WO2011105227A1 - カラーフィルタ及びカラー液晶表示素子 - Google Patents
カラーフィルタ及びカラー液晶表示素子 Download PDFInfo
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- WO2011105227A1 WO2011105227A1 PCT/JP2011/052889 JP2011052889W WO2011105227A1 WO 2011105227 A1 WO2011105227 A1 WO 2011105227A1 JP 2011052889 W JP2011052889 W JP 2011052889W WO 2011105227 A1 WO2011105227 A1 WO 2011105227A1
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- pigment
- color filter
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Definitions
- the present invention relates to a color filter including a red pixel containing a specific organic pigment, and a color liquid crystal display element including the color filter.
- color liquid crystal display elements have been used in various applications such as personal computer (PC) monitors, mobile phone displays, notebook PCs, personal digital assistants, and televisions because of their low power consumption and space saving advantages. Yes.
- Patent Document 1 discloses C.I. as a color filter suitable for a liquid crystal display device using a white LED as a light source. I. Pigment red 177 and C.I. I. Color filters with red pixels containing pigment red 254 have been proposed.
- the present invention has been made in view of the above circumstances, and its object is to provide a color filter having high luminance and excellent visibility when a white LED is used as a backlight light source. is there.
- the present invention is a color filter used in a liquid crystal display device including a color filter having red pixels, green pixels, and blue pixels, and a backlight light source disposed on the back side thereof,
- the red pixel is (1) C.I. I. Pigment red 242 and (2) C.I. I. Pigment red 177 and C.I. I. Including at least one selected from the group consisting of CI Pigment Red 254,
- the present invention provides a color filter, wherein the backlight light source is a white LED.
- the present invention also provides a color liquid crystal display element comprising the color filter and a white LED as a backlight light source on the back side.
- the color filter of the present invention has high brightness and excellent visibility when a white LED is used as a backlight light source. Therefore, the color filter of the present invention can be used very suitably for various liquid crystal display elements such as PC monitors, mobile phone displays, notebook PCs, personal digital assistants, and televisions. Thereby, energy saving of these liquid crystal display elements is realized.
- Color filter The color filter of the present invention comprises a red pixel, a green pixel and a blue pixel.
- the color filter can also have fourth and fifth colored pixels.
- a fourth pixel yellow pixel
- a fifth pixel for expanding the color display range Cyan pixels
- Each color pixel is usually composed of a colored composition.
- the coloring composition contains at least a colorant, a binder resin, and a polyfunctional monomer, and if necessary, the photopolymerization initiator can be included to impart radiation sensitivity to the coloring composition. it can.
- the colored composition is usually used as a liquid composition by blending a solvent. Hereinafter, each component will be described.
- the red pixel constituting the color filter of the present invention includes (1) C.I. I. Pigment red 242 and (2) C.I. I. Pigment red 177 and C.I. I. And at least one selected from the group consisting of CI Pigment Red 254.
- FIG. 1 shows a typical emission spectrum of a white LED that generates white light by mixing colors of light emitted from a blue LED and a YAG phosphor.
- the present inventors have made it possible to reduce the transmittance in the wavelength band of 430 nm to 470 nm where the emission intensity of the blue LED is maximum as low as possible, and to increase the transmittance in the wavelength band of 500 nm or more where the emission intensity is weaker than that of the blue LED as much as possible.
- the transmittance in the wavelength band of 430 nm to 470 nm is C.I. I.
- the transmittance in a wavelength band lower than that of CI Pigment Red 177 and 500 nm or more is C.I. I. Higher than C.I. Pigment Red 254 I. It has been found that Pigment Red 242 is effective as a colorant used for red pixels.
- the red pixel constituting the color filter of the present invention is (1) C.I. I. Pigment red 242 and (2) C.I. I. Pigment red 177 and C.I. I. If it contains at least 1 sort (s) chosen from the group which consists of pigment red 254, it will not specifically limit, You may contain another red coloring agent and / or a yellow coloring agent. Although it does not specifically limit as another red coloring agent or a yellow coloring agent, C.I. I. From the viewpoint of co-dispersibility with Pigment Red 242, an organic pigment or an organic dye is preferable, and an organic pigment is particularly preferable. Examples of such red or yellow organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following colors: An index (CI) name is given.
- CI color index
- yellow pigment an inclusion compound comprising a compound represented by the following formula (I) or a tautomer thereof and a guest represented by the following formula (II) (hereinafter referred to as “specific yellow pigment”) (hereinafter referred to as “specific yellow pigment”) (hereinafter referred to as “specific yellow pigment”) (hereinafter referred to as “specific yellow pigment”) (hereinafter referred to as “specific yellow pigment”) (hereinafter referred to as “specific yellow pigment”) can also be used.)
- R a to R c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.
- the alkyl group having 1 to 4 carbon atoms in R a to R c may be either linear or branched, and specifically includes a methyl group, an ethyl group, and an n-propyl group. Isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.
- Examples of the alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group include groups in which at least one hydrogen atom of the above alkyl group is substituted with a hydroxyl group. Specific examples include hydroxymethyl, 2-hydroxy Examples thereof include ethyl, 1,2-dihydroxypropyl, 1,2,3-trihydroxybutyl and the like.
- red pixel constituting the color filter of the present invention these other red pigments or yellow pigments can be used alone or in admixture of two or more.
- the color filter of the present invention has a relatively low color purity, such as a notebook PC, in other words, the chromaticity coordinates to be reproduced of a red pixel in the CIE 1931 standard color system are 0.50 ⁇ x ⁇ 0.64, 0 .27 ⁇ y ⁇ 0.37, preferably 0.53 ⁇ x ⁇ 0.62 and 0.28 ⁇ y ⁇ 0.37, the red pixels constituting the color filter of the present invention C. I. Pigment red 242 and C.I. I. Pigment Red 254 is contained, and it is preferably toned with a yellow pigment or another red pigment as necessary. In that case, the content ratio of each pigment is C.I. in all colorants constituting the red pixel. I.
- Pigment Red 242 is 1 to 74% by mass, C.I. I. Pigment Red 254 is preferably 1 to 84% by mass, C.I. I. Pigment Red 242 is 20 to 80% by mass, C.I. I. More preferably, the pigment red 254 is 10 to 70% by mass. I. Pigment Red 242 is 50 to 70 mass%, C.I. I. It is particularly preferable that the pigment red 254 is 20 to 48% by mass.
