WO2014199872A1 - Film de protection infrarouge, corps de protection infrarouge l'utilisant et verre stratifié réfléchissant les rayons thermiques - Google Patents

Film de protection infrarouge, corps de protection infrarouge l'utilisant et verre stratifié réfléchissant les rayons thermiques Download PDF

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Publication number
WO2014199872A1
WO2014199872A1 PCT/JP2014/064782 JP2014064782W WO2014199872A1 WO 2014199872 A1 WO2014199872 A1 WO 2014199872A1 JP 2014064782 W JP2014064782 W JP 2014064782W WO 2014199872 A1 WO2014199872 A1 WO 2014199872A1
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Prior art keywords
refractive index
layer
infrared shielding
film
hard coat
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PCT/JP2014/064782
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English (en)
Japanese (ja)
Inventor
治加 増田
丈範 熊谷
小沼　太朗
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コニカミノルタ株式会社
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Priority to JP2015522726A priority Critical patent/JPWO2014199872A1/ja
Publication of WO2014199872A1 publication Critical patent/WO2014199872A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10651—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising colorants, e.g. dyes or pigments
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/285—Interference filters comprising deposited thin solid films
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical 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
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes

Definitions

  • the present invention relates to an infrared shielding film, an infrared shielding body using the same, and a heat ray reflective laminated glass.
  • the light emitted from the sun has a wide spectrum from the ultraviolet region to the infrared light region.
  • infrared light occupies about 50% of sunlight, and the infrared light mainly includes near infrared light having a wavelength close to that of visible light (wavelength of about 750 to 2500 nm) and mid-infrared light having a wavelength longer than that. (About 2500 to 4000 nm) and far infrared (wavelength of about 4000 nm or more).
  • Such infrared light has a long wavelength compared to ultraviolet light, so its energy is small.
  • its thermal effect is large, and when it is absorbed by a substance, it is released as heat and causes a temperature rise. For this reason, infrared light is also called heat rays, and by reflecting infrared light, for example, an increase in indoor temperature can be suppressed.
  • the film that reflects infrared light is attached to the window glass of buildings and vehicles, and the load on the cooling equipment is reduced by reflecting the transmission of solar heat rays. An attempt is being made. On the other hand, if such an infrared shielding film reflects visible light having a wavelength close to that of infrared light, the transparency of the film cannot be secured and the film is colored. Therefore, it can be said that an infrared shielding film that selectively reflects infrared light and transmits visible light is preferable.
  • Such an infrared shielding film capable of selectively reflecting infrared light and transmitting visible light is usually a low refractive index layer having a relatively low refractive index and a relatively high refractive index. And a high-refractive index layer having a dielectric multilayer film. At this time, for the high refractive index layer and the low refractive index layer, infrared light can be selectively reflected by controlling the optical film thickness, which is the product of the refractive index and the film thickness, to cause interference.
  • the hard coat layer is used for the purpose of preventing the surface from being scratched during cleaning. Sometimes formed.
  • JP 2010-191969 A discloses a transparent hard coat film having a transparent hard coat film composed of a cured product of a coating liquid containing an ionizing radiation curable resin and a blue inorganic pigment.
  • An invention relating to a coat film is described.
  • JP 2010-191969 discloses, L * values in the material of the film thickness and the L * a * b * color system constituting the transparent hard coat film, a * value, and b * controls the value of By doing so, it is described that a desired hue can be obtained.
  • the optical film thickness of the above-described infrared shielding film is controlled so that infrared rays can be selectively reflected.
  • the infrared shielding film in which the control of the optical film thickness is controlled may have a different color tone depending on the viewing angle.
  • an object of the present invention is to provide an infrared shielding film having excellent heat shielding performance while reducing the angle dependency of the color tone.
  • the present inventors have found that the above problem can be solved by controlling the values of a * and b * in the L * a * b * color system of an infrared shielding film provided with a hard coat layer. The inventors have found that this can be solved, and have completed the present invention.
  • the dielectric multi-layer film comprising a high refractive index layer and the low refractive index layer comprises a hard coat layer, a, L * a * b * a in the color system * is a * ⁇ -3.5, And an infrared shielding film in which b * is ⁇ 12 ⁇ b * ⁇ 5; (2) The infrared shielding film according to (1), wherein b * is ⁇ 12 ⁇ b * ⁇ 2.
  • an infrared shielding film including a dielectric multilayer film including a high refractive index layer and a low refractive index layer, and a hard coat layer.
  • a * in the L * a * b * color system of the infrared shielding film is a * ⁇ -3.5, and wherein the b * is -12 ⁇ b * ⁇ 5 .
  • the infrared shielding film which concerns on this form, the infrared shielding film which is excellent in heat-shielding performance can be provided, reducing the angle dependence of a color tone.
  • the infrared shielding film includes a dielectric multilayer film and a hard coat layer.
  • L * a * b * color system was developed by the International Commission on Illumination (CIE).
