の含有量は、例えば、90質量%以上が好ましく、95質量%以上がより好ましい。上限値に特に制限はないが、100質量%とすることもできる。
(resin)
The resin constituting the diffusion-preventing layer is preferably a water-soluble resin. The water-soluble resin may be either a thermosetting resin or a thermoplastic resin, and if it is a thermoplastic resin, it may be crystalline or amorphous.
For example, preferred water-soluble resins include polyvinyl alcohol, polyvinylpyridine, (meth)acrylic resins, polyurethanes, polyesters, epoxy resins, cellulose resins, etc. These water-soluble resins may be at least partially modified.
The polyvinyl alcohol may be modified or unmodified. Examples of modified polyvinyl alcohol include modified polyvinyl alcohols into which groups such as acetoacetyl groups and carboxy groups have been introduced.
The degree of saponification of the polyvinyl alcohol is preferably 60.0 mol% or more, more preferably 80.0 mol% or more, and even more preferably 90.0 mol% or more, from the viewpoint of further improving the barrier properties (permeation suppression performance) of organic solvents. There is no particular upper limit, but 99.99 mol% or less is practical. The degree of saponification of the polyvinyl alcohol is a value calculated based on the method described in JIS K 6726 (1994).
The (meth)acrylic resin may be any resin containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid ester, and is preferably a resin containing a structural unit derived from (meth)acrylic acid. The proportion of the structural units derived from (meth)acrylic acid in all structural units constituting the (meth)acrylic resin is preferably 70 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 90 to 100 mol %.
In particular, the resin constituting the diffusion-preventing layer is preferably at least one of polyvinyl alcohol and (meth)acrylic resin, and more preferably at least one of polyvinyl alcohol and poly(meth)acrylic acid, because the crystalline portion can effectively suppress the permeation of solvent molecules and swelling due to the organic solvent used in the dye layer is unlikely to occur.
Furthermore, from the viewpoint of achieving excellent adhesion between the layers constituting the laminate I, it is more preferable that the resin constituting the diffusion-preventing layer is poly(meth)acrylic acid.
The weight average molecular weight (Mw) of the resin constituting the diffusion-preventing layer is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000.
The content of the resin (preferably a water-soluble resin) in the diffusion-preventing layer is, for example, preferably 90% by mass or more, more preferably 95% by mass or more. There is no particular upper limit, but it can be 100% by mass.

 拡散阻害層の厚みは、拡散阻害能をより向上させる観点から、0.1~5.0μmが好ましく、0.2~4.0μmがより好ましい。 From the viewpoint of further improving the diffusion-inhibiting ability, the thickness of the diffusion-inhibiting layer is preferably 0.1 to 5.0 μm, and more preferably 0.2 to 4.0 μm.

(拡散阻害層の製造方法)
 拡散阻害層を形成する方法は特に制限されないが、例えば、常法により、スピン塗布及びスリット塗布等のキャスト法により、波長選択吸収層又は光吸収消失性層上に作製する方法が挙げられる。
 この際に使用される溶剤は、所望の拡散阻害層を得られる限り特に制限なく使用することができる。例えば、拡散阻害層を構成する樹脂が水溶性樹脂である場合には、水;エタノール、イソプロピルアルコール等のアルコール等の水溶性溶剤を好ましく用いることができる。
(Method for manufacturing diffusion-preventing layer)
The method for forming the diffusion-preventing layer is not particularly limited, but examples thereof include a method of forming the diffusion-preventing layer on the wavelength-selective absorption layer or the light-absorbing/disappearing layer by a conventional casting method such as spin coating or slit coating.
The solvent used in this case is not particularly limited as long as the desired diffusion-preventing layer can be obtained. For example, when the resin constituting the diffusion-preventing layer is a water-soluble resin, water-soluble solvents such as water, alcohols such as ethanol and isopropyl alcohol can be preferably used.

 なお、拡散阻害層は、上記積層体Iにおける波長選択吸収層と光吸収消失性層との間に設けることに限定されず、積層体I、積層体II、積層体pre-IIIにおいて、各積層体を構成する隣接する2層間に適宜設けることができる。例えば、積層体pre-IIIにおいて、支持体フィルム、拡散阻害層及び光吸収消失性層がこの順に直接接するようにして配置されている構成も好ましく挙げられる。
 この場合、支持体フィルム上に、上述の方法により拡散阻害層を作製することができる。
The diffusion-preventing layer is not limited to being provided between the wavelength-selective absorption layer and the light-absorbing and dissipating layer in the laminate I, but may be provided as appropriate between two adjacent layers constituting each of the laminates I, II, and pre-III. For example, in the laminate pre-III, a preferred configuration is one in which the support film, the diffusion-preventing layer, and the light-absorbing and dissipating layer are arranged in this order so as to be in direct contact with each other.
In this case, the diffusion-preventing layer can be formed on the support film by the above-mentioned method.

<光吸収消失性層及び波長選択吸収層の膜厚>
 光吸収消失性層及び波長選択吸収層の膜厚は、特に制限されないが、それぞれ、1~18μmが好ましく、1~12μmがより好ましく、1~8μmがさらに好ましい。上記好ましい上限値以下であれば、薄いフィルムに高濃度で染料を添加することにより、染料(色素)が発する蛍光による偏光度の低下を抑えることができる。また、光吸収消失性層においては、消光剤の効果も発現しやすい。一方、上記好ましい下限値以上であると、面内の吸光度の均一度を維持しやすくなる。
 本発明において膜厚が1~18μmであるとは、光吸収消失性層又は波長選択吸収層の厚さを、どの部位で測っても1~18μmの範囲内にあることを意味する。このことは、膜厚1~12μm、1~8μmについても同様である。膜厚は、電子マイクロメーター(例えば、アンリツ社製)により測定することができる。
<Film Thickness of Light-Absorbing and Disappearing Layer and Wavelength-Selective Absorbing Layer>
The film thicknesses of the light-absorbing and disappearing layer and the wavelength-selective absorption layer are not particularly limited, but are preferably 1 to 18 μm, more preferably 1 to 12 μm, and even more preferably 1 to 8 μm. When the thickness is equal to or less than the above-mentioned preferred upper limit, the addition of a dye at a high concentration to a thin film can suppress a decrease in polarization degree due to fluorescence emitted by the dye (pigment). Furthermore, the effect of the quencher is also easily manifested in the light-absorbing and disappearing layer. On the other hand, when the thickness is equal to or greater than the above-mentioned preferred lower limit, it becomes easier to maintain uniformity of in-plane absorbance.
In the present invention, a film thickness of 1 to 18 μm means that the thickness of the light-absorbing and disappearing layer or the wavelength-selective and absorbing layer is within the range of 1 to 18 μm no matter where it is measured. This also applies to film thicknesses of 1 to 12 μm and 1 to 8 μm. The film thickness can be measured using an electronic micrometer (for example, manufactured by Anritsu Corporation).

<積層体I、積層体II、及び積層体pre-IIIの吸光度>
 積層体I、積層体II、及び積層体pre-IIIにおいて、波長400~700nmにおいて、極大吸収を示す波長における吸光度(以下、単に「Ab(λmax)」とも称す。)のうち、最も大きい吸光度は、0.3以上が好ましく、0.5以上がより好ましく、0.7以上がさらに好ましい。
 ただし、積層体I、積層体II、及び積層体pre-IIIの吸光度は、染料の種類、添加量又は膜厚により調整することができる。
<Absorbance of Laminate I, Laminate II, and Laminate pre-III>
In the laminate I, laminate II, and laminate pre-III, the largest absorbance at a wavelength showing maximum absorption within a wavelength range of 400 to 700 nm (hereinafter also simply referred to as "Ab(λ max )") is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.7 or more.
However, the absorbance of the laminate I, laminate II, and laminate pre-III can be adjusted by the type of dye, the amount added, or the film thickness.

<光吸収消失性層の消色率>
 積層体I及び積層体pre-IIIにおける光吸収消失性層は、25℃での紫外線照射による消色率が、85%以上であることが好ましく、87%以上であることがより好ましく、90%以上であることがさらに好ましい。上限値は特に制限はなく、100%であることも好ましい。
 なお、上記消色率は、紫外線照射試験前後における上記Ab(λmax)の値を用いて、下記式より算出される。
  消色率(%)=100-
   (紫外線照射後のAb(λmax)/紫外線照射前のAb(λmax))×100
 ここで、紫外線照射試験は、大気圧(101.33kPa)下、超高圧水銀灯(例えば、HOYA社製、商品名:UL750)を用いて、照度100mW/cm、照射量2000mJ/cmの紫外線を室温(45℃)で、積層体I及び積層体pre-IIIに照射する。
 上記吸光度、紫外線照射試験は、[第一、及び第二の部位の吸光度測定]に記載の方法により測定、算出することができる。
<Decolorization rate of light-absorbing and disappearing layer>
The light-absorbing and dispersible layer in the laminate I and laminate pre-III preferably has a discoloration rate of 85% or more, more preferably 87% or more, and even more preferably 90% or more, when irradiated with ultraviolet light at 25° C. There is no particular upper limit, and a value of 100% is also preferred.
The decolorization rate is calculated from the following formula using the values of Ab(λ max ) before and after the ultraviolet irradiation test.
Decolorization rate (%) = 100-
(Ab(λ max ) after ultraviolet irradiation/Ab(λ max ) before ultraviolet irradiation)×100
Here, the ultraviolet irradiation test is carried out by irradiating the laminate I and laminate pre-III with ultraviolet light at an illuminance of 100 mW/cm 2 and an irradiation dose of 2000 mJ/cm 2 at room temperature (45°C) using an ultra-high pressure mercury lamp (for example, UL750 manufactured by HOYA Corporation) under atmospheric pressure (101.33 kPa).
The absorbance and ultraviolet irradiation test can be measured and calculated by the method described in [Measurement of absorbance at first and second sites].

 また、上記光吸収消失性層は、色素の分解に伴う新たな着色構造由来の吸収(二次的な吸収)をほとんど生じないことが好ましい。
 例えば、色素の分解に伴う新たな着色構造由来の吸収の有無は、上記Ab(λmax)に対する特定の波長における吸光度の比率に基づき、確認することができる。特定の波長は、紫外線照射前の色素が吸収をほとんど示さず、かつ、色素の分解による新たな吸収が見られる波長を選択する。
 具体例としては、色素の分解に伴う新たな着色構造由来の吸収の有無は、上記Ab(λmax)に対する特定の波長における吸光度の比率に基づき、確認することができる。特定の波長は、紫外線照射前の色素が吸収をほとんど示さず、かつ、色素の分解による新たな吸収が見られる波長を選択する。
 具体例としては、色素の分解に伴う新たな着色構造由来の吸収の有無を、上記Ab(λmax)に対する波長450nmにおける吸光度(以下、単に「Ab(450)」とも称す。)の比率に基づき、確認することができる。すなわち、下記(II)の比率から下記(I)の比率を引いた値が小さいほど、色素の分解に伴う新たな着色構造由来の吸収が生じていないことを意味し、この値は、8.5%未満が好ましく、7.0%以下がより好ましく、5.0%以下がさらに好ましい。下限値に特に制限はないが、色素の分解に伴う二次的な吸収の有無に係る評価を妥当なものとする観点から、-10%以上が実際的であり、-6%以上であることが好ましい。
 (I) (紫外線照射前のAb(450)/紫外線照射前のAb(λmax))×100%
 (II) (紫外線照射後のAb(450)/紫外線照射前のAb(λmax))×100%
 
 また、波長450nmにおける吸光度に代えて波長650nmにおける吸光度(以下、単に「Ab(650)」とも称す。)の値を用い、下記(IV)の比率から下記(III)の比率を引いた値によっても、評価することができる。下記(IV)の比率から下記(III)の比率を引いた値の好ましい範囲は、上記の式(II)の比率から(I)の比率を引いた値と同義である。
 (III) (紫外線照射前のAb(650)/紫外線照射前のAb(λmax))×100%
 (IV) (紫外線照射後のAb(650)/紫外線照射前のAb(λmax))×100%
 ここで、紫外線照射試験は、上記消光率における紫外線照射試験の記載を好ましく適用することができる。
It is also preferable that the light-absorbing and dissipative layer hardly generates absorption (secondary absorption) derived from a new colored structure accompanying decomposition of the dye.
For example, the presence or absence of absorption due to a new colored structure accompanying decomposition of the dye can be confirmed based on the ratio of absorbance at a specific wavelength to the above Ab(λ max ). The specific wavelength is selected to be a wavelength at which the dye shows almost no absorption before UV irradiation and at which new absorption due to decomposition of the dye is observed.
Specifically, the presence or absence of absorption due to the new colored structure accompanying the decomposition of the dye can be confirmed based on the ratio of absorbance at a specific wavelength to the above Ab(λ max ). The specific wavelength is selected to be a wavelength at which the dye shows almost no absorption before UV irradiation and at which new absorption due to the decomposition of the dye is observed.
As a specific example, the presence or absence of absorption derived from a new colored structure accompanying dye decomposition can be confirmed based on the ratio of the absorbance at a wavelength of 450 nm (hereinafter also simply referred to as "Ab(450)") to the above Ab( λ max ). That is, the smaller the value obtained by subtracting the ratio (I) below from the ratio (II) below, the less absorption derived from a new colored structure accompanying dye decomposition is occurring, and this value is preferably less than 8.5%, more preferably 7.0% or less, and even more preferably 5.0% or less. There is no particular restriction on the lower limit, but from the viewpoint of validating the evaluation of the presence or absence of secondary absorption accompanying dye decomposition, -10% or more is practical, and -6% or more is preferable.
(I) (Ab(450) before ultraviolet irradiation/Ab(λ max ) before ultraviolet irradiation)×100%
(II) (Ab(450) after ultraviolet irradiation/Ab(λ max ) before ultraviolet irradiation)×100%

Alternatively, the absorbance at a wavelength of 650 nm (hereinafter also referred to simply as "Ab(650)") may be used instead of the absorbance at a wavelength of 450 nm, and the evaluation can also be performed based on the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV). The preferred range of the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV) is the same as the value obtained by subtracting the ratio of the above formula (I) from the ratio of the above formula (II).
(III) (Ab(650) before ultraviolet irradiation/Ab(λ max ) before ultraviolet irradiation)×100%
(IV) (Ab(650) after ultraviolet irradiation/Ab(λ max ) before ultraviolet irradiation)×100%
Here, the ultraviolet irradiation test can be preferably carried out in the same manner as described above for the extinction rate.

 上記光吸収消失性層は、上記の消色率及び色素の分解に伴う新たな着色構造由来の吸収の有無を確認する値が、いずれも好ましい範囲を満たすことにより、優れた消色性を示すことができる。 The light-absorbing and dissipative layer can exhibit excellent discoloration properties if both the discoloration rate and the value used to confirm the presence or absence of absorption due to the new colored structure resulting from the decomposition of the dye fall within the preferred ranges.

 積層体Iを用いて得られる光透過吸収フィルタI及び積層体pre-IIIを用いて得られる光透過吸収フィルタIIにおいて、光吸収消失性層における紫外線未照射部位(光吸収効果を有する部位)は、上記積層体I、積層体II、及び積層体pre-IIIに係るAb(λmax)の記載を満たすことが好ましい。 In the light transmission-absorption filter I obtained using the laminate I and the light transmission-absorption filter II obtained using the laminate pre-III, it is preferable that the ultraviolet-unirradiated portion of the light-absorbing and disappearing layer (the portion having the light-absorbing effect) satisfies the description of Ab(λ max ) for the laminate I, laminate II, and laminate pre-III described above.

<積層体I、積層体II、及び積層体pre-IIIの処理>
 積層体I、積層体II、及び積層体pre-IIIには任意のグロー放電処理、コロナ放電処理、又は、アルカリ鹸化処理などにより親水化処理を施してもよく、コロナ放電処理が好ましく用いられる。特開平6-94915号公報、又は同6-118232号公報などに開示されている方法などを適用することも好ましい。
<Treatment of Laminate I, Laminate II, and Laminate Pre-III>
The laminate I, laminate II, and laminate pre-III may be subjected to a hydrophilization treatment such as a glow discharge treatment, a corona discharge treatment, or an alkaline saponification treatment, and the corona discharge treatment is preferably used. It is also preferable to apply the methods disclosed in JP-A-6-94915 or JP-A-6-118232.

 なお、得られた膜には、必要に応じて、熱処理工程、過熱水蒸気接触工程、有機溶媒接触工程などを実施することができる。また、適宜に表面処理を実施してもよい。 The resulting film may be subjected to a heat treatment process, a superheated steam contact process, an organic solvent contact process, etc. as needed. Surface treatment may also be performed as appropriate.

 また、粘着剤層として、(メタ)アクリル系樹脂、スチレン系樹脂、シリコーン系樹脂等をベースポリマーとし、そこに、イソシアネート化合物、エポキシ化合物、アジリジン化合物のような架橋剤を加えた粘着剤組成物からなる層を適用することもできる。
 好ましくは、後述のOLED表示装置における粘着剤層の記載を適用することができる。
Furthermore, as the pressure-sensitive adhesive layer, a layer made of a pressure-sensitive adhesive composition having a base polymer such as a (meth)acrylic resin, a styrene resin, a silicone resin, or the like, to which a crosslinking agent such as an isocyanate compound, an epoxy compound, or an aziridine compound has been added can also be applied.
Preferably, the description of the adhesive layer in the OLED display device described later can be applied.

<ガスバリア層>
 積層体Iは、少なくとも片面にガスバリア層を有していてもよい。積層体Iがガスバリア層を有する場合、積層体Iを、優れた消色性と優れた耐光性との両立を実現した積層体Iとすることができ、上述の光透過吸収フィルタIの作製に好適に用いることができる。
 積層体IIは、ガスバリア層を有していてもよい。なかでも、積層体IIが前述の第一波長選択吸収層と第二波長選択吸収層の2層を有する場合には、これらの層の間にガスバリア層を有することが好ましい。これにより、酸素ガスによる染料の分解を抑制できるだけでなく、第一及び第二の波長選択吸収層間でのエネルギー移動を抑制でき、染料の分解をさらに抑えることができる。
 また、積層体pre-IIIは、少なくとも片面にガスバリア層を有していてもよい。積層体pre-IIIがガスバリア層を有する場合、積層体pre-IIIを、優れた消色性と優れた耐光性との両立を実現した積層体pre-IIIとすることができ、上述の光透過吸収フィルタIIの作製に好適に用いることができる。
<Gas barrier layer>
The laminate I may have a gas barrier layer on at least one surface. When the laminate I has a gas barrier layer, the laminate I can be a laminate I that achieves both excellent decolorization properties and excellent light fastness, and can be suitably used to produce the light transmission-absorption filter I described above.
The laminate II may have a gas barrier layer. In particular, when the laminate II has two layers, the first wavelength selective absorption layer and the second wavelength selective absorption layer, it is preferable to have a gas barrier layer between these layers. This not only can suppress decomposition of the dye by oxygen gas, but also can suppress energy transfer between the first and second wavelength selective absorption layers, thereby further suppressing decomposition of the dye.
Furthermore, the laminate pre-III may have a gas barrier layer on at least one surface. When the laminate pre-III has a gas barrier layer, the laminate pre-III can be made to have both excellent decolorization properties and excellent light resistance, and can be suitably used to produce the light transmission-absorption filter II described above.