- the color filter of the present invention has high color purity, such as a television, in other words, the chromaticity coordinates to be reproduced of red pixels in the CIE 1931 standard color system are 0.60 ⁇ x ⁇ 0.69, 0.25. ⁇ y ⁇ 0.38, preferably 0.62 ⁇ x ⁇ 0.68, 0.28 ⁇ y ⁇ 0.38, the red pixel constituting the color filter of the present invention is C.I. I. Pigment red 242 and C.I. I. Pigment Red 177 is contained, and it is preferably toned with a yellow pigment or another red pigment as necessary. In that case, the content ratio of each pigment is C.I. in all colorants constituting the red pixel. I.
- Pigment Red 242 is 1 to 61% by mass, C.I. I. Pigment Red 177 is preferably 1 to 76% by mass, and C.I. I. Pigment Red 242 is 10 to 60% by mass, C.I. I. More preferably, the pigment red 177 is 30 to 75% by mass. I. Pigment Red 242 is 20 to 50 mass%, C.I. I. Pigment Red 177 is preferably 50 to 70% by mass.
- yellow pigments used for toning C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150 and a specific yellow pigment are preferable.
- the green pixel constituting the color filter of the present invention is not particularly limited as long as it contains a green colorant, but the color filter is required to have high purity and high light transmittance color development and heat resistance. It is preferable to contain a green organic pigment or organic dye, and it is particularly preferable to contain a green organic pigment.
- the green organic pigment include C.I. I. Pigment green 7, C.I. I. Pigment green 10, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. And CI Pigment Green 58.
- these green organic pigments can be used alone or in admixture of two or more.
- the green pixel constituting the color filter of the present invention has C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Green 58. I. Pigment Green 58 is preferably contained.
- the green pixel constituting the color filter of the present invention preferably further contains a yellow colorant.
- the yellow colorant contained in the green pixel is not particularly limited, but an organic pigment or an organic dye is preferable, and an organic pigment is particularly preferable.
- an organic pigment is particularly preferable.
- As such a yellow organic pigment the same thing as the yellow organic pigment illustrated in the said red pixel can be mentioned.
- the yellow organic pigment can be used alone or in admixture of two or more.
- the green pixel constituting the color filter of the present invention includes C.I. I. Pigment yellow 138, C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Yellow 150 and a specific yellow pigment, and it is particularly preferable to include a specific yellow pigment.
- the green pixel constituting the color filter of the present invention is C.I. in all colorants constituting the green pixel regardless of the application.
- Pigment yellow 138 C.I. I. More preferably, it contains 20 to 50% by mass of at least one selected from the group consisting of CI Pigment Yellow 150 and a specific yellow pigment.
- white LED when used as a backlight light source, it can be set as a green pixel with high brightness
- the blue pixel that constitutes the color filter of the present invention is not particularly limited as long as it contains a blue colorant, but the color filter is required to have high purity and high light transmission color development and heat resistance. It is preferable to contain a blue organic pigment or organic dye, and it is particularly preferable to contain a blue organic pigment.
- the blue organic pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Blue 80.
- these blue organic pigments can be used alone or in admixture of two or more.
- the blue pixel constituting the color filter of the present invention has C.I. I. Pigment Blue 15: 6 is preferably contained.
- the blue pixel constituting the color filter of the present invention preferably further contains a purple colorant.
- the purple colorant contained in the blue pixel is not particularly limited, but an organic pigment or an organic dye is preferable, and an organic pigment is particularly preferable.
- Examples of such purple organic pigments include C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. And CI Pigment Violet 38.
- the purple organic pigment can be used alone or in admixture of two or more.
- the blue pixel constituting the color filter of the present invention includes C.I. I. Pigment Violet 23 is preferably contained.
- the blue pixel constituting the color filter of the present invention is C.I. in all colorants constituting the blue pixel regardless of the application.
- I. Pigment Blue 15: 6 at 60 to 100% by mass C.I. I. Pigment Violet 23 is preferably contained in an amount of 0 to 40% by mass.
- I. Pigment Blue 15: 6 is 70 to 100% by mass, C.I. I. More preferably, the pigment violet 23 is contained in an amount of 0 to 30% by mass.
- a coloring agent such as CI Pigment Red 242 may be used by modifying the particle surface with a resin if desired.
- the resin that modifies the pigment particle surface include a vehicle resin described in JP-A No. 2001-108817, or various commercially available resins for dispersing pigments.
- C.I. I. It is preferable to use organic pigments such as CI Pigment Red 242 by refining primary particles by salt milling.
- a salt milling method for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.
- the organic pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.
- the coloring composition for forming each color pixel constituting the color filter of the present invention can contain a binder resin.
- a coating film can be formed on the substrate, and a pixel pattern can be formed by alkali development.
- the binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, or a sulfo group.
- a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”).
- unsaturated monomer an ethylenically unsaturated monomer having one or more carboxyl groups
- unsaturated monomer (2) an ethylenically unsaturated monomer having one or more carboxyl groups
- unsaturated monomer (1) examples include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (meta ) Acrylate and the like. These unsaturated monomers (1) can be used alone or in admixture of two or more.
- N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
- Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
- Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane
- a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
- These unsaturated monomers (2) can be used alone or in admixture of two or more.
- the copolymerization ratio of the unsaturated monomer (1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
- copolymer of the unsaturated monomer (1) and the unsaturated monomer (2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-9-31144.
- a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.
- the blue pixel constituting the color filter of the present invention contains a binder resin having an alicyclic hydrocarbon group.
- the binder resin having an alicyclic hydrocarbon group include a polymer obtained by copolymerizing an ethylenically unsaturated monomer having an alicyclic hydrocarbon group in the carboxyl group-containing polymer.
- ethylenically unsaturated monomer having an alicyclic hydrocarbon group examples include N-cyclohexylmaleimide, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate exemplified as the unsaturated monomer (2), Tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2, 6 ] Decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yloxyethyl (meth) acrylate, adamantyl (meth) acrylate, di- Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ) Acrylate, decahydro
- the copolymerization ratio of the ethylenically unsaturated monomer having an alicyclic hydrocarbon group is preferably 5 to 60% by mass from the viewpoint of enhancing a desired effect,
- the amount is preferably 10 to 40% by mass.
- the weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 300,000. Preferably, it is 3,000 to 100,000. If Mw is too small, the remaining film rate of the obtained pixel may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, the pattern shape is impaired. There is a risk of
- the ratio (Mw / Mn) of the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter sometimes referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). ) Is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
- the binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc.
- the structure, Mw, and Mw / Mn can be controlled by the method.