  • L * is called “lightness index” and indicates lightness
  • a * ” and “b * ” are called “chromicness index” and indicate positions corresponding to hue and saturation. Is. Regarding the hue and saturation, if the value of a * is negative, the color is green, and if the value of a * is positive, the color is red. If the value of b * is negative, the color is blue. If the value of b * is positive, the color is yellow.
  • the value of a * in the L * a * b * color system is ⁇ 3.5 or less (a * ⁇ ⁇ 3.5), preferably ⁇ 10 to ⁇ 3.5 ( ⁇ 10 ⁇ a * ⁇ ⁇ 3.5), more preferably ⁇ 5.0 to ⁇ 3.5 ( ⁇ 5.0 ⁇ a * ⁇ ⁇ 3.5).
  • the value of b * in the L * a * b * color system is ⁇ 12 to 5 ( ⁇ 12 ⁇ b * ⁇ 5), preferably ⁇ 12 to 2 ( ⁇ 12 ⁇ b * ⁇ 2). More preferably, it is ⁇ 10 to ⁇ 1.0 ( ⁇ 10 ⁇ b * ⁇ ⁇ 1.0).
  • the combinations of the values of a * and b * in the L * a * b * color system are a * ⁇ ⁇ 3.5 and ⁇ 12 ⁇ b * ⁇ 5, preferably a * ⁇ ⁇ . 3.5 and ⁇ 12 ⁇ b * ⁇ 2, more preferably ⁇ 5.0 ⁇ a * ⁇ ⁇ 3.5 and ⁇ 10 ⁇ b * ⁇ ⁇ 1.0.
  • L * is not particularly limited, but is preferably 80 or more, and more preferably 80 to 90. It is preferable that the value of L * is 80 or more because the transmittance can be increased.
  • the “a * value”, “b * value”, and “L * value” in the L * a * b * color system refer to a spectrophotometer U-4100 (manufactured by Shimadzu Corporation). The value obtained by measuring the transmittance in the visible light region (360 to 740 nm) is used.
  • the optical film thickness of the infrared shielding film having the dielectric multilayer film in which the high refractive index layer and the low refractive index layer are laminated is controlled so that infrared rays can be selectively reflected.
  • the optical film thickness is adjusted to be 1 ⁇ 4 of the desired wavelength. For this reason, the longer the optical film thickness, the longer the wavelength of light is reflected.
  • the optical film thickness is relatively increased as compared with the case where the light is incident vertically. As a result, compared with the case where the infrared shielding film is viewed from the front, a red color based on long wavelength light can be observed when viewed from an oblique direction.
  • the color tone depending on the observation angle is controlled by controlling the a * value and b * in the L * a * b * color system of the infrared shielding film in which the hard coat layer is provided on the dielectric multilayer film. Changes can be prevented.
  • the value of a * and the value of b * tend to decrease by reducing the optical film thickness of the dielectric multilayer film.
  • the value of a * tends to decrease by adding a green pigment or dye to the hard coat layer.
  • the value of b * tends to decrease by adding a blue pigment or dye to the hard coat layer.
  • the degree of color tone change depending on the observation angle can be evaluated using reflectance. Specifically, the change in color tone depending on the observation angle is evaluated by comparing the regular reflectance with an incident angle of 5 degrees with the regular reflectance with an incident angle of 60 degrees with respect to the normal of the dielectric multilayer film. can do. At this time, the wavelength of the irradiated light is 730 nm.
  • the value of “regular reflectance” is a value measured using a spectrophotometer U-4100 (manufactured by Shimadzu Corporation).
  • the dielectric multilayer film includes a high refractive index layer and a low refractive index layer.
  • the dielectric multilayer film includes a refractive index layer having a different refractive index, so that when infrared light is irradiated, at least part of the infrared light is reflected and an infrared shielding effect is exhibited. it can.
  • whether the refractive index layer constituting the dielectric multilayer film is a high refractive index layer or a low refractive index layer is determined by comparing the refractive index with the adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer.
  • the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer). Therefore, whether the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.
  • refractive index layer a refractive index layer formed using a dry film forming method, a refractive index layer formed by extrusion molding of a resin, and a refractive index layer formed using a wet film forming method Is mentioned.
  • the layer is a low refractive index layer or a high refractive index layer is a relative one that is determined by the relationship with the adjacent refractive index layer.
  • the structure of a typical high refractive index layer and low refractive index layer among the refractive index layers that can be formed by the respective methods will be described below.
  • the refractive index layer can be formed by evaporating a dielectric material.
  • the material of the high refractive index layer in this embodiment is not particularly limited, but is preferably a transparent dielectric material.
  • Specific examples include titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), niobium oxide (Nb 2 O 5 ), aluminum oxide (Al 2 O 3 ), and the like.
  • the material of the high refractive index layer is preferably titanium oxide or zinc oxide.
  • the material of said high refractive index layer may be used independently, or may be used in combination of 2 or more type.
  • the material of the low refractive index layer is not particularly limited, but is preferably a transparent dielectric material. Specific examples include silicon oxide (SiO 2 ), calcium fluoride (CaF 2 ), magnesium fluoride (MgF 2 ), indium tin oxide (ITO), antimony tin oxide (ATO), and the like. Of these, the material of the low refractive index layer is preferably silicon oxide or magnesium fluoride. In addition, the material of said low refractive index layer may be used independently, or may be used in combination of 2 or more type.
