WO2009148045A1 - Base de résine thermo-protectrice et élément de construction utilisant celle-ci - Google Patents

Base de résine thermo-protectrice et élément de construction utilisant celle-ci Download PDF

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Publication number
WO2009148045A1
WO2009148045A1 PCT/JP2009/060047 JP2009060047W WO2009148045A1 WO 2009148045 A1 WO2009148045 A1 WO 2009148045A1 JP 2009060047 W JP2009060047 W JP 2009060047W WO 2009148045 A1 WO2009148045 A1 WO 2009148045A1
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Prior art keywords
layer
refractive index
heat
base material
gas
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English (en)
Japanese (ja)
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達也 廣瀬
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Konica Minolta Inc
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Konica Minolta Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present invention relates to a heat shield resin substrate having a heat ray reflective layer formed on a resin substrate and having antiglare properties, and a building member using the heat shield resin substrate.
  • a heat ray reflective layer With a structure in which a metal thin film layer made of gold, silver, copper, etc. is sandwiched between transparent dielectric layers with a high refractive index on a transparent substrate such as glass or resin film, visible light can be transmitted.
  • the characteristic which reflects the light ray (heat ray) from near infrared region to infrared region can be obtained.
  • a resin film provided with a heat ray reflective layer can be used as a heat ray shielding film to reduce heat radiation from the monitoring window in high-temperature work or to enter from the windows of buildings, automobiles, trains, etc. It is used for the purpose of cutting off energy to improve the cooling / heating effect, improving the heat shielding property of the transparent plant container, or improving the cooling effect in the refrigerated showcase (for example, see Patent Document 1). ).
  • the heat ray reflection film may be provided with a gray metal (mainly nickel chrome) that absorbs and scatters sunlight. It is disclosed (for example, see Patent Document 2).
  • the metal thin film and gray metal used for such a heat ray shielding substrate are generally produced by using a dry process such as sputtering, vapor deposition, or CVD, but when a metal thin film is provided on a resin substrate, The glass substrate is affected by moisture, gas, plasticizer, etc. inherent in the resin base material, and since the resin base material has almost no gas barrier performance. It has been found that the visible light transmittance and environmental resistance are reduced compared to those on the material. In particular, when gray metal is exposed to light, oxygen, and / or moisture, it corrodes and its anti-glare function is impaired. Further, it has been found that the heat ray blocking layer is corroded and the heat shielding performance is lowered.
  • a dry process such as sputtering, vapor deposition, or CVD
  • an object of the present invention is to provide a heat shielding resin base material having an antiglare property excellent in light resistance, moisture resistance, and weather resistance, and further, a building member using the heat shielding resin base material. Is to provide.
  • At least one of a heat ray shielding component layer including at least one metal layer made of gold, silver, copper, aluminum alone or an alloy thereof and at least one of titanium, chromium, stainless steel and nickel-chromium alone or an alloy containing them.
  • a gray metal layer and at least one low refractive index ceramic constituent layer mainly composed of an oxide containing Si or Al, a nitride oxide containing Si or Al, or a nitride containing Si or Al. Heat insulation resin base material.
  • the heat ray blocking component layer is provided on a first transparent substrate, the gray metal layer is provided on a second transparent substrate, and the first transparent substrate and the second transparent substrate are bonded to each other. 4.
  • the heat-shielding resin base material according to any one of 1 to 3, wherein the heat-shielding resin base material is bonded together.
  • the low refractive index ceramic constituent layer includes at least one silicon oxide film having a carbon content of less than 0.1 at% and one silicon oxide film having a carbon content of 1 to 40 at%. 5.
  • the heat shielding resin substrate according to any one of 1 to 4.
  • the low-refractive index ceramic constituent layer supplies a gas containing a thin film forming gas and a discharge gas to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, thereby exciting the gas by forming a high-frequency electric field in the discharge space.
  • the discharge gas is nitrogen gas
  • the high-frequency electric field applied to the discharge space is a superposition of the first high-frequency electric field and the second high-frequency electric field.
  • the frequency ⁇ 2 of the high-frequency electric field is high, and the relationship among the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge starting electric field strength IV is V1 ⁇ IV> V2 or V1 7.
  • the thermal barrier resin substrate according to 6 above, which satisfies a relationship of> IV ⁇ V2 and the output density of the second high-frequency electric field is 1 W / cm 2 or more.
  • the water vapor permeability (JIS K7129-1992 B method) of the low refractive index ceramic constituent layer is 0.01 g / (m 2 ⁇ 24 h) or less (40 ° C., 90% RH condition) 9.
  • the heat shielding resin substrate according to any one of 1 to 8.
  • the heat ray blocking constituent layer is an oxide containing at least Zn, Ti, Sn, In, Nb, Si or Al, a nitride oxide containing Zn, Ti, Sn, In, Nb, Si or Al, Zn, Ti, Sn
  • a high refractive index ceramic constituent layer comprising at least one layer mainly composed of nitride containing In, Nb, Si or Al, the metal layer, an oxide containing at least Zn, Ti, Sn, In, Nb, Si or Al High refractive index consisting of at least one layer mainly composed of nitrides containing Zn, Ti, Sn, In, Nb, Si or Al, nitrides containing Zn, Ti, Sn, In, Nb, Si or Al 10.
  • the heat-insulating resin base material according to any one of 1 to 9, wherein the thermal barrier resin base material has a structure in which a ceramic layer is sequentially laminated.
  • one or more metal layers made of a simple substance of gold, silver, copper, aluminum or an alloy thereof and at least Zn, Ti, Sn, In, Nb, Si Or an oxide containing Al, a nitride oxide containing Zn, Ti, Sn, In, Nb, Si or Al, or a nitride containing Zn, Ti, Sn, In, Nb, Si or Al as a main component.
  • the heat ray blocking layer is a Fabry-Perot interference filter, and the Fabry-Perot interference filter includes a first oxide layer, a first metal layer, a second oxide layer, a second metal layer, and a third oxidation. 10.
  • thermoplastic resin substrate according to any one of 1 to 16, wherein the first transparent substrate and the second transparent substrate are polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate. .
  • 21 The heat shielding resin substrate as described in 19 or 20 above, wherein the polymer layer contains at least one of an ultraviolet absorber or an antioxidant.
  • a building member comprising the heat shielding resin substrate according to any one of 1 to 21 bonded to glass or a glass substitute resin substrate through an adhesive.
  • a heat shielding resin substrate having an antiglare property excellent in light resistance, moisture resistance and weather resistance was obtained, and a building member using the heat shielding resin substrate could be provided.
  • the present invention relates to a heat-shielding resin base material that exhibits a high heat ray reflection effect, and more specifically, has excellent heat ray reflectivity and also has an antireflection property of visible light to the outdoor side, excellent visibility, a window,
  • the present invention relates to a heat shielding resin base material (heat ray reflective film) that has a high heat ray reflection effect and prevents reflection of room lights or the like when pasted on a building window or a display window.
  • the heat-reflective film used in conventional windows has a structure in which a transparent base film, in particular a polyester thin film, is sandwiched between a metal thin film layer made of gold, silver, copper, etc. with a transparent dielectric layer having a high refractive index. Although it is a laminated film provided with a heat ray reflective layer, it transmits visible light, but has the property of reflecting light rays (heat rays) from the near infrared part to the infrared part.
  • heat ray reflective films are used for applications such as reducing heat radiation, blocking solar energy incident from windows to improve the cooling / heating effect, and improving the cooling effect in the refrigerated case. Moreover, when these heat ray reflective films are bonded together, even if the glass is broken, there is an advantage that the scattering of the glass can be prevented if the heat ray shielding film is stuck.
  • the present invention is such that the above heat-shielding resin substrate (heat ray reflective film) is less susceptible to white turbidity due to the influence of moisture, oxygen, etc., and the visible light transmittance is unlikely to decrease, and environmental resistance performance such as long-term use and long-term storage.
  • the present invention relates to a heat shielding resin base material excellent in handling performance.
  • the heat-shielding resin substrate of the present invention includes a heat ray shielding component layer including at least one metal layer made of a simple substance of gold, silver, copper, or aluminum, or an alloy thereof, and partially blocks light transmission and is visible.
  • a heat ray shielding component layer including at least one metal layer made of a simple substance of gold, silver, copper, or aluminum, or an alloy thereof, and partially blocks light transmission and is visible.
  • the heat-shielding resin substrate of the present invention is preferably used in a heat ray reflective film that is attached to glass.
  • the heat shielding resin substrate of the present invention is used by being attached to the outdoor side of glass through an adhesive layer, from the side on which the heat rays (sunlight) are incident, the low refractive index ceramic constituting layer, the heat ray shielding constituting layer, The gray metal layers are preferably arranged in this order.
  • the heat shielding resin substrate of the present invention is used by being attached to the indoor side of the glass via an adhesive layer, the heat ray blocking component layer, the gray metal layer, the low
  • the layers are preferably arranged in the order of the refractive index ceramic constituent layers.
  • the heat ray blocking constituent layer is preferably an oxide containing at least Zn, Ti, Sn, In, Nb, Si or Al, a nitride oxide containing Zn, Ti, Sn, In, Nb, Si or Al, Zn,
  • a high refractive index ceramic constituent layer comprising at least one layer mainly composed of a nitride containing Ti, Sn, In, Nb, Si or Al, the metal layer, and at least Zn, Ti, Sn, In, Nb, Si or At least one layer mainly composed of an oxide containing Al, a nitride oxide containing Zn, Ti, Sn, In, Nb, Si or Al, or a nitride containing Zn, Ti, Sn, In, Nb, Si or Al
  • the metal layer is a metal layer such as Au, Ag, Cu, Al, etc., and most of the visible light is absorbed. Na Ag metal is particularly preferred. Moreover, you may use a metal layer as an alloy which used 2 or more
  • the heat ray blocking component layer is a Fabry-Perot interference filter including a first oxide layer, a first metal layer, a second oxide layer, a second metal layer, and a third oxide layer. Also good.
  • the metal layer in the Fabry-Perot interference filter is mainly silver, and is a gold or copper alloy having a mass of less than 50% with respect to silver or a clad layer, and imparts chemical and light durability.