- binder resin can be used individually or in mixture of 2 or more types.
- the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts per 100 parts by mass of the colorant. Part by mass.
- the content of the binder resin is too small, for example, the storage stability and alkali developability of the resulting colored composition may be reduced.
- the colorant concentration is relatively lowered. Therefore, it may be difficult to achieve a target color density as a thin film.
- the coloring composition for forming each color pixel constituting the color filter of the present invention can contain a polyfunctional monomer. Thereby, it has curability accompanying exposure and / or heating.
- the polyfunctional monomer is not particularly limited as long as it is a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group.
- the polyfunctional monomer is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.
- the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid
- the polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.
- examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds.
- Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned.
- Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
- acid anhydrides examples include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid.
- acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid.
- dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.
- Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.
- Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide-modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide-modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di
- Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure.
- a melamine structure and a benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are a concept including a melamine compound, a benzoguanamine compound, or a condensate thereof.
- the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.
- polyfunctional monomers trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid esters, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, carboxyl groups , N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′, N′-tetra (alkoxymethyl) benzoguanamine Is preferred.
- esters of trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have many carboxyl groups.
- functional (meth) acrylates compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride have high pixel strength, and pixels It is particularly preferable in that it has excellent surface smoothness.
- a polyfunctional monomer can be used individually or in mixture of 2 or more types.
- the content of the polyfunctional monomer is preferably 5 to 500 parts by mass, particularly 50 parts per 100 parts by mass of the binder resin. ⁇ 300 parts by weight are preferred. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, when there is too much content of a polyfunctional monomer, there exists a tendency for alkali developability to fall, when alkali developability is provided to the coloring composition of this invention.
- the coloring composition for forming each color pixel constituting the color filter of the present invention can be provided with radiation sensitivity by incorporating a photopolymerization initiator.
- the photopolymerization initiator is a compound that can generate an active species capable of initiating the curing reaction of the polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. is there.
- photopolymerization initiators examples include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like.
- the photopolymerization initiators can be used alone or in admixture of two or more.
- the photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.
- thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.
- acetophenone compound examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
- biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′.
- -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.
- a hydrogen donor in terms of improving sensitivity.
- the “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
- the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
- an amine-based hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.
- triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (t
- O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl.
- a sensitizer when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination.
- a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl.
- Ethyl aminobenzoate 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.
- the content of the photopolymerization initiator is usually 0.01 to 120 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
- the amount is preferably 1 to 100 parts by mass.
- each color pixel constituting the color filter of the present invention is usually prepared as a liquid composition by blending a solvent.
- a solvent as long as each component which comprises a coloring composition is disperse
- solvents examples include propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2 -Heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 -Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate Amyl, n- butyl propionate, ethyl
- the content of the solvent is not particularly limited, but from the viewpoint of applicability and stability of the resulting colored composition, the total concentration of each component excluding the solvent from the composition is 5 to 50 mass. %, Preferably 10 to 40% by mass.
- the coloring composition of the present invention can further contain other additives as required.
- the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, anionic surfactants Surfactant such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-ch
- the coloring composition can be prepared by an appropriate method, and can be prepared by mixing the above-described components.
- the coloring agent is mixed and dispersed in a solvent in the presence of a dispersing agent, optionally together with a part of a binder resin, for example, using a bead mill, a roll mill or the like, while being mixed and dispersed.
- a dispersion liquid a method of adding a polyfunctional monomer, a binder resin, and the like to the colorant dispersion liquid, and further adding an additional solvent as required, and mixing them may be mentioned.
- an appropriate dispersant such as a cation system, an anion system, or a nonion system
- a polymer dispersant is preferable.
- an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.
- Such a dispersant is commercially available.
- Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation)
- As polyurethane Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)
- Solsperse 76500 manufactured by Lubrizol Corp.
- polyethylene As imine Solsperse 24000 (manufactured by Lubrizol Co., Ltd.)
- dispersants can be used alone or in admixture of two or more.
- the content of the dispersant is usually 100 parts by mass or less, preferably 1 to 70 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the colorant.
- a dispersion aid When dispersing the colorant, a dispersion aid can be used together with the above dispersant.
- the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.
- a method for producing a color filter first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, (1) C.I. I. Pigment red 242 and (2) C.I. I. Pigment red 177 and C.I. I. After applying a liquid composition of a colored composition in which a red colorant containing at least one selected from the group consisting of CI Pigment Red 254 is dispersed, pre-baking is performed to evaporate the solvent and form a coating film.
- the liquid composition of each colored composition in which a green or blue colorant is dispersed is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above.
- a pixel array and a blue pixel array are sequentially formed on the same substrate.
- a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- a black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the composition, it can be formed in the same manner as in the case of forming the pixel.
- the film thickness of the black matrix made of a metal thin film is usually 0.1 to 0.2 ⁇ m, while the film thickness of the resin black matrix formed using the black composition is about 1 ⁇ m.
- the substrate used when forming the pixel examples include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
- these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
- an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. should be adopted.
- the spin coating method and the slit die coating method are particularly preferable.
- Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed at 0.1 to 1 Torr. The conditions for heat drying are usually about 70 to 110 ° C. and about 1 to 10 minutes.
- Examples of radiation used in forming the color filter include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and other lamp light sources, argon ion lasers, Examples of the laser light source include a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable. The exposure dose of radiation is preferably 10 to 10,000 J / m 2 .
- alkali developer examples include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5.
- An aqueous solution of -diazabicyclo- [4.3.0] -5-nonene is preferred.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
- a shower development method As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
- the development conditions are preferably 5 to 300 seconds at room temperature.
- the post-baking conditions are usually 180 to 280 ° C. and about 20 to 40 minutes.
- the film thickness of the pixel thus formed is usually 0.5 to 5.0 ⁇ m, preferably 1.0 to 3.0 ⁇ m.
- a method for obtaining pixels of each color by an ink jet method is also known.
- a partition having a light shielding function is formed on the surface of the substrate.
- a liquid composition of a colored composition in which a red colorant containing at least one selected from the group consisting of CI Pigment Red 254 is dispersed is ejected by an inkjet apparatus, and then pre-baked to evaporate the solvent.
- this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.
- a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using a liquid composition of each colored composition in which a green or blue colorant is dispersed, in the same manner as described above.
- a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick.
- the film thickness is usually 1 to 3 ⁇ m. Therefore, a partition is normally formed using a black composition.
- the substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above.
- the film thickness of the pixel formed by the ink jet method is approximately the same as the film thickness of the partition wall.