  • Examples of a method for forming a refractive index layer formed by resin extrusion include a method in which a molten resin obtained by melting a resin is extruded onto a casting drum from a multilayer extrusion die and then rapidly cooled. At this time, after extruding and cooling the molten resin, the resin sheet may be stretched.
  • the stretching ratio of the resin can be appropriately selected according to the resin, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
  • Refractive Index Layer In this embodiment, a high refractive index layer and a low refractive index layer will be described together as a refractive index layer.
  • the resin constituting the refractive index layer is not particularly limited as long as it is a thermoplastic resin.
  • a thermoplastic resin for example, polyalkylene resin, polyester resin, polycarbonate resin, (meth) acrylic resin, amide resin, silicone resin And fluorine-based resins.
  • polyalkylene resin examples include polyethylene (PE) and polypropylene (PP).
  • polyester resin examples include polyester resins having a dicarboxylic acid component and a diol component as main components.
  • the dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexane.
  • Examples include dicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4- Hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol fluorange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • polycarbonate resin examples include a reaction product of bisphenol A or its derivative bisphenol and phosgene or phenyl dicarbonate.
  • Examples of the (meth) acrylic resin include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid-2.
  • amide resin examples include aliphatic amide resins such as 6,6-nylon, 6-nylon, 11-nylon, 12-nylon, 4,6-nylon, 6,10-nylon, and 6,12-nylon;
  • aromatic polyamide such as an aromatic diamine such as phenylenediamine and an aromatic dicarboxylic acid such as terephthaloyl chloride or isophthaloyl chloride or a derivative thereof may be used.
  • silicone resin examples include resins containing a siloxane bond having an organic group such as an alkyl group or an aromatic group as a structural unit.
  • the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
  • the aromatic group is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a benzyl group.
  • those having a methyl group and / or a phenyl group are preferable, and dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and modified products thereof are more preferable.
  • fluororesin examples include homopolymers or copolymers such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ether.
  • the above-described resins may be used alone or in combination of two or more.
  • a preferable combination of materials of a high refractive index layer and a low refractive index layer includes PET-PEN and the like.
  • the refractive index layer can be formed by a method of sequentially applying and drying a coating solution, a method of applying and drying a coating solution in multiple layers, or the like.
  • the high refractive index layer includes a first water-soluble resin.
  • the first metal oxide particles, a curing agent, a surfactant, and other additives may be included as necessary.
  • the first water-soluble resin is not particularly limited, and polyvinyl alcohol resins, gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups can be used. . Of these, it is preferable to use a polyvinyl alcohol-based resin.
  • water-soluble means a G2 glass filter (maximum pores 40 to 40) when dissolved in water at a temperature at which the polymer is most dissolved at a concentration of 0.5% by mass. Means that the mass of the insoluble matter to be filtered out is within 50% by mass of the added polymer.
  • Polyvinyl alcohol resin As the polyvinyl alcohol resin, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate (unmodified polyvinyl alcohol), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, vinyl alcohol Examples thereof include modified polyvinyl alcohol such as a polymer.
  • the modified polyvinyl alcohol may improve the film adhesion, water resistance, and flexibility.
  • the polyvinyl alcohol may be a synthetic product or a commercially available product.
  • Commercially available products include PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-203, PVA-205, PVA-210, PVA-217, PVA -220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04, JF-05, JP-03, JP-04JP-05, JP-45 (Nippon Vinegar & Poval Co., Ltd.).
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A-61-10383 in the main chain or side chain of the polyvinyl alcohol. And polyvinyl alcohol.
  • the cation-modified polyvinyl alcohol can be obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride, trimethyl- (3-acrylamido-3,3-dimethylpropyl).
  • the ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • anion-modified polyvinyl alcohol examples include polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-30779. And a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group as described in JP-A-7-285265, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • nonionic modified polyvinyl alcohol for example, a polyvinyl alcohol derivative obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A No. 7-9758, JP-A No. 8-25795 Reactive group modification having reactive groups such as block copolymers of vinyl compounds having a hydrophobic group and vinyl alcohol, silanol modified polyvinyl alcohol having silanol groups, acetoacetyl group, carbonyl group, carboxy group Polyvinyl alcohol etc. are mentioned.
  • polyvinyl alcohol-based water-soluble polymer examples include EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Gelatin As the gelatin, various gelatins conventionally used widely in the field of silver halide photographic light-sensitive materials can be applied. For example, acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin that undergoes enzyme treatment in the production process of gelatin, a group having an amino group, imino group, hydroxyl group, carboxyl group as a functional group in the molecule, and a group that can react with it And gelatin derivatives modified by treatment with a reagent having
  • gelatin When gelatin is used, a gelatin hardener can be added as necessary.
  • a water-soluble cellulose derivative can be preferably used.
  • water-soluble cellulose derivatives such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; carboxylic acid group-containing celluloses such as carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose; Examples thereof include cellulose derivatives such as cellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
  • the thickening polysaccharide is a polymer of saccharides and has many hydrogen bonding groups in the molecule.