  • Indium oxide is preferable for the oxide layer, but in the case of a transparent dielectric layer having a refractive index of 1.8 or more and a visible light absorption level of less than 10%, zinc oxide, tin oxide, titanium oxide, oxide Other oxides such as niobium may be used. If it is suitably transparent and has a refractive index greater than 1.8, nitride or fluoride can also be used. More detailed design, behavior and techniques for manufacturing Fabry-Perot filters are described in US Pat. No. 4,799,745.
  • the thickness of the metal layer is such that the first transparent substrate of the heat-shielding resin substrate of the present invention has an integrated visible light transmittance (average value of visible light transmittance in this wavelength region) of 55% at a wavelength of 400 to 750 nm. It is preferable that the integral infrared reflectivity (average value of infrared reflectivity in this wavelength region) with a wavelength of 5 to 30 ⁇ m satisfies 75% or more.
  • the thickness of one metal layer is preferably in the range of 5 to 1000 nm. When the thickness is less than 5 nm, sufficient heat ray reflection effect is not exhibited and the infrared transmittance is increased. On the other hand, when the thickness exceeds 1000 nm, the visible light reflectance is increased and the antiglare property is deteriorated.
  • a more preferable range is 5 to 30 nm. Visible light transmittance can be sufficiently ensured by setting the metal layer to 30 nm or less, and a heat ray blocking layer having both antiglare property and visible transmittance can be formed by providing together with the gray metal layer.
  • the high-refractive index ceramic constituent layer includes an oxide containing at least Zn, Ti, Sn, In, Nb, Si, or Al, a nitrided oxide containing Zn, Ti, Sn, In, Nb, Si, or Al, Zn, It is composed of at least one layer mainly composed of nitride containing Ti, Sn, In, Nb, Si or Al, and has a refractive index of 1.8 or more and less than 2.5, and the aforementioned metal layer is sandwiched. It is more preferable to take a laminated structure between the two because the effect of improving transparency is increased.
  • the thickness of the high refractive index ceramic constituting layer is preferably set in combination with the above-described metal layer to be laminated so as to satisfy the optical characteristics of the heat ray shielding constituting layer.
  • the thickness of one layer of the high refractive index ceramic constituting layer is preferably in the range of 2 to 1000 nm.
  • the high refractive index ceramic constituting layer and the metal layer from one layer or more consisting of 0.1 nm or more and less than 30 nm consisting of a simple substance of gold, silver, copper, aluminum or an alloy thereof.
  • There are at least one set of high refractive index ceramic constituent layers composed of at least one layer mainly composed of a nitride containing Nb, Si or Al.
  • the heat-shielding resin base material (heat ray reflective film) of the present invention is a laminated film formed by laminating a heat ray shielding constituent layer on at least one side of the base film as described above, and preferably has a visible light reflectance of 5% or less. This is achieved with a transparent laminated film having an infrared reflectance of 75% or more.
  • a heat ray blocking constituent layer having a structure in which a metal thin film layer made of gold, silver, copper or the like having a high heat ray reflecting effect is sandwiched between transparent dielectric layers having a high refractive index is formed by an oxidation containing at least Si or Al.
  • a transparent base material on which a low refractive index ceramic constituent layer having a refractive index of 1.3 or more and less than 1.8 is mainly composed of an oxide, a nitride oxide containing Si or Al, or a nitride containing Si or Al It is characterized by having.
  • the gray metal is titanium, chromium, stainless steel, nickel-chromium, and alloys containing them.
  • a metal or an alloy such as nickel-chromium (nichrome or NiCr) is desirable, and is formed on the second transparent substrate with a thickness of 2 to 20 nm.
  • Other usable gray metals or alloys include Inconel and Monel.
  • those that are “gray” and deposited in a thin or non-continuous coating aid include copper, gold, aluminum and silver and can be used.
  • a thin film means a thickness of 2 to 50 nm.
  • a preferred thickness is 2 to 20 nm.
  • a VIS / R VIS of the nickel chromium layer is larger than 0.6, more preferably A VIS / R VIS is 1.07 to 1.44.
  • a VIS refers to the percentage of visible or emitted light that is absorbed by the window
  • R VIS refers to the percentage of visible or emitted light that is reflected at the window.
  • the low refractive index ceramic constituent layer is mainly composed of an oxide containing at least Si or Al, a nitride oxide containing Si or Al, a nitride containing Si or Al, and a refractive index of 1.3 or more and less than 2.0. It is a certain ceramic constituent layer, and is particularly preferably made of silicon oxide.
  • the method for forming the low refractive index ceramic constituent layer is preferably a vapor deposition method, and more preferably a vacuum deposition method, a sputtering method, an ion plating method, a catalytic chemical vapor deposition (Cat-CVD) method, or a plasma CVD method.
  • a gas containing a thin film forming gas and a discharge gas is supplied to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, and the gas is excited by applying a high-frequency electric field to the discharge space, thereby exciting the transparent substrate.
  • a film formed by a so-called atmospheric pressure plasma CVD method which is formed by a thin film forming method in which a thin film is formed on the transparent substrate by being exposed to gas, has a low residual stress and is preferable.
  • the discharge space refers to a space that generates a discharge sandwiched between two opposing electrodes.
  • the low refractive index ceramic constituent layer formed in the atmospheric pressure plasma CVD method includes at least a silicon oxide film having a carbon content of less than 0.1 at% and a silicon oxide film having a carbon content of 1 to 40 at%, respectively. It is preferable to include one layer at a time.
  • a ceramic constituent layer formed by laminating films having different carbon contents is preferable because it is a low refractive index film having a relatively high moisture and low gas permeability (gas barrier property) and a relatively high flexibility. For example, a configuration in which these layers are alternately laminated by 2 to 5 layers is preferable.
  • low-refractive index ceramic layer mainly composed of oxide containing at least Si or Al, nitride oxide containing Si or Al, nitride containing Si or Al by atmospheric pressure plasma method and atmospheric pressure plasma method Will be described later.
  • the high refractive index ceramic component layer is made of an oxide containing at least Zn, Ti, Sn, In, Nb, Si or Al, Zn, Ti, Sn, In, Nb, Si or Al.
  • TiO derived from an organic compound comprising at least one layer mainly composed of a nitride containing nitride oxide, Zn, Ti, Sn, In, Nb, Si or Al, and obtained by hydrolysis of, for example, alkyl titanate 2 is preferable because of excellent workability.
  • zinc oxide, indium oxide, and tin oxide can be applied in a single layer or multiple layers.
  • Such a high refractive index ceramic constituent layer is preferable because it can increase the effect of improving transparency by adopting a laminated structure in which the aforementioned metal layer is sandwiched.
  • the thickness of the high refractive index ceramic constituent layer is preferably set in combination with the above metal layer so as to satisfy the optical characteristics of the heat ray blocking constituent layer.
  • the refractive index of the high refractive index ceramic constituting layer according to the present invention is preferably 1.8 to 2.5. More preferably, it is 2.0 to 2.5.
  • the refractive index of the high refractive index ceramic constituent layer is larger than the refractive index of the low refractive index ceramic constituent layer.
  • the presence of the low refractive index ceramic constituent layer can reduce the visible light reflectance.
  • a vapor phase growth method is preferable, and a vacuum deposition method, a sputtering method, an ion plating method, a Cat-CVD method, or a plasma CVD method is particularly preferable. Moreover, you may form using the atmospheric pressure plasma CVD method mentioned later.
  • the metal constituting the metal layer is preferably a metal such as gold, silver, copper, or aluminum.
  • a metal such as gold, silver, copper, or aluminum.
  • Ag metal that hardly absorbs visible light is particularly preferable.
  • the thickness of the metal layer in the first transparent substrate of the heat-shielding resin substrate of the present invention is the integrated visible light transmittance (average value of visible light transmittance in this wavelength region) of the laminated film at a wavelength of 400 to 750 nm. ) Is 55% or more, and the integrated infrared reflectance (average value of infrared reflectance in this wavelength region) of 5 to 30 ⁇ m is preferably 75% or more.
  • the thickness of one metal layer is preferably in the range of 5 to 1000 nm. If the thickness is less than 5 nm, sufficient heat ray reflection effect is not exhibited and the infrared transmittance is increased. On the other hand, if it exceeds 1000 nm, the visible light reflectance is increased and the antiglare property is deteriorated.
  • a more preferable range is 5 to 30 nm. Visible light transmittance can be sufficiently ensured by setting the metal layer to 30 nm or less, and a heat ray blocking layer having both antiglare property and visible transmittance can be formed by providing it together with the gray metal layer.
  • a vapor phase growth method is preferable, and a vacuum deposition method, a sputtering method, or a plasma CVD method is more preferable.
  • the heat ray blocking constituent layer in the present invention preferably has a low refractive index layer in addition to a high refractive index layer.
  • the refractive index of the low refractive index ceramic constituting layer By reducing the refractive index of the low refractive index ceramic constituting layer to less than 1.8, in order to improve durability and handling properties without substantially affecting the visible light transmittance and infrared reflectance, Layer design can be done relatively freely. Further, when the refractive index is 1.3 or more, the film becomes dense, and improvement in durability can be expected.
  • the reflectance is 15% or less in the wavelength region of 400 nm to 700 nm.
  • the reflectance at 550 nm is preferably 10% or less, and more preferably 5% or less, and this can be obtained by setting the thickness of each layer based on a predetermined relationship.
  • a polymer layer is provided on the base film for improving the scratch resistance of the visible light reflection preventing layer, and the heat ray blocking constitution is provided thereon.
  • a layer may be provided.
  • the polymer layer preferably contains a photocurable or thermosetting resin as a main component.
  • an acrylic resin coating film to which at least one of an ultraviolet absorber or a hindered amine light stabilizer is added as a polymer layer may be provided on one side or both sides of the transparent substrate.
  • a polymer layer containing the light stabilizer when used for external pasting, it is preferable to use a polymer layer containing the light stabilizer in order to improve weather resistance.
  • an ultraviolet absorber having a hydroxyl group when used and an isocyanate compound is added, the isocyanate compound improves the adhesion to the polyester film, and the ultraviolet absorber is connected to the hydroxyl group-introduced acrylic resin by a urethane bond, and the ultraviolet absorber is bleeded. Since it becomes difficult to go out, the weather resistance can be further improved.