- a protective film is formed on the color filter thus obtained as necessary, and then a transparent conductive film is formed by sputtering. Furthermore, a spacer is formed on the transparent conductive film as necessary.
- the transparent conductive film include a NESA film made of tin oxide (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide, an IZO film made of indium oxide-zinc oxide, and the like.
- a protective film inorganic films, such as an organic film formed from a thermosetting resin composition, a SiNx film
- the spacer is usually formed from a radiation-sensitive composition.
- the color liquid crystal display element of the present invention comprises the color filter of the present invention and a backlight unit having a white LED as a light source on the back side thereof.
- the type of white LED used in the backlight unit is not particularly limited as long as it is an LED that generates white light. For example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra.
- LED white LED that obtains white light by mixing red LED, green LED, and blue LED
- white LED that obtains white light by mixing blue LED, red LED, and green phosphor
- White LED that obtains white light by mixing colors with a green LED
- a white LED that obtains white light by mixing colors of a blue LED and a YAG phosphor
- UV LED red light emitting phosphor, green light emitting phosphor and blue light emitting phosphor It can be mentioned white LED or the like to obtain white light by color mixing combined viewed.
- the emission spectrum of a white LED has a maximum emission peak derived from a blue LED in a wavelength band of 430 nm to 470 nm, and one or two or more weak in intensity in the wavelength band of 500 nm to 700 nm. It is particularly suitable when it has a maximum emission peak of.
- white LED a blue LED, a red light emitting phosphor and a green light emitting phosphor are combined to obtain white light by color mixing, a white LED to obtain white light by mixing color of blue LED and YAG phosphor, blue LED and orange color
- a white LED that obtains white light by mixing colors by combining a light emitting phosphor and a green light emitting phosphor can be exemplified.
- FIG. 1 An example of the emission spectrum of a white LED is shown in FIG. 1, and a combination of a blue LED, a red light emitting phosphor and a green light emitting phosphor is combined.
- FIG. 1 An example of the emission spectrum of the white LED is shown in FIG.
- Examples of the blue LED in the backlight unit include an indium gallium nitride semiconductor element and a gallium nitride semiconductor element.
- the YAG phosphor absorbs blue light emitted from a blue LED and emits yellow light.
- Examples of a red light-emitting phosphor that absorbs blue light and emits red light and a green light-emitting phosphor that absorbs blue light and emits green light include, for example, the fluorescence disclosed in WO 2006/104319.
- the body can be mentioned.
- Examples of the orange light-emitting phosphor that absorbs blue light and emits orange light include the phosphors disclosed in Japanese Patent Application Laid-Open No. 2008-24791.
- a white LED that obtains white light by mixing colors by combining an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor
- a white LED disclosed in JP-A-2002-133910 is disclosed. Can be mentioned.
- the color liquid crystal display element of the present invention can take an appropriate structure.
- the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween.
- TFT thin film transistor
- a typical example of this is the structure disclosed in International Publication No. 2007/102386 pamphlet.
- a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate in which a transparent electrode is formed can be opposed to each other with a liquid crystal layer interposed therebetween.
- This structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display element can be obtained.
- the color liquid crystal display element of the present invention includes a TN (twisted nematic) type, a STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical aligned) type, and an OCB (optically concentrated type).
- TN twisted nematic
- STN super twisted nematic
- IPS in-plane switching
- VA vertical aligned
- OCB optical concentrated type
- binder resin solution (B-1) This binder resin solution is referred to as “binder resin solution (B-1)”.
- Synthesis example 2 A flask equipped with a condenser and a stirrer was charged with 156 parts by mass of propylene glycol monomethyl ether acetate and heated to 80 ° C. while injecting nitrogen gas. At the same temperature, 15 parts by weight of methacrylic acid, 12 parts by weight of N-phenylmaleimide, 12.5 parts by weight of succinic acid-2-methacryloyloxyethyl, 10 parts by weight of styrene, 12.5 parts by weight of 2-hydroxyethyl methacrylate, methyl A solution in which 13 parts by weight of methacrylate and 25 parts by weight of cyclohexyl methacrylate are dissolved in 46 parts by weight of propylene glycol monomethyl ether acetate and 6 parts by weight of 2,2′-azobisisobutyronitrile are added to 28 parts by weight of propylene glycol monomethyl ether acetate.
- binder resin (B-2) This binder resin is referred to as “binder resin (B-2)”.
- Preparation Examples 2 to 22 Colorant dispersions (A-2) to (A-) were prepared in the same manner as in Preparation Example 1, except that the type and mixing ratio of the colorant and the type of binder resin were changed as shown in Table 1. 22) was prepared.
- R254 means C.I. I. Pigment Red 254, “R242” is C.I. I. Pigment Red 242, “R177” is C.I. I. Pigment Red 177, “Y139” is C.I. I. Pigment Yellow 139, “Specific Y” means that the guest represented by the above formula (II) is melamine, and a specific yellow pigment comprising an inclusion compound of the melamine and the host represented by the above formula (I) "G36” means C.I. I. Pigment Green 36, “G58” is C.I. I. Pigment Green 58, “B15: 6” is C.I. I. Pigment Blue 15: 6, “V23” means C.I. I. Pigment Violet 23 is meant.
- Reference example 1 Preparation of radiation-sensitive coloring composition 46.7 parts by weight of colorant dispersion (A-1) as a colorant, 10.7 parts by weight of a binder resin (B-1) solution as a binder resin, a polyfunctional monomer As a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.0 part by mass, propylene glycol monomethyl ether 4.5 parts by mass and ethyl 3-ethoxypropionate as a solvent 32.0 parts by mass was mixed to prepare a liquid composition (S-1).
- the liquid composition (S-1) was evaluated according to the following procedure.
- Substrate preparation The liquid composition (S-1) was applied on a soda glass substrate having a SiO 2 film formed on its surface to prevent elution of sodium ions using a spin coater, and then heated on a 90 ° C hot plate. Pre-baking was performed for 3 minutes to form a coating film. Next, after the substrate on which the coating film is formed is cooled to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film at 1,000 J / m 2 without using a high pressure mercury lamp and without a photomask. The exposure amount was as follows. Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C.
- the substrate for evaluation on which the red cured film was formed was produced by performing post-baking at 230 ° C. for 20 minutes.
- the substrate obtained was measured for transmission spectrum using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.). From the obtained transmission spectrum and the emission spectrum of the white LED shown in FIG. 1, chromaticity coordinate values (x, y) and stimulation values (Y) in the CIE 1931 color system were determined. The evaluation results are shown in Table 2.