  • the thickening polysaccharide has a characteristic that the viscosity difference at low temperature and the viscosity at high temperature are large due to the difference in hydrogen bonding force between molecules depending on temperature. Further, when metal oxide fine particles are added to the thickening polysaccharide, the viscosity is increased due to hydrogen bonding with the metal oxide fine particles at a low temperature.
  • the viscosity at 15 ° C. is usually 1.0 mPa ⁇ s or more, preferably 5.0 mPa ⁇ s or more, more preferably 10.0 mPa ⁇ s or more.
  • the thickening polysaccharide that can be used is not particularly limited, and examples include generally known natural polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides.
  • synthetic simple polysaccharides for details of these polysaccharides, reference can be made to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.
  • thickening polysaccharides include, for example, galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), glucomanno Glycan (for example, potato mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (for example, softwood-derived glycan), arabinogalactoglycan (for example, soybean-derived glycan, microorganism-derived glycan, etc.) Derived from red algae such as glycans (eg gellan gum), glycosaminoglycans (eg hyaluronic acid, keratan sulfate, etc.), alginic acid and alginate, agar, ⁇ -carrageenan, ⁇ -carrageenan, etc.
  • a carboxylic acid group or sulfonic acid is used as the structural unit. It is preferable that it does not have a group.
  • thickening polysaccharides include pentoses such as L-arabitose, D-ribose, 2-deoxyribose and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose and D-galactose. The polysaccharide which consists only of is mentioned.
  • tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose
  • guar gum and cationized guar gum known as galactomannan whose main chain is mannose and side chain is glucose
  • Hydroxypropyl guar gum whose main chain is galactose and whose side chain is arabinose
  • Polymer having reactive functional group examples include polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid.
  • Acrylic resins such as ester copolymers and acrylic acid-acrylic acid ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- Styrene acrylic resin such as ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer; styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl Acrylate copolymer Len-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl
  • the above water-soluble resins may be used alone or in combination of two or more.
  • a preferred example of the first water-soluble polymer is a polyvinyl alcohol resin.
  • the polymerization degree of the polyvinyl alcohol-based resin is preferably 1000 or more, more preferably 1500 to 5000, and still more preferably 2000 to 5000.
  • degree of polymerization refers to the viscosity average degree of polymerization, and a value measured according to JIS-K6726 (1994) is adopted. Specifically, after the polyvinyl alcohol-based resin is completely re-saponified and purified, the intrinsic viscosity [ ⁇ ] (dl / g) measured in water at 30 ° C. can be obtained by the following formula.
  • P represents the degree of polymerization
  • ⁇ represents the intrinsic viscosity
  • the first water-soluble resin include water-soluble resins other than polyvinyl alcohol resins having a mass average molecular weight of 1,000 to 200,000, and more preferably a mass average molecular weight of 3,000 to 40,000.
  • the value measured by gel permeation chromatography (GPC) is adopted as the value of “mass average molecular weight”.
  • the content of the first water-soluble resin is preferably 5 to 50% by mass and more preferably 10 to 40% by mass with respect to 100% by mass of the solid content of the high refractive index layer.
  • the first metal oxide particles mean metal oxide particles that can be contained in the high refractive index layer.
  • the first metal oxide particles are not particularly limited, but are preferably metal oxide particles having a refractive index of 2.0 to 3.0. Specifically, titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, water Examples thereof include magnesium oxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. Among these, the first metal oxide particles are preferably titanium oxide or zirconium oxide from the viewpoint of forming a transparent and high refractive index layer having a high refractive index. From the viewpoint of improving weather resistance, the first metal oxide particles are preferably a rutile type (tetragonal type). ) Titanium oxide is more preferable.
  • the titanium oxide may be in the form of core / shell particles coated with a silicon-containing hydrated oxide.
  • the core / shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on titanium oxide serving as a core.
  • the volume average particle size of the titanium oxide particles serving as the core portion is preferably more than 1 nm and less than 30 nm, and more preferably 4 nm or more and less than 30 nm.
  • the first metal oxide particles described above may be used alone or in combination of two or more.
  • the content of the first metal oxide particles is 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer from the viewpoint of increasing the refractive index difference from the low refractive index layer. It is preferably 20 to 77% by mass, more preferably 30 to 75% by mass.
  • the first metal oxide particles preferably have a volume average particle size of 30 nm or less, more preferably 1 to 30 nm, and even more preferably 5 to 15 nm.
  • a volume average particle size of 30 nm or less is preferable because it has less haze and is excellent in visible light transmittance.
  • the value measured by the following method is adopted as the value of “volume average particle diameter”. Specifically, arbitrary 1000 particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope to measure the particle size, and particles having particle sizes of d1, d2,. In the group of n1, n2... Ni... Nk metal oxide particles, where the volume per particle is vi, the volume average particle size (mv) is calculated by the following formula.
  • the curing agent has a function of reacting with a water-soluble resin (preferably a polyvinyl alcohol-based resin) contained in the high refractive index layer to form a hydrogen bond network.