  • the acrylic resin a plurality of monomers are often copolymerized from monomers such as methacrylic acid, methacrylic acid ester or acrylic acid, acrylic acid ester. Specifically, they are methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate and modified products thereof. Hydroxyethyl methacrylate, hydroxybutyl methacrylate, etc., in which hydroxyl groups are introduced at the monomer stage, are added together with the above monomers at the time of polymerization, so that a hydroxyl group-introduced acrylic resin in which hydroxyl groups are introduced into the side chains of the acrylic resin skeleton is obtained. Obtainable.
  • HBA 4-hydroxybutyl acrylate
  • HPA 2-hydroxyethyl acrylate
  • HPA 2-hydroxypropyl acrylate
  • 2-HEMA 2-hydroxyethyl methacrylate
  • a weather-resistant prescription agent such as an ultraviolet absorber (benzotriazole-based, triazine-based, benzophenone-based, etc.) is added in order to perform a weather-resistant formulation.
  • the added part may be added according to the desired weather resistance, but is 0.1 to 50% by mass, preferably 1 to 30% by mass, based on the resin solid content.
  • UV absorbers 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 -T-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 , 5-Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-octylphenyl) benzoto Examples thereof include riazole and the like, mixtures thereof, modified products, polymers, and derivatives.
  • triazines examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[(2-hydroxy -3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3 -Tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) Examples include -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine, mixtures thereof, modified products, polymers, and derivatives.
  • examples of the benzophenone series include octabenzone, modified products, polymers, and derivatives. Since the ultraviolet absorber can be bonded to the resin component by crosslinking by addition of an isocyanate compound, one having a hydroxyl group is suitable.
  • silicon oxide films have substantially the same composition
  • the manufacturing conditions and the thin film forming gas used (raw material gas)
  • the physical properties such as the density differ due to the difference in the degree of filling of the silicon oxide particles and the small amount of impurity particles mixed therein.
  • the refractive index of the low refractive index ceramic constituent layer according to the present invention is preferably 1.3 or more and less than 1.8.
  • the refractive index of the silicon oxide film is a value obtained by the X-ray reflectance method. Use.
  • ⁇ X-ray reflectivity method > The outline of the X-ray reflectivity method is described in page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000, International Literature Printing Co., Ltd.) 22 can be performed.
  • Curve fitting is performed using 1, and each parameter is obtained so that the residual sum of squares of the actual measurement value and the fitting curve is minimized.
  • the refractive index, thickness and density of the laminated film can be obtained from each parameter.
  • the film thickness evaluation of the laminated film in the present invention can also be obtained from the X-ray reflectivity measurement.
  • the density of the silicon oxide film is closely correlated with the carbon content as a trace component.
  • a film having a low carbon atom concentration (less than 0.1 at%) is a film having a high density and a high gas barrier property. Films with higher atomic concentrations (1-40 at%) are softer compositions with lower film density.
  • the carbon content (at%) of the ceramic layer represents an atomic concentration (%).
  • the atomic concentration% (at%) indicating the carbon content can be determined using a known analysis means, but in the present invention, it is calculated by the following XPS method and is defined below.
  • Atomic concentration% number of carbon atoms / number of all atoms ⁇ 100
  • ESCALAB-200R manufactured by VG Scientific, Inc. was used in the present invention. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.
  • a range of binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.
  • the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.
  • the obtained spectrum is on COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. Then, the processing was performed with the same software, and the content values of the elements (carbon, oxygen, silicon, titanium, etc.) of each analysis target were determined as atomic concentration (atomic concentration: at%).
  • the method for manufacturing the low refractive index ceramic constituent layer according to the present invention for example, the first, second, or third silicon oxide film, among the vapor phase growth methods, in particular, the manufacturing method by the atmospheric pressure plasma CVD method.
  • the raw material compound used will be described.
  • the silicon oxide film according to the present invention is an oxide or nitride oxide containing Si or Al by selecting conditions such as an organometallic compound as a raw material, a decomposition gas, a decomposition temperature, and input power in an atmospheric pressure plasma CVD method.
  • the composition of the low refractive index ceramic constituent layer mainly composed of nitride can be made differently.
  • silicon oxide is generated.
  • silazane or the like is used as a raw material compound, silicon oxynitride is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multi-step chemical reactions are accelerated very rapidly in the plasma space. This is because it is converted into a mechanically stable compound in a very short time.
  • the raw material for forming such a silicon oxide film may be in the state of gas, liquid, or solid at normal temperature and pressure as long as it is a silicon compound.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.
  • the solvent may be diluted with a solvent, and an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof may be used as the solvent.
  • these dilution solvents are decomposed
  • silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide
  • Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, and the like. Can be mentioned.
  • a decomposition gas for decomposing the source gas containing silicon or aluminum to obtain silicon oxide or an aluminum oxide film hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, Ammonia gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc.
  • hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, Ammonia gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc.
  • a silicon oxide film containing silicon oxide, nitride, carbide, or the like can be obtained by appropriately selecting a source gas containing silicon and a decomposition gas.
  • a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to a plasma discharge generator.
  • a discharge gas nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are particularly preferably used.
  • the film is formed by mixing the discharge gas and the reactive gas and supplying them to a plasma discharge generator (plasma generator) as a thin film forming (mixed) gas.
  • a plasma discharge generator plasma generator
  • the reactive gas is supplied with the ratio of the discharge gas to 50% or more of the entire mixed gas.
  • the organic silicon compound is further combined with oxygen gas or nitrogen gas at a predetermined ratio, and at least O atoms and N atoms are combined.
  • a silicon oxide film mainly containing silicon oxide according to the present invention containing any of them and Si atoms can be obtained.
  • the low refractive index ceramic constituting layer according to the present invention is preferably formed by forming one set of units made of the first, second, etc. silicon oxide films on one or more transparent resin base materials, and two sets, Further, more units may be formed.
  • the unit includes at least one silicon oxide film having a low carbon atom concentration (less than 0.1 at%) and a silicon oxide film having a higher carbon atom concentration (1 to 40 at%) than the silicon oxide film. It refers to a layer composed of one layer.
  • each silicon oxide layer in the low refractive index ceramic constituent layer may be in the range of 1 to 500 nm.
  • the entire low refractive index ceramic constituting layer is preferably in the range of 10 nm to 5 ⁇ m.
  • a releasable transparent substrate may be provided in order to prevent scratches and foreign matter adhesion on the layer already provided in each transparent substrate.
  • the releasable transparent substrate those described below can be used.
  • a low refractive index ceramic constituent layer is formed by plasma treatment on one surface side (A surface) of a transparent substrate, and then the back surface side (B Before providing the low refractive index ceramic constituent layer on the surface), a resin material having releasability is laminated on the already formed low refractive index ceramic constituent layer on the A side.
  • the resin material having releasability according to the present invention is not particularly limited, but includes at least a film and an adhesive layer containing an adhesive formed on one side of the film, and the adhesive is an acrylic adhesive, a silicon-based adhesive It is at least one selected from a pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive is preferably 1 mN / cm or more and 2 N / cm or less, more preferably 1 mN / cm or more and 200 mN / cm or less. Preferably there is.
  • the adhesive strength of the pressure-sensitive adhesive is 1 mN / cm or more, sufficient adhesion between the resin material and the low refractive index ceramic constituent layer can be obtained, and peeling during continuous conveyance does not occur. The influence on the already formed low refractive index ceramic constituent layer due to contact with a roll or the like can be prevented. Further, if the adhesive force is 2 N / cm or less, the low refractive index ceramic constituent layer layer is destroyed or the low refractive index ceramic is not excessively applied to the low refractive index ceramic constituent layer when the resin material is peeled off. Does not cause the adhesive to remain on the constituent layers.
  • the adhesive strength of the pressure-sensitive adhesive according to the present invention can be determined by measuring 20 minutes after the resin material is pressure-bonded to the test plate using Corning 1737 as a test plate according to a measurement method based on JIS Z 0237.
  • the thickness of the pressure-sensitive adhesive is preferably 0.1 ⁇ m or more and 30 ⁇ m or less. If the thickness of the pressure-sensitive adhesive is 0.1 ⁇ m or more, sufficient adhesion between the resin material and the transparent substrate can be obtained, peeling during continuous conveyance does not occur, and rolls during conveyance, etc. The influence of the contact on the already formed low refractive index ceramic constituent layer can be prevented. Moreover, if the thickness of the pressure-sensitive adhesive is 30 ⁇ m or less, the low refractive index ceramic constituent layer is destroyed or adhered to the top without applying excessive force to the low refractive index ceramic constituent layer when the resin material is peeled off. There will be no residual agent.
  • the weight average molecular weight of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably 400,000 or more and 1.4 million or less. If the weight average molecular weight is 400,000 or more, the adhesive strength is not excessive, and if it is 1.4 million or less, sufficient adhesive strength can be obtained. When the weight average molecular weight is within the range specified in the present invention, it is possible to prevent the adhesive from remaining on the low refractive index ceramic constituent layer, and particularly when the low refractive index ceramic constituent layer is formed by the plasma treatment method. Since heat and energy are applied, the adhesive material may be transferred or peeled off if the molecular weight is not within an appropriate range.
  • the resin material having releasability according to the present invention mainly includes a base material, an adhesive layer formed on one side of the base material, and a surface of the adhesive layer, that is, a surface opposite to the base material. It is comprised from the peeling layer which consists of a transparent base material etc. which were made.
  • Base material used for releasable resin material Although there is no restriction
  • a polyethylene terephthalate film is preferably used from the viewpoint of heat resistance and availability.
  • the thickness of the base material is not particularly limited, but 10 to 300 ⁇ m is used. It is preferably 25 to 150 ⁇ m. When the thickness is 10 ⁇ m or less, handling is difficult because the film is thin, and when the thickness is 300 ⁇ m or more, the film becomes hard and the transportability and the adhesion to the roll are deteriorated.
  • the type of pressure-sensitive adhesive used for the releasable resin material is not particularly limited.
  • a rubber-based pressure-sensitive adhesive an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive
  • the ultraviolet curable pressure-sensitive adhesive include at least one selected from an acrylic pressure-sensitive adhesive, a silicon pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive.