- Reference Examples 2-12 and Comparative Reference Examples 1-2 Liquid compositions (S-2) to (S-14) were prepared in the same manner as in Reference Example 1, except that the colorant dispersion and binder resin shown in Table 2 were used. Next, a substrate on which each cured film was formed in the same manner as in Reference Example 1 except that the liquid compositions (S-2) to (S-14) were used in place of the liquid composition (S-1). Evaluation was performed. The evaluation results are shown in Table 2.
- Reference Examples 13 to 34 and Comparative Reference Examples 3 to 6 In Reference Example 1, a liquid composition was prepared using the colorant dispersion and the binder resin shown in Table 3, and the cured film was formed on the substrate using these liquid compositions. Thus, each substrate was evaluated. In the evaluation of the chromaticity characteristics and the contrast ratio, in Reference Examples 13 to 23 and Comparative Reference Examples 3 to 4, white LEDs having the emission spectrum of FIG. 2 were used, and in Reference Examples 24 to 34 and Comparative Reference Examples 5 to 6, A white LED that generates white light by color mixing using a blue LED, an orange light emitting phosphor, and a green light emitting phosphor was used. The evaluation results are shown in Table 3.
- Example 1 Color filter preparation The liquid composition (S-1) was applied on a glass substrate on which a black matrix was formed using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film. Formed. Next, after the substrate on which the coating film is formed is cooled to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a striped photomask using a high-pressure mercury lamp at 1,000 J / m. The exposure amount was 2 . Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C.
- Example 2 each color filter was evaluated in the same manner as in Example 1 except that the liquid composition shown in Table 4 was used to form a color filter by forming red, green, and blue stripe pixel patterns. did.
- Examples 2 to 8 and Comparative Examples 1 and 2 use white LEDs having the emission spectrum of FIG.
- the white LEDs having the emission spectrum shown in FIG. 2 are used in 3-4, and in Examples 16-22 and Comparative Examples 5-6, white light is generated by mixing the blue LED, the orange-emitting phosphor, and the green-emitting phosphor. A white LED was used.
- Table 4 The evaluation results are shown in Table 4.
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Abstract
Description
赤色画素が(1)C.I.ピグメントレッド242と、(2)C.I.ピグメントレッド177及びC.I.ピグメントレッド254よりなる群から選ばれる少なくとも1種とを含み、
バックライト光源が白色LEDであることを特徴とするカラーフィルタを提供するものである。
したがって、本発明のカラーフィルタは、PCのモニター、携帯電話のディスプレイ、ノート型PC、携帯情報端末、テレビ等の各種の液晶表示素子に極めて好適に使用することができる。これにより、これらの液晶表示素子の省エネルギー化が実現される。
カラーフィルタ
本発明のカラーフィルタは赤色画素、緑色画素及び青色画素を備えるものであるが、これらの着色画素に加えて、第4や第5の着色画素を有することもできる。例えば、特表2005-523465号公報などに開示されているように、赤色、緑色及び青色の三原色の画素に加え、表色範囲を広げるための第4の画素(黄色画素)や第5の画素(シアン色画素)を配置することができる。各色画素は通常着色組成物により構成されている。
着色組成物は、着色剤、バインダー樹脂及び多官能性単量体を少なくとも含有するが、必要に応じて、光重合開始剤を含有せしめることにより、着色組成物に感放射線性を付与することができる。また、着色組成物は、通常、溶媒を配合して液状組成物として使用される。以下、各成分について説明する。
本発明のカラーフィルタを構成する赤色画素は、(1)C.I.ピグメントレッド242と、(2)C.I.ピグメントレッド177及びC.I.ピグメントレッド254よりなる群から選ばれる少なくとも1種とを含有することを特徴とする。図1に、青色LEDとYAG蛍光体からの発光の混色により白色光を生成する白色LEDの代表的な発光スペクトルを示す。
本発明者らは、青色LEDの発光強度が最大となる430nm~470nmの波長帯域における透過率をできるだけ低く、青色LEDより発光強度が弱い500nm以上の波長帯域における透過率をできるだけ高くするよう赤色画素の透過スペクトルを調整することにより、高輝度化と高色純度化の両立が実現できるものと考えた。そして、鋭意検討の結果、430nm~470nmの波長帯域における透過率がC.I.ピグメントレッド177より低く、かつ500nm以上の波長帯域における透過率がC.I.ピグメントレッド254より高いC.I.ピグメントレッド242が、赤色画素に使用される着色剤として有効であることを見出した。