 ガスバリア層を形成する材料は特に限定されず、例えば、ポリビニルアルコール及びポリ塩化ビニリデンなどの有機材料(好ましくは結晶性樹脂)、ゾルゲル材料などの有機-無機ハイブリッド系材料、SiO、SiO、SiON、SiN及びAlなどの無機材料を挙げることができる。ガスバリア層は単層であっても多層であってもよく、多層である場合は、無機の誘電体多層膜、及び、有機材料と無機材料を交互に積層した多層膜などの構成を挙げることができる。 The material for forming the gas barrier layer is not particularly limited, and examples thereof include organic materials (preferably crystalline resins) such as polyvinyl alcohol and polyvinylidene chloride, organic-inorganic hybrid materials such as sol-gel materials, and inorganic materials such as SiO 2 , SiO x , SiON, SiN x and Al 2 O 3. The gas barrier layer may be a single layer or a multilayer, and in the case of a multilayer, examples of the gas barrier layer include an inorganic dielectric multilayer film and a multilayer film in which organic materials and inorganic materials are alternately laminated.

 積層体Iは、ガスバリア層を、上述の光透過吸収フィルタIを用いた場合に空気と接することとなる面に少なくとも有することで、光透過吸収フィルタI中の染料の吸収強度の低下を抑制することができる。積層体Iの空気と接する界面にガスバリア層を設ける限り、ガスバリア層は、積層体Iの片面にのみ設けられていてもよく、両面に設けられていてもよい。
 積層体pre-IIIは、ガスバリア層を、光吸収消失性層のうち空気と接することとなる面に少なくとも有することで、積層体pre-III及びこれをマスク露光して得られる積層体IIIの状態において、光吸収消失性層中の染料の吸収強度の低下を抑制することができる。積層体pre-IIIの空気と接する界面にガスバリア層を設ける限り、ガスバリア層は、積層体pre-IIIの片面にのみ設けられていてもよく、両面に設けられていてもよい。
 なお、積層体Iを用いて得られる光透過吸収フィルタIと同様の観点から、本発明の光透過吸収フィルタにおいてもガスバリア層を設けることが好ましく、積層体Iにおける記載を適用することができる。
The laminate I has a gas barrier layer at least on the surface that comes into contact with air when the above-described light transmission-absorption filter I is used, thereby making it possible to suppress a decrease in the absorption intensity of the dye in the light transmission-absorption filter I. As long as a gas barrier layer is provided at the interface of the laminate I that comes into contact with air, the gas barrier layer may be provided on only one surface of the laminate I or on both surfaces.
The laminate pre-III has a gas barrier layer at least on the surface of the light-absorbing and dissipating layer that comes into contact with air, so that a decrease in the absorption intensity of the dye in the light-absorbing and dissipating layer can be suppressed in the state of the laminate pre-III and the laminate III obtained by exposing the laminate pre-III with a mask. As long as a gas barrier layer is provided at the interface of the laminate pre-III that comes into contact with air, the gas barrier layer may be provided on only one surface or both surfaces of the laminate pre-III.
From the same viewpoint as in the case of the light transmission-absorption filter I obtained using the laminate I, it is preferable to provide a gas barrier layer in the light transmission-absorption filter of the present invention, and the description of the laminate I can be applied.

 なかでも、ガスバリア層が結晶性樹脂を含有する構成である場合、上記ガスバリア層は、結晶性樹脂を含有し、層の厚みが0.1μm~10μmであって、層の酸素透過度が60cc/m・day・atm以下であることが好ましい。
 上記ガスバリア層において、上記「結晶性樹脂」は、温度を上げた際に結晶から液体に相転移する融点が存在する樹脂であって、上記ガスバリア層に、酸素ガスに係るガスバリア性を付与できるものである。
 上記の「結晶性樹脂を含有し、層の厚みが0.1μm~10μmであって、層の酸素透過度が60cc/m・day・atm以下であるガスバリア層」は、国際公開第2022/149510号の[0180]~[0184]に記載のガスバリア層と同じであり、これらの記載をそのまま適用することができる。
In particular, when the gas barrier layer contains a crystalline resin, it is preferable that the gas barrier layer contains a crystalline resin, has a layer thickness of 0.1 μm to 10 μm, and has an oxygen permeability of 60 cc/ m2 day atm or less.
In the gas barrier layer, the "crystalline resin" is a resin that has a melting point at which it undergoes a phase transition from crystal to liquid when the temperature is increased, and is capable of imparting gas barrier properties to oxygen gas to the gas barrier layer.
The above-mentioned "gas barrier layer containing a crystalline resin, having a layer thickness of 0.1 μm to 10 μm, and having an oxygen permeability of 60 cc/ m2 ·day·atm or less" is the same as the gas barrier layer described in paragraphs [0180] to [0184] of WO 2022/149510, and the descriptions therein can be applied as is.

<ガスバリア層の製造方法>
 ガスバリア層を形成する方法は特に制限されないが、常法により、例えば、有機材料の場合は、スピン塗布及びスリット塗布等のキャスト法により作製する方法が挙げられる。また、市販の樹脂製ガスバリアフィルム又はあらかじめ作製しておいた樹脂製ガスバリアフィルムを貼り合せる方法などを挙げることができる。また、無機材料の場合はプラズマCVD(Plasma Enhanced Chemical Vapor Deposition)法、スパッタ法及び蒸着法などを挙げることができる。
<Method of manufacturing gas barrier layer>
The method for forming the gas barrier layer is not particularly limited, but may be a conventional method. For example, in the case of an organic material, examples include a casting method such as spin coating or slit coating. Other examples include a method of laminating a commercially available resin gas barrier film or a pre-prepared resin gas barrier film. Furthermore, in the case of an inorganic material, examples include a plasma enhanced chemical vapor deposition (CVD) method, a sputtering method, and a vapor deposition method.

 積層体Iが上述のガスバリア層を有する場合、例えば、上述の製造方法により作製したガスバリア層を有しない積層体I上に、直接、上述のガスバリア層を形成する方法が挙げられる。この場合、積層体Iのうち、ガスバリア層を設ける面には、コロナ処理を施しておくことも好ましい。
 積層体IIが上述のガスバリア層を有する場合、例えば、上述の製造方法により作製した第一波長選択吸収層又は第二波長選択吸収層上に、直接、上述のガスバリア層を形成する方法が挙げられる。この場合、ガスバリア層を設ける第一波長選択吸収層及び第二波長選択吸収層のうちの少なくとも一方(好ましくは両方)は、前述のオキサゾリン環基を有するポリマーを含有することが、層間密着性の観点から好ましい。
 積層体pre-IIIが上述のガスバリア層を有する場合、例えば、上述の製造方法により作製した光吸収消失性層上に、直接、上述のガスバリア層を作製する方法が挙げられる。この場合、光吸収消失性層のうちガスバリア層を設ける面には、コロナ処理を施しておくことも好ましい。
 また、下記任意の光学機能フィルムを有する場合には、粘着剤層を介して貼り合わせることも好ましい。例えば、積層体I、積層体II、積層体pre-IIIの積層体上にガスバリア層を設けた後、さらに粘着剤層を介して光学機能フィルムを貼り合わせることも好ましい。
When the laminate I has the gas barrier layer, for example, the gas barrier layer can be formed directly on the laminate I that has no gas barrier layer and that has been produced by the above-mentioned production method. In this case, it is also preferable to subject the surface of the laminate I on which the gas barrier layer is to be formed to a corona treatment.
When the laminate II has the gas barrier layer, for example, the gas barrier layer may be formed directly on the first wavelength selective absorption layer or the second wavelength selective absorption layer produced by the above-mentioned production method. In this case, it is preferable that at least one (preferably both) of the first wavelength selective absorption layer and the second wavelength selective absorption layer on which the gas barrier layer is provided contains the polymer having the oxazoline ring group described above, from the viewpoint of interlayer adhesion.
When the laminate pre-III has the gas barrier layer, for example, the gas barrier layer may be formed directly on the light-absorbing and disappearing layer formed by the above-mentioned production method. In this case, it is also preferable to subject the surface of the light-absorbing and disappearing layer on which the gas barrier layer is to be formed to a corona treatment.
In addition, when any of the optically functional films described below is used, it is also preferable to bond them via a pressure-sensitive adhesive layer. For example, it is also preferable to provide a gas barrier layer on the laminate of Laminate I, Laminate II, or Laminate pre-III, and then bond the optically functional film via a pressure-sensitive adhesive layer.

<光学機能フィルム>
 積層体I、積層体II、積層体pre-IIIは、本発明の効果を損なわない範囲で、上記ガスバリア層、又は、任意の光学機能フィルムを適宜有していてもよい。
 上記任意の光学機能フィルムについては、光学特性及び材料のいずれについても特に制限はないが、セルロースエステル樹脂、アクリル樹脂、環状オレフィン樹脂及びポリエチレンテレフタレート樹脂の少なくともいずれかを含む(あるいは主成分とする)フィルムを好ましく用いることができる。なお、光学的に等方性のフィルムを用いても、光学的に異方性の位相差フィルムを用いてもよい。
 上記任意の光学機能フィルムについて、セルロースエステル樹脂を含むものとしては、例えばフジタックTD80UL(商品名、富士フイルム社製)などを利用することができる。
 上記任意の光学機能フィルムについて、アクリル樹脂を含むものとしては、特許第4570042号公報に記載のスチレン系樹脂を含有する(メタ)アクリル樹脂を含む光学フィルム、特許第5041532号公報に記載のグルタルイミド環構造を主鎖に有する(メタ)アクリル樹脂を含む光学フィルム、特開2009-122664号公報に記載のラクトン環構造を有する(メタ)アクリル系樹脂を含む光学フィルム、特開2009-139754号公報に記載のグルタル酸無水物単位を有する(メタ)アクリル系樹脂を含む光学機能フィルムを利用することができる。
 また、上記任意の光学機能フィルムについて、環状オレフィン樹脂を含むものとしては、特開2009-237376号公報の段落[0029]以降に記載の環状オレフィン系樹脂フィルム、特許第4881827号公報、特開2008-063536号公報に記載のRthを低減する添加剤を含有する環状オレフィン樹脂フィルムを利用することができる。
<Optical functional film>
The laminate I, laminate II, and laminate pre-III may appropriately include the gas barrier layer or any optically functional film as long as the effects of the present invention are not impaired.
The optical properties and materials of the above-mentioned optional optical functional film are not particularly limited, but a film containing (or having as its main component) at least one of cellulose ester resin, acrylic resin, cyclic olefin resin, and polyethylene terephthalate resin can be preferably used. Note that either an optically isotropic film or an optically anisotropic retardation film can be used.
As the optional optical functional film, for example, Fujitac TD80UL (trade name, manufactured by Fujifilm Corporation) can be used as the film containing a cellulose ester resin.
As the above-mentioned arbitrary optical functional film, examples of the film containing an acrylic resin include an optical film containing a (meth)acrylic resin containing a styrene-based resin as described in Japanese Patent No. 4570042, an optical film containing a (meth)acrylic resin having a glutarimide ring structure in the main chain as described in Japanese Patent No. 5041532, an optical film containing a (meth)acrylic resin having a lactone ring structure as described in Japanese Patent Laid-Open No. 2009-122664, and an optical functional film containing a (meth)acrylic resin having a glutaric anhydride unit as described in Japanese Patent Laid-Open No. 2009-139754.
Furthermore, as the above-mentioned arbitrary optical functional film, as a film containing a cyclic olefin resin, a cyclic olefin resin film described in paragraph [0029] and thereafter of JP-A-2009-237376, and a cyclic olefin resin film containing an additive that reduces Rth described in JP-A-4881827 and JP-A-2008-063536 can be used.

<光透過吸収フィルタIの製造方法>
 上記光透過吸収フィルタIは、上記積層体Iに対して、紫外線を照射してマスク露光することにより得ることができる。
 マスクパターンは、OLED表示素子における非発光部(表示光が出射されない部位)に対応する部位が上述の第二の部位となり、OLED表示素子における発光部(表示光が出射される部位)に対応する部位が上述の第一の部位となるようなマスクパターンとすることが好ましい。すなわち、積層体Iにおいて、OLED表示素子における非発光部に対応する部位をマスクし、OLED表示素子における発光部に対応する部位をマスクしないマスクパターンにより紫外線照射することによって、光透過吸収フィルタIを好適に得ることができる。
 OLED表示素子の非発光部とOLED表示素子の発光部との面積比率については、前述の通りである。
 紫外線照射の条件は、光吸収性消失部位を含む第一の部位を有する光透過吸収フィルタIが得られるよう、適宜調整して行うことができる。例えば、圧力条件については大気圧(101.33kPa)下で行うことができ、温度条件については、10~60℃の穏和な温度条件で行うことができ、ランプ出力は10~320W/cmとすることができ、使用するランプとしては空冷メタルハライドランプ、超高圧水銀ランプ等の水銀ランプ、等を用いることができる。また、照射量は200~5000mJ/cmとすることができる。
<Method of Manufacturing Light Transmission/Absorption Filter I>
The light transmission/absorption filter I can be obtained by irradiating the laminate I with ultraviolet light and exposing it using a mask.
The mask pattern is preferably such that the portions corresponding to the non-light-emitting portions of the OLED display element (portions from which display light is not emitted) become the above-mentioned second portions, and the portions corresponding to the light-emitting portions of the OLED display element (portions from which display light is emitted) become the above-mentioned first portions. That is, the light transmission-absorption filter I can be suitably obtained by irradiating the laminate I with ultraviolet light using a mask pattern that masks the portions corresponding to the non-light-emitting portions of the OLED display element and does not mask the portions corresponding to the light-emitting portions of the OLED display element.
The area ratio between the non-light-emitting portion of the OLED display element and the light-emitting portion of the OLED display element is as described above.
The conditions for ultraviolet irradiation can be adjusted as appropriate to obtain a light transmission-absorption filter I having a first region that includes a light-absorbency-eliminating region. For example, the pressure can be atmospheric pressure (101.33 kPa), the temperature can be a mild temperature of 10 to 60°C, the lamp output can be 10 to 320 W/cm, and the lamp used can be an air-cooled metal halide lamp, an ultra-high pressure mercury lamp, or the like. The irradiation dose can be 200 to 5000 mJ/ cm2 .

<光透過吸収フィルタIIの製造方法>
 上記光透過吸収フィルタIIは、上記積層体IIと、上記積層体pre-IIIに紫外線を照射してマスク露光することにより得られる積層体IIIとを積層することにより得ることができる。
 マスクパターン、OLED表示素子の非発光部とOLED表示素子の発光部との面積比率、及び、紫外線照射の条件については、上記光透過吸収フィルタIにおけるマスクパターン、OLED表示素子の非発光部とOLED表示素子の発光部との面積比率、及び、紫外線照射の条件に係る記載を、積層体Iを積層体pre-IIIに読み替え、光透過吸収フィルタIを積層体IIIに読み替えて適用することができる。
 上記積層体IIと上記積層体IIIとの積層方法については特に限定されず、粘着剤層を介して積層されていてもよいし、貼り合わせで積層構造を作製してもよい。粘着剤層としては、後述の粘着剤層の記載を適用することができる。
<Method of manufacturing the light transmission/absorption filter II>
The light transmission/absorption filter II can be obtained by laminating the laminate II and a laminate III obtained by irradiating the laminate pre-III with ultraviolet light and exposing it using a mask.
With regard to the mask pattern, the area ratio between the non-light-emitting portions of the OLED display element and the light-emitting portions of the OLED display element, and the conditions for ultraviolet light irradiation, the descriptions relating to the mask pattern, the area ratio between the non-light-emitting portions of the OLED display element and the light-emitting portions of the OLED display element, and the conditions for ultraviolet light irradiation in the above-mentioned light-transmitting-absorbing filter I can be applied by replacing laminate I with laminate pre-III and light-transmitting-absorbing filter I with laminate III.
The method for laminating the laminate II and the laminate III is not particularly limited, and they may be laminated via a pressure-sensitive adhesive layer, or they may be attached to each other to form a laminate structure. As the pressure-sensitive adhesive layer, the description of the pressure-sensitive adhesive layer described below can be applied.

 本発明の光透過吸収フィルタは、上述の光学機能フィルムを有していてもよい。
 また、本発明の光透過吸収フィルタは、紫外線吸収剤を含有する層を有していてもよい。紫外線吸収剤としては、特に制限することなく常用の化合物を使用でき、例えば、後述の紫外線吸収層における紫外線吸収剤を挙げることができる。紫外線吸収剤を含有する層を構成する樹脂についても、特に制限することなく、例えば、後述の紫外線吸収層における樹脂を挙げることができる。
 上記紫外線吸収剤を含有する層中の紫外線吸収剤の含有量は目的に応じて適宜に調整される。
The light transmission/absorption filter of the present invention may have the above-mentioned optically functional film.
The light transmission/absorption filter of the present invention may also have a layer containing an ultraviolet absorber. As the ultraviolet absorber, any commonly used compound can be used without any particular limitations, and examples thereof include the ultraviolet absorbers in the ultraviolet absorbing layer described below. The resin constituting the layer containing the ultraviolet absorber is also without any particular limitations, and examples thereof include the resins in the ultraviolet absorbing layer described below.
The content of the ultraviolet absorber in the layer containing the ultraviolet absorber is adjusted appropriately depending on the purpose.