  • acrylic pressure-sensitive adhesive for example, a homopolymer of (meth) acrylic acid ester or a copolymer with another copolymerizable monomer is used. Further, examples of monomers or copolymerizable monomers constituting these copolymers include alkyl esters of (meth) acrylic acid (for example, methyl esters, ethyl esters, butyl esters, 2-ethylhexyl esters, octyl esters, isoforms).
  • Nonyl esters, etc. hydroxyalkyl esters of (meth) acrylic acid (eg, hydroxyethyl ester, hydroxybutyl ester, hydroxyhexyl ester), (meth) acrylic acid glycidyl ester, (meth) acrylic acid, itaconic acid, maleic anhydride (Meth) acrylic acid amide, (meth) acrylic acid N-hydroxymethylamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate) Over DOO), vinyl acetate, styrene, and acrylonitrile.
  • an alkyl acrylate having a homopolymer glass transition point of ⁇ 50 ° C. or lower is usually used.
  • the curing agent for the acrylic pressure-sensitive adhesive for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used.
  • an isocyanate curing agent an aromatic type such as toluylene diisocyanate (TDI) can be preferably used for the purpose of obtaining a stable adhesive force even after long-term storage and making it a harder adhesive layer.
  • the pressure-sensitive adhesive may contain, for example, a stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent as additives.
  • organic resin such as wax, silicone, fluorine, etc.
  • a higher fatty acid ester or a low molecular weight phthalate ester may be used.
  • Rubber-based adhesives polyisobutylene rubber, butyl rubber and mixtures thereof, or tackifiers such as abietic rosin ester, terpene / phenol copolymer, terpene / indene copolymer, etc. were blended with these rubber-based adhesives. Things are used.
  • Examples of the base polymer of the rubber adhesive include natural rubber, isoprene rubber, styrene-butadiene rubber, recycled rubber, polyisobutylene rubber, styrene-isoprene-styrene rubber, and styrene-butadiene-styrene rubber. Etc.
  • the block rubber-based pressure-sensitive adhesive is a block copolymer represented by the general formula ABA or a block copolymer represented by the general formula AB (where A is a styrene polymer block, B Is a butadiene polymer block, an isoprene polymer block, or an olefin polymer block obtained by hydrogenating them, hereinafter referred to as a styrene-based thermoplastic elastomer), and a tackifier resin, a softener and the like are blended.
  • a composition is a styrene polymer block, B Is a butadiene polymer block, an isoprene polymer block, or an olefin polymer block obtained by hydrogenating them, hereinafter referred to as a styrene-based thermoplastic elastomer
  • a composition is a block copolymer represented by the general formula ABA or a block copolymer represented by the general formula AB (
  • the styrene polymer block A preferably has an average molecular weight of about 4,000 to 120,000, and more preferably about 10,000 to 60,000.
  • the glass transition temperature is preferably 15 ° C. or higher.
  • the butadiene polymer block, the isoprene polymer block, or the olefin polymer block B obtained by hydrogenation thereof preferably has an average molecular weight of about 30,000 to 400,000, and more preferably 60,000 to 200,000. About 000 is more preferable.
  • the glass transition temperature is preferably ⁇ 15 ° C. or lower.
  • a / B 5/95 to 50/50
  • a / B 10/90 to 30/70.
  • the releasability from the release paper or release film can be improved.
  • the polyolefin resin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene- ⁇ olefin copolymer, propylene- ⁇ olefin copolymer, and ethylene-ethyl acrylate copolymer. , Ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, and mixtures thereof.
  • the polyolefin-based resin preferably has a low molecular weight, and specifically, the low molecular weight extracted by boiling boiling with n-pentane is preferably less than 1.0% by mass. This is because if the low molecular weight component exceeds 1.0% by mass, the low molecular weight component adversely affects the adhesive properties in accordance with temperature changes and changes with time, and decreases the adhesive force.
  • silicone oil is a polymer compound with a polyalkoxysiloxane chain in the main chain, which increases the hydrophobicity of the adhesive layer and further bleeds to the adhesive interface, that is, the surface of the adhesive layer. There is a function that makes it difficult for a phenomenon to occur.
  • a cross-linking agent is added to the above rubber-based pressure-sensitive adhesive and crosslinked to form an adhesive layer.
  • crosslinking agent for example, sulfur, a vulcanization aid, and a vulcanization accelerator (typically, dibutylthiocarbamate zinc, etc.) are used for crosslinking the natural rubber-based pressure-sensitive adhesive.
  • a vulcanization accelerator typically, dibutylthiocarbamate zinc, etc.
  • Polyisocyanates are used as a cross-linking agent capable of cross-linking an adhesive made from natural rubber and carboxylic acid copolymerized polyisoprene at room temperature.
  • Polyalkylphenol resins are used as cross-linking agents that have heat-resistant and non-fouling characteristics in cross-linking agents such as butyl rubber and natural rubber.
  • organic peroxides such as benzoyl peroxide and dicumyl peroxide in the crosslinking of pressure-sensitive adhesives made from butadiene rubber, styrene-butadiene rubber and natural rubber, and non-fouling pressure-sensitive adhesives can be obtained.
  • Polyfunctional methacrylic esters are used as a crosslinking aid.
  • a pressure-sensitive adhesive by crosslinking such as ultraviolet crosslinking or electron beam crosslinking.
  • the silicone-based pressure-sensitive adhesive includes an addition reaction curable type silicone pressure sensitive adhesive and a condensation polymerization curable type silicone pressure sensitive adhesive.
  • an addition reaction curable type is preferably used.
  • composition of the addition reaction curable silicone pressure-sensitive adhesive composition those listed below are preferably used.
  • R is a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • X is an alkenyl group-containing organic group.
  • R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group or a tolyl group.
  • An aryl group such as, for example, is mentioned, and a methyl group and a phenyl group are particularly preferable.
  • X is an organic group containing 2 to 10 carbon atoms containing an alkenyl group, and specifically, vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenyl. Examples thereof include an ethyl group and a vinyloxypropyl group, and a vinyl group and a hexenyl group are particularly preferable.
  • the properties of the polydiorganosiloxane may be oily or raw rubbery, and the viscosity of the component (A) is preferably 100 mPa ⁇ s or more, particularly 1,000 mPa ⁇ s or more at 25 ° C.
  • the viscosity of the component (A) is preferably 100 mPa ⁇ s or more, particularly 1,000 mPa ⁇ s or more at 25 ° C.
  • a polymerization degree may be 20,000 or less from the ease of mixing with another component.
  • (A) component may be used individually by 1 type, and may use 2 or more types together.
  • the polyorganosiloxane containing SiH groups as the component (B) is a crosslinking agent, and is an organohydropolysiloxane having at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule. , Branched, annular, etc. can be used.
  • R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 6 carbon atoms.
  • b is an integer of 0 to 3
  • x and y are integers, respectively, and indicate the number at which the viscosity of this organohydropolysiloxane at 25 ° C. is 1 to 5,000 mPa ⁇ s.
  • the viscosity of this organohydropolysiloxane at 25 ° C. is preferably 1 to 5,000 mPa ⁇ s, particularly 5 to 1000 mPa ⁇ s, and may be a mixture of two or more.
  • Crosslinking by addition reaction occurs between the component (A) and the component (B) of the crosslinking agent, and the gel fraction of the adhesive layer after curing is determined by the ratio of the crosslinking component.
  • Component (B) is used so that the molar ratio of SiH groups in component (B) to alkenyl groups in component (A) is in the range of 0.5 to 20, particularly 0.8 to 15. It is preferable. If it is less than 0.5, the crosslinking density is lowered, and the holding force may be lowered accordingly. On the other hand, if it exceeds 20, the adhesive strength and tack may be reduced, or the usable time of the treatment liquid may be shortened.
  • the proportion of the cross-linking component in the composition may be increased. There may be effects such as reduced flexibility. From such a point, the blending mass ratio of the component (A) / (B) may be 20/80 to 80/20, and particularly preferably 45/55 to 70/30. When the blending ratio of the component (A) is less than 20/80, adhesive properties such as adhesive strength and tack may be deteriorated, and when it is more than 80/20, sufficient heat resistance cannot be obtained.
  • Component (C) is an addition reaction control agent, so that when a silicone pressure-sensitive adhesive composition is prepared and applied to a substrate, the treatment liquid does not thicken or gel before heat curing. It is to be added.
  • component (C) 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.
  • the amount of component (C) is preferably in the range of 0 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on a total of 100 parts by weight of components (A) and (B). Is preferred. If it exceeds 5.0 parts by mass, curability may be lowered.
  • Component (D) is a platinum catalyst, containing chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group
  • a reaction product with siloxane can be used.
  • the addition amount of the component (D) is preferably 1 to 5,000 ppm, particularly 5 to 2,000 ppm in terms of platinum with respect to the total amount of the components (A) and (B). If it is less than 1 ppm, the curability is lowered, the crosslinking density is lowered, and the holding power may be lowered. If it exceeds 5,000 ppm, the usable time of the treatment bath may be shortened.
  • the shape of the conductive fine particles of the component is not particularly limited, such as spherical, dendritic, and needle-like.
  • the particle size is not particularly limited, but it is preferable that the maximum particle size does not exceed 1.5 times the coating thickness of the pressure-sensitive adhesive. Therefore, the floating from the adherend tends to occur starting from this portion.
  • a crosslinking agent for example, a crosslinking agent, a catalyst, a plasticizer, an antioxidant, a colorant, an antistatic agent, a filler, a tackifier, a surfactant, and the like may be added.
  • a crosslinking agent for example, a crosslinking agent, a catalyst, a plasticizer, an antioxidant, a colorant, an antistatic agent, a filler, a tackifier, a surfactant, and the like may be added.
  • the adhesive layer onto the substrate it is performed by a roll coater, blade coater, bar coater, air knife coater, gravure coater, reverse coater, die coater, lip coater, spray coater, comma coater, etc.
  • An adhesive layer is formed through smoothing, drying, heating, electron beam exposure processes such as ultraviolet rays, and the like.
  • the material used as the release layer is preferably a plastic film that does not generate dust.
  • a plastic film used for the peeling layer which concerns on this invention.