本発明のカラーフィルタを構成する緑色画素は、緑色の着色剤を含有する限り特に限定されるものではないが、カラーフィルタには高純度で高光透過性の発色と耐熱性が求められることから、緑色の有機顔料又は有機染料を含有することが好ましく、緑色の有機顔料を含有することが特に好ましい。緑色の有機顔料としては、例えば、C.I.ピグメントグリーン7、C.I.ピグメントグリーン10、C.I.ピグメントグリーン36、C.I.ピグメントグリーン37、C.I.ピグメントグリーン58等を挙げることができる。
本発明のカラーフィルタを構成する青色画素は、青色の着色剤を含有する限り特に限定されるものではないが、カラーフィルタには高純度で高光透過性の発色と耐熱性が求められることから、青色の有機顔料又は有機染料を含有することが好ましく、青色の有機顔料を含有することが特に好ましい。青色の有機顔料としては、例えば、C.I.ピグメントブルー15、C.I.ピグメントブルー15:3、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:6、C.I.ピグメントブルー60、C.I.ピグメントブルー80等を挙げることができる。
本発明のカラーフィルタを構成する青色画素は、用途に関わらず、青色画素を構成する全着色剤中、C.I.ピグメントブルー15:6を60~100質量%、C.I.ピグメントバイオレット23を0~40質量%含有することが好ましく、C.I.ピグメントブルー15:6を70~100質量%、C.I.ピグメントバイオレット23を0~30質量%含有することがより好ましい。このような態様にすることにより、白色LEDをバックライト光源とした場合に、輝度及び色純度の高い青色画素とすることができる。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物は、バインダー樹脂を含有することができる。これにより、基板上に塗膜を形成することが可能となると共に、アルカリ現像により画素パターンを形成することができる。このようなバインダー樹脂としては、特に限定されるものではないが、カルボキシル基、フェノール性水酸基、スルホ基等の酸性官能基を有する樹脂であることが好ましい。中でも、カルボキシル基を有する重合体(以下、「カルボキシル基含有重合体」という。)が好ましく、特に、1個以上のカルボキシル基を有するエチレン性不飽和単量体(以下、「不飽和単量体(1)」ということがある。)と、他の共重合可能なエチレン性不飽和単量体(以下、「不飽和単量体(2)」ということがある。)との共重合体が好ましい。
N-フェニルマレイミド、N-シクロヘキシルマレイミドの如きN位置換マレイミド;
スチレン、α-メチルスチレン、p-ヒドロキシスチレン、p-ヒドロキシ-α-メチルスチレン、p-ビニルベンジルグリシジルエーテル、アセナフチレンの如き芳香族ビニル化合物;
これらの不飽和単量体(2)は、単独で又は2種以上を混合して使用することができる。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物において、バインダー樹脂の含有量は、着色剤100質量部に対して、通常10~1,000質量部、好ましくは20~500質量部である。この場合、バインダー樹脂の含有量が少なすぎると、例えば、得られる着色組成物の保存安定性やアルカリ現像性が低下するおそれがあり、一方多すぎると、相対的に着色剤濃度が低下するため、薄膜として目的とする色濃度を達成することが困難となるおそれがある。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物は、多官能性単量体を含有することができる。これにより、露光及び/又は加熱に伴う硬化性を有するものとなる。
多官能性単量体は、2個以上の重合可能な基を有する化合物であれば特に限定されるものではない。重合可能な基としては、例えば、エチレン性不飽和基、オキシラニル基、オキセタニル基、N-アルコキシメチルアミノ基等を挙げることができる。本発明において、多官能性単量体としては、2個以上の(メタ)アクリロイル基を有する化合物、又は2個以上のN-アルコキシメチルアミノ基を有する化合物が好ましい。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物において、多官能性単量体の含有量は、バインダー樹脂100質量部に対して、5~500質量部が好ましく、特に50~300質量部が好ましい。この場合、多官能性単量体の含有量が少なすぎると、十分な硬化性が得られないおそれがある。一方、多官能性単量体の含有量が多すぎると、本発明の着色組成物にアルカリ現像性を付与した場合に、アルカリ現像性が低下する傾向がある。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物には、光重合開始剤を含有せしめることにより、感放射線性を付与することができる。光重合開始剤は、可視光線、紫外線、遠紫外線、電子線、X線などの放射線の露光により、上記多官能性単量体の硬化反応を開始し得る活性種を発生することができる化合物である。
このような光重合開始剤としては、例えば、チオキサントン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、O-アシルオキシム系化合物、オニウム塩系化合物、ベンゾイン系化合物、ベンゾフェノン系化合物、α-ジケトン系化合物、多核キノン系化合物、ジアゾ系化合物、イミドスルホナート系化合物等を挙げることができる。
本発明のカラーフィルタを構成する各色画素を形成するための着色組成物は、通常、溶媒を配合して液状組成物として調製される。溶媒としては、着色組成物を構成する各成分を分散又は溶解し、かつこれらの成分と反応せず、適度の揮発性を有するものである限り、適宜に選択して使用することができる。
前記溶媒は、単独で又は2種以上を混合して使用することができる。
本発明の着色組成物は、必要に応じてその他の添加剤を更に含有することもできる。
上記添加剤としては、例えば、ガラス、アルミナ等の充填剤;ポリビニルアルコール、ポリ(フロオロアルキルアクリレート)類等の高分子化合物;ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤等の界面活性剤;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-クロロプロピルメチルジメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メタクリロイロキシプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン等の密着促進剤;2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノール等の酸化防止剤;2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、アルコキシベンゾフェノン類等の紫外線吸収剤;ポリアクリル酸ナトリウム等の凝集防止剤;マロン酸、アジピン酸、イタコン酸、シトラコン酸、フマル酸、メサコン酸、2-アミノエタノール、3-アミノ-1-プロパノール、5-アミノ-1-ペンタノール、3-アミノ-1,2-プロパンジオール、2-アミノ-1,3-プロパンジオール、4-アミノ-1,2-ブタンジオール等の残渣改善剤;こはく酸モノ〔2-(メタ)アクリロイロキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイロキシエチル〕、ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の現像性改善剤等を挙げることができる。
カラーフィルタを製造する方法としては、第一に次の方法が挙げられる。まず、基板の表面上に、必要に応じて、画素を形成する部分を区画するように遮光層(ブラックマトリックス)を形成する。次いで、この基板上に、(1)C.I.ピグメントレッド242と、(2)C.I.ピグメントレッド177及びC.I.ピグメントレッド254よりなる群から選ばれる少なくとも1種とを含む赤色の着色剤が分散された着色組成物の液状組成物を塗布したのち、プレベークを行って溶媒を蒸発させ、塗膜を形成する。次いで、この塗膜にフォトマスクを介して露光したのち、アルカリ現像液を用いて現像して、塗膜の未露光部を溶解除去する。その後、ポストベークすることにより、赤色の画素パターンが所定の配列で配置された画素アレイを形成する。