  • a water-soluble resin preferably a polyvinyl alcohol-based resin
  • the curing agent is not particularly limited as long as it causes a curing reaction with the first water-soluble resin, but in general, a compound having a group capable of reacting with the water-soluble resin or a different group possessed by the water-soluble resin.
  • stimulates mutual reaction is mentioned.
  • boric acid and its salt as a curing agent.
  • curing agents other than boric acid and its salt may be used.
  • Examples of the known curing agent include epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (eg, formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3) , 5, -s-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, and the like.
  • epoxy curing agents diglycidyl eth
  • boric acid and its salt mean oxygen acid and its salt having a boron atom as a central atom.
  • Specific examples include orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid, and salts thereof.
  • the content of the curing agent is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer.
  • the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, and more preferably 100 to 600 mg per 1 g of polyvinyl alcohol. preferable.
  • the surfactant is not particularly limited, and examples thereof include amphoteric surfactants, cationic surfactants, anionic surfactants, and nonionic surfactants. Among these, betaine-type zwitterionic surfactants, quaternary ammonium salt-type cationic surfactants, fluorine-type cationic surfactants, dialkylsulfosuccinate-type anionic surfactants, acetylene glycol-type nonionic interfaces It is preferred to use an activator.
  • additives examples include amino acids, emulsion resins, and lithium compounds.
  • the low refractive index layer contains a second water-soluble resin.
  • the second metal oxide particles, a curing agent, a surfactant, other additives, and the like may be included as necessary.
  • the second water-soluble resin may be the same as the first water-soluble resin.
  • the high refractive index layer and the low refractive index layer both use a polyvinyl alcohol-based resin as the first water-soluble resin and the second water-soluble resin
  • the polyvinyl alcohol-based resins having different degrees of saponification are used. It is preferable to use a resin. Thereby, mixing of the interface is suppressed, the infrared reflectance (infrared shielding rate) becomes better, and the haze can be lowered.
  • the “degree of saponification” means the ratio of hydroxy groups to the total number of acetyloxy groups (derived from vinyl acetate as a raw material) and hydroxy groups in polyvinyl alcohol.
  • the difference in the absolute value of the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is preferably 3 mol% or more, more preferably 5 mol% or more.
  • the difference between the absolute values of the saponification degree is 3 mol% or more, the interlayer mixed state of the high refractive index layer and the low refractive index layer can be brought to a preferable level.
  • the difference in absolute value of the saponification degree is preferably as large as possible, but from the viewpoint of solubility of polyvinyl alcohol in water, the difference in absolute value of the saponification degree is preferably 20 mol% or less. .
  • the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is preferably 75 mol% or more from the viewpoint of solubility in water.
  • the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is 90 mol% or more for one refractive index layer and 90 mol% for the other refractive index layer.
  • the saponification of one refractive index layer is preferably 90 mol% or less, and the saponification degree of the refractive index layer is more preferably 95 mol% or more.
  • the degree of saponification of the polyvinyl alcohol-based resin in the high refractive index layer and the low refractive index layer is in the above relationship because the intermixed state of the high refractive index layer and the low refractive index layer can be brought to a preferable level.
  • the upper limit of the saponification degree of the polyvinyl alcohol-based resin is not particularly limited, but is preferably less than 100 mol%, and more preferably 99.9 mol% or less.
  • the saponification degree and the polymerization degree are determined in the refractive index layer. It means the saponification degree and polymerization degree of the polyvinyl alcohol resin having the highest content.
  • the polyvinyl alcohol resin having the highest content in the refractive index layer when determining the “polyvinyl alcohol resin having the highest content in the refractive index layer”, the polyvinyl alcohol resin having a difference in saponification degree of 3 mol% or less is regarded as the same polyvinyl alcohol resin. to decide.
  • a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is handled as a different polyvinyl alcohol. That is, even if there is a low polymerization degree polyvinyl alcohol having a difference in saponification degree within 3 mol%, the low polymerization degree polyvinyl alcohol is not treated as the same polyvinyl alcohol.
  • polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively.
  • the three polyvinyl alcohols are the same polyvinyl alcohol, and the mixture of these three is the “polyvinyl alcohol resin having the highest content in the refractive index layer”.
  • the “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” may be 3 mol% or less when attention is paid to any polyvinyl alcohol.
  • the polyvinyl alcohol is included, since the difference in the saponification degree of any polyvinyl alcohol is within 3 mol% when paying attention to 91 mol% of the polyvinyl alcohol, they all become the same polyvinyl alcohol.
  • polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each.
  • PVA203 5% by mass
  • PVA117 25% by mass
  • PVA217 10% by mass
  • PVA220 10% by mass
  • PVA224 10% by mass
  • PVA235 20% by mass
  • PVA245 20% by mass
  • most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, and is the same polyvinyl alcohol).