  • Polyolefin films such as a polyethylene film and a polypropylene film
  • Polyester films such as a polyethylene terephthalate and a polybutylene terephthalate
  • Polyamide type such as a hexamethylene adipamide Film: Halogen-containing film such as polyvinyl chloride, polyvinylidene chloride, polyfluoroethylene, etc .
  • Vinyl acetate such as polyvinyl acetate, polyvinyl alcohol, ethylene vinyl acetate copolymer and its derivative films are used.
  • a polyester film is preferred, and for example, polyethylene terephthalate. It is because it has moderate elasticity.
  • the plastic film used for the release layer may be one to which a release agent is applied.
  • the coating solution for performing the mold release treatment include: solvent-free 636, 919, 920, 921, 924, emulsion type 929, 430, 440 in DEHESIVE series manufactured by Asahi Kasei Wacker Silicone Co., Ltd. 39005, 39006, solvent type 940, 942, 952, 953, 811, etc.
  • TPR6500 are release paper silicones manufactured by GE Toshiba Silicone Co., Ltd .: TPR6500, TPR6501, UV9300, UV9315, XS56-A2775, XS56-A2982, TPR6600, TPR6605, TPR6604, TPR6705, TPR6722, TPR6721, TPR6702, XS56-B3884, XS56-A8012, XS56-B2654, TPR6700, TPR6701, TPR6707, T R6710, TPR6712, XS56-A3969, XS56-A3075, YSR3022 and the like.
  • the transparent substrate used in the heat-shielding resin substrate according to the present invention is not particularly limited as long as it is a resin film that can hold the various layers described above.
  • a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polybutylene naphthalate, polyethylene-2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol Polyvinyl alcohol resin such as copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin , Polycar Nate (PC) resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin,
  • PO
  • a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate
  • a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof.
  • oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof.
  • ZEONEX and ZEONOR manufactured by ZEON Corporation
  • ARTON of amorphous cyclopolyolefin resin film manufactured by JSR Corporation
  • pure ace of polycarbonate film manufactured by Teijin Limited
  • Konica of cellulose triacetate film Commercial products such as Tack KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.
  • the resin film is preferably transparent, high light resistance, and high weather resistance.
  • the resin film listed above may be an unstretched film or a stretched film.
  • the resin film according to the present invention can be manufactured by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • aromatic polyesters represented by polyethylene terephthalate and polyethylene-2,6-naphthalate
  • aliphatic polyamides represented by nylon 6 and nylon 66
  • aromatic polyamides polyethylene and polypropylene Representative polyolefins and polycarbonates are preferred.
  • aromatic polyesters, polyethylene terephthalate, polybutylene naphthalate, and polyethylene-2,6-naphthalate, particularly polyethylene terephthalate films are more preferred.
  • thermoplastic resin film is preferably a biaxially stretched film with increased mechanical strength, and further a biaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene-2,6-naphthalate film having excellent heat resistance and mechanical strength.
  • a biaxially stretched polyethylene terephthalate film is preferred.
  • the aromatic polyester can contain an appropriate filler if necessary.
  • the filler include those conventionally known as a slipperiness-imparting agent for polyester films.
  • the filler include calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, and carbon black. , Silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, crosslinked silicone resin particles, and the like.
  • the average particle diameter of the slipperiness-imparting agent is 0.01 to 10 ⁇ m, and the content is within an amount range in which the film maintains transparency, and is preferably 0.0001 to 5% by mass.
  • the aromatic polyester can contain a colorant, an antistatic agent, an antioxidant, an organic lubricant, catalyst residue fine particles and the like as appropriate.
  • a polyester film containing a light stabilizer is preferable when the heat-shielding resin substrate of the present invention is used for external application.
  • the light stabilizer has an effect of preventing polyester from being deteriorated by ultraviolet irradiation, and examples thereof include an ultraviolet absorber, a radical scavenger, and an antioxidant.
  • examples of such light stabilizers include hindered amines, salicylic acids, benzophenones, benzotriazoles, cyanoacrylates, triazines, benzoates, oxalic acid anilides, and other organic light stabilizers, or sol-gel inorganics.
  • the light stabilizer can be used. Specific examples of the light stabilizer suitably used are shown below, but of course not limited thereto.
  • Hindered amines bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine
  • Salicylic acid series pt-butylphenyl salicylate, p-octylphenyl salicylate
  • Benzophenone series 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone 2,2'-4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2-methoxy-4- Hydroxy-5-benzoylphenyl) methane ben
  • Triazole series 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5-methyl
  • At least one of hindered amine, benzophenone, and benzotriazole is preferably used, and more preferably used in combination.
  • the heat shielding resin substrate of the present invention before forming the low refractive index ceramic constituent layer, the metal layer, the high refractive index ceramic constituent layer, etc., corona treatment, flame treatment, plasma treatment, glow discharge treatment, Surface treatment such as roughening treatment or chemical treatment may be performed.
  • Resin film is conveniently a long product rolled up.
  • the thickness of the resin film is preferably in the range of 10 to 400 ⁇ m, and more preferably in the range of 30 to 200 ⁇ m, from the viewpoint of suitability as a heat shielding resin substrate.
  • the water vapor transmission rate of the low refractive index ceramic constituent layer As the water vapor transmission rate of the low refractive index ceramic constituent layer according to the present invention, the water vapor transmission rate measured according to JIS K7129: 1992 B method (manufactured by MOCON, using a water vapor transmission rate measuring device PERMATRAN-W3 / 33 MG module) 0.01 g / (m 2 ⁇ 24 h) or less (under 40 ° C. and 90% RH), more preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less, more preferably 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the water vapor permeability of the low refractive index ceramic constituent layer may be measured by providing at least only the low refractive index ceramic constituent layer on the resin fat substrate.
  • the physical or chemical vapor deposition method is used to form the low refractive index ceramic laminated film according to the present invention, for example, a silicon oxide film, or a laminated body thereof.
  • the atmospheric pressure plasma CVD method which is the most preferable method among them will be described below.
  • the atmospheric pressure plasma CVD method is described in, for example, Japanese Patent Application Laid-Open No. 10-154598, Japanese Patent Application Laid-Open No. 2003-49272, pamphlet of International Publication No. 02/048428, etc., and particularly in Japanese Patent Application Laid-Open No. 2004-68143.
  • the described thin film forming method is preferable for forming a dense silicon oxide film having a high gas barrier property.
  • a web-like transparent base material is drawn out from a roll-shaped original winding, and silicon oxide films having different compositions can be continuously formed.
  • the atmospheric pressure plasma CVD method used for forming the low refractive index ceramic constituent layer according to the present invention is a plasma CVD method performed under atmospheric pressure or a pressure in the vicinity thereof. What is atmospheric pressure or a pressure in the vicinity thereof? The pressure is about 20 to 110 kPa, and 93 to 104 kPa is preferable for obtaining the good effects described in the present invention.
  • the discharge condition is that two or more electric fields having different frequencies are applied to the discharge space.
  • An electric field is applied by superimposing the electric field.
  • the frequency ⁇ 2 of the second high-frequency electric field is higher than the frequency ⁇ 1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge start electric field
  • the relationship with strength IV of V1 ⁇ IV> V2 Alternatively, V1> IV ⁇ V2 is satisfied, and the output density of the second high-frequency electric field is 1 W / cm 2 or more.
  • ⁇ High frequency means that having a frequency of at least 0.5 kHz.
  • the superimposed high-frequency electric field When the superimposed high-frequency electric field is a sine wave, it becomes a component obtained by superimposing the frequency ⁇ 1 of the first high-frequency electric field and the frequency ⁇ 2 of the second high-frequency electric field higher than the frequency ⁇ 1, and the waveform is a sine of the frequency ⁇ 1.
  • a sawtooth waveform in which a sine wave with a higher frequency ⁇ 2 is superimposed on the wave is obtained.
  • the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method.
  • the discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.
  • the present invention is not limited to this, and both pulse waves may be used, one may be continuous waves and the other may be pulse waves. Further, a third electric field having a different frequency may be included.
  • the first high-frequency electric field having the frequency ⁇ 1 and the electric field strength V1 is applied to the first electrode constituting the counter electrode.
  • An atmospheric pressure plasma discharge processing apparatus is used in which a first power source is connected, and a second power source is connected to the second electrode to apply a second high-frequency electric field having a frequency ⁇ 2 and an electric field strength V2.
  • the above atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.
  • the first filter facilitates passage of a first high-frequency electric field current from the first power source to the first electrode, and grounds the second high-frequency electric field current to provide a second from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field.
  • the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source.
  • a power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used.
  • the phrase “difficult to pass” means that only 20% or less, more preferably 10% or less of the current is passed.
  • being easy to pass means that preferably 80% or more, more preferably 90% or more of the current is passed.
  • a capacitor of several tens of pF to tens of thousands of pF or a coil of about several ⁇ H can be used depending on the frequency of the second power source.
  • a coil of 10 ⁇ H or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.
  • the first power source of the atmospheric pressure plasma discharge treatment apparatus according to the present invention has a capability of applying a higher electric field strength than the second power source.
  • the applied electric field strength and the discharge start electric field strength referred to in the present invention are those measured by the following method.
  • Measuring method of applied electric field strengths V1 and V2 (unit: kV / mm): A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.
  • P6015A high-frequency voltage probe
  • TDS3012B oscilloscope
  • Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm): A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV.
  • the measuring instrument is the same as the applied electric field strength measurement.
  • discharge can be started even with a discharge gas with a high discharge starting electric field strength, such as nitrogen gas, and a high-density thin film can be formed while maintaining a high density and stable plasma state. be able to.
  • a discharge gas with a high discharge starting electric field strength such as nitrogen gas
  • the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ⁇ 3.7 kV / mm, the nitrogen gas can be excited and put into a plasma state.
  • the frequency of the first power source is preferably 200 kHz or less.
  • the electric field waveform may be a continuous wave or a pulse wave.
  • the lower limit is preferably about 1 kHz.
  • the frequency of the second power source is preferably 800 kHz or more.
  • the upper limit is preferably about 200 MHz.
  • the application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field.
  • the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes as described above, changes the gas introduced between the counter electrodes into a plasma state, and allows the gas to stand between the counter electrodes or transfer between the electrodes. A thin film is formed on the base material by exposing the base material to the plasma state gas.