また、これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。
着色組成物の液状組成物を基板に塗布する際には、スプレー法、ロールコート法、回転塗布法(スピンコート法)、スリットダイ塗布法、バー塗布法等の適宜の塗布法を採用することができるが、特に、スピンコート法、スリットダイ塗布法が好ましい。
プレベークは、通常、減圧乾燥と加熱乾燥を組み合わせて行われる。減圧乾燥は、通常0.1~1Torrで行う。また、加熱乾燥の条件は、通常70~110℃で1~10分程度である。
放射線の露光量は、好ましくは10~10,000J/m2である。
アルカリ現像液には、例えばメタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。なお、アルカリ現像後は、通常、水洗する。
現像処理法としては、シャワー現像法、スプレー現像法、ディップ(浸漬)現像法、パドル(液盛り)現像法等を適用することができる。現像条件は、常温で5~300秒が好ましい。
ポストベークの条件は、通常180~280℃で20~40分程度である。
このようにして形成された画素の膜厚は、通常0.5~5.0μm、好ましくは1.0~3.0μmである。
カラーフィルタを形成する際に使用される基板や放射線の光源、また、プレベークやポストベークの方法や条件は、上記した第一の方法と同様である。このようにして、インクジェット方式により形成された画素の膜厚は、隔壁の膜厚と同程度である。
本発明のカラー液晶表示素子は、本発明のカラーフィルタと、その背面側に白色LEDを光源とするバックライトユニットを具備するものである。
バックライトユニットに使用する白色LEDは、白色光を発生するLEDであればその種類は特に限定されず、例えば、独立したスペクトルを有する赤色LEDと緑色LEDと青色LEDを用いて白色光を得る白色LED、赤色LEDと緑色LEDと青色LEDを組み合わせて混色により白色光を得る白色LED、青色LEDと赤色LEDと緑色蛍光体を組み合わせて混色により白色光を得る白色LED、青色LEDと赤色発光蛍光体と緑色発光蛍光体を組み合わせて混色により白色光を得る白色LED、青色LEDとYAG蛍光体の混色により白色光を得る白色LED、青色LEDと橙色発光蛍光体と緑色発光蛍光体を組み合わせて混色により白色光を得る白色LED、紫外線LEDと赤色発光蛍光体と緑色発光蛍光体と青色発光蛍光体を組み合わせて混色により白色光を得る白色LED等を挙げることができる。
また、青色光を吸収し赤色光を発光する赤色発光蛍光体、青色光を吸収し緑色光を発光する緑色発光蛍光体としては、例えば、国際公開第2006/104319号パンフレットに開示されている蛍光体を挙げることができる。また、青色光を吸収し橙色光を発光する橙色発光蛍光体としては、例えば、特開2008-24791号公報に開示されている蛍光体を挙げることができる。また、紫外線LEDと赤色発光蛍光体と緑色発光蛍光体と青色発光蛍光体を組み合わせて混色により白色光を得る白色LEDについては、例えば、特開2002-133910号公報に開示されている白色LEDが挙げられる。
合成例1
冷却管、攪拌機を備えたフラスコに、2,2'-アゾビスイソブチロニトリル3質量部及びプロピレングリコールモノメチルエーテルアセテート235質量部を仕込み、引き続きメタクリル酸15質量部、N-フェニルマレイミド30質量部、ベンジルメタクリレート35質量部、スチレン20質量部及びα-メチルスチレンダイマー(連鎖移動剤)5質量部を仕込んで、窒素置換したのち、ゆるやかに攪拌しつつ、反応溶液を80℃に昇温し、この温度を保持して3時間重合した。その後、反応溶液を100℃に昇温して、2,2'-アゾビスイソブチロニトリル0.5質量部を追加し、更に1時間重合を継続することにより、バインダー樹脂溶液(固形分濃度=30質量%)を得た。得られたバインダー樹脂は、Mw=10,000、Mn=5,600であった。このバインダー樹脂溶液を「バインダー樹脂溶液(B-1)」とする。
冷却管、攪拌機を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート156質量部を仕込み、窒素ガスを注入しながら80℃に加温した。同温度で、メタクリル酸15質量部、N-フェニルマレイミド12質量部、コハク酸-2-メタクリロイロキシエチル12.5質量部、スチレン10質量部、2-ヒドロキシエチルメタクリレート12.5質量部、メチルメタクリレート13質量部及びシクロヘキシルメタクリレート25質量部をプロピレングリコールモノメチルエーテルアセテート46質量部に溶解させた溶液と、2,2'-アゾビスイソブチロニトリル6質量部をプロピレングリコールモノメチルエーテルアセテート28質量部に溶解させた溶液を、同時に2時間かけて滴下した。その後、反応溶液の温度を100℃に上昇させ、この温度を1時間保持して重合することにより、バインダー樹脂溶液(固形分濃度=30質量%)を得た。得られたバインダー樹脂は、Mw=12,000、Mn=6,400であった。このバインダー樹脂を「バインダー樹脂(B-2)」とする。
調製例1
着色剤としてC.I.ピグメントレッド254とC.I.ピグメントレッド242との45/55(質量比)混合物15質量部、分散剤としてBYK-LPN21116(ビックケミー(BYK)社製)10質量部(固形分濃度=40質量%)、バインダー樹脂としてバインダー樹脂(B-1)溶液13質量部、溶媒としてプロピレングリコールモノメチルエーテルアセテート62質量部を用いて、ビーズミルにより12時間混合・分散して、着色剤分散液(A-1)を調製した。
調製例1において、着色剤の種類及び混合比率、並びにバインダー樹脂の種類を表1に示すように変更した以外は調製例1と同様にして、着色剤分散液(A-2)~(A-22)を調製した。
感放射線性着色組成物の調製
着色剤として着色剤分散液(A-1)46.7質量部、バインダー樹脂としてバインダー樹脂(B-1)溶液を10.7質量部、多官能性単量体としてジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物(日本化薬社製、商品名KAYARAD DPHA)5.1質量部、光重合開始剤として2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)ブタン-1-オン(チバ・スペシャルティー・ケミカルズ社製、商品名イルガキュア369)1.0質量部、及び溶媒としてプロピレングリコールモノメチルエーテル4.5質量部と3-エトキシプロピオン酸エチル32.0質量部を混合して、液状組成物(S-1)を調製した。
液状組成物(S-1)を、表面にナトリウムイオンの溶出を防止するSiO2膜が形成されたソーダガラス基板上に、スピンコーターを用いて塗布したのち、90℃のホットプレートで3分間プレベークを行って、塗膜を形成した。
次いで、塗膜が形成された基板を室温に冷却したのち、高圧水銀ランプを用い、フォトマスクを介さずに、塗膜に365nm、405nm及び436nmの各波長を含む放射線を1,000J/m2の露光量で露光した。その後、得られた基板に対して23℃の0.04質量%水酸化カリウム水溶液からなる現像液を現像圧1kgf/cm2(ノズル径1mm)で吐出しシャワー現像を行った後、超純水で洗浄し、更に230℃で20分間ポストベークを行うことにより、赤色硬化膜が形成された評価用基板を作製した。
得られた基板について、カラーアナライザー(大塚電子(株)製MCPD2000)を用い、透過スペクトルを測定した。得られた透過スペクトルと、図1に示す白色LEDの発光スペクトルから、CIE1931表色系における色度座標値(x,y)及び刺激値(Y)を求めた。評価結果を表2に示す。
得られた基板を2枚の偏向板で挟み、図1の発光スペクトルを示す白色LEDで照射しつつ前面側の偏向板を回転させ、透過する光強度を輝度計BM5-AS((株)トプコン製)にて最大値と最小値を測定した。そして、その最大値を最小値で割った値を、コントラスト比として評価した。評価結果を表2に示す。