[表示素子中間品]
 上記光透過吸収フィルタIを含む本発明のOLED表示素子の作製においては、積層体Iを含む表示素子中間品を用いることも好ましい。表示素子中間品は、積層体Iを含む限り、その他の構成としては、表示装置に通常用いられているOLED表示素子の構成を特に制限なく用いることができる。
 上記表示素子中間品において、積層体IとOLED表示素子とは、直接接するようにして積層されていてもよく、粘着剤層を介して貼り合わされていてもよい。粘着剤層としては、後述の粘着剤層の記載を適用することができる。また、粘着剤層の他に、バリアフィルム等の任意の層をさらに介して積層されていてもよい。バリアフィルム等の任意の層については、OLED表示素子において常用される任意の層を適宜用いることができ、バリアフィルムについては、例えば、前述のガスバリア層の記載を適用することができる。
 上記表示素子中間品において、積層体Iにおける波長選択吸収層及び光吸収消失性層のうち、いずれの層がOLED表示素子に近くなるような積層構造でも構わない。上記表示素子中間品においては、積層体Iにおける波長選択吸収層がOLED表示素子に対して光吸収消失性層よりも近くなるような積層構造であることが、少ない紫外線照射量により光吸収消失性層を消色させられる観点から好ましい。
[Display element intermediate product]
In producing the OLED display element of the present invention including the light-transmitting-absorbing filter I, it is also preferable to use a display element intermediate including the laminate I. As long as the display element intermediate includes the laminate I, the other configurations of the display element intermediate can be any configuration of an OLED display element that is commonly used in display devices, without any particular limitations.
In the display element intermediate, the laminate I and the OLED display element may be laminated so as to be in direct contact with each other, or may be bonded together via an adhesive layer. The adhesive layer may be the same as the adhesive layer described below. Furthermore, in addition to the adhesive layer, an optional layer such as a barrier film may be laminated via the adhesive layer. Any layer commonly used in OLED display elements may be used as the optional layer such as the barrier film, and the barrier film may be the same as the gas barrier layer described above.
The display element intermediate product may have a laminate structure in which either the wavelength-selective absorption layer or the light-absorbing and dissipating layer in the laminate I is closer to the OLED display element. From the viewpoint of being able to discolor the light-absorbing and dissipating layer with a small amount of ultraviolet light irradiation, it is preferable that the display element intermediate product have a laminate structure in which the wavelength-selective absorption layer in the laminate I is closer to the OLED display element than the light-absorbing and dissipating layer.

[OLED表示素子]
 本発明のOLED表示素子は、本発明の光吸収フィルタを含み、上述の光吸収フィルタI又はIIを含むことが好ましい。本発明のOLED表示素子は、本発明の光吸収フィルタを含む限り、その他の構成としては、表示装置に通常用いられているOLED表示素子の構成を特に制限なく用いることができる。
(光透過吸収フィルタIを含むOLED表示素子)
 上記表示素子中間品を紫外線照射によりマスク露光することにより、上記表示素子中間品が含む積層体Iを光透過吸収フィルタIに変換してなる、本発明のOLED表示素子が得られる。すなわち、上記表示素子中間品は、本発明のOLED表示素子の前段階としての中間品であり、本発明のOLED表示素子は、OLED表示素子としての完成品を意味する。
 なお、本発明のOLED表示素子は、前述の通り、本発明の光透過吸収フィルタにおける上記第一の部位がOLED表示素子の発光部上に配置され、本発明の光透過吸収フィルタにおける上記第二の部位がOLED表示素子の非発光部上に配置されてなる構成を有する。
[OLED display element]
The OLED display element of the present invention includes the light-absorbing filter of the present invention, and preferably includes the above-mentioned light-absorbing filter I or II. As long as the OLED display element of the present invention includes the light-absorbing filter of the present invention, the OLED display element may use, without any particular limitation, the configuration of an OLED display element that is normally used in a display device, as the other configuration.
(OLED display element including light-transmitting/absorbing filter I)
The display element intermediate is exposed to ultraviolet light through a mask, thereby obtaining the OLED display element of the present invention, in which the laminate I contained in the display element intermediate is converted into a light-transmitting/absorbing filter I. In other words, the display element intermediate is an intermediate product as a precursor to the OLED display element of the present invention, and the OLED display element of the present invention means a finished product as an OLED display element.
As described above, the OLED display element of the present invention has a configuration in which the first portion of the light transmission-absorption filter of the present invention is disposed on a light-emitting portion of the OLED display element, and the second portion of the light transmission-absorption filter of the present invention is disposed on a non-light-emitting portion of the OLED display element.

(光透過吸収フィルタIIを含むOLED表示素子)
 また、上記光透過吸収フィルタIIを含む本発明のOLED表示素子については、例えば、OLED表示素子の発光部及び非発光部のパターンに応じた第一の部位及び第二の部位を有する上記光透過吸収フィルタIIを予め作製しておき、この光透過吸収フィルタIIを上記OLED表示素子に貼り合わせるか、他の層を介して積層することにより得られる。
 光透過吸収フィルタIIとOLED表示素子との積層については、上記の積層体IとOLED表示素子との積層に係る記載をそのまま適用することができる。
 上記光透過吸収フィルタIIを含む本発明のOLED表示素子において、光透過吸収フィルタIIにおける積層体II及び積層体IIIのうち、いずれの層がOLED表示素子に近くなるような積層構造でも構わない。なお、以下に記載するように、表示光の視野角による色味変化の抑制を実現しやすい観点から、積層体IIIがOLED表示素子に対して積層体IIよりも近くなるような積層構造であること好ましい。
(OLED display element including light-transmitting/absorbing filter II)
Furthermore, an OLED display element of the present invention including the above-mentioned light-transmitting-absorbing filter II can be obtained, for example, by previously producing the above-mentioned light-transmitting-absorbing filter II having first and second regions corresponding to the pattern of the light-emitting portions and non-light-emitting portions of the OLED display element, and then bonding this light-transmitting-absorbing filter II to the OLED display element or laminating it via another layer.
The above description of the lamination of the laminate I and the OLED display element can be applied as is to the lamination of the light transmitting/absorbing filter II and the OLED display element.
In an OLED display element of the present invention including the light-transmitting-absorbing filter II, the layer structure may be such that either layer of the laminate II or the laminate III in the light-transmitting-absorbing filter II is closer to the OLED display element. Note that, as described below, from the viewpoint of easily realizing suppression of color shift due to viewing angle of display light, it is preferable that the laminate III be closer to the OLED display element than the laminate II.

 光透過吸収フィルタIIを含むOLED表示素子においては、光透過吸収フィルタIIにおける積層体IIIとOLED表示素子層との距離を調節することにより、表示光の透過性に対する影響(輝度の低下)を抑えつつ、マイクロキャビティ構造を有するOLED表示装置に適用した際には、表示光色味の視野角依存性を調節することができる。これは、光透過吸収フィルタIIにおける積層体IIIとOLED表示素子層との距離が長くなると、視差の影響により、視認者が視覚する表示光全体に占める、第二の部位を透過した光の比率が高くなることによる。
 上記積層体IIIとOLED表示素子層との距離は、例えば、2~45μmとすることができる。視認者が視覚する表示光全体に占める、第二の部位を透過した光の比率を一定以上とすることによる、表示光の視野角による色味変化の抑制と、視覚する表示光全体に対する第二の部位で吸収される光の比率を一定以下とすることによる、輝度の低下抑制とを両立する観点からは、上記積層体IIIとOLED表示素子層との距離は、5~35μmが好ましく、10~30μmがより好ましく、15~28μmが更に好ましく、20~25μmが最も好ましい。
 なお、「積層体IIIとOLED表示素子層との距離」とは、後述のOLED表示素子II-1~II-3における「積層体IIIと発光素子層との距離d」と同義である。
In an OLED display element including a light-transmitting-absorbing filter II, by adjusting the distance between the laminate III in the light-transmitting-absorbing filter II and the OLED display element layer, it is possible to suppress the effect on the transmittance of display light (reduction in brightness) and, when applied to an OLED display device having a microcavity structure, to adjust the viewing angle dependence of the color of the display light. This is because, as the distance between the laminate III in the light-transmitting-absorbing filter II and the OLED display element layer increases, the proportion of light transmitted through the second portion in the total display light perceived by the viewer increases due to the effect of parallax.
The distance between the laminate III and the OLED display element layer may be, for example, 2 to 45 μm. From the viewpoint of simultaneously suppressing a change in color of the display light due to the viewing angle by making the ratio of the light transmitted through the second portion to the entire display light perceived by the viewer equal to or greater than a certain level, and suppressing a decrease in brightness by making the ratio of the light absorbed by the second portion to the entire display light perceived equal to or less than a certain level, the distance between the laminate III and the OLED display element layer is preferably 5 to 35 μm, more preferably 10 to 30 μm, even more preferably 15 to 28 μm, and most preferably 20 to 25 μm.
The "distance between the laminate III and the OLED display element layer" is synonymous with the "distance d between the laminate III and the light emitting element layer" in the OLED display elements II-1 to II-3 described later.

 光透過吸収フィルタIIを含むOLED表示素子において、上述の表示光の視野角による色味変化の抑制と、輝度の低下抑制とを両立する観点からは、以下のOLED表示素子II-1~II-3が好ましく挙げられる。
 なお、以下のOLED表示素子II-1~II-3においては、積層体II、積層体III、及び発光素子層がこの順に配置されてなり、積層体IIが視認者側となるようにOLED表示装置に組み込まれる。
(OLED表示素子II-1)
 積層体IIIと発光素子層との距離dと、上記発光素子層を構成する各発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各発光素子の直上に位置する部分の平均面積Sfとが、下記式(1)及び(2)の関係を満たす、OLED表示素子。
    式(1)  0.6≦d/√S≦7.5
    式(2)  0.7≦Sf/S≦1.5
(OLED表示素子II-2)
 積層体IIIと発光素子層との距離dと、上記発光素子層を構成する各青色発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各青色発光素子の直上に位置する部分の平均面積Sfとが、下記式(3)及び(4)の関係を満たす、OLED表示素子。
    式(3)  1.0≦d/√S≦7.0
    式(4)  0.8≦Sf/S≦1.2
(OLED表示素子II-3)
 積層体IIIと発光素子層との距離dと、上記発光素子層を構成する各緑色発光素子の平均面積Sと、上記第一の光透過吸収部位のうち上記各緑色発光素子の直上に位置する部分の平均面積Sfとが、下記式(5)及び(6)の関係を満たす、OLED表示素子。
    式(5)  1.0≦d/√S≦7.0
    式(6)  0.8≦Sf/S≦1.2
In an OLED display element including a light-transmitting/absorbing filter II, from the viewpoint of simultaneously suppressing the color change of the display light due to the viewing angle and suppressing a decrease in brightness, the following OLED display elements II-1 to II-3 are preferred.
In the following OLED display elements II-1 to II-3, a laminate II, a laminate III, and a light-emitting element layer are arranged in this order, and the elements are incorporated into an OLED display device so that the laminate II faces the viewer.
(OLED display element II-1)
An OLED display element, wherein a distance d between the laminate III and the light-emitting element layer, an average area S of each light-emitting element constituting the light-emitting element layer, and an average area Sf of a portion of the first light-transmitting/absorbing site located directly above each light-emitting element satisfy the relationships of the following formulas (1) and (2):
Formula (1) 0.6≦d/√S≦7.5
Formula (2) 0.7≦Sf/S≦1.5
(OLED display element II-2)
an OLED display element, wherein a distance d between the laminate III and the light-emitting element layer, an average area S B of each blue light-emitting element constituting the light-emitting element layer, and an average area Sf B of a portion of the first light-transmitting and absorbing site located directly above each blue light-emitting element satisfy the relationships of the following formulas (3) and (4):
Formula (3) 1.0≦d/√S B ≦7.0
Formula (4) 0.8≦Sf B /S B ≦1.2
(OLED display element II-3)
An OLED display element, wherein a distance d between the laminate III and the light-emitting element layer, an average area S G of each green light-emitting element constituting the light-emitting element layer, and an average area Sf G of a portion of the first light-transmitting and absorbing site located directly above each green light-emitting element satisfy the relationships of the following formulas (5) and (6):
Formula (5) 1.0≦d/ √SG ≦7.0
Formula (6) 0.8≦Sf G /S G ≦1.2

 上記式(1)~(6)において、積層体IIIと発光素子層との距離dの単位はμmであり、各平均面積S、Sf、S、Sf、S及びSfの単位はμmである。
 上記OLED表示素子II-1~II-3において、「積層体IIIと発光素子層との距離d」とは、積層体IIIにおけるマスク露光された光吸収消失性層と、発光素子層との距離を意味し、積層体IIIと発光素子層を含む素子の断面を観察することにより測定される値である。断面の観察方法は特に限定されないが、例えばミクロトームを用いて削り出した断面を走査型電子顕微鏡(SEM)により観察する方法などが挙げられる。
 発光素子層を構成する各青色発光素子の平均面積S及び発光素子層を構成する各緑色発光素子の平均面積Sは、いずれも、光学顕微鏡で観察することにより測定される値である。また、発光素子層を構成する各発光素子の平均面積Sは、各色発光素子の面積の数平均を意味し、各色発光素子の面積の総和を発光素子の総数で除することにより測定、算出される値である。なお、各色発光素子の面積の総和は、光学顕微鏡で観察することにより測定される。
 「上記第一の光透過吸収部位のうち上記各発光素子の直上に位置する部分の平均面積Sf」とは、各発光素子の面から、この面に垂直な光が出射された場合に、この出射光と重なる第一の部位の面積の数平均値を意味する。このことは、「上記第一の光透過吸収部位のうち上記各青色発光素子の直上に位置する部分の平均面積Sf」及び「上記第一の光透過吸収部位のうち上記各緑色発光素子の直上に位置する部分の平均面積Sf」についても同様であり、各青色発光素子又は各緑色発光素子の面から、この面に垂直な光が出射された場合に、この出射光と重なる第一の部位の面積の数平均値をそれぞれ意味する。
 各平均面積Sf、Sf及びSfについては、光学顕微鏡で観察することにより測定される値である。
In the above formulas (1) to (6), the unit of the distance d between the laminate III and the light emitting element layer is μm, and the unit of each of the average areas S, Sf, S B , Sf B , S G and Sf G is μm 2 .
In the above OLED display elements II-1 to II-3, the "distance d between the laminate III and the light-emitting element layer" means the distance between the mask-exposed light-absorbing and dissipative layer in the laminate III and the light-emitting element layer, and is a value measured by observing a cross section of an element including the laminate III and the light-emitting element layer. The method for observing the cross section is not particularly limited, and examples thereof include a method in which a cross section cut out with a microtome is observed with a scanning electron microscope (SEM).
The average area S B of each blue light-emitting element constituting the light-emitting element layer and the average area S G of each green light-emitting element constituting the light-emitting element layer are both values measured by observation with an optical microscope. The average area S of each light-emitting element constituting the light-emitting element layer means the number average of the areas of each color light-emitting element, and is a value measured and calculated by dividing the sum of the areas of each color light-emitting element by the total number of light-emitting elements. The sum of the areas of each color light-emitting element is measured by observation with an optical microscope.
The "average area Sf of the portions of the first light-transmitting and absorbing sites located directly above each light-emitting element" refers to the number average value of the areas of the first sites that overlap with the emitted light when light is emitted from the surface of each light-emitting element perpendicular to the surface. The same applies to the "average area Sf B of the portions of the first light-transmitting and absorbing sites located directly above each blue light-emitting element" and the "average area Sf G of the portions of the first light-transmitting and absorbing sites located directly above each green light-emitting element," which respectively refer to the number average value of the areas of the first sites that overlap with the emitted light when light is emitted from the surface of each blue light-emitting element or each green light-emitting element perpendicular to the surface.
The average areas Sf, Sf B , and Sf G are values measured by observation with an optical microscope.

 上記式(1)は、1.5≦d/√S≦7.0であることが好ましく、2.5≦d/√S≦6.0であることがより好ましく、3.5≦d/√S≦5.7であることが更に好ましい。
 上記式(2)は、0.8≦Sf/S≦1.3であることが好ましく、0.9≦Sf/S≦1.1であることがより好ましい。
 上記式(3)は、1.5≦d/√S≦7.0であることが好ましく、2.5≦d/√S≦5.7であることがより好ましく、3.5≦d/√S≦5.5であることが更に好ましい。
 上記式(4)は、0.9≦Sf/S≦1.1であることが好ましい。
 上記式(5)は、1.5≦d/√S≦7.0であることが好ましく、2.7≦d/√S≦6.7であることがより好ましく、4.0≦d/√S≦5.0であることが更に好ましい。
 上記式(6)は、0.9≦Sf/S≦1.1であることが好ましい。
The above formula (1) preferably satisfies 1.5≦d/√S≦7.0, more preferably 2.5≦d/√S≦6.0, and further preferably 3.5≦d/√S≦5.7.
The above formula (2) preferably satisfies 0.8≦Sf/S≦1.3, and more preferably satisfies 0.9≦Sf/S≦1.1.
The above formula (3) preferably satisfies 1.5≦d/√S B ≦7.0, more preferably 2.5≦d/√S B ≦5.7, and further preferably 3.5≦d/√S B ≦5.5.
In the above formula (4), it is preferable that 0.9≦Sf B /S B ≦1.1.
The above formula (5) preferably satisfies 1.5≦d/√SG 7.0, more preferably 2.7≦d/√SG 6.7, and further preferably 4.0≦d/ √SG ≦5.0.
In the above formula (6), it is preferable that 0.9≦Sf G /S G ≦1.1.