  • the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrodes.
  • FIG. 1 is a schematic view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
  • the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting means.
  • the plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency ⁇ ⁇ b> 1 from the first power supply 21 is output from the first electrode 11 between the counter electrodes.
  • a first high-frequency electric field of electric field strength V1 and current I1 is applied, and a second high-frequency electric field of frequency ⁇ 2, electric field strength V2, and current I2 from the second power source 22 is applied from the second electrode 12. It has become.
  • the first power supply 21 applies a higher frequency electric field strength (V1> V2) than the second power supply 22, and the first frequency ⁇ 1 of the first power supply 21 is lower than the second frequency ⁇ 2 of the second power supply 22. Apply.
  • a first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of a current from the first power source 21 to the first electrode 11, and a current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.
  • a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.
  • the above-described thin film forming gas G is introduced from the gas supply means as illustrated in FIG. 2 described later into the space (discharge space) 13 between the opposing electrodes of the first electrode 11 and the second electrode 12, and the first power source 21. And a second power source 22 to apply the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 to generate a discharge, while the above-described thin film forming gas G is in a plasma state.
  • the processing space formed by the lower surface of the counter electrode and the base material F is filled with a gas G ° in a plasma state, and is unwound from a base winding (unwinder) (not shown).
  • a thin film is formed in the vicinity of the processing position 14 on the base material F that is transported or transported from the previous process. During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG.
  • the physical properties and composition of the resulting thin film may change, and it is desirable to appropriately control this.
  • the temperature control medium an insulating material such as distilled water or oil is preferably used.
  • it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or the longitudinal direction of the substrate does not occur as much as possible.
  • FIG. 1 shows a measuring instrument and a measurement position used for measuring the applied electric field strength and the discharge starting electric field strength.
  • Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.
  • FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a method for treating a substrate between counter electrodes useful for the present invention.
  • the atmospheric pressure plasma discharge processing apparatus is an apparatus having at least a plasma discharge processing apparatus 30, an electric field applying means 40 having two power sources, a gas supply means 50, and an electrode temperature adjusting means 60.
  • the base material F is plasma-discharged to form a thin film.
  • the roll rotating electrode 35 receives a first high-frequency electric field of frequency ⁇ 1, electric field strength V1, current I1 from the first power source 41, and A second high-frequency electric field having a frequency ⁇ 2, an electric field strength V2, and a current I2 is applied to the fixed electrode group 36 from the second power source 42.
  • a first filter 43 is installed between the roll rotation electrode 35 and the first power supply 41.
  • the first filter 43 facilitates the passage of current from the first power supply 41 to the first electrode, and the second power supply. It is designed to ground the current from 42 and make it difficult to pass the current from the second power source 42 to the first power source.
  • a second filter 44 is installed between the fixed electrode group 36 and the second power source 42, and the second filter 44 facilitates passage of current from the second power source 42 to the second electrode, It is designed to ground the current from the first power supply 41 and make it difficult to pass the current from the first power supply 41 to the second power supply.
  • the roll rotating electrode 35 may be the second electrode, and the square tube type fixed electrode group 36 may be the first electrode.
  • the first power source is connected to the first electrode, and the second power source is connected to the second electrode.
  • the first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ⁇ 1 ⁇ 2.
  • the current is preferably I1 ⁇ I2.
  • the current I1 of the first high-frequency electric field is preferably 0.3 mA / cm 2 to 20 mA / cm 2 , more preferably 1.0 mA / cm 2 to 20 mA / cm 2 .
  • the current I2 of the second high frequency electric field is preferably 10 mA / cm 2 to 100 mA / cm 2 , more preferably 20 mA / cm 2 to 100 mA / cm 2 .
  • the thin film forming gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while the flow rate is controlled by a gas flow rate adjusting means (not shown).
  • the resin film substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed in the direction of the arrow from the previous process, and accompanied by the nip roll 65 via the guide roll 64 and the substrate.
  • the incoming air or the like is cut off and transferred to the rectangular tube fixed electrode group 36 while being wound while being in contact with the roll rotating electrode 35.
  • the base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.
  • a plurality of rectangular tube-shaped fixed electrodes are provided along a circumference larger than the circumference of the roll electrode, and the discharge areas of the electrodes are all the corners facing the roll rotating electrode 35. It is represented by the sum of the areas of the surface of the cylindrical fixed electrode facing the roll rotation electrode 35.
  • Resin film base material F passes through nip roll 66 and guide roll 67 and is wound up by a winder (not shown) or transferred to the next step.
  • Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.
  • the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is sent to both electrodes via the pipe 61 by the liquid feed pump P, and from inside the electrodes. Adjust the temperature.
  • Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.
  • FIG. 3 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 2 and the dielectric material coated thereon.
  • a roll electrode 35a has a conductive metallic base material 35A and a dielectric 35B coated thereon.
  • a temperature adjusting medium such as water or silicon oil
  • FIG. 4 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube type electrode and a dielectric material coated thereon.
  • a rectangular tube electrode 36a has a coating of a dielectric 36B similar to that of FIG. 3 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.
  • the rectangular tube electrode 36a shown in FIG. 4 may be a cylindrical electrode, but the rectangular tube electrode is preferably used in the present invention because it has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode.
  • the roll electrode 35a and the rectangular tube electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing the inorganic compound. Is subjected to a sealing treatment.
  • the ceramic dielectric may be covered by about 1 mm with a single wall.
  • As the ceramic material used for thermal spraying alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed.
  • the dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.
  • Examples of the conductive metallic base materials 35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.
  • the distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metal base material of the other electrode.
  • a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.
  • the distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing the above, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.
  • the plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes.
  • polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. It is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the base material surface) with the material as described above.
  • Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500 A2 Shinko Electric 5kHz SPG5-4500 A3 Kasuga Electric 15kHz AGI-023 A4 Shinko Electric 50kHz SPG50-4500 A5 HEIDEN Laboratory 100kHz * PHF-6k A6 Pearl Industry 200kHz CF-2000-200k A7 Pearl Industry 400kHz CF-2000-400k And the like, and any of them can be used.
  • * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.
  • an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.
  • the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm 2 or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma.
  • the energy is applied to the thin film forming gas to form a thin film.
  • the upper limit value of the power supplied to the second electrode is preferably 50 W / cm 2 , more preferably 20 W / cm 2 .
  • the lower limit is preferably 1.0 W / cm 2 .
  • the discharge area (cm 2 ) refers to the area in which discharge occurs between the electrodes.
  • the output density can be improved while maintaining the uniformity of the second high frequency electric field. Can do. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved.
  • it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the second electrode side second
  • the high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.
  • the electrodes used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance.
  • Such an electrode is preferably a metal base material coated with a dielectric.
  • the characteristics match between various metallic base materials and dielectrics.
  • One of the characteristics is linear thermal expansion between the metallic base material and the dielectric.
  • the combination is such that the difference in coefficient is 10 ⁇ 10 ⁇ 6 / ° C. or less. It is preferably 8 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 5 ⁇ 10 ⁇ 6 / ° C. or less, and particularly preferably 2 ⁇ 10 ⁇ 6 / ° C. or less.
  • the linear thermal expansion coefficient is a well-known physical property value of a material.
  • Metal base material is pure titanium or titanium alloy
  • dielectric is ceramic spray coating
  • Metal base material is pure titanium or titanium alloy
  • dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above-mentioned item 1 or item 2 and item 5 to 8 are preferable, and item 1 is particularly preferable.
  • titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics.
  • the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.
  • the metallic base material of the electrode useful for the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium.
  • the content of titanium in the titanium alloy or titanium metal can be used without any problem as long as it is 70% by mass or more, but preferably contains 80% by mass or more of titanium.
  • the titanium alloy or titanium metal useful in the present invention those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of industrial pure titanium include TIA, TIB, TIC, TID, etc., all of which contain very little iron, carbon, nitrogen, oxygen, hydrogen, etc. As content, it has 99 mass% or more.
  • T15PB can be preferably used, and it contains lead in addition to the above-mentioned contained atoms, and the titanium content is 98% by mass or more.
  • titanium alloy T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin other than the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more.
  • These titanium alloys or titanium metals have a thermal expansion coefficient smaller than that of stainless steel, for example, AISI 316, by a dielectric material described later applied on the titanium alloy or titanium metal as a metallic base material. The combination is good and it can withstand use at high temperature for a long time.
  • the required characteristics of the dielectric are preferably inorganic compounds having a relative dielectric constant of 6 to 45, and such dielectrics include ceramics such as alumina and silicon nitride, or silica.
  • dielectrics include ceramics such as alumina and silicon nitride, or silica.
  • glass lining materials such as acid salt glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable.
  • a dielectric provided by spraying alumina is preferable.
  • the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is.
  • the porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity.
  • Examples of the dielectric having such a void and a low void ratio include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform a sealing treatment.
  • the above-mentioned atmospheric plasma spraying method is a technique in which fine powders such as ceramics, wires, and the like are put into a plasma heat source and sprayed onto a metal base material to be coated as fine particles in a molten or semi-molten state to form a film.
  • a plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. This plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, it is possible to obtain a coating film with high adhesion strength and high density.
  • a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655 can be referred to.
  • the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.
  • the dielectric thickness is 0.5 to 2 mm.
  • the film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.
  • the thermal sprayed film of ceramics or the like is further sealed with an inorganic compound as described above.
  • an inorganic compound a metal oxide is preferable, and among these, a compound containing silicon oxide (SiO x ) as a main component is particularly preferable.
  • the inorganic compound for sealing is preferably formed by curing by a sol-gel reaction.
  • a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction.
  • the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.
  • the energy treatment includes thermosetting (preferably 200 ° C. or less) and ultraviolet irradiation.
  • thermosetting preferably 200 ° C. or less
  • ultraviolet irradiation preferably UV irradiation
  • the content of the metal oxide after curing is 60 It is preferably at least mol%.
  • the cured SiO x (x is 2 or less) content is preferably 60 mol% or more.
  • the SiO x content after curing is measured by analyzing the tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).
  • the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the base material of the electrode may be adjusted to 10 ⁇ m or less.
  • the maximum value of the surface roughness is more preferably 8 ⁇ m or less, and particularly preferably 7 ⁇ m or less.