  • the “polyvinyl alcohol resin having a high content” is preferably 40 to 100% by mass, more preferably 60 to 95% by mass with respect to the total mass of all the polyvinyl alcohol resins in the high refractive index layer. Further, the “polyvinyl alcohol resin having the highest content in the refractive index layer” in the low refractive index layer is 40 to 100% by mass with respect to the total mass of all polyvinyl alcohol resins in the low refractive index layer. Preferably, it is 60 to 95% by mass.
  • a water-soluble resin when polyvinyl alcohol having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol having a low saponification degree is used for the low refractive index layer, Is preferably 40 to 100% by mass, more preferably 60 to 95% by mass with respect to the total mass of all polyvinyl alcohol resins in the high refractive index layer. preferable. Further, the “polyvinyl alcohol resin having the highest content in the refractive index layer” in the low refractive index layer is 40 to 100% by mass with respect to the total mass of all polyvinyl alcohol resins in the low refractive index layer. Preferably, it is 60 to 95% by mass.
  • the second metal oxide particles mean typical metal oxide particles that can be contained in the low refractive index layer.
  • the second metal oxide particles are not particularly limited, but silica (silicon dioxide) such as synthetic amorphous silica and colloidal silica is preferably used, and acidic colloidal silica sol is more preferably used. Further, from the viewpoint of further reducing the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles, and it is particularly preferable to use hollow fine particles of silica (silicon dioxide). .
  • the colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer.
  • colloidal silica may be a synthetic product or a commercially available product.
  • examples of commercially available products include the Snowtex series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) sold by Nissan Chemical Industries, Ltd.
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • the second metal oxide particles may be surface-coated with a surface coating component.
  • the average particle diameter (number average; diameter) of the first metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer of the present invention is preferably 3 to 100 nm, and preferably 3 to 50 nm. It is more preferable.
  • the “average particle diameter (number average; diameter)” of the metal oxide fine particles is 1,000 particles observed by an electron microscope on the particles themselves or on the cross section or surface of the refractive index layer. The particle size of any of the particles is measured and determined as a simple average value (number average).
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm. .
  • the refractive index of the low refractive index layer is sufficiently lowered.
  • the “average particle pore diameter of the hollow particles” is an average value of the inner diameters of the hollow particles.
  • the value of “average particle pore diameter” is determined by observing 50 or more random pore diameters that can be observed as a circle, an ellipse, or substantially a circle or an ellipse by electron microscope observation. And the value obtained by obtaining the number average value thereof is adopted.
  • the “average particle hole diameter” means the minimum distance among the distances between the outer edges of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. To do.
  • the content of the second metal oxide particles in the low refractive index layer is preferably 0.1 to 75% by mass, and preferably 30 to 70% by mass with respect to 100% by mass of the total solid content of the low refractive index layer. More preferred is 45 to 65% by mass.
  • the above-described second metal oxide may be used alone or in combination of two or more from the viewpoint of adjusting the refractive index.
  • curing agent the same materials as those for the high refractive index layer can be used, and thus the description thereof is omitted here.
  • the dielectric multilayer film including the high refractive index layer and the low refractive index layer that can have the above-described configuration, at least one of the high refractive index layer and the low refractive index layer is formed by a wet film forming method.
  • the refractive index layer is preferable, and both the high refractive index layer and the low refractive index layer are more preferably refractive index layers formed by a wet film forming method.
  • at least one of the high refractive index layer and the low refractive index layer includes metal oxide particles, and it is more preferable that both the high refractive index layer and the low refractive index layer include metal oxide particles.
  • the difference in refractive index between the adjacent low refractive index layer and high refractive index layer may be 0.1 or more.
  • it is 0.3 or more, more preferably 0.35 or more, and particularly preferably 0.4 or more.
  • the refractive index difference between the high refractive index layer and the low refractive index layer in all the laminated bodies is within the above-mentioned preferable range.
  • the refractive index layers constituting the uppermost layer and the lowermost layer of the dielectric multilayer film may have a configuration outside the above preferred range.
  • the reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers.
  • the refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain an infrared reflectance of 90% or more, if the refractive index difference is smaller than 0.1, it is necessary to stack 200 layers or more. In such cases, productivity loss, increased scattering at the stack interface, reduced transparency, and manufacturing failures can occur.
  • the refractive index of the high refractive index layer is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.
  • the refractive index of the low refractive index layer is preferably 1.10 to 1.60, and more preferably 1.30 to 1.50.
  • the number of refractive index layers of the dielectric multilayer film (total number of high refractive index layers and low refractive index layers) is preferably 6 to 50 layers, and preferably 8 to 40 layers from the above viewpoint. Is more preferably 9 to 30 layers, and particularly preferably 11 to 31 layers. It is preferable that the number of refractive index layers in the dielectric multilayer film be in the above range because excellent heat shielding performance and transparency, suppression of film peeling and cracking, and the like can be realized.
  • each high refractive index layer and / or each low refractive index layer is the same or different. It may be.
  • the dielectric multilayer film may be provided only on one side of the base material, or may be provided on both sides of the base material. Whether the dielectric multilayer film is provided on one side or both sides can be appropriately determined from the viewpoint of film properties. For example, when another layer is provided on one side of the substrate, depending on the physical properties of the other layer, it may be possible to solve problems such as curling by providing a dielectric multilayer film on the opposite side. Moreover, these problems may be solved by providing the dielectric multilayer film on both sides.