[OLED表示装置]
 本発明の有機エレクトロルミネッセンス表示装置(有機EL(electroluminescence)表示装置またはOLED(Organic Light Emitting Diode)表示装置と称され、本発明においては、OLED表示装置とも略す。)は、本発明の光透過吸収フィルタ又は本発明のOLED表示素子を含む。
 本発明のOLED表示装置としては、本発明の光透過吸収フィルタ又は本発明のOLED表示素子を含む限り、その他の構成としては、通常用いられているOLED表示装置の構成を特に制限なく用いることができる。なお、本発明のOLED表示素子は、本発明の光透過吸収フィルタが外光側になるようにして本発明のOLED表示装置に組み込まれる。また、本発明の光透過吸収フィルタは、前述の通り、上記第一の部位がOLED表示素子の発光部上に配置され、上記第二の部位がOLED表示素子の非発光部上に配置されるようにして、本発明のOLED表示装置に組み込まれる。
 OLED表示装置において、OLED表示素子の非発光部と発光部との面積比率は、通常、非発光部:発光部=90/10~60/40である。
 本発明のOLED表示装置の構成例としては、特に制限されないが、本発明の光透過吸収フィルタを含む場合には、例えば、外光に対して反対側から順に、ガラス、TFT(薄膜トランジスタ)を含む層、OLED表示素子、バリアフィルム、粘着剤層、本発明の光透過吸収フィルタ、粘着剤層、ガラス、粘着剤層、及び表面フィルムを含む表示装置が挙げられる。また、本発明のOLED表示素子を含む場合には、例えば、外光に対して反対側から順に、ガラス、TFT(薄膜トランジスタ)を含む層、本発明のOLED表示素子、バリアフィルム、ガラス、粘着剤層及び表面フィルムを含む表示装置が挙げられる。
 上記OLED表示素子は、アノード電極、発光層及びカソード電極の順に配置した構成を有する。アノード電極及びカソード電極の間には、発光層の他に、ホール注入層、ホール輸送層、電子輸送層及び電子注入層等を含んでいる。この他、例えば、特開2014-132522号公報の記載も参照することができる。
 上記ガラスに代えて、樹脂フィルムを採用することもできる。
[OLED display device]
The organic electroluminescence display device of the present invention (also referred to as an organic EL (electroluminescence) display device or OLED (organic light emitting diode) display device, and in the present invention, also abbreviated as an OLED display device) includes the light transmission/absorption filter of the present invention or the OLED display element of the present invention.
As long as the OLED display device of the present invention includes the light transmission-absorption filter of the present invention or the OLED display element of the present invention, the other components of a commonly used OLED display device can be used without any particular limitations. The OLED display element of the present invention is incorporated into the OLED display device of the present invention so that the light transmission-absorption filter of the present invention is on the external light side. Furthermore, as described above, the light transmission-absorption filter of the present invention is incorporated into the OLED display device of the present invention so that the first region is disposed on the light-emitting portion of the OLED display element and the second region is disposed on the non-light-emitting portion of the OLED display element.
In an OLED display device, the area ratio between the non-light-emitting portion and the light-emitting portion of the OLED display element is usually 90/10 to 60/40.
Examples of the configuration of the OLED display device of the present invention are not particularly limited, but when it includes the light transmission-absorbing filter of the present invention, examples include a display device comprising, from the opposite side to external light, glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a pressure-sensitive adhesive layer, the light transmission-absorbing filter of the present invention, a pressure-sensitive adhesive layer, glass, a pressure-sensitive adhesive layer, and a surface film. Also, when it includes the OLED display element of the present invention, examples include a display device comprising, from the opposite side to external light, glass, a layer including a TFT (thin film transistor), the OLED display element of the present invention, a barrier film, glass, a pressure-sensitive adhesive layer, and a surface film.
The OLED display element has a configuration in which an anode electrode, a light-emitting layer, and a cathode electrode are arranged in this order. In addition to the light-emitting layer, layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer are included between the anode electrode and the cathode electrode. For further details, see, for example, the description in Japanese Patent Application Laid-Open No. 2014-132522.
Instead of the glass, a resin film may be used.

<粘着剤層>
 本発明のOLED表示装置において、本発明の光透過吸収フィルタ又は本発明のOLED表示素子の外光側の面は粘着剤層を介して、ガラス、バリアフィルム、反射防止層等を有する光学機能フィルム、あるいは偏光子及び偏光板保護フィルムを含む偏光板と貼り合わされていてもよい。また、本発明の光透過吸収フィルタ又は本発明のOLED表示素子の、外光とは反対側に位置する面は、粘着剤層を介してガラス(基材)、バリアフィルム、TFTを含む層と貼り合わされていることが好ましい。
 なお、本発明のOLED表示素子がその最表面に粘着剤層を有する形態である場合には、上記の粘着剤層の説明については、本発明のOLED表示素子が最表面に有する粘着剤層に係る説明として読み替えるものとする。
 上記粘着剤層としては、国際公開第2021/132674号の[0239]~[0290]に記載のOLED表示装置における粘着剤層及び形成方法に係る記載をそのまま適用することができる。
 なお、国際公開第2021/132674号に記載の粘着剤組成物は、本発明の光透過吸収フィルタ及び本発明のOLED表示素子に含まれる光透過吸収フィルタの耐光性の点から後述の紫外線吸収剤を含有することが好ましい。
<Adhesive Layer>
In the OLED display device of the present invention, the surface of the light transmission-absorption filter of the present invention or the OLED display element of the present invention facing external light may be bonded, via an adhesive layer, to glass, a barrier film, an optically functional film having an antireflection layer or the like, or a polarizing plate including a polarizer and a polarizing plate protective film. Furthermore, the surface of the light transmission-absorption filter of the present invention or the OLED display element of the present invention facing the external light is preferably bonded, via an adhesive layer, to glass (substrate), a barrier film, or a layer including a TFT.
In addition, when the OLED display element of the present invention has a pressure-sensitive adhesive layer on its outermost surface, the above description of the pressure-sensitive adhesive layer shall be read as a description relating to the pressure-sensitive adhesive layer that the OLED display element of the present invention has on its outermost surface.
As the pressure-sensitive adhesive layer, the descriptions relating to the pressure-sensitive adhesive layer and the forming method in the OLED display device described in [0239] to [0290] of WO 2021/132674 can be applied as is.
In addition, the pressure-sensitive adhesive composition described in WO 2021/132674 preferably contains an ultraviolet absorber described later in terms of the light resistance of the light transmission-absorption filter of the present invention and the light transmission-absorption filter contained in the OLED display element of the present invention.

<基材>
 本発明のOLED表示装置において、本発明の光透過吸収フィルタ又は本発明のOLED表示素子は、外光側に位置する面において、粘着剤層を介して光学機能フィルムと貼り合わされていてもよい。また、本発明の光透過吸収フィルタ又は本発明のOLED表示素子は、外光とは反対側に位置する面において、粘着剤層を介してガラス(基材)と貼り合わされていることが好ましい。
<Base material>
In the OLED display device of the present invention, the light transmission-absorption filter of the present invention or the OLED display element of the present invention may be bonded to an optically functional film via a pressure-sensitive adhesive layer on the surface facing the external light side. Also, the light transmission-absorption filter of the present invention or the OLED display element of the present invention is preferably bonded to glass (substrate) via a pressure-sensitive adhesive layer on the surface facing the external light side.

 上記粘着剤層を形成する方法は特に限定されず、例えば、積層体I、本発明の光透過吸収フィルタ(好ましくは光透過吸収フィルタI)又は本発明のOLED表示素子にバーコーターなどの通常の手段で粘着剤組成物を塗布し、乾燥及び硬化させる方法;粘着剤組成物をまず、剥離性基材の表面に塗布、乾燥した後、剥離性基材を用いて粘着剤層を積層体I、本発明の光透過吸収フィルタ(好ましくは光透過吸収フィルタI)又は本発明のOLED表示素子に転写し、熟成、硬化させる方法などが用いられる。
 剥離性基材としては、特に制限されず、任意の剥離性基材を使用することができ、例えば上述の積層体I、積層体II、積層体pre-IIIの製造方法における支持体フィルムが挙げられる。
 その他、塗布、乾燥、熟成及び硬化の条件についても、常法に基づき、適宜調整することができる。
The method for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a method in which a pressure-sensitive adhesive composition is applied to the laminate I, the light transmission-absorption filter of the present invention (preferably light transmission-absorption filter I) or the OLED display element of the present invention by a conventional means such as a bar coater, followed by drying and curing; and a method in which the pressure-sensitive adhesive composition is first applied to the surface of a release substrate, dried, and then the pressure-sensitive adhesive layer is transferred to the laminate I, the light transmission-absorption filter of the present invention (preferably light transmission-absorption filter I) or the OLED display element of the present invention using the release substrate, followed by aging and curing.
The release substrate is not particularly limited, and any release substrate can be used, for example, the support film in the above-mentioned production methods of Laminate I, Laminate II, and Laminate pre-III.
In addition, the conditions for application, drying, aging and curing can be appropriately adjusted based on conventional methods.

<紫外線吸収層>
 本発明の光透過吸収フィルタ又は本発明のOLED表示素子を含む、本発明のOLED表示装置は、本発明の光透過吸収フィルタ又は本発明のOLED表示素子に対して視認者側に、上記紫外線照射によりラジカルを生成する化合物の光吸収(紫外線吸収)を阻害する層(以下、「紫外線吸収層」とも称す。)を有することが好ましい。上記紫外線吸収層を設けることにより、外光による本発明の光透過吸収フィルタ又は本発明のOLED表示素子に含まれる本発明の光透過吸収フィルタの褪色を防止することができる。
 以下に本発明に用いられる紫外線吸収層について説明する。
<Ultraviolet absorbing layer>
The OLED display device of the present invention, including the light transmission-absorption filter of the present invention or the OLED display element of the present invention, preferably has a layer (hereinafter also referred to as an "ultraviolet absorbing layer") that inhibits light absorption (ultraviolet absorption) of the compound that generates radicals upon ultraviolet irradiation, on the viewer side of the light transmission-absorption filter of the present invention or the OLED display element of the present invention. By providing the ultraviolet absorbing layer, it is possible to prevent fading of the light transmission-absorption filter of the present invention or the light transmission-absorption filter of the present invention included in the OLED display element of the present invention due to external light.
The ultraviolet absorbing layer used in the present invention will be described below.

(紫外線吸収剤)
 上記紫外線吸収層は、通常、樹脂および紫外線吸収剤を含む。
 本発明に好ましく用いられる紫外線吸収剤の具体例としては、例えばヒンダードフェノール系化合物、ヒドロキシベンゾフェノン系化合物等のベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物などが挙げられる。
 ヒンダードフェノール系化合物及びベンゾトリアゾール系化合物の例としては、国際公開第2023/234353号の段落[0227]に記載のヒンダードフェノール系化合物及びベンゾトリアゾール系化合物を、本発明においても好適に用いることができる。
 これらの紫外線吸収剤の添加量は、紫外線吸収層を構成する樹脂100質量部に対して0.1質量部~30.0質量部が好ましい。
(ultraviolet absorber)
The ultraviolet absorbing layer generally contains a resin and an ultraviolet absorbing agent.
Specific examples of ultraviolet absorbers preferably used in the present invention include hindered phenol compounds, benzophenone compounds such as hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds, and nickel complex salt compounds.
As examples of the hindered phenol compounds and benzotriazole compounds, the hindered phenol compounds and benzotriazole compounds described in paragraph [0227] of WO 2023/234353 can also be suitably used in the present invention.
The amount of these ultraviolet absorbents added is preferably 0.1 to 30.0 parts by mass relative to 100 parts by mass of the resin constituting the ultraviolet absorbing layer.

 また、本発明の光透過吸収フィルタ又は本発明の表示素子に含まれる本発明の光透過吸収フィルタの耐光性をより向上させる観点から、紫外線吸収剤として国際公開第2023/234353号の段落[0229]~[0283]に記載の式(1)で表される化合物(1)を用いることも好ましい。国際公開第2023/234353号に記載の式(1)で表される化合物(1)の吸収特性、合成法、含有量については、国際公開第2023/234353号の段落[0279]~[0283]における記載を、本発明においても好適に用いることができる。 Furthermore, from the viewpoint of further improving the light resistance of the light transmission/absorption filter of the present invention or the light transmission/absorption filter of the present invention contained in the display element of the present invention, it is also preferable to use compound (1) represented by formula (1) described in paragraphs [0229] to [0283] of WO 2023/234353 as the ultraviolet absorber. With regard to the absorption characteristics, synthesis method, and content of compound (1) represented by formula (1) described in WO 2023/234353, the descriptions in paragraphs [0279] to [0283] of WO 2023/234353 can also be suitably used in the present invention.

(樹脂)
 上記紫外線吸収層に用いられる樹脂としては、公知の樹脂を用いることができ、本発明の趣旨に反しない限りにおいて特に制限はない。上記樹脂としては、例えば、セルロースアシレート樹脂、アクリル樹脂、シクロオレフィン系樹脂、ポリエステル系樹脂、エポキシ樹脂を挙げることができる。
(resin)
The resin used in the ultraviolet absorbing layer may be any known resin, and is not particularly limited as long as it does not deviate from the spirit of the present invention. Examples of the resin include cellulose acylate resin, acrylic resin, cycloolefin resin, polyester resin, and epoxy resin.

(紫外線吸収層の設置位置)
 上記紫外線吸収層の配置は、本発明の光透過吸収フィルタ又は本発明の表示素子に対して視認者側であれば特に限定されず、いずれの位置でも設置でき、例えば、偏光板の保護膜、反射防止フィルム等の部材に紫外線吸収剤を添加し、紫外線吸収層の機能を持たせることも可能である。また、前述の粘着剤層に紫外線吸収剤を添加することもできる。
(Installation position of ultraviolet absorbing layer)
The location of the ultraviolet absorbing layer is not particularly limited as long as it is on the viewer side of the light transmission-absorption filter of the present invention or the display element of the present invention, and it can be installed at any position. For example, it is possible to add an ultraviolet absorber to a member such as a protective film of a polarizing plate or an antireflection film to give it the function of an ultraviolet absorbing layer. In addition, an ultraviolet absorber can be added to the pressure-sensitive adhesive layer.

 以下に、実施例に基づき本発明についてさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の範囲は以下に示す実施例に限定されるものではない。
 なお、以下の実施例において組成を表す「部」及び「%」は、特に断らない限り質量基準である。室温とは「25℃」を意味する。
 なお、光吸収消失性層形成液の調製工程から、光吸収消失性層形成液を用いた積層体の作製工程及び紫外線照射試験に用いるまでの工程は、いずれも、紫外線が照射されないよう、黄色灯下で行った。
 λmaxは、後述の[第一、及び第二の部位の吸光度測定]に記載の方法により測定された値である。
The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.
In the following examples, "parts" and "%" representing compositions are by mass unless otherwise specified. Room temperature means "25°C."
All of the steps from the preparation of the light-absorbing and dissipating layer-forming solution to the production of a laminate using the light-absorbing and dissipating layer-forming solution and the use in the ultraviolet irradiation test were carried out under yellow light to prevent ultraviolet irradiation.
λ max is a value measured by the method described below in [Measurement of absorbance at first and second sites].

 積層体の作製に用いた材料を次に示す。
<ポリマー(樹脂)>
(樹脂1)
 東亞合成社製のARUFON UC-3920(商品名)、カルボキシ基含有アクリルポリマー、重量平均分子量15500。
(樹脂2)
 アダマンチルメタクリレート-アクリル酸ランダム共重合体、アクリル酸含有率52モル%、重量平均分子量46300。
 なお、樹脂2のアクリル酸部が本発明で規定する酸基を有する化合物Aに相当する。
(樹脂3)
 ベンジルメタクリレート-メタクリル酸系共重合体(藤倉化成社製、アクリベースFF-187(商品名)、ベンジルメタクリレート比率70%)を、樹脂3として用いた。
(樹脂4)
 ポリスチレン主鎖にオキサゾリン基がペンダント化された非晶性タイプの反応性ポリマー(日本触媒社製、エポクロスRPS-1005(商品名)、オキサゾリン基含有構成単位の比率:3モル%)を、樹脂4として用いた。
(樹脂5)
 環状ポリオレフィン樹脂であるアートンR5000(商品名、JSR社製、ノルボルネン系ポリマー、Tg:135℃)を、樹脂5として用いた。
 なお、後述の各形成液の組成における配合量(単位:質量部)は、樹脂が溶液として販売されている場合には、溶媒を除く樹脂そのものの配合量を記載する。
 また、上記樹脂1及び3~5を波長選択吸収層の形成に使用し、上記樹脂2を光吸収消失性層の形成に使用した。
The materials used to prepare the laminate are as follows:
<Polymer (resin)>
(Resin 1)
ARUFON UC-3920 (trade name) manufactured by Toagosei Co., Ltd., a carboxyl group-containing acrylic polymer, weight average molecular weight 15,500.
(Resin 2)
Adamantyl methacrylate-acrylic acid random copolymer, acrylic acid content 52 mol%, weight average molecular weight 46,300.
The acrylic acid portion of Resin 2 corresponds to Compound A having an acid group as defined in the present invention.
(Resin 3)
A benzyl methacrylate-methacrylic acid copolymer (manufactured by Fujikura Kasei Co., Ltd., Acribase FF-187 (trade name), benzyl methacrylate ratio 70%) was used as resin 3.
(Resin 4)
An amorphous reactive polymer having oxazoline groups pendant on a polystyrene main chain (Epocross RPS-1005 (trade name), manufactured by Nippon Shokubai Co., Ltd., proportion of oxazoline group-containing structural units: 3 mol%) was used as resin 4.
(Resin 5)
A cyclic polyolefin resin, Arton R5000 (trade name, manufactured by JSR Corporation, norbornene-based polymer, Tg: 135° C.), was used as resin 5.
In addition, when the resin is sold as a solution, the blending amount (unit: parts by mass) in the composition of each forming liquid described below is the blending amount of the resin itself excluding the solvent.
The resins 1 and 3 to 5 were used to form the wavelength selective absorption layer, and the resin 2 was used to form the light absorbing and disappearing layer.

<化合物B>
 4-メチルキノリン(東京化成社製、Lepidine、pKaH5.1)
<Compound B>
4-Methylquinoline (Tokyo Chemical Industry Co., Ltd., Lepidine, pKaH 5.1)

<染料>
 下記構造式中において、Buはブチル基を示す。
<Dye>
In the following structural formula, Bu represents a butyl group.

(光吸収消失性層に含有させる染料)
(Dye to be contained in the light-absorbing and dissipating layer)

(波長選択吸収層に含有させる染料)
(Dye to be contained in wavelength selective absorption layer)

 ソルベントブルー35(富士フイルム和光純薬社製、アントラキノン染料、λmax652nm)を染料H-1として用いた。
 PD-311F(商品名、山本化成社製、テトラアザポルフィリン銅錯体染料、λmax585nm)を染料I-2として用いた。
 FDB-002(商品名、山田化学工業社製、ポルフィリン系染料、λmax432nm)を染料J-1として用いた。
Solvent Blue 35 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., anthraquinone dye, λ max 652 nm) was used as dye H-1.
PD-311F (trade name, manufactured by Yamamoto Chemical Industries, Ltd., tetraazaporphyrin copper complex dye, λ max 585 nm) was used as dye I-2.
FDB-002 (trade name, manufactured by Yamada Chemical Industry Co., Ltd., porphyrin dye, λ max 432 nm) was used as dye J-1.

(密着改良剤1)
 特許第6722602号公報の合成例22に記載の含フッ素共重合体(A-19-1)の合成例において、2-(パーフルオロヘキシル)エチルアクリレート(C6FA)を25質量部、特許第6722602号公報の段落[0063]に記載の単量体II-12を5質量部、アクリル酸(AA)を70質量部にそれぞれ変更した以外は、上記含フッ素共重合体(A-19-1)の合成と同様にして合成した、下記構成成分で構成される含フッ素共重合体を、密着改良剤1として用いた。
(Adhesion improver 1)
A fluorine-containing copolymer composed of the following components was used as adhesion improver 1, synthesized in the same manner as in the synthesis of the fluorine-containing copolymer (A-19-1) described in Synthesis Example 22 of Japanese Patent No. 6722602, except that 2-(perfluorohexyl)ethyl acrylate (C6FA) was changed to 25 parts by mass, monomer II-12 described in paragraph [0063] of Japanese Patent No. 6722602 was changed to 5 parts by mass, and acrylic acid (AA) was changed to 70 parts by mass.