  • the dielectric surface of the dielectric-coated electrode can be polished and the dielectric thickness and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and the heat shrinkage difference and residual It is possible to eliminate distortion and cracking due to stress, and to greatly improve durability with high accuracy.
  • the polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate.
  • the center line average surface roughness (Ra) specified by JIS B 0601 is preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
  • the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C.
  • the heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such heat-resistant temperature can be applied within the range of the difference between the linear thermal expansion coefficient of the metallic base material and the dielectric material by applying the dielectric material provided by the above-mentioned ceramic spraying or layered glass lining with different bubble mixing amounts. This can be achieved by appropriately combining means for appropriately selecting the materials.
  • a ceramic layer mainly composed of a nitride containing In, Nb, Si, or Al can be produced in the same manner as the low-refractive index ceramic constituent layer by selecting a raw material compound by the atmospheric pressure plasma CVD method. it can.
  • Examples of the organic metal compound used as a raw material for the high refractive index ceramic constituent layer include, in addition to the silicon compound and aluminum compound, titanium compounds such as titanium methoxide, titanium ethoxide, titanium isopropoxide, and titanium tetraisopoloxide. Poxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis- 2,4-pentanedionate), titanium acetylacetonate, butyl titanate dimer and the like.
  • titanium compounds such as titanium methoxide, titanium ethoxide, titanium isopropoxide, and titanium tetraisopoloxide.
  • Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.
  • tin compounds tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin , Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetate
  • tin halides such as nates, tin hydride compounds, etc. include tin dichloride and tin tetrach
  • organometallic compounds include, for example, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate, niobium methoxide, niobium trifluoroethoxide, zinc acetylacetonate, diethylzinc, and the like.
  • the surface resistance of the heat ray shielding constituent layer (metal layer) of the heat shielding resin substrate thus obtained is preferably 8 ⁇ / ⁇ or less. When this surface resistance value exceeds 8 ⁇ / ⁇ , the electromagnetic wave shielding effect is not sufficiently exhibited. A more preferable surface resistance value is 6 ⁇ / ⁇ or less. Further, by providing an electrode having a surface resistance value lower than the surface resistance value of the metal layer at the end of the metal layer and taking out the ground, the electromagnetic wave shielding effect is further exhibited.
  • the heat shielding resin base material thus obtained is coated with an adhesive layer so as to be bonded to a substrate such as glass.
  • the adhesive layer may be provided on either the resin film substrate side or the side with the heat ray blocking component layer, but when bonded to a substrate such as glass, the heat ray blocking component layer is formed between the substrate and the resin film substrate. Since it can be sealed from ambient gas such as moisture, it is preferably provided on the outermost surface layer of the heat shielding resin substrate.
  • an adhesive mainly composed of a photocurable or thermosetting resin can be used.
  • the adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic pressure-sensitive adhesive or a silicone pressure-sensitive adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.
  • preferred examples of the main monomer as a skeleton include acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and acryl acrylate.
  • Preferred examples of the comonomer for improving the cohesive force include vinyl acetate, acrylonitrile, styrene, and methyl methacrylate.
  • methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, glycidyl can be used as functional group-containing monomers to promote cross-linking and to provide stable adhesive strength and to maintain a certain level of adhesive strength even in the presence of water.
  • Preferred examples include methacrylate.
  • the production of the pressure-sensitive adhesive can be performed by a known method. For example, in the presence of an organic solvent such as ethyl acetate or toluene, a predetermined starting material is introduced into the reaction kettle, and heated using a peroxide system such as benzoyl peroxide or an azobis system such as azobisisobutyronitrile as a catalyst. It can manufacture by polymerizing under.
  • a peroxide system such as benzoyl peroxide or an azobis system such as azobisisobutyronitrile
  • ethyl acetate is preferably used rather than toluene, which has a large chain transfer coefficient and suppresses polymer growth in a method in which monomers are added all at the beginning of the reaction or in an organic solvent species to be used.
  • the weight average molecular weight (Mw) of the polymer is preferably 400,000 or more, and more preferably 500,000 or more.
  • Mw weight average molecular weight
  • the curing agent for the adhesive general isocyanate curing agents and epoxy curing agents can be used, particularly in the acrylic solvent system, but in order to obtain a uniform film, the fluidity and crosslinking of the adhesive over time are required. Therefore, an isocyanate curing agent is preferable.
  • the adhesive layer may contain, for example, a stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent and the like as an additive.
  • the thickness of the adhesive layer is preferably 5 to 50 ⁇ m.
  • any known method can be used as a method for coating and forming the adhesive layer, and examples thereof include a die coater method, a gravure coater method, a blade coater method, a spray coater method, an air knife coating method, and a dip coating method.
  • the surface of the film is subjected to physical surface treatment such as flame treatment, corona discharge treatment, plasma discharge treatment, organic or inorganic, which is easily adhesive, for the purpose of improving adhesion and coating properties as necessary. It is preferable to perform a chemical surface treatment such as resin coating.
  • the above-mentioned pressure-sensitive adhesive material can also be used for an adhesive layer for bonding the first transparent substrate and the second transparent substrate according to the present invention.
  • the thickness of the adhesive layer for adhering the first transparent base material and the second transparent base material is set so that the reflected light from the heat ray blocking constituent layer does not generate color due to light interference due to re-reflection from the gray metal layer. It must be at least 2 ⁇ m thick.
  • Example 1 Formation of polymer layer on PET >> PET / CHC Using a Teijin DuPont PET (polyethylene terephthalate) film (thickness 38 ⁇ m) HS as a first transparent base material, an actinic radiation curable resin layer coating solution having the following composition was prepared thereon, and the cured film thickness was 2 ⁇ m. Then, it was applied using a microgravure coater, and after evaporating and drying the solvent, it was cured by irradiation with ultraviolet rays of 0.2 J / cm 2 using a high-pressure mercury lamp to form a polymer film composed of an acrylic cured layer.
  • ⁇ Coating liquid for active ray curable resin layer Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Dimethoxybenzophenone photoinitiator 4 parts by weight Methyl ethyl ketone 75 parts by weight Propylene Glycol monomethyl ether 75 parts by mass ⁇ Formation of low refractive index ceramic constituent layer >>
  • low refractive index ceramic constituent layer 1 50 nm, C content 7.8 at%)
  • low refractive index ceramic constituent layer 2 50 nm, C content ⁇ 0.1 at%)
  • low refractive index ceramic constituting layer 3 500 nm, C content 7.8 at%) and low refractive index ceramic constituting layer were sequentially formed under the conditions described below ( The refractive index ceramic constituent layer 1 (50 nm, C content 7.8 at%), low refractive index
  • the gas in the vacuum chamber is switched to Ar gas so that the first pressure is 0.45 Pa, and direct current is applied to the cathode on which the silver target is set to perform sputtering.
  • the silver film was formed to 10 nm.
  • ⁇ Formation of gray metal layer >> Ni-Cr
  • a direct current was applied to the substrate to cause sputtering, and a Ni—Cr film was formed to 8.45 nm.
  • ⁇ Formation of adhesive layer> An acrylic pressure-sensitive adhesive in which an isocyanate crosslinking agent is added to a pressure-sensitive adhesive polymer having a weight average molecular weight of 650,000 obtained by copolymerizing butyl acrylate and methyl acrylate in a molar ratio of 3: 1 is prepared. A coating solution in which 15% by mass of the pressure-sensitive adhesive was dissolved on the surface of the heat ray blocking constitution layer was applied and dried at a rate of 10 g / m 2 to provide an adhesive layer having a thickness of 5 ⁇ m.
  • Each of the above layers is laminated on a PET (polyethylene terephthalate) film (thickness 38 ⁇ m) HS (PET) manufactured by Teijin DuPont as shown in FIG. A resin substrate was prepared.
  • Example 2 ⁇ Formation of gray metal layer >> Ni-Cr Teijin DuPont PET (polyethylene terephthalate) film (thickness 38 ⁇ m) HS as a first transparent substrate on one side, the gas in the vacuum chamber Ar gas, the first pressure is 0.45 Pa, A direct current was applied to the cathode on which the Ni—Cr target was set to cause sputtering to form a Ni—Cr film of 3.8 nm. Further, a 3.8 nm Ni—Cr film was similarly formed on the opposite surface of the transparent substrate on which the Ni—Cr film was formed.
  • low refractive index ceramic constituent layer On the first transparent substrate having Ni—Cr films on both sides, in the same manner as in Example 1, component layer 1 (50 nm, C content 7.8 at%), low refractive index ceramic component layer 2 (50 nm , C content ⁇ 0.1 at%), low refractive index ceramic constituting layer 3 (500 nm, C content 7.8 at%) and low refractive index ceramic constituting layer were sequentially formed under the conditions described below (refractive The rate was 1.46).
  • FIG. 6B shows the first transparent base material on which the first low refractive index ceramic constituent layer and the gray metal layer are formed, and the second transparent base material formed in the same manner as in Example 1. And a heat shielding resin substrate composed of a PET-low refractive index ceramic constituent layer was produced.
  • Example 3 Formation of Heat Ray Blocking Component Layer >> In 2 O 3 / Ag / In 2 O 3 / Ag / In 2 O 3 ⁇ Formation of first high refractive index ceramic constituent layer>
  • the gas in the vacuum chamber is switched to Ar gas, the first pressure is set to 0.45 Pa, and direct current is applied to the cathode on which the silver target is set to perform sputtering.
  • a silver film having a thickness of 10 nm was formed.
  • the gas in the vacuum chamber is switched to Ar gas, the first pressure is set to 0.45 Pa, and direct current is applied to the cathode on which the silver target is set to perform sputtering.
  • a silver film having a thickness of 9 nm was formed.
  • Example 1 Using each layer in Example 1 and the heat ray blocking constituent layer, lamination was performed as shown in FIG. 6C to prepare a heat shielding resin base material composed of PET to a low refractive index ceramic constituent layer.