  • the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.
  • the thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.
  • the composition when measuring the thickness per layer, the composition may change continuously without having a clear interface at the boundary between the high refractive index layer and the low refractive index layer.
  • the above composition can be observed from the concentration profile of the metal oxide particles.
  • the metal oxide concentration profile is formed by etching from the surface to the depth direction using a sputtering method, and using an XPS surface analyzer, sputtering is performed at a rate of 0.5 nm / min, with the outermost surface being 0 nm. It can be seen by measuring the ratio. Further, the laminated film may be cut and the cut surface may be confirmed by measuring the atomic composition ratio with an XPS surface analyzer.
  • the XPS surface analyzer is not particularly limited, and any model can be used.
  • the XPS surface analyzer for example, ESCALAB-200R manufactured by VG Scientific, Inc. can be used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
  • the hard coat layer has a function of preventing scratches on the infrared shielding film.
  • the hard coat layer includes a hard coat material.
  • infrared absorbers, pigments and dyes, surfactants, inorganic particles and the like may be included as necessary.
  • the film thickness of the hard coat layer is preferably from 0.1 to 50 ⁇ m, and more preferably from 1 to 20 ⁇ m.
  • a film thickness of 0.1 ⁇ m or more is preferable because hard coat properties can be improved.
  • the film thickness of 50 ⁇ m or less is preferable because the transparency of the infrared shielding film can be improved.
  • the hardness of the hard coat layer is preferably at least 2H because the moldability is easy.
  • the hard coat material is not particularly limited, and examples thereof include a cured resin.
  • the curable resin is not particularly limited, and examples thereof include a thermosetting resin and an active energy ray curable resin.
  • the “active energy ray” represents an active ray such as an ultraviolet ray or an electron beam, and preferably means an ultraviolet ray.
  • thermosetting resin is not particularly limited, and examples thereof include a cured resin obtained from a polysiloxane precursor represented by the following formula.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms.
  • Specific polysiloxane precursors are not particularly limited, but include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-popoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, Tetra-tert-butoxysilane, terapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxys
  • polysiloxane precursors include ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxy.
  • polysiloxane precursor commercially available products such as Surcoat Series (manufactured by Doken), SR2441 (Toray Dow Corning), and Perma-New 6000 (California Hardcoating Company) may be used.
  • Surcoat Series manufactured by Doken
  • SR2441 Toray Dow Corning
  • Perma-New 6000 California Hardcoating Company
  • the active energy ray curable resin is not particularly limited, but is an ultraviolet curable urethane (meth) acrylate resin, an ultraviolet curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, an ultraviolet curable polyol (meth) acrylate resin, or the like. Is mentioned. Among these, it is preferable to use an ultraviolet curable (meth) acrylate resin.
  • the active energy ray-curable resin can be usually obtained by curing a resin precursor with active energy rays.
  • the resin precursor of the ultraviolet curable urethane (meth) acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth). It can be easily obtained by reacting a (meth) acrylate monomer having a hydroxyl group such as acrylate or 2-hydroxypropyl (meth) acrylate.
  • a mixture of 100 parts Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) described in JP-A-59-151110 is preferably used.
  • the resin precursor of the UV curable polyester (meth) acrylate resin is obtained by reacting 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid or the like with the hydroxyl group or carboxy group of the polyester terminal. (E.g., JP-A-59-151112).
  • a resin precursor of an ultraviolet curable epoxy (meth) acrylate resin is obtained by reacting a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate with a hydroxyl group at the terminal of the epoxy resin.
  • a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate with a hydroxyl group at the terminal of the epoxy resin.
  • a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate
  • a hydroxyl group at the terminal of the epoxy resin.
  • Unidic V-5500 manufactured by DIC Corporation
  • the resin precursor of the UV curable polyol (meth) acrylate resin is not particularly limited, but ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate. .
  • the above resin precursors may be used alone or in combination of two or more.
  • the hard coat material can be usually obtained by curing the polysiloxane precursor, the resin precursor, and the like.
  • the resin precursor is cured through a crosslinking reaction or the like, and becomes an active energy ray curable resin as a hard coat material.
  • the curing method include heating and active energy ray irradiation, but active energy ray irradiation is preferable from the viewpoint of curing temperature, curing time, cost, and the like.
  • the infrared absorbing agent has a function of imparting a certain infrared absorbing ability to the hard coat layer.
  • a hard-coat layer contains an infrared absorber.
  • the infrared absorber is not particularly limited, and examples thereof include inorganic infrared absorbers and organic infrared absorbers.
  • Inorganic infrared absorbers include zinc oxide, aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), gallium-doped zinc oxide (GZO), tin oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide ( ITO), lanthanum boride, and nickel complex compounds.
  • the infrared absorber is preferably a zinc oxide-based infrared absorber from the viewpoints of visible light transmittance, infrared absorptivity, dispersibility in the resin, and the like, and is AZO, ATO, ITO, zinc antimonate. It is more preferable that
  • examples of the organic infrared absorber include imonium compounds, phthalocyanine compounds, aminium compounds, and the like.