(密着改良剤2)
 タフテックM-1913(商品名、旭化成社製、無水マレイン酸変性されたスチレン/エチレン/ブチレン/スチレンのブロック共重合樹脂)
(Adhesion improver 2)
Tuftec M-1913 (trade name, manufactured by Asahi Kasei Corporation, maleic anhydride-modified styrene/ethylene/butylene/styrene block copolymer resin)

(レベリング剤1)
 下記構成成分で構成されるポリマー界面活性剤をレベリング剤1として用いた。下記構造式中、各構成成分の割合はモル比であり、t-Buはtert-ブチル基を意味する。
(Leveling Agent 1)
A polymer surfactant composed of the following components was used as leveling agent 1. In the following structural formula, the ratio of each component is a molar ratio, and t-Bu means a tert-butyl group.

(基材1)
 ポリエチレンテレフタレートフィルム ルミラーXD-510P(商品名、膜厚50μm、東レ社製)を基材1として用いた。
(基材11)
 セルロースアシレートフィルム(富士フイルム社製、商品名:TG60UL、膜厚60μm)
(基材21)
 セルロースアシレートフィルム(富士フイルム社製、商品名:ZRD40SL、膜厚40μm)
(Base material 1)
A polyethylene terephthalate film Lumirror XD-510P (trade name, film thickness 50 μm, manufactured by Toray Industries, Inc.) was used as the substrate 1.
(Base material 11)
Cellulose acylate film (manufactured by Fujifilm Corporation, product name: TG60UL, film thickness 60 μm)
(Base material 21)
Cellulose acylate film (manufactured by Fujifilm Corporation, product name: ZRD40SL, film thickness 40 μm)

<<積層体I:波長選択吸収層と光吸収消失性層とを含む積層体の作製>>
実施例1
[ガスバリア層を有する積層体No.101の作製]
<1.波長選択吸収層の作製>
(1)波長選択吸収層形成液1の調製
 各成分を下記に示す組成で混合し、波長選択吸収層形成液1を調製した。
――――――――――――――――――――――――――――――――――
波長選択吸収層形成液1の組成
――――――――――――――――――――――――――――――――――
 樹脂1                     86.56質量部
 レベリング剤1                  0.08質量部
 染料A-321                  6.19質量部
 染料7-23                   1.80質量部
 染料C-122                  1.42質量部
 染料H-1                    3.95質量部
 テトラヒドロフラン(溶媒)          566.7 質量部
――――――――――――――――――――――――――――――――――
<<Laminate I: Preparation of laminate including wavelength-selective absorption layer and light-absorbing and dissipating layer>>
Example 1
[Preparation of Laminate No. 101 Having a Gas Barrier Layer]
<1. Fabrication of wavelength-selective absorption layer>
(1) Preparation of Wavelength-Selective Absorbing Layer Forming Solution 1 The components were mixed in the composition shown below to prepare wavelength-selective absorbing layer forming solution 1.
----------------------------------------------------------------------------------
Composition of wavelength selective absorption layer forming liquid 1 ----------------------------------------------------------------
Resin 1 86.56 parts by mass Leveling agent 1 0.08 parts by mass Dye A-321 6.19 parts by mass Dye 7-23 1.80 parts by mass Dye C-122 1.42 parts by mass Dye H-1 3.95 parts by mass Tetrahydrofuran (solvent) 566.7 parts by mass

 続いて、得られた波長選択吸収層形成液1を絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting wavelength-selective absorption layer forming solution 1 was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

(2)波長選択吸収層1の形成
 上記濾過処理後の波長選択吸収層形成液1を、基材1上に、乾燥後の膜厚が2.5μmとなるようにバーコーターを用いて塗布し、120℃で乾燥し、波長選択吸収層つき基材2を作製した。
(2) Formation of Wavelength-Selective Absorption Layer 1 The wavelength-selective absorption layer-forming liquid 1 after the above-mentioned filtration treatment was applied to the substrate 1 using a bar coater so that the film thickness after drying would be 2.5 μm, and the applied coating was dried at 120° C. to prepare a substrate 2 with a wavelength-selective absorption layer.

<2.拡散阻害層つき基材3の作製>
(1)拡散阻害層形成液Aの調製
 各成分を下記に示す組成で混合し、50℃の恒温槽で1時間撹拌し、ポリ(メタクリル酸)(富士フイルム和光純薬社製、重量平均分子量100000、δt値=19.0)を溶解させ、拡散阻害層形成液Aを調製した。
――――――――――――――――――――――――――――――――――
拡散阻害層形成液Aの組成
――――――――――――――――――――――――――――――――――
ポリ(メタクリル酸)
(富士フイルム和光純薬社製、重量平均分子量100000)4.0質量部
純水                         60.0質量部
エタノール                      36.0質量部
――――――――――――――――――――――――――――――――――
<2. Preparation of substrate 3 with diffusion-preventing layer>
(1) Preparation of Diffusion-Preventing Layer-Forming Solution A The components were mixed in the composition shown below and stirred in a thermostatic bath at 50°C for 1 hour to dissolve poly(methacrylic acid) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight 100,000, δt value = 19.0), thereby preparing Diffusion-Preventing Layer-Forming Solution A.
----------------------------------------------------------------------------------
Composition of diffusion-preventing layer forming solution A ----------------------------------------------------------------
Poly(methacrylic acid)
(Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 100,000) 4.0 parts by mass Pure water 60.0 parts by mass Ethanol 36.0 parts by mass

 続いて、得られた拡散阻害層形成液Aを絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting diffusion-preventing layer-forming solution A was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

(2)拡散阻害層の形成
 上記濾過処理後の拡散阻害層形成液Aを、波長選択吸収層つき基材2の波長選択吸収層上に、乾燥後の膜厚が1.1μmとなるようにバーコーターを用いて塗布し、120℃で60秒間乾燥し、拡散阻害層つき基材3を作製した。
(2) Formation of Diffusion-Improving Layer The diffusion-improving layer-forming solution A after the above-mentioned filtration treatment was applied to the wavelength-selective absorption layer of the substrate 2 with a wavelength-selective absorption layer using a bar coater so that the film thickness after drying would be 1.1 μm, and the coating was dried at 120° C. for 60 seconds to prepare a substrate 3 with a diffusion-improving layer.

<3.積層体Iの作製>
(1)光吸収消失性層形成液の調製
 各成分を下記に示す組成で混合し、光吸収消失性層形成液(組成物)Ba-1を調製した。
――――――――――――――――――――――――――――――――――
光吸収消失性層形成液Ba-1の組成
――――――――――――――――――――――――――――――――――
樹脂2                      76.75質量部
レベリング剤1                   0.08質量部
染料B-18                    2.86質量部
染料D-7                     3.11質量部
4-メチルキノリン(東京化成社製)        17.2 質量部
テトラヒドロフラン(溶媒、δt値=23.6)  566.7 質量部
――――――――――――――――――――――――――――――――――
<3. Preparation of Laminate I>
(1) Preparation of Light-Absorbing and Disappearing Layer Forming Solution The components were mixed in the composition shown below to prepare a light-absorbing and disappearing layer forming solution (composition) Ba-1.
----------------------------------------------------------------------------------
Composition of light-absorbing and dissipative layer forming solution Ba-1
Resin 2 76.75 parts by mass Leveling agent 1 0.08 parts by mass Dye B-18 2.86 parts by mass Dye D-7 3.11 parts by mass 4-methylquinoline (Tokyo Chemical Industry Co., Ltd.) 17.2 parts by mass Tetrahydrofuran (solvent, δt value = 23.6) 566.7 parts by mass

 続いて、得られた光吸収消失性層形成液Ba-1を絶対濾過精度10μmの濾紙(#63、東洋濾紙社製)を用いて濾過し、さらに絶対濾過精度2.5μmの金属焼結フィルター(商品名:ポールフィルター PMF、メディアコード:FH025、ポール社製)を用いて濾過した。 The resulting light-absorbing, dissipative layer-forming solution Ba-1 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 μm, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 μm.

(2)積層体Iの作製
 上記濾過処理後の光吸収消失性層形成液Ba-1を、拡散阻害層つき基材3の拡散阻害層上に、乾燥後の膜厚が2.2μmとなるようにバーコーターを用いて塗布し、120℃で乾燥して光吸収消失性層を形成し、積層体No.101を作製した。
(2) Preparation of Laminate I The above-mentioned filtered light-absorbing and dissipating layer-forming solution Ba-1 was applied to the diffusion-preventing layer of the diffusion-preventing layer-attached substrate 3 using a bar coater so that the film thickness after drying would be 2.2 μm, and the coating was dried at 120° C. to form a light-absorbing and dissipating layer, thereby preparing Laminate No. 101.

<4.ガスバリア層を有する積層体の作製>
 積層体No.101について、下記のようにして、積層体No.101の光吸収消失性層の上にさらにガスバリア層を積層してなる積層体No.101(「ガスバリア層を有する積層体No.101」とも称す。)を作製した。
<4. Preparation of Laminate Having Gas Barrier Layer>
Regarding Laminate No. 101, a gas barrier layer was further laminated on the light-absorbing and dissipative layer of Laminate No. 101 in the following manner to prepare Laminate No. 101 (also referred to as "Laminate No. 101 having a gas barrier layer").

(1)ガスバリア層形成液1の調製
 各成分を下記に示す組成比となるようにして、クラレエクセバール AQ-4105(商品名、クラレ社製、変性ポリビニルアルコール、けん化度98~99モル%)を純水及びイソプロピルアルコール中、90℃の恒温槽で1時間撹拌することにより溶解させた後、室温まで冷却し、ポリエチレンイミン(富士フイルム和光純薬社製、重量平均分子量約10000)を添加し、ガスバリア層形成液1を調製した。
――――――――――――――――――――――――――――――――――
ガスバリア層形成液1の組成
――――――――――――――――――――――――――――――――――
クラレエクセバール AQ-4105(商品名、クラレ社製)3.6質量部
ポリエチレンイミン
(富士フイルム和光純薬社製、重量平均分子量約10000)0.4質量部
純水                         88.5質量部
イソプロピルアルコール                 7.5質量部
――――――――――――――――――――――――――――――――――
(1) Preparation of Gas Barrier Layer-Forming Solution 1 Kuraray Exeval AQ-4105 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, with the components adjusted to the composition ratio shown below. The solution was then cooled to room temperature, and polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) was added to prepare Gas Barrier Layer-Forming Solution 1.
----------------------------------------------------------------------------------
Composition of gas barrier layer forming liquid 1 ----------------------------------------------------------------
Kuraray Exeval AQ-4105 (product name, manufactured by Kuraray Co., Ltd.) 3.6 parts by mass Polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) 0.4 parts by mass Pure water 88.5 parts by mass Isopropyl alcohol 7.5 parts by mass

 続いて、得られたガスバリア層形成液1を絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting gas barrier layer forming solution 1 was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

(2)ガスバリア層1の積層
 上記濾過処理後のガスバリア層形成液1を、積層体の光吸収消失性層側に、乾燥後の膜厚が0.6μmとなるようにバーコーターを用いて塗布し、120℃で60秒間乾燥し、ガスバリア層を有する積層体No.101を作製した。
 このガスバリア層を有する積層体No.101は、基材1、波長選択吸収層、拡散阻害層、光吸収消失性層及びガスバリア層1がこの順に積層された構成を有する。
(2) Lamination of Gas Barrier Layer 1 The filtered gas barrier layer-forming solution 1 was applied to the light-absorbing and disappearing layer side of the laminate using a bar coater so that the film thickness after drying would be 0.6 μm, and the laminate was dried at 120° C. for 60 seconds to prepare Laminate No. 101 having a gas barrier layer.
This gas barrier layer-containing laminate No. 101 has a configuration in which a substrate 1, a wavelength selective absorption layer, a diffusion-preventing layer, a light absorbing and disappearing layer, and a gas barrier layer 1 are laminated in this order.

[ガスバリア層を有する積層体No.102~104及びc201~c202の作製]
 ガスバリア層を有する積層体No.101の作製において、光吸収消失性層の各染料の添加量、および波長選択吸収層の各染料の添加量の少なくともいずれかを表1に記載の値に変更したこと以外はガスバリア層を有する積層体No.101の作製と同様にして、ガスバリア層を有する積層体No.102~No.104及びc201~c202を作製した。
 なお、ガスバリア層を有する積層体No.102~104及びc201~c202の作製においては、波長選択吸収層としての質量は変わらないようにして、染料の配合量の変更にあわせて樹脂1の配合量を調整し、光吸収消失性層としての質量は変わらないようにして、染料の配合量の変更にあわせて樹脂2の配合量を調整した。
[Preparation of Laminates Nos. 102 to 104 and c201 to c202 Having Gas Barrier Layer]
Laminates Nos. 102 to 104 and c201 to c202 each having a gas barrier layer were prepared in the same manner as in the preparation of laminate No. 101 having a gas barrier layer, except that in the preparation of laminate No. 101 having a gas barrier layer, at least one of the amount of each dye added in the light-absorbing and disappearing layer and the amount of each dye added in the wavelength-selective absorption layer was changed to the value shown in Table 1.
In producing laminates Nos. 102 to 104 and c201 to c202 each having a gas barrier layer, the amount of resin 1 was adjusted in accordance with the change in the amount of dye blended, while keeping the mass of the wavelength-selective absorption layer constant, and the amount of resin 2 was adjusted in accordance with the change in the amount of dye blended, while keeping the mass of the light-absorbing and disappearing layer constant.

[ガスバリア層を有する積層体No.r301の作製]
 ガスバリア層を有する積層体No.101の作製において、波長選択吸収層形成液中の染料A-321、7-23、C-122及びH-1を除き、さらに、光吸収消失性層形成液中の染料B-18及びD-7並びに4-メチルキノリンを除いたこと以外はガスバリア層を有する積層体No.101の作製と同様にして、ガスバリア層を有する積層体No.r301を作製した。
[Preparation of Laminate No. r301 Having a Gas Barrier Layer]
A laminate No. r301 having a gas barrier layer was prepared in the same manner as in the preparation of the laminate No. 101 having a gas barrier layer, except that in the preparation of the laminate No. 101 having a gas barrier layer, dyes A-321, 7-23, C-122, and H-1 were removed from the wavelength-selective absorption layer-forming solution, and further, dyes B-18 and D-7, and 4-methylquinoline were removed from the light-absorbing and disappearing layer-forming solution.

(表の注)
 波長選択吸収層及び光吸収消失性層における染料の配合量は、波長選択吸収層100質量部中における染料の質量部、光吸収消失性層100質量部中における染料の質量部をそれぞれ意味する。
 波長選択吸収層の厚み及び光吸収消失性層の厚みの単位は、いずれもμmである。
(Table notes)
The blending amounts of the dye in the wavelength selective absorption layer and the light absorbing and dissipating layer refer to parts by mass of the dye in 100 parts by mass of the wavelength selective absorption layer and parts by mass of the dye in 100 parts by mass of the light absorbing and dissipating layer, respectively.
The unit of thickness of the wavelength selective absorption layer and the thickness of the light absorbing and disappearing layer is both μm.

<光透過吸収フィルタIを備えたOLED表示装置のシミュレーション>
 上記で作製したガスバリア層を有する積層体No.101~104、c201~c202及びr301を用いて、視認者側から、光吸収消失性層をマスク露光して得られる層、波長選択吸収層をこの順に備える積層体(光透過吸収フィルタI)を備えたOLED表示装置のシミュレーションを下記のようにして行った。
<Simulation of an OLED display device equipped with a light-transmitting/absorbent filter I>
Using the laminates Nos. 101 to 104, c201 to c202, and r301 having the gas barrier layer prepared above, a simulation of an OLED display device having a laminate (light transmission-absorption filter I) having, from the viewer side, a layer obtained by mask exposure of the light-absorbing and disappearing layer and a wavelength-selective absorption layer in this order was carried out as follows.

[第一、及び第二の部位の吸光度測定]
(1)吸光度の測定
 島津製作所社製のUV3600分光光度計(商品名)を用いて、縦40mm×横40mmに切り出した測定用サンプルについて、380~780nmの波長範囲における吸光度を、1nmごとに測定した。
 なお、第二の部位の吸光度については、上記で作製したガスバリア層を有する積層体を測定用サンプルとして用いて測定した。
 また、第一の部位の吸光度については、上記で作製したガスバリア層を有する積層体に対して、パターニングを行わずに以下の紫外線照射試験を行って得られた積層体を、測定用サンプルとして用いて測定した。
(紫外線照射試験)
 大気圧(101.33kPa)下、超高圧水銀灯(HOYA社製、商品名:UL750)を用いて45℃のホットプレート上で、ガスバリア層を有する積層体に対して、照度100mW/cm、照射量2000mJ/cmの紫外線(UV)をガスバリア層側(基材1とは反対側)から照射した。
[Measurement of absorbance at first and second sites]
(1) Measurement of absorbance Using a UV3600 spectrophotometer (trade name) manufactured by Shimadzu Corporation, the absorbance of a measurement sample cut into a size of 40 mm length x 40 mm width was measured in 1 nm increments in the wavelength range of 380 to 780 nm.
The absorbance of the second region was measured using the laminate having the gas barrier layer prepared above as a measurement sample.
Furthermore, the absorbance of the first portion was measured using the laminate obtained by carrying out the following ultraviolet irradiation test without patterning the laminate having the gas barrier layer produced above as a measurement sample.
(Ultraviolet irradiation test)
Under atmospheric pressure (101.33 kPa), the laminate having the gas barrier layer was irradiated with ultraviolet (UV) rays at an illuminance of 100 mW/cm 2 and an exposure dose of 2000 mJ/cm 2 from the gas barrier layer side (the side opposite to the substrate 1) using an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) on a hot plate at 45°C.