参考例1において、表2に示す着色剤分散液及びバインダー樹脂に変更した以外は参考例1と同様にして、液状組成物(S-2)~(S-14)を調製した。
次いで、液状組成物(S-1)に代えてそれぞれ液状組成物(S-2)~(S-14)を用いた以外は、参考例1と同様にして各硬化膜が形成された基板について評価を行った。評価結果を表2に示す。
参考例1において、表3に示す着色剤分散液及びバインダー樹脂を用いて液状組成物を調製し、それら液状組成物を用いて基板上に硬化膜を形成したこと以外は、参考例1と同様にして各基板について評価を行った。なお、色度特性及びコントラスト比の評価において、参考例13~23及び比較参考例3~4では図2の発光スペクトルを示す白色LEDを用い、参考例24~34及び比較参考例5~6では青色LEDと橙色発光蛍光体と緑色発光蛍光体を組み合わせて混色により白色光を生成する白色LEDを用いた。評価結果を表3に示す。
カラーフィルタの作製
液状組成物(S-1)を、ブラックマトリックスが形成されたガラス基板上に、スピンコーターを用いて塗布したのち、90℃のホットプレートで3分間プレベークを行って、塗膜を形成した。
次いで、塗膜が形成された基板を室温に冷却したのち、高圧水銀ランプを用い、ストライプ状フォトマスクを介して、塗膜に365nm、405nm及び436nmの各波長を含む放射線を1,000J/m2の露光量で露光した。その後、得られた基板に対して23℃の0.04質量%水酸化カリウム水溶液からなる現像液を現像圧1kgf/cm2(ノズル径1mm)で吐出しシャワー現像を行った後、超純水で洗浄し、更に230℃で20分間ポストベークを行うことにより、基板上に、上記参考例1と同等の色度座標値(x,y)を示す赤色のストライプ状画素パターンを形成した。
次いで、同様の方法により、液状組成物(S-7)を用いて、赤色のストライプ状画素パターンの隣に、上記参考例7と同等の色度座標値(x,y)を示す緑色のストライプ状画素パターンを形成した。
次いで、同様の方法により、液状組成物(S-11)を用いて、緑色のストライプ状画素パターンの隣に、上記参考例11と同等の色度座標値(x,y)を示す青色のストライプ状画素パターンを形成することによりカラーフィルタを作製した。
得られたカラーフィルタに、図1の発光スペクトルを示す白色LEDを照射したときの、CIE1931表色系における白表示での色度座標値(x,y)、刺激値(Y)を測定した。評価結果を表4に示す。
また、黒表示での視認性を評価した。評価結果を表4に示す。
実施例1において、表4に示す液状組成物を用い、赤色、緑色及び青色のストライプ状画素パターンを形成してカラーフィルタを作製したこと以外は、実施例1と同様にして各カラーフィルタについて評価した。なお、色度特性及び視認性の評価において、実施例2~8及び比較例1~2では実施例1と同様の図1の発光スペクトルを示す白色LEDを用い、実施例9~15及び比較例3~4では図2の発光スペクトルを示す白色LEDを用い、実施例16~22及び比較例5~6では青色LEDと橙色発光蛍光体と緑色発光蛍光体を組み合わせて混色により白色光を生成する白色LEDを用いた。評価結果を表4に示す。
Claims (7)
- 赤色画素、緑色画素及び青色画素を有するカラーフィルタと、その背面側に配置されたバックライト光源を備える液晶表示素子に用いられるカラーフィルタであって、
前記赤色画素が(1)C.I.ピグメントレッド242と、(2)C.I.ピグメントレッド177及びC.I.ピグメントレッド254よりなる群から選ばれる少なくとも1種とを含み、
前記バックライト光源が白色LEDであることを特徴とするカラーフィルタ。 - 前記緑色画素がC.I.ピグメントグリーン58を含有する、請求項1記載のカラーフィルタ。
- 前記青色画素がC.I.ピグメントブルー15:6を含有する、請求項1~3のいずれか1項に記載のカラーフィルタ。
- 前記青色画素が更に脂環式炭化水素基を有するバインダー樹脂を含有する、請求項4に記載のカラーフィルタ。
- 前記白色LEDは、青色LED由来の最大発光ピークと、500~700nmの波長帯域に前記最大発光ピークより強度の弱い1又は2以上の極大発光ピークとを有する発光スペクトルを示すものである、請求項1~5のいずれか1項に記載のカラーフィルタ。
- 請求項1~6のいずれか1項に記載のカラーフィルタと、その背面側にバックライト光源としての白色LEDを具備するカラー液晶表示素子。
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| PCT/JP2011/052889 Ceased WO2011105227A1 (ja) | 2010-02-24 | 2011-02-10 | カラーフィルタ及びカラー液晶表示素子 |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5720670B2 (ja) |
| KR (1) | KR20120120353A (ja) |
| TW (1) | TWI521241B (ja) |
| WO (1) | WO2011105227A1 (ja) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012053183A (ja) * | 2010-08-31 | 2012-03-15 | Dainippon Printing Co Ltd | カラーフィルタ及び表示装置 |
| JP2014048556A (ja) * | 2012-09-03 | 2014-03-17 | Sumitomo Chemical Co Ltd | 感光性樹脂組成物 |
| CN114846366A (zh) * | 2019-12-25 | 2022-08-02 | 富士胶片株式会社 | 滤色器、滤色器的制造方法、固体摄像元件及显示装置 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102217045B1 (ko) * | 2016-07-29 | 2021-02-18 | 후지필름 가부시키가이샤 | 착색 조성물, 컬러 필터, 패턴 형성 방법, 고체 촬상 소자, 및 화상 표시 장치 |
| CN113296310A (zh) * | 2020-02-24 | 2021-08-24 | 广东普加福光电科技有限公司 | 一种量子点光转换层及其制备方法 |
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- 2011-02-16 TW TW100105011A patent/TWI521241B/zh active
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| JP2012053183A (ja) * | 2010-08-31 | 2012-03-15 | Dainippon Printing Co Ltd | カラーフィルタ及び表示装置 |
| JP2014048556A (ja) * | 2012-09-03 | 2014-03-17 | Sumitomo Chemical Co Ltd | 感光性樹脂組成物 |
| CN114846366A (zh) * | 2019-12-25 | 2022-08-02 | 富士胶片株式会社 | 滤色器、滤色器的制造方法、固体摄像元件及显示装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011105227A1 (ja) | 2013-06-20 |
| JP5720670B2 (ja) | 2015-05-20 |
| KR20120120353A (ko) | 2012-11-01 |
| TWI521241B (zh) | 2016-02-11 |
| TW201142373A (en) | 2011-12-01 |
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