  • Example 4 Formation of low refractive index ceramic constituent layer >> Using Teijin DuPont's PET (polyethylene terephthalate) film (thickness 38 ⁇ m) HS as a first transparent substrate on one side, in the same manner as in Example 1, component layer 1 (50 nm, C content 7.8 at%) ), Low refractive index ceramic constituent layer 2 (50 nm, C content ⁇ 0.1 at%), low refractive index ceramic constituent layer 3 (500 nm, C content 7.8 at%), and low refraction in order An index ceramic constituent layer was formed (refractive index was 1.46).
  • the low refractive index ceramic structure layer is disposed on the target side, the gas in the vacuum chamber is Ar gas, and the first pressure is 0.45 Pa. Then, direct current was applied to the cathode on which the Ni—Cr target was set to cause sputtering, and a Ni—Cr film of 8.45 nm was formed on the low refractive index ceramic constituent layer.
  • Example 3 Using each layer in Example 3 and the heat ray blocking constitution layer, the layers were laminated as shown in FIG. 6 (d) to produce a heat shielding resin substrate composed of PET to a low refractive index ceramic constituting layer.
  • Example 5 Using the first transparent base material in Example 2 and the heat ray blocking constitution layer in Example 3, lamination was performed as shown in FIG. 6E to prepare a heat shielding resin base material made of PET to PET.
  • Example 6 Formation of gray metal layer >> Ni-Cr Teijin DuPont PET (polyethylene terephthalate) film (thickness 38 ⁇ m) HS as a first transparent substrate on one side, the gas in the vacuum chamber Ar gas, the first pressure is 0.45 Pa, A direct current was applied to the cathode on which the Ni—Cr target was set to cause sputtering to form a 8.45 nm Ni—Cr film.
  • the first transparent substrate and the second transparent substrate were laminated as shown in FIG. 6 (f) to produce a heat shielding resin substrate made of PET to PET.
  • Polyester A1 was obtained by polymerization using magnesium acetate, antimony trioxide, and phosphoric acid.
  • the polyester A1 and 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) as an ultraviolet absorber were mixed with a vented twin screw extruder with an ultraviolet absorber of 15 It compounded so that it might become mass%, and obtained polyester A2 containing a ultraviolet absorber.
  • Polyester A1 and polyester A2 were charged so that the UV absorber was 0.5% by mass with respect to the total polyester, first vacuum dried at 150 ° C. for 2 hours, and then vacuum dried at 175 ° C. for 3 hours.
  • the film was melt-extruded with a casting drum and rapidly solidified on cast while electrostatically applied with a tape-like electrode to obtain an unstretched film. This was preheated at 75 ° C., and stretched 3.3 times in the longitudinal direction with an 80 ° C. roll while using a radiation heater together to obtain a uniaxially stretched film. Thereafter, a water-dispersible acrylic resin (concentration: 4.0% by mass) containing a lubricant (a colloidal silica solid content ratio of 0.35 parts by mass with a particle size of 0.1 ⁇ m) as a laminated film on both surfaces of the uniaxially stretched film. was applied to both sides with a # 4 metabar, stretched 3.6 times in the width direction at 110 ° C., and heat treated at 220 ° C. to obtain a biaxially stretched polyester film having a total film thickness of 125 ⁇ m.
  • an actinic radiation curable resin layer coating solution having the following composition is prepared thereon, and applied using a micro gravure coater so that the film thickness after curing is 2 ⁇ m.
  • the solvent was evaporated and dried, and then cured by irradiation with 0.2 J / cm 2 of ultraviolet light using a high-pressure mercury lamp to form a polymer film composed of an acrylic cured layer.
  • low refractive index ceramic constituent layer On the polymer layer of the first transparent substrate, in the same manner as in Example 1, component layer 1 (50 nm, C content 7.8 at%), low refractive index ceramic component layer 2 (50 nm, C content) ⁇ 0.1 at%), low refractive index ceramic constituent layer 3 (500 nm, C content 7.8 at%) and low refractive index ceramic constituent layers were sequentially formed (refractive index was 1). .46).
  • the first transparent base material and the second transparent base material were laminated as shown in FIG. 6G to produce a heat shielding resin base material made of PET to PET + light stabilizer.
  • Example 8 Formation of UV Absorber-Containing Polymer Layer >> CHC + UV Absorber Methyl methacrylate 65% by mass and 2-hydroxyethyl methacrylate 35% by mass were copolymerized to obtain a hydroxyl group-introduced methacrylate resin having an average molecular weight of 50000.
  • 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol TINUVIN328; Ciba Japan Co., Ltd.
  • TINUVIN328 Ciba Japan Co., Ltd.
  • Decanedioic acid bis [2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl] ester (TINUVIN123; Ciba (Made by Japan Co., Ltd.) was blended in an amount of 5% by mass, diluted with methyl ethyl ketone to adjust the viscosity, and the main component (a) adjusted to a solid content of 20% by mass was obtained.
  • a polyisocyanate compound serving as a cross-linking agent (curing agent) a curing agent (b) obtained by adjusting adduct-type hexamethylene diisocyanate with methyl ethyl ketone so that the solid content was 75% by mass was obtained.
  • a coating liquid was prepared by adding 15% by mass of the curing agent (b) to the main agent (a).
  • This coating solution was continuously coated on the light stabilizer-containing PET prepared in Example 7 so that the coating amount was 5 g / m 2 in terms of solid content, and dried at a drying temperature of 60 ° C.
  • Example 1 Each layer in Example 1, the heat ray blocking constitution layer in Example 3, and the UV absorber-containing polymer layer on the light stabilizer-containing PET are laminated as shown in FIG. A thermal insulation resin substrate composed of layers was prepared.
  • the release resin material described below is laminated on the low refractive index ceramic constituent layer, and the low refractive index ceramic layer is scratched. And a heat ray blocking component layer was provided to prevent adhesion of foreign matter.
  • a silicone release agent is applied onto a 38 ⁇ m thick polyethylene terephthalate film, and 100 parts by mass of an acrylic pressure-sensitive adhesive (polymer containing butyl acrylate as a main monomer) is applied to the surface on which the silicone release agent is applied.
  • ⁇ Durability Test 1 >> Using a sunshine weather meter (Suga Test Instruments Co., Ltd., WEL-SUN-HCL type), irradiating the film for 3000 hours (equivalent to outdoor exposure for 3 years) according to JIS R 5759 went. Each measurement was performed on the sample after the test.
  • the tensile strength in the longitudinal direction and the transverse direction of the film was determined according to the following criteria using a tensile stress measuring device (manufactured by Ulm, Zwick 010) according to ISO 527-1-2.
  • A 80% or more with respect to the tensile strength before the weathering test ⁇ : 60% or more and less than 80% with respect to the tensile strength before the weathering test ⁇ : Less than 60% with respect to the tensile strength before the weathering test
  • shielding coefficient Slightly degraded
  • SC Majorly degraded SC
  • the shielding coefficient was measured and calculated based on JIS R5756.
  • thermal barrier resin substrate of the present invention is superior to comparison in all durability tests.
  • Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 21 1st power supply 22 2nd power supply 24 2nd filter 30 Plasma discharge processing apparatus 32 Discharge space 35 Roll rotation electrode 35a Roll electrode 35A Metal base material 35B Dielectric 36 Angle Cylindrical fixed electrode group 40 Electric field applying means 41 1st power supply 42 2nd power supply 43 1st filter 44 2nd filter 50 Gas supply means 51 Gas generator 52 Air supply port 53 Exhaust port 60 Electrode temperature adjusting means G Thin film forming gas G ° Gas in plasma G 'treated exhaust gas F Base material

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une résine thermo-protectrice antireflet ayant d’excellentes résistance à la lumière, résistance à l’humidité et résistance aux intempéries. La présente invention concerne en outre un élément de construction utilisant la base de résine thermo-protectrice. La base de résine thermo-protectrice est caractérisée en ce qu’elle comporte : une couche de constituant thermo-protecteur comprenant au moins une couche métallique composée d’une substance simple d’or, d’argent, de cuivre ou d’aluminium, ou d’un alliage de ces métaux ; une couche de métal gris composée d’au moins un élément choisi parmi des substances simples de titane, de chrome, d’acier inoxydable et de nickel-chrome ou un alliage contenant l’un quelconque de ces métaux ; et au moins une couche de constituant céramique à faible indice de réfraction principalement composé d’un oxyde contenant Si ou Al, un oxynitrure contenant Si ou Al, ou un nitrure contenant Si ou Al.
PCT/JP2009/060047 2008-06-06 2009-06-02 Base de résine thermo-protectrice et élément de construction utilisant celle-ci Ceased WO2009148045A1 (fr)

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WO2013161785A1 (fr) * 2012-04-26 2013-10-31 コニカミノルタ株式会社 Pellicule transparente formant barrière aux gaz et dispositif électronique
JPWO2013161893A1 (ja) * 2012-04-24 2015-12-24 コニカミノルタ株式会社 積層ガスバリア性樹脂基材の製造方法
JP2018517938A (ja) * 2015-06-03 2018-07-05 サン−ゴバン パフォーマンス プラスティックス コーポレイション ソーラーコントロールフィルム

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JP2006297868A (ja) * 2005-04-25 2006-11-02 Dainippon Printing Co Ltd 金属積層体
JP2008056967A (ja) * 2006-08-30 2008-03-13 Konica Minolta Holdings Inc ガスバリア性樹脂基材および有機エレクトロルミネッセンスデバイス
JP2008063402A (ja) * 2006-09-06 2008-03-21 Mitsubishi Engineering Plastics Corp ポリカーボネート樹脂組成物及び熱線遮蔽能を備えた成形体

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JP2006297868A (ja) * 2005-04-25 2006-11-02 Dainippon Printing Co Ltd 金属積層体
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Publication number Priority date Publication date Assignee Title
JPWO2013161893A1 (ja) * 2012-04-24 2015-12-24 コニカミノルタ株式会社 積層ガスバリア性樹脂基材の製造方法
WO2013161785A1 (fr) * 2012-04-26 2013-10-31 コニカミノルタ株式会社 Pellicule transparente formant barrière aux gaz et dispositif électronique
JPWO2013161785A1 (ja) * 2012-04-26 2015-12-24 コニカミノルタ株式会社 透明ガスバリアーフィルム及び電子デバイス
JP2018517938A (ja) * 2015-06-03 2018-07-05 サン−ゴバン パフォーマンス プラスティックス コーポレイション ソーラーコントロールフィルム

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