(2)吸光度の算出
 上記(1)で測定した、第一の部位及び第二の部位の各波長λnmにおける吸光度の値Ab(λ)と、同じ樹脂を含有し、染料を含有しない積層体No.r301の各波長λnmにおける吸光度の値Ab(λ)とを用いて、下記式より、第一の部位及び第二の部位の吸光度Ab(λ)を算出した。
  Ab(λ)=Ab(λ)-Ab(λ)
 
 なお、波長380~780nmの領域における第一の部位及び第二の部位の吸光度Ab(λ)のうち、極大吸収を示す波長のうち最も大きい吸光度Ab(λ)を示す波長を極大吸収波長(以下、単に「λmax」とも称す。)とし、このλmaxにおける吸光度を吸収極大値(以下、単に「Ab(λmax)」とも称す。)とした。得られた各染料のAb(λmax)について、上述の染料の説明において、又は上述の染料の化学構造と共に記載した。
(2) Calculation of Absorbance Using the absorbance values Ab x (λ) at each wavelength λ nm of the first portion and the second portion measured in (1) above and the absorbance value Ab 0 (λ) at each wavelength λ nm of Laminate No. r301 containing the same resin but no dye, the absorbance Ab(λ) of the first portion and the second portion was calculated according to the following formula:
Ab (λ) = Ab x (λ) - Ab 0 (λ)

Among the absorbances Ab(λ) of the first and second portions in the wavelength range of 380 to 780 nm, the wavelength showing the largest absorbance Ab(λ) among the wavelengths showing maximum absorption was defined as the maximum absorption wavelength (hereinafter also simply referred to as "λ max "), and the absorbance at this λ max was defined as the maximum absorption value (hereinafter also simply referred to as "Ab(λ max )"). The Ab(λ max ) of each of the obtained dyes is described in the above description of the dye or together with the chemical structure of the above dye.

[第一、及び第二の部位の透過率シミュレーション]
 上記の第一の部位及び第二の部位の吸光度Ab(λ)から得られた吸収スペクトルを用いて、波長380~780nmの範囲の透過率を計算した。
 得られた波長380~780nmの範囲の透過率に明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより、透過光の色味(a、b)を算出した。
[Transmittance Simulation of First and Second Regions]
The transmittance in the wavelength range of 380 to 780 nm was calculated using the absorption spectrum obtained from the absorbance Ab(λ) of the first and second regions.
The obtained transmittance in the wavelength range of 380 to 780 nm was multiplied by the photopic standard relative luminosity factor and summed (luminosity correction) to calculate the color (a * , b * ) of the transmitted light.

[OLED基板の反射スペクトル測定]
 OLED基板の反射スペクトルとしては、OLED表示装置から、OLED発光層よりも視認者側の層に存在する円偏光板、カラーフィルタ及びブラックマトリックス等の反射防止のための層を取り除いたもの(詳細は後述の通り)を用いた。得られたOLED基板において、発光部である各画素の各波長における反射率、並びに、非発光部である、基板、金属細線及びブラックバンク(黒隔壁)の各波長における反射率は、一般的な顕微分光法により測定した。反射率は、保護膜付き銀ミラーの反射率に対する相対反射率として計算した。
[Measurement of Reflection Spectrum of OLED Substrate]
The reflectance spectrum of the OLED substrate was measured using an OLED display device from which anti-reflection layers, such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later). For the obtained OLED substrate, the reflectance at each wavelength of each pixel, which is the light-emitting portion, and the reflectance at each wavelength of the substrate, thin metal wires, and black bank (black partition wall), which are non-light-emitting portions, were measured using a conventional microspectroscopy method. The reflectance was calculated as the relative reflectance to the reflectance of a silver mirror with a protective film.

[反射スペクトルのシミュレーション]
 反射スペクトルのシミュレーションは、発光部、非発光部に分けて各部位ごとに行った。
(1)発光部の反射率
 発光部の反射スペクトルR(λ)は、顕微分光法で測定したOLED基板の発光部の反射スペクトルRx0(λ)と、第一の部位の透過スペクトルT(λ)と、表面反射率Rとを用い、以下の式により算出した。なお、表面反射率Rは、第一の部位より表面側(視認者側)の透明部材の積層体の表面反射率であり、具体的には、ガスバリア層の表面反射率を意味する。(xは、青色画素(B)、緑色画素(G)、赤色画素(R)等がある。)
 R(λ)=Rx0(λ)×T(λ)+R
(2)非発光部の反射率
 非発光部の反射スペクトルR(λ)は、顕微分光法で測定したOLED基板の非発光部の反射スペクトルRy0(λ)と、第二の部位の透過スペクトルT(λ)と、表面反射率Rとを用い、以下の式により算出した。なお、表面反射率Rは、第二の部位より表面側(視認者側)の透明部材の積層体の表面反射率であり、具体的には、ガスバリア層の表面反射率を意味する。
 R(λ)=Ry0(λ)×T(λ)+R
(3)平均反射率
 表示装置全体の反射スペクトルは、上記で算出した発光部の反射スペクトルR(λ)及び非発光部の反射スペクトルR(λ)に対して、各部位の面積比率を掛け合わせた和として算出し、得られた反射スペクトルにCIE標準光源D65スペクトルと明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより、視感度補正反射率Y(以下、単に「反射率」とも称す。)、および反射光の色味(a、b)を算出した。
 なお、本シミュレーションにおいては、OLED基板として、市販のスマートフォンiPhone(登録商標)14Pro(商品名、APPLE社製)を使用し、OLED発光層とタッチセンサー層との間で剥離して、タッチセンサー層より上(視認者側)の層を取り除いたものを用いた。iPhone(登録商標)14Proの発光部(BGRの各色発光部)及び非発光部の面積比率は、B(青):G(緑):R(赤):非発光部=15:10:5:70として計算した。
[Simulation of Reflection Spectrum]
The simulation of the reflection spectrum was carried out for each part, divided into a light-emitting part and a non-light-emitting part.
(1) Reflectance of Light-Emitting Section The reflection spectrum R x (λ) of the light-emitting section was calculated by the following formula using the reflection spectrum R x0 (λ) of the light-emitting section of the OLED substrate measured by microspectroscopy, the transmission spectrum T 1 (λ) of the first section, and the surface reflectance R S. Note that the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the first section, and specifically means the surface reflectance of the gas barrier layer. (x can be a blue pixel (B), a green pixel (G), a red pixel (R), etc.)
R x (λ) = R x0 (λ) x T 1 (λ) 2 + R S
(2) Reflectance of Non-Emitting Portion The reflection spectrum R y (λ) of the non-emitting portion was calculated by the following formula using the reflection spectrum R y0 (λ) of the non-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 2 (λ) of the second portion, and the surface reflectance R S. Note that the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the second portion, and specifically means the surface reflectance of the gas barrier layer.
R y (λ)=R y0 (λ)×T 2 (λ) 2 +R S
(3) Average Reflectance The reflectance spectrum of the entire display device was calculated as the sum of the reflectance spectrum R x (λ) of the light-emitting portion and the reflectance spectrum R y (λ) of the non-light-emitting portion calculated above, multiplied by the area ratio of each portion. The resulting reflectance spectrum was then multiplied by the CIE standard illuminant D65 spectrum and the photopic standard relative luminosity factor to obtain the sum (luminosity correction), thereby calculating the luminosity-corrected reflectance Y (hereinafter simply referred to as "reflectance") and the color (a * , b * ) of the reflected light.
In this simulation, a commercially available smartphone, iPhone (registered trademark) 14 Pro (trade name, manufactured by Apple Inc.), was used as the OLED substrate, and the OLED light-emitting layer was peeled off from the touch sensor layer, and the layer above the touch sensor layer (on the viewer's side) was removed. The area ratio of the light-emitting portion (each color light-emitting portion of BGR) and the non-light-emitting portion of the iPhone (registered trademark) 14 Pro was calculated as B (blue):G (green):R (red):non-light-emitting portion = 15:10:5:70.

 結果を表2にまとめて示す。
 なお、No.101~104が、上記で作製した積層体No.101~104を用いて得られた第一の部位及び第二の部位の透過率シミュレーションの結果を用いて行った、本発明の光透過吸収フィルタのシミュレーション結果である。No.c201~c202が、上記で作製した積層体No.c201~c202を用いて得られた第一の部位及び第二の部位の透過率シミュレーションの結果を用いて行った、比較のための光透過吸収フィルタのシミュレーション結果である。
The results are summarized in Table 2.
Note that Nos. 101 to 104 are simulation results for the light transmission-absorption filter of the present invention, performed using the transmittance simulation results for the first and second regions obtained using the laminate Nos. 101 to 104 prepared above. Nos. c201 and c202 are simulation results for a light transmission-absorption filter for comparison, performed using the transmittance simulation results for the first and second regions obtained using the laminate Nos. c201 and c202 prepared above.

(表の注)
 色味の、第一の部位及び第二の部位の欄には、いずれも透過光のa及びbを記載する。
(Table notes)
In the columns for the first and second regions of color, the a * and b * of transmitted light are entered.

 表2に示されるように、No.c201及びc202の光透過吸収フィルタは、透過光のL色空間におけるa及びbがいずれも、第一の部位の値の符号と第二の部位の値の符号が逆転していない点で、本発明の規定を満たしていない。これらのうち、No.c201の光透過吸収フィルタでは、反射率が8.9%と大きく、外光反射を抑制できておらず、No.c202の光透過吸収フィルタでは、反射光のaの値が大きく、反射色味をニュートラルに調節できていなかった。
 これに対して、No.101~104の光透過吸収フィルタは、表示装置に組み込んだ際に表示光の所望の透過率が担保される光透過吸収フィルタであって、反射率が6.7%以下と小さく外光反射の抑制を高度なレベルで実現でき、しかも、反射光のa及びbが-2.8~6.3の範囲内にあって、表示光(第一の部位及び第二の部位)のa及びbが-9.3~28.0の範囲内にあり、反射光の色味及び表示光の色味を共にニュートラルに調整できることがわかった。
As shown in Table 2, the light transmission-absorption filters No. c201 and c202 do not satisfy the requirements of the present invention in that the signs of the values in the first region and the second region for a * and b * in the L*a * b * color space of transmitted light are not reversed. Of these, the light transmission-absorption filter No. c201 had a high reflectance of 8.9%, failing to suppress external light reflection, while the light transmission-absorption filter No. c202 had a high a * value for reflected light, failing to adjust the reflected color to a neutral tone.
In contrast, the light transmission-absorption filters Nos. 101 to 104 are light transmission-absorption filters that ensure the desired transmittance of display light when incorporated into a display device, have a reflectance as low as 6.7% or less, can achieve a high level of suppression of external light reflection, and furthermore, a * and b * of the reflected light are within the range of −2.8 to 6.3, and a * and b * of the display light (first portion and second portion) are within the range of −9.3 to 28.0, making it possible to adjust both the color of the reflected light and the color of the display light to a neutral color.

<<波長選択吸収層を含む積層体IIと光吸収消失性層を含む積層体pre-IIIの作製>>
実施例2
[基材つき波長選択吸収フィルタNo.501(積層体II)の作製]
<1.波長選択吸収層形成液11の調製>
 各成分を下記に示す組成で混合し、波長選択吸収層形成液11を調製した。
――――――――――――――――――――――――――――――――――
波長選択吸収層形成液11の組成
――――――――――――――――――――――――――――――――――
樹脂3                     14.8質量部
樹脂4                     78.4質量部
密着改良剤1                   0.9質量部
染料J-1                    4.1質量部
染料I-2                    1.8質量部
トルエン(溶媒)               693.0質量部
シクロヘキサノン(溶媒)            99.0質量部
イソプロパノール(溶媒)           198.0質量部
――――――――――――――――――――――――――――――――――
<<Preparation of Laminate II Including Wavelength-Selective Absorption Layer and Laminate Pre-III Including Light-Absorbing Disappearing Layer>>
Example 2
[Preparation of Substrate-Attached Wavelength-Selective Absorption Filter No. 501 (Laminate II)]
<1. Preparation of wavelength-selective absorption layer forming liquid 11>
The components were mixed in the composition shown below to prepare a wavelength selective absorption layer forming solution 11.
----------------------------------------------------------------------------------
Composition of wavelength selective absorption layer forming liquid 11
Resin 3 14.8 parts by mass Resin 4 78.4 parts by mass Adhesion improver 1 0.9 parts by mass Dye J-1 4.1 parts by mass Dye I-2 1.8 parts by mass Toluene (solvent) 693.0 parts by mass Cyclohexanone (solvent) 99.0 parts by mass Isopropanol (solvent) 198.0 parts by mass

 続いて、得られた波長選択吸収層形成液11を絶対濾過精度10μmの濾紙(#63、東洋濾紙社製)を用いて濾過し、さらに絶対濾過精度2.5μmの金属焼結フィルター(商品名:ポールフィルター PMF、メディアコード:FH025、ポール社製)を用いて濾過した。 The resulting wavelength-selective absorption layer forming liquid 11 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 μm, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 μm.

<2.波長選択吸収層形成液12の調製>
 各成分を下記に示す組成で混合し、波長選択吸収層形成液12を調製した。
――――――――――――――――――――――――――――――――――
波長選択吸収層形成液12の組成
――――――――――――――――――――――――――――――――――
樹脂5                    82.1質量部
レベリング剤1                 0.16質量部
密着改良剤2                  9.25質量部
染料7-23                  1.5質量部
染料H-1                   6.0質量部
トルエン(溶媒)              601.3質量部
シクロヘキサノン(溶媒)           66.0質量部
イソプロパノール(溶媒)            66.0質量部
――――――――――――――――――――――――――――――――――
<2. Preparation of wavelength-selective absorption layer forming liquid 12>
The components were mixed in the composition shown below to prepare a wavelength selective absorption layer forming solution 12.
----------------------------------------------------------------------------------
Composition of wavelength selective absorption layer forming liquid 12
Resin 5 82.1 parts by mass Leveling agent 1 0.16 parts by mass Adhesion improver 2 9.25 parts by mass Dye 7-23 1.5 parts by mass Dye H-1 6.0 parts by mass Toluene (solvent) 601.3 parts by mass Cyclohexanone (solvent) 66.0 parts by mass Isopropanol (solvent) 66.0 parts by mass

 続いて、得られた波長選択吸収層形成液12を波長選択吸収層形成液11と同様にして濾過した。 Subsequently, the obtained wavelength-selective absorption layer forming liquid 12 was filtered in the same manner as wavelength-selective absorption layer forming liquid 11.

<3.ガスバリア層形成液2の調製>
 各成分を下記に示す組成比となるようにして、クラレエクセバール AQ-4104(商品名、クラレ社製、変性ポリビニルアルコール、けん化度98~99モル%)を純水及びイソプロピルアルコール中、90℃の恒温槽で1時間撹拌することにより溶解させた後、室温まで冷却し、エポミンP-1000(商品名、日本触媒社製、ポリエチレンイミンの30質量%溶液、重量平均分子量約70000)を添加し、ガスバリア層形成液2を調製した。
――――――――――――――――――――――――――――――――――
ガスバリア層形成液2の組成
――――――――――――――――――――――――――――――――――
クラレエクセバール AQ-4104(商品名、クラレ社製)3.8質量部
エポミンP-1000(商品名、日本触媒社製)
(ポリエチレンイミン自体の配合量を示す。)       0.2質量部
純水                         88.5質量部
イソプロピルアルコール                 7.5質量部
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<3. Preparation of gas barrier layer-forming liquid 2>
Kuraray Exeval AQ-4104 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, with the components adjusted to the composition ratio shown below. The solution was then cooled to room temperature, and Epomin P-1000 (trade name, manufactured by Nippon Shokubai Co., Ltd., 30% by mass solution of polyethyleneimine, weight average molecular weight approximately 70,000) was added to prepare gas barrier layer-forming solution 2.
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Composition of gas barrier layer forming liquid 2 -------------------------------------------------
3.8 parts by mass of Kuraray Exeval AQ-4104 (trade name, manufactured by Kuraray Co., Ltd.) Epomin P-1000 (trade name, manufactured by Nippon Shokubai Co., Ltd.)
(Indicating the amount of polyethyleneimine itself) 0.2 parts by mass Pure water 88.5 parts by mass Isopropyl alcohol 7.5 parts by mass

 続いて、得られたガスバリア層形成液2を絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting gas barrier layer-forming solution 2 was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

<4.基材つき波長選択吸収フィルタNo.501の作製>
 上記濾過処理後の波長選択吸収層形成液11を、基材11上に、乾燥後の膜厚が2.0μmとなるようにバーコーターを用いて塗布し、130℃で乾燥して、基材つき第一波長選択吸収層11を形成した。その後、上記濾過処理後のガスバリア層形成液2を、第一波長選択吸収層上に、乾燥後の膜厚が0.4μmとなるようにバーコーターを用いて塗布し、130℃で乾燥し、ガスバリア層2を形成した。さらに、ガスバリア層2上に、上記濾過処理後の波長選択吸収層形成液12を、乾燥後の膜厚が2.0μmとなるようにバーコーターを用いて塗布し、130℃で乾燥して、第二波長選択吸収層12を形成し、基材つき波長選択吸収フィルタNo.501(積層体II)を作製した。
<4. Preparation of wavelength-selective absorption filter No. 501 with substrate>
The filtered wavelength-selective absorption layer-forming liquid 11 was applied to a substrate 11 using a bar coater so that the film thickness after drying would be 2.0 μm, and the applied film was dried at 130° C. to form a substrate-attached first wavelength-selective absorption layer 11. Thereafter, the filtered gas-barrier layer-forming liquid 2 was applied to the first wavelength-selective absorption layer using a bar coater so that the film thickness after drying would be 0.4 μm, and the applied film was dried at 130° C. to form a gas-barrier layer 2. Furthermore, the filtered wavelength-selective absorption layer-forming liquid 12 was applied to the gas-barrier layer 2 using a bar coater so that the film thickness after drying would be 2.0 μm, and the applied film was dried at 130° C. to form a substrate-attached wavelength-selective absorption filter No. 501 (laminate II).

[基材つき光吸収消失性フィルタNo.601の作製]
<1.拡散阻害層つき基材22の作製>
(1)拡散阻害層形成液Bの調製
 各成分を下記に示す組成で混合し、50℃の恒温槽で1時間撹拌し、ポリ(メタクリル酸)(富士フイルム和光純薬社製、重量平均分子量100000、δt値=19.0)を溶解させ、拡散阻害層形成液Bを調製した。
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拡散阻害層形成液Bの組成
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ポリ(メタクリル酸)
(富士フイルム和光純薬社製、重量平均分子量100000)4.0質量部
純水                         60.0質量部
エタノール                      36.0質量部
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[Preparation of Substrate-Attached Light-Absorbing and Dissipating Filter No. 601]
<1. Preparation of substrate 22 with diffusion-preventing layer>
(1) Preparation of Diffusion-Preventing Layer-Forming Solution B The components were mixed in the composition shown below and stirred in a thermostatic bath at 50°C for 1 hour to dissolve poly(methacrylic acid) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight 100,000, δt value = 19.0), thereby preparing Diffusion-Preventing Layer-Forming Solution B.
----------------------------------------------------------------------------------
Composition of diffusion-preventing layer forming solution B ----------------------------------------------------------------
Poly(methacrylic acid)
(Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 100,000) 4.0 parts by mass Pure water 60.0 parts by mass Ethanol 36.0 parts by mass

 続いて、得られた拡散阻害層形成液Bを絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting diffusion-preventing layer-forming solution B was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

(2)拡散阻害層の形成
 上記濾過処理後の拡散阻害層形成液Bを、基材21上に、乾燥後の膜厚が0.9μmとなるようにバーコーターを用いて塗布し、120℃で60秒間乾燥し、拡散阻害層つき基材22を作製した。
(2) Formation of diffusion-preventing layer The diffusion-preventing layer-forming solution B after the above-mentioned filtration treatment was applied to the substrate 21 using a bar coater so that the film thickness after drying would be 0.9 μm, and then dried at 120° C. for 60 seconds to produce a substrate 22 with a diffusion-preventing layer.

<2.基材つき光吸収消失性フィルタNo.601の作製> <2. Preparation of Substrate-Attached Light-Absorbing and Dissipative Filter No. 601>

(1)光吸収消失性層形成液の調製
 各成分を下記に示す組成で混合し、光吸収消失性層形成液(組成物)Ba-2を調製した。
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光吸収消失性層形成液Ba-2の組成
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樹脂2                      79.25質量部
レベリング剤1                   0.08質量部
染料B-18                    1.79質量部
染料D-7                     1.68質量部
4-メチルキノリン(東京化成社製)        17.2 質量部
テトラヒドロフラン(溶媒、δt値=23.6)  566.7 質量部
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(1) Preparation of Light-Absorbing and Disappearing Layer Forming Solution The components were mixed in the composition shown below to prepare a light-absorbing and disappearing layer forming solution (composition) Ba-2.
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Composition of light-absorbing and dissipative layer forming solution Ba-2
Resin 2 79.25 parts by mass Leveling agent 1 0.08 parts by mass Dye B-18 1.79 parts by mass Dye D-7 1.68 parts by mass 4-methylquinoline (Tokyo Chemical Industry Co., Ltd.) 17.2 parts by mass Tetrahydrofuran (solvent, δt value = 23.6) 566.7 parts by mass

 続いて、得られた光吸収消失性層形成液Ba-2を絶対濾過精度10μmの濾紙(#63、東洋濾紙社製)を用いて濾過し、さらに絶対濾過精度2.5μmの金属焼結フィルター(商品名:ポールフィルター PMF、メディアコード:FH025、ポール社製)を用いて濾過した。 The resulting light-absorbing, dissipative layer-forming solution Ba-2 was then filtered using filter paper (#63, manufactured by Toyo Roshi Kaisha) with an absolute filtration accuracy of 10 μm, and further filtered using a sintered metal filter (product name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) with an absolute filtration accuracy of 2.5 μm.

(2)基材つき光吸収消失性フィルタNo.601の作製
 上記濾過処理後の光吸収消失性層形成液Ba-2を、拡散阻害層つき基材22の拡散阻害層の上に、乾燥後の膜厚が2.5μmとなるようにバーコーターを用いて塗布し、120℃で乾燥して光吸収消失性層を形成し、基材つき光吸収消失性フィルタNo.601を作製した
(2) Preparation of substrate-attached light-absorbing and dissipating filter No. 601 The light-absorbing and dissipating layer-forming solution Ba-2 after the filtration process was applied using a bar coater onto the diffusion-preventing layer of the diffusion-preventing layer-attached substrate 22 so that the film thickness after drying would be 2.5 μm, and the applied solution was dried at 120° C. to form a light-absorbing and dissipating layer, thereby preparing substrate-attached light-absorbing and dissipating filter No. 601.

<3.ガスバリア層を有する光吸収消失性フィルタ(積層体pre-III)の作製>
 基材つき光吸収消失性フィルタNo.601について、下記のようにして、光吸収消失性層の上にさらにガスバリア層を積層してなる積層体pre-IIIを作製した。
<3. Preparation of Light-Absorbing and Dissipating Filter Having a Gas Barrier Layer (Laminate Pre-III)>
For the substrate-attached light-absorbing and dissipating filter No. 601, a gas barrier layer was further laminated on the light-absorbing and dissipating layer in the following manner to prepare a laminate pre-III.

(1)ガスバリア層形成液3の調製
 各成分を下記に示す組成比となるようにして、クラレエクセバール AQ-4104(商品名、クラレ社製、変性ポリビニルアルコール、けん化度98~99モル%)を純水及びイソプロピルアルコール中で、90℃の恒温槽で1時間撹拌することにより溶解させた後、室温まで冷却し、ポリエチレンイミン(富士フイルム和光純薬社製、重量平均分子量約10000)を添加し、ガスバリア層形成液3を調製した。
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ガスバリア層形成液3の組成
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クラレエクセバール AQ-4104(商品名、クラレ社製)3.8質量部
ポリエチレンイミン
(富士フイルム和光純薬社製、重量平均分子量約10000)0.2質量部
純水                         88.5質量部
イソプロピルアルコール                 7.5質量部
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(1) Preparation of Gas Barrier Layer-Forming Solution 3 Kuraray Exeval AQ-4104 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) was dissolved in pure water and isopropyl alcohol by stirring for 1 hour in a thermostatic bath at 90°C, and then the solution was cooled to room temperature, and polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) was added to prepare Gas Barrier Layer-Forming Solution 3.
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Composition of gas barrier layer forming liquid 3 -------------------------------------------------
Kuraray Exeval AQ-4104 (product name, manufactured by Kuraray Co., Ltd.) 3.8 parts by mass Polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight-average molecular weight approximately 10,000) 0.2 parts by mass Pure water 88.5 parts by mass Isopropyl alcohol 7.5 parts by mass

 続いて、得られたガスバリア層形成液3を絶対濾過精度5μmのフィルター(商品名:HydrophobicFluorepore Membrane、Millex社製)を用いて濾過した。 The resulting gas barrier layer-forming solution 3 was then filtered using a filter with an absolute filtration accuracy of 5 μm (product name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

(2)ガスバリア層の積層
 上記濾過処理後のガスバリア層形成液3を、基材つき光吸収消失性フィルタNo.601の光吸収消失性層側に、乾燥後の膜厚が0.3μmとなるようにバーコーターを用いて塗布し、130℃で60秒間乾燥し、ガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)を作製した。
(2) Lamination of Gas Barrier Layer The gas barrier layer-forming liquid 3 after the filtration treatment was applied to the light-absorbing and dissipating layer side of substrate-attached light-absorbing and dissipating filter No. 601 using a bar coater so as to give a film thickness after drying of 0.3 μm, and the applied film was dried at 130° C. for 60 seconds to prepare light-absorbing and dissipating filter No. 601 (laminate pre-III) having a gas barrier layer.

[第一、及び第二の部位の透過率シミュレーション]
 前述の実施例1と同様にして、基材つき波長選択吸収フィルタNo.501(積層体II)と、ガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)を用いて、積層体IIにおける第二波長選択吸収層12と、積層体pre-IIIをマスク露光してられる積層体IIIにおけるガスバリア層とを貼り合わせて得られる積層体No.701に係る、第一の部位及び第二の部位の透過率シミュレーションを行った。
 その結果、第一の部位の各波長における透過率は、T(460)=65%、T(530)=48%、T(620)=40%であり、第一の部位の色味はa=-1.8、b=-7.2であって、第二の部位の色味はa=6.3、b=-6.3であり、第一の部位と第二の部位とは透過光のL色空間におけるaの符号が逆となる関係を満たしていた。この積層体No.701を表示装置に組み込んだ際には、反射率は6.0%と小さく外光反射の抑制を高度なレベルで実現でき、しかも、反射光のa=1.4、b=-4.7であり、表示光(第一の部位及び第二の部位)のa及びbが-7.2~6.3の範囲内にあり、反射光の色味及び表示光の色味を共にニュートラルに調整できることがわかった。
[Transmittance Simulation of First and Second Regions]
In the same manner as in Example 1 described above, a transmittance simulation was performed for the first region and the second region of laminate No. 701, which was obtained by bonding the second wavelength-selective absorption layer 12 in laminate II and the gas barrier layer in laminate III obtained by mask-exposing the laminate pre-III, using wavelength-selective absorption filter No. 501 with a substrate (laminate II) and light-absorbing and disappearing filter No. 601 (laminate pre-III) having a gas barrier layer.
As a result, the transmittance at each wavelength of the first portion was T(460) = 65%, T(530) = 48%, T(620) = 40%, the color of the first portion was a * = -1.8, b * = -7.2, and the color of the second portion was a * = 6.3, b * = -6.3, and the first portion and the second portion satisfied a relationship in which the signs of a * in the L * a * b * color space of transmitted light were opposite. When this laminate No. 701 was incorporated into a display device, the reflectance was as low as 6.0%, achieving a high level of suppression of external light reflection. Moreover, the reflected light had a * = 1.4, b * = -4.7, and the a * and b * of the display light (first portion and second portion) were within the range of -7.2 to 6.3, and it was found that both the color of the reflected light and the color of the display light could be adjusted to a neutral color.

<光透過吸収フィルタIIを備えたOLED表示装置のシミュレーション>
 上記で作製した基材つき波長選択吸収フィルタNo.501(積層体II)と、ガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)を用いて、視認者側から、積層体II、積層体pre-IIIをマスク露光して得られる積層体IIIをこの順に備える積層体No.701(光透過吸収フィルタII)を備えたOLED表示装置のシミュレーションを下記のようにして行った。
<Simulation of an OLED display device equipped with a light-transmitting/absorbent filter II>
Using the wavelength-selective absorption filter No. 501 (laminate II) with a substrate prepared above and light-absorbing and dissipating filter No. 601 (laminate pre-III) having a gas barrier layer, a simulation was performed as follows for an OLED display device equipped with laminate No. 701 (light-transmitting and absorbing filter II) comprising, from the viewer's side, laminate II and laminate III obtained by mask-exposing laminate pre-III, in that order.

[第一、及び第二の部位の吸光度測定]
(1)吸光度の測定
 島津製作所社製のUV3600分光光度計(商品名)を用いて、縦40mm×横40mmに切り出した測定用サンプルについて、380~780nmの波長範囲における吸光度を、1nmごとに測定した。
 なお、第二の部位の吸光度については、上記で作製した基材つき波長選択吸収フィルタNo.501(積層体II)とガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)を、積層体IIにおける第二波長選択吸収層12と、積層体pre-IIIにおけるガスバリア層とを貼り合わせて得られる積層体を測定用サンプルとして用いて測定した。
 また、第一の部位の吸光度については、上記で作製したガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)に対して、パターニングを行わずに以下の紫外線照射試験を行って得られた積層体IIIと、基材つき波長選択吸収フィルタNo.501(積層体II)とを貼り合わせて得られる積層体を、測定用サンプルとして用いて測定した。
(紫外線照射試験)
 大気圧(101.33kPa)下、超高圧水銀灯(HOYA社製、商品名:UL750)を用いて45℃のホットプレート上で、ガスバリア層を有する光吸収消失性フィルタNo.601(積層体pre-III)に対して、照度100mW/cm、照射量2000mJ/cmの紫外線(UV)をガスバリア層側(基材21とは反対側)から照射した。
[Measurement of absorbance at first and second sites]
(1) Measurement of absorbance Using a UV3600 spectrophotometer (trade name) manufactured by Shimadzu Corporation, the absorbance of a measurement sample cut into a size of 40 mm length x 40 mm width was measured in 1 nm increments in the wavelength range of 380 to 780 nm.
The absorbance of the second portion was measured using, as a measurement sample, the wavelength-selective absorption filter No. 501 (laminate II) with a substrate and the light-absorbing and disappearing filter No. 601 (laminate pre-III) having a gas barrier layer prepared above, and a laminate obtained by bonding the second wavelength-selective absorption layer 12 in the laminate II to the gas barrier layer in the laminate pre-III.
Furthermore, the absorbance of the first portion was measured using, as a measurement sample, a laminate obtained by bonding together Laminate III obtained by subjecting the above-prepared light-absorbing and dissipating filter No. 601 (laminate pre-III) having a gas barrier layer to the following ultraviolet irradiation test without patterning, and wavelength-selective absorption filter No. 501 (laminate II) with a substrate.
(Ultraviolet irradiation test)
Under atmospheric pressure (101.33 kPa), a light-absorbing and dissipative filter No. 601 (laminate pre-III) having a gas barrier layer was irradiated with ultraviolet (UV) rays at an illuminance of 100 mW/cm 2 and an exposure dose of 2000 mJ/cm 2 from the gas barrier layer side (the side opposite to the substrate 21) using an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) on a hot plate at 45°C.

(2)吸光度の算出
 上記(1)で測定した、第一の部位及び第二の部位の各波長λnmにおける吸光度の値Ab(λ)と、同じ樹脂を含有し、染料を含有しない積層体No.r701の各波長λnmにおける吸光度の値Ab(λ)とを用いて、下記式より、第一の部位及び第二の部位の吸光度Ab(λ)を算出した。
  Ab(λ)=Ab(λ)-Ab(λ)
 
 なお、波長380~780nmの領域における第一の部位及び第二の部位の吸光度Ab(λ)のうち、極大吸収を示す波長のうち最も大きい吸光度Ab(λ)を示す波長を極大吸収波長(以下、単に「λmax」とも称す。)とし、このλmaxにおける吸光度を吸収極大値(以下、単に「Ab(λmax)」とも称す。)とした。得られた各染料のAb(λmax)について、上述の染料の説明において、又は上述の染料の化学構造と共に記載した。
(2) Calculation of Absorbance Using the absorbance values Ab x (λ) at each wavelength λ nm of the first portion and the second portion measured in (1) above and the absorbance value Ab 0 (λ) at each wavelength λ nm of Laminate No. r701 containing the same resin but no dye, the absorbance Ab(λ) of the first portion and the second portion was calculated according to the following formula:
Ab (λ) = Ab x (λ) - Ab 0 (λ)

Among the absorbances Ab(λ) of the first and second portions in the wavelength range of 380 to 780 nm, the wavelength showing the largest absorbance Ab(λ) among the wavelengths showing maximum absorption was defined as the maximum absorption wavelength (hereinafter also simply referred to as "λ max "), and the absorbance at this λ max was defined as the maximum absorption value (hereinafter also simply referred to as "Ab(λ max )"). The Ab(λ max ) of each of the obtained dyes is described in the above description of the dye or together with the above chemical structure of the dye.

[第一、及び第二の部位の透過率シミュレーション]
 上記の第一の部位及び第二の部位の吸光度Ab(λ)から得られた吸収スペクトルを用いて、波長380~780nmの範囲の透過率を計算した。
 得られた波長380~780nmの範囲の透過率に明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより、透過光の色味(a、b)を算出した。
[Transmittance Simulation of First and Second Regions]
The transmittance in the wavelength range of 380 to 780 nm was calculated using the absorption spectrum obtained from the absorbance Ab(λ) of the first and second regions.
The obtained transmittance in the wavelength range of 380 to 780 nm was multiplied by the photopic standard relative luminosity factor and summed (luminosity correction) to calculate the color (a * , b * ) of the transmitted light.

[OLED基板の反射スペクトル測定]
 OLED基板の反射スペクトルとしては、OLED表示装置から、OLED発光層よりも視認者側の層に存在する円偏光板、カラーフィルタ及びブラックマトリックス等の反射防止のための層を取り除いたもの(詳細は後述の通り)を用いた。得られたOLED基板において、発光部である各画素の各波長における反射率、並びに、非発光部である、基板、金属細線及びブラックバンク(黒隔壁)の各波長における反射率は、一般的な顕微分光法により測定した。反射率は、保護膜付き銀ミラーの反射率に対する相対反射率として計算した。
[Measurement of Reflection Spectrum of OLED Substrate]
The reflectance spectrum of the OLED substrate was measured using an OLED display device from which anti-reflection layers, such as a circular polarizer, color filter, and black matrix, which are present on the viewer's side of the OLED light-emitting layer, had been removed (details will be described later). For the obtained OLED substrate, the reflectance at each wavelength of each pixel, which is the light-emitting portion, and the reflectance at each wavelength of the substrate, thin metal wires, and black bank (black partition wall), which are non-light-emitting portions, were measured using a conventional microspectroscopy method. The reflectance was calculated as the relative reflectance to the reflectance of a silver mirror with a protective film.

[反射スペクトルのシミュレーション]
 反射スペクトルのシミュレーションは、発光部、非発光部に分けて各部位ごとに行った。
(1)発光部の反射率
 発光部の反射スペクトルR(λ)は、顕微分光法で測定したOLED基板の発光部の反射スペクトルRx0(λ)と、第一の部位の透過スペクトルT(λ)と、表面反射率Rとを用い、以下の式により算出した。なお、表面反射率Rは、第一の部位より表面側(視認者側)の透明部材の積層体の表面反射率であり、具体的には、基材11の表面反射率を意味する。(xは、青色画素(B)、緑色画素(G)、赤色画素(R)等がある。)
 R(λ)=Rx0(λ)×T(λ)+R
(2)非発光部の反射率
 非発光部の反射スペクトルR(λ)は、顕微分光法で測定したOLED基板の非発光部の反射スペクトルRy0(λ)と、第二の部位の透過スペクトルT(λ)と、表面反射率Rとを用い、以下の式により算出した。なお、表面反射率Rは、第二の部位より表面側(視認者側)の透明部材の積層体の表面反射率であり、具体的には、基材11の表面反射率を意味する。
 R(λ)=Ry0(λ)×T(λ)+R
(3)平均反射率
 表示装置全体の反射スペクトルは、上記で算出した発光部の反射スペクトルR(λ)及び非発光部の反射スペクトルR(λ)に対して、各部位の面積比率を掛け合わせた和として算出し、得られた反射スペクトルにCIE標準光源D65スペクトルと明所視標準比視感度を掛け合わせて和をとる(視感度補正する)ことにより、視感度補正反射率Y(以下、単に「反射率」とも称す。)、および反射光の色味(a、b)を算出した。
 なお、本シミュレーションにおいては、OLED基板として、市販のスマートフォンGalaxy Z Fold3(商品名、Samsung社製)を使用し、OLED発光層とカラーフィルタ層との間で剥離して、カラーフィルタ層より上(視認者側)の層を取り除いたものを用いた。Galaxy Z Fold3(商品名)の発光部(BGRの各色発光部)及び非発光部の面積比率は、B(青):G(緑):R(赤):非発光部=5.4:6.9:3.8:84として計算した。また、Galaxy Z Fold3(商品名)の極角60°の輝度は正面(極角0°)の輝度(100%)に対して20%であった。
[Simulation of Reflection Spectrum]
The simulation of the reflection spectrum was carried out for each part, divided into a light-emitting part and a non-light-emitting part.
(1) Reflectance of Light-Emitting Portion The reflection spectrum R x (λ) of the light-emitting portion was calculated by the following formula using the reflection spectrum R x0 (λ) of the light-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 1 (λ) of the first portion, and the surface reflectance R S. Note that the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the first portion, and specifically means the surface reflectance of the substrate 11. (x can be a blue pixel (B), a green pixel (G), a red pixel (R), etc.)
R x (λ) = R x0 (λ) x T 1 (λ) 2 + R S
(2) Reflectance of Non-Emitting Portion The reflection spectrum R y (λ) of the non-emitting portion was calculated by the following formula using the reflection spectrum R y0 (λ) of the non-emitting portion of the OLED substrate measured by microspectroscopy, the transmission spectrum T 2 (λ) of the second portion, and the surface reflectance R S. Note that the surface reflectance R S is the surface reflectance of the laminate of transparent members on the surface side (viewer side) of the second portion, and specifically means the surface reflectance of the substrate 11.
R y (λ)=R y0 (λ)×T 2 (λ) 2 +R S
(3) Average Reflectance The reflectance spectrum of the entire display device was calculated as the sum of the reflectance spectrum R x (λ) of the light-emitting portion and the reflectance spectrum R y (λ) of the non-light-emitting portion calculated above, multiplied by the area ratio of each portion. The resulting reflectance spectrum was then multiplied by the CIE standard illuminant D65 spectrum and the photopic standard relative luminosity factor to obtain the sum (luminosity correction), thereby calculating the luminosity-corrected reflectance Y (hereinafter simply referred to as "reflectance") and the color (a * , b * ) of the reflected light.
In this simulation, a commercially available smartphone, Galaxy Z Fold3 (product name, manufactured by Samsung Electronics), was used as the OLED substrate. The OLED light-emitting layer was separated from the color filter layer, and the layer above the color filter layer (on the viewer's side) was removed. The area ratio of the light-emitting portion (each color light-emitting portion of BGR) and the non-light-emitting portion of the Galaxy Z Fold3 (product name) was calculated as B (blue): G (green): R (red): non-light-emitting portion = 5.4: 6.9: 3.8: 84. Furthermore, the brightness of the Galaxy Z Fold3 (product name) at a polar angle of 60° was 20% of the brightness (100%) at the front (polar angle of 0°).

(4)視野角による表示光の色味変化と相対輝度
 表示光の色味は、B、G、R及び白表示について、極角0°方位角0°の発光スペクトルをそれぞれB(λ)、G(λ)、R(λ)及びW(λ)とし、極角60°方位角0°の発光スペクトルをそれぞれB60(λ)、G60(λ)、R60(λ)及びW60(λ)として、分光放射計SR-UL1(商品名、テクノオプティス社製)を用いて測定した。
 発光部の面積に対する、極角60°無限遠から観察した場合における、第一の部位と発光部からの出射光との重なる割合をRO60とし、B画素、G画素、R画素のRO60をそれぞれROB60、ROG60、ROR60とした。これらのROB60、ROG60及びROR60を用いて、以下の式により極角60°での発光スペクトルEx60(λ)(xは、B画素(B)、G画素(G)、R画素(G)がある。)をBGRそれぞれについて求め、白表示時のB/G/R比と同じ比率で、得られた極角60°でのBGRの各発光スペクトルEx60(λ)を合計し、光吸収フィルタII(光吸収消失性層)を用いた場合の極角60°の視感度補正輝度Y(以下、単に「輝度」とも称す。)、および白色味(x、y)を算出した。
 
 EB60(λ)=B60(λ)×T(λ)×ROB60+B60(λ)×T(λ)×(1-ROB60
 EG60(λ)=G60(λ)×T(λ)×ROG60+G60(λ)×T(λ)×(1-ROG60
 ER60(λ)=R60(λ)×T(λ)×ROR60+R60(λ)×T(λ)×(1-ROR60
 
 なお、RO60は、発光部と第一の部位の大きさ、および正面から見た場合の位置が全く同じ場合(すなわち、上述の式(2)における「Sf/S」が1である場合)において、発光部と光吸収消失性層との距離、および発光部と第一の部位の直径とから幾何的に算出した。なお、極角60°の表示光の表示装置内部での角度はスネルの法則に基づき約33°として計算した。
(4) Change in color of display light due to viewing angle and relative brightness The color of the display light was measured for B, G, R and white display using a spectroradiometer SR-UL1 (trade name, manufactured by Techno Optis Co., Ltd.) with the emission spectra at a polar angle of 0° and an azimuth angle of 0° as B 0 (λ), G 0 (λ), R 0 ( λ) and W 0 (λ), respectively, and the emission spectra at a polar angle of 60° and an azimuth angle of 0° as B 60 (λ), G 60 (λ), R 60 (λ) and W 60 (λ), respectively.
The ratio of overlap between the first portion and the light emitted from the light-emitting portion relative to the area of the light-emitting portion when observed from infinity at a polar angle of 60° was defined as RO 60 , and the RO 60s for the B pixel, G pixel, and R pixel were defined as RO B60 , RO G60 , and RO R60 , respectively. Using RO B60 , RO G60 , and RO R60 , the emission spectrum E x60 (λ) (x represents the B pixel (B), G pixel (G), or R pixel (G)) at a polar angle of 60° was determined for each of B, G, and R using the following formula, and the resulting emission spectra E x60 (λ) for B, G, and R at a polar angle of 60° were summed in the same ratio as the B/G/R ratio during white display to calculate the luminosity-corrected luminance Y (hereinafter also simply referred to as "luminance") and whiteness (x, y) at a polar angle of 60° when a light-absorbing filter II (light-absorbing disappearing layer) was used.

E B60 (λ) = B 60 (λ) x T 1 (λ) x RO B60 + B 60 (λ) x T 2 (λ) x (1-RO B60 )
E G60 (λ) = G 60 (λ) x T 1 (λ) x RO G60 + G 60 (λ) x T 2 (λ) x (1-RO G60 )
E R60 (λ) = R 60 (λ) x T 1 (λ) x RO R60 + R 60 (λ) x T 2 (λ) x (1-RO R60 )

RO 60 was calculated geometrically from the distance between the light-emitting section and the light-absorbing and dissipative layer and the diameter of the light-emitting section and the first section when the sizes of the light-emitting section and the first section and their positions when viewed from the front are exactly the same (i.e., when "Sf/S" in the above formula (2) is 1). The angle of the display light with a polar angle of 60° inside the display device was calculated as approximately 33° based on Snell's law.

 結果を表3にまとめて示す。
 なお、上記積層体No.701(光透過吸収フィルタII)を用いた表示装置のうち、No.801~806が実施例であり、No.r901及びr902が参考例である。
The results are summarized in Table 3.
Among the display devices using the laminate No. 701 (light transmission/absorption filter II), Nos. 801 to 806 are examples, and Nos. r901 and r902 are reference examples.

(表の注)
 「距離」は、OLED基板の発光部(発光素子層)と光吸収消失性層との膜厚方向の距離(距離d)である。
 「B画素距離比率」は、第一の光透過吸収部位における光吸収消失性層と発光素子層との距離dを、発光素子層を構成する各青色発光素子の平均面積Sの平方根で除した値(d/√S)であり、「G画素距離比率」は第一の光透過吸収部位における光吸収消失性層と発光素子層との距離dを、発光素子層を構成する各緑色発光素子の平均面積Sの平方根で除した値(d/√S)である。
 なお、上記評価はあくまでシミュレーションであるため、上記「距離」並びに上記「B画素距離比率」及び「G画素距離比率」の計算に用いられる「距離d」は、積層体pre-IIIをマスク露光してられる積層体IIIが有する基材21及び拡散阻害層の膜厚よりも短くなっている。
 「相対輝度」は、極角60°方位角0°の輝度であって、光吸収フィルタII(光吸収消失性層)を用いない場合を100とした時の、光吸収フィルタII(光吸収消失性層)を用いた場合の相対値である。
 「色味変化」は、白表示時における、極角0°方位角0°の白色味と、極角60°方位角0°の白色味とをxy色度図上で比較した場合の2つの白色味間の距離(Δxy)であり、下記式により算出される値である。
(Table notes)
The "distance" is the distance (distance d) in the film thickness direction between the light-emitting portion (light-emitting element layer) of the OLED substrate and the light-absorbing and dissipating layer.
The "B pixel distance ratio" is the value (d/√S B ) obtained by dividing the distance d between the light-absorbing and disappearing layer in the first light-transmitting and absorbing portion and the light-emitting element layer by the square root of the average area S B of each blue light-emitting element that constitutes the light-emitting element layer, and the "G pixel distance ratio" is the value (d/√S G ) obtained by dividing the distance d between the light-absorbing and disappearing layer in the first light-transmitting and absorbing portion and the light-emitting element layer by the square root of the average area S G of each green light-emitting element that constitutes the light-emitting element layer.
It should be noted that the above evaluation is merely a simulation, and therefore the "distance d" used in calculating the "distance" and the "B pixel distance ratio" and "G pixel distance ratio" is shorter than the film thickness of the substrate 21 and diffusion-preventing layer of the laminate III obtained by mask-exposing the laminate pre-III.
The "relative luminance" is the luminance at a polar angle of 60° and an azimuth angle of 0°, and is a relative value when the light-absorbing filter II (light-absorbing disappearing layer) is used, with the value when the light-absorbing filter II (light-absorbing disappearing layer) is not used being taken as 100.
The "color change" is the distance (Δxy) between the whiteness at a polar angle of 0° and an azimuth angle of 0° when displaying white, and the whiteness at a polar angle of 60° and an azimuth angle of 0° when comparing the two whitenesses on an xy chromaticity diagram, and is a value calculated using the following formula.

 x及びyが、それぞれ、極角0°方位角0°の白色味のxy色度図上のx及びyであり、x60及びy60が、それぞれ、極角60°方位角0°白色味のxy色度図上のx及びyである。 x 0 and y 0 are respectively x and y on the xy chromaticity diagram of white at a polar angle of 0° and an azimuth angle of 0°, and x 60 and y 60 are respectively x and y on the xy chromaticity diagram of white at a polar angle of 60° and an azimuth angle of 0°.

 表3の結果から、本発明の光透過吸収フィルタを、OLED表示素子の距離比率(B画素距離比率(d/√S)及びG画素距離比率(d/√S))が1.0~7.0の範囲になるようにして配置する実施例のNo.801~806の表示装置は、OLED表示素子の距離比率が上記範囲外となるようにして配置する参考例のNo.r901及びr902の表示装置と比較して、輝度の向上と視野角による色味変化の抑制とを高度なレベルで両立することができ、好ましいことがわかる。 The results in Table 3 show that the display devices of Example Nos. 801 to 806, in which the light transmission-absorption filters of the present invention are arranged so that the distance ratios of the OLED display elements (B pixel distance ratio (d/√S B ) and G pixel distance ratio (d/√S G )) are in the range of 1.0 to 7.0, are preferable because they are able to achieve a high level of both improved luminance and suppressed color shift due to viewing angle, compared to the display devices of Reference Examples Nos. r901 and r902, in which the OLED display elements are arranged so that the distance ratios are outside the above range.

 本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。 Although the present invention has been described in conjunction with its embodiments, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the appended claims should be interpreted broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

 本願は、2024年8月8日に日本国で特許出願された特願2024-131811及び2025年7月25日に日本国で特許出願された特願2025-124623に基づく優先権を主張するものであり、これらはここに参照してその内容を本明細書の記載の一部として取り込む。 This application claims priority based on Japanese Patent Application No. 2024-131811, filed in Japan on August 8, 2024, and Japanese Patent Application No. 2025-124623, filed in Japan on July 25, 2025, the contents of which are incorporated herein by reference.

1 第一の部位(第一の光透過吸収部位)
2 第二の部位(第二の光透過吸収部位)
3 マスク露光された波長選択吸収層
4 マスク露光された光吸収消色性層
5 光吸収性消失部位
6 光吸収性部位
7 表示素子の発光部
8 表示素子の非発光部
10 光透過吸収フィルタI
1. First section (first light transmitting/absorbing section)
2. Second region (second light transmitting/absorbing region)
3: Wavelength-selective absorption layer exposed with a mask 4: Light-absorbing and decolorizable layer exposed with a mask 5: Light-absorbing disappearance portion 6: Light-absorbing portion 7: Light-emitting portion of display element 8: Non-light-emitting portion of display element 10: Light-transmitting and absorbing filter I

Claims (8)

 第一の光透過吸収部位と第二の光透過吸収部位とを有し、
 前記第一の光透過吸収部位の、波長460nmにおける透過率T(460)、波長530nmにおける透過率T(530)及び波長620nmにおける透過率T(620)がそれぞれ下記関係を満たし、
 前記第一の光透過吸収部位と前記第二の光透過吸収部位との間で、透過光のL色空間におけるa及びbのうちの少なくとも一方の値の符号が逆となる関係を満たす、光透過吸収フィルタ。
  T(460)≧30%
  T(530)≧40%
  T(620)≧30%
having a first light-transmitting-absorbing portion and a second light-transmitting-absorbing portion;
the transmittance T(460) at a wavelength of 460 nm, the transmittance T(530) at a wavelength of 530 nm, and the transmittance T(620) at a wavelength of 620 nm of the first light transmitting/absorbing site each satisfy the following relationships:
A light-transmitting-absorbing filter in which the first light-transmitting-absorbing portion and the second light-transmitting-absorbing portion satisfy a relationship in which the sign of at least one of the values a * and b * in the L * a * b * color space of transmitted light is opposite.
T(460)≧30%
T(530)≧40%
T(620)≧30%
 前記の第一の光透過吸収部位の透過光のa及びbが下記関係を満たす、請求項1に記載の光透過吸収フィルタ。
  -20.0≦a≦+20.0
  -20.0≦b≦+20.0
2. The light transmission-absorption filter according to claim 1, wherein a * and b * of the transmitted light of the first light transmission-absorption site satisfy the following relationship:
−20.0≦a * ≦+20.0
−20.0≦b * ≦+20.0
 光吸収透過特性が異なる2つ以上の層を含む、請求項1に記載の光透過吸収フィルタ。 The light-transmitting-absorbing filter described in claim 1, comprising two or more layers with different light-absorbing and transmitting properties.  請求項1に記載の光透過吸収フィルタを含む、有機エレクトロルミネッセンス表示素子。 An organic electroluminescent display element comprising the light-transmitting/absorbing filter of claim 1.  前記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 前記有機エレクトロルミネッセンス表示素子が、前記積層体II、前記積層体III、及び発光素子層がこの順に配置されてなり、
 前記積層体IIIと前記発光素子層との距離dと、前記発光素子層を構成する各発光素子の平均面積Sと、前記第一の光透過吸収部位のうち前記各発光素子の直上に位置する部分の平均面積Sfとが、下記式(1)及び(2)の関係を満たす、請求項4に記載の有機エレクトロルミネッセンス表示素子。
    式(1)  0.6≦d/√S≦7.5
    式(2)  0.7≦Sf/S≦1.5
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order,
5. The organic electroluminescent display element according to claim 4, wherein a distance d between the laminate III and the light-emitting element layer, an average area S of each light-emitting element constituting the light-emitting element layer, and an average area Sf of the first light-transmitting/absorbing portion located directly above each light-emitting element satisfy the relationships of the following formulas (1) and (2):
Formula (1) 0.6≦d/√S≦7.5
Formula (2) 0.7≦Sf/S≦1.5
 前記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 前記有機エレクトロルミネッセンス表示素子が、前記積層体II、前記積層体III、及び発光素子層がこの順に配置されてなり、
 前記積層体IIIと前記発光素子層との距離dと、前記発光素子層を構成する各青色発光素子の平均面積Sと、前記第一の光透過吸収部位のうち前記各青色発光素子の直上に位置する部分の平均面積Sfとが、下記式(3)及び(4)の関係を満たす、請求項4に記載の有機エレクトロルミネッセンス表示素子。
    式(3)  1.0≦d/√S≦7.0
    式(4)  0.8≦Sf/S≦1.2
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is configured by arranging the laminate II, the laminate III, and a light-emitting element layer in this order,
5. The organic electroluminescent display element according to claim 4, wherein a distance d between the laminate III and the light-emitting element layer, an average area S B of each blue light-emitting element constituting the light-emitting element layer, and an average area Sf B of a portion of the first light-transmitting and absorbing site located directly above each blue light-emitting element satisfy the relationships of the following formulas (3) and (4):
Formula (3) 1.0≦d/√S B ≦7.0
Formula (4) 0.8≦Sf B /S B ≦1.2
 前記光透過吸収フィルタが、波長選択吸収層を含む積層体IIと、光吸収消失性層を含む積層体を紫外線照射によりマスク露光して得られた積層体IIIとを含む光透過吸収フィルタであり、
 前記有機エレクトロルミネッセンス表示素子が、前記積層体II、前記積層体III、及び発光素子層がこの順に配置されてなり、
 前記積層体IIIと前記発光素子層との距離dと、前記発光素子層を構成する各緑色発光素子の平均面積Sと、前記第一の光透過吸収部位のうち前記各緑色発光素子の直上に位置する部分の平均面積Sfとが、下記式(5)及び(6)の関係を満たす、請求項4に記載の有機エレクトロルミネッセンス表示素子。
    式(5)  1.0≦d/√S≦7.0
    式(6)  0.8≦Sf/S≦1.2
the light transmission-absorption filter comprises a laminate II including a wavelength-selective absorption layer and a laminate III obtained by mask-exposing a laminate including a light-absorbing and disappearing layer to ultraviolet light irradiation,
the organic electroluminescence display element is formed by arranging the laminate II, the laminate III, and a light-emitting element layer in this order,
5. The organic electroluminescent display element according to claim 4, wherein a distance d between the laminate III and the light-emitting element layer, an average area S G of each green light-emitting element constituting the light-emitting element layer, and an average area Sf G of a portion of the first light-transmitting and absorbing site located directly above each green light-emitting element satisfy the relationships of the following formulas (5) and (6):
Formula (5) 1.0≦d/ √SG ≦7.0
Formula (6) 0.8≦Sf G /S G ≦1.2
 請求項1~3のいずれか1項に記載の光透過吸収フィルタ又は請求項4~7のいずれか1項に記載の有機エレクトロルミネッセンス表示素子を含む、有機エレクトロルミネッセンス表示装置。 An organic electroluminescent display device comprising the light-transmitting/absorbing filter described in any one of claims 1 to 3 or the organic electroluminescent display element described in any one of claims 4 to 7.
PCT/JP2025/028193 2024-08-08 2025-08-07 Light-transmitting absorption filter, organic electroluminescence display element, and organic electroluminescence display device Pending WO2026034603A1 (en)

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