  • the infrared absorber may be used as the infrared absorber. Although it does not restrict
  • the above-mentioned infrared absorbers may be used alone or in combination of two or more.
  • the content of the infrared absorber varies depending on the type of the infrared absorber to be used, but is preferably 25% by mass or more, and preferably 25 to 65% by mass with respect to the total mass of the hard coat layer. Preferably, it is 45 to 65% by mass. It is preferable for the content of the infrared absorber to be 25% by mass or more because the hard coat layer can suitably absorb infrared rays.
  • the pigment and the dye have a function of adjusting the color tone of the infrared shielding film.
  • the hard coat layer preferably contains at least one of a pigment and a dye.
  • Such commercial products include Ceres Blue RR-J Gran. (Bayer Chemicals AG) Savinyl Blue RS (CLARIANT) and the like.
  • pigments and dyes may be used singly or in combination of two or more, but control the value of a * and b * of L * a * b * of the infrared shielding film. From the viewpoint, it is preferable to adjust the color tone by mixing two or more pigments and / or dyes.
  • the content of at least one of the pigment and the dye varies depending on the pigment / dye to be used, but is preferably 0.002% by mass or more based on the total mass of the hard coat layer, and 0.002 to 0.02 More preferably, the mass is 0.002 to 0.01 mass%. It is preferable that the content of at least one of the pigment and the dye is 0.002% by mass or more because the hue of the hard coat layer can be changed.
  • the hard coat layer includes an infrared absorber
  • the pigment and the dye The content of at least one of the dyes varies depending on the pigment / dye used, but is preferably 0.001 to 0.01% by mass, and 0.001 to 0.005% by mass with respect to the mass of the infrared absorber. % Is more preferable.
  • the surfactant has a function of imparting leveling properties, water repellency, slipperiness, and the like.
  • the surfactant is not particularly limited, and examples thereof include acrylic surfactants, silicon surfactants, and fluorine surfactants. Among these, it is preferable to use a fluorochemical surfactant.
  • a commercially available product may be used as the surfactant.
  • the commercial products include F series (Megafax F-430, F-477, F-552 to F-559, F-561, F-562, etc., manufactured by DIC Corporation), RS-76-E (DIC stock) Company-made), Surflon series (manufactured by AGC Seimi Chemical Co., Ltd.), POLYFOX series (manufactured by OMNOVA SOLUTIONS), ZX series (manufactured by T & K TOKA), OPTOOL series (manufactured by Daikin) and the like.
  • Inorganic particles Although it does not restrict
  • the average particle diameter of the inorganic particles is preferably 1000 nm or less, more preferably 10 to 500 nm, from the viewpoint of ensuring visible light transmittance.
  • inorganic particles have a higher bonding force with the hard coat material, and can be prevented from falling off the hard coat layer. Therefore, a photosensitive group having photopolymerization reactivity such as monofunctional or polyfunctional acrylate is introduced on the surface. What is doing is preferable.
  • the refractive index of the substrate and the hard coat layer is preferably a close value from the viewpoint of uneven interference.
  • the refractive index of the hard coat layer is preferably 1.50 to 1.65.
  • the substrate has a function of supporting the dielectric multilayer film.
  • the substrate is preferably transparent, and various resin films can be used.
  • polyolefin film polyethylene, polypropylene, etc.
  • polyester film polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride polyvinyl chloride
  • cellulose triacetate polyimide
  • polybutyral film polybutyral film
  • cycloolefin polymer film transparent cellulose nanofiber film, etc.
  • polyester films from the viewpoint of transparency, mechanical strength and dimensional stability, dicarboxylic acid components such as terephthalic acid and 2,6-naphthalenedicarboxylic acid, and diols such as ethylene glycol and 1,4-cyclohexanedimethanol It is preferable that it is polyester which has the film formation property which makes a component a main structural component.
  • polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
  • the material and film thickness of the base material are preferably set so that the value obtained by dividing the thermal shrinkage rate of the infrared shielding film by the thermal shrinkage rate of the base material is in the range of 1 to 3.
  • the thickness of the substrate is preferably 30 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and most preferably 35 to 125 ⁇ m. It is preferable that the thickness of the substrate is 30 ⁇ m or more because wrinkles during handling are less likely to occur. On the other hand, when the thickness of the substrate is 200 ⁇ m or less, for example, when the substrate is bonded to the transparent substrate, the followability to the curved transparent substrate is improved and wrinkles are less likely to occur.
  • the substrate is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used.
  • a stretched film is preferable from the viewpoint of improving strength and suppressing thermal expansion. In particular, when used as a windshield of an automobile, a stretched film is more preferable.
  • the refractive index of the substrate is preferably a value close to the refractive index of the layer adjacent to the substrate.
  • the refractive index of the base material is 1.50 to 1.70 in relation to the refractive index of a general resin. Is preferred.
  • the intermediate layer has a function of improving the adhesion between adjacent layers.
  • the intermediate layer is usually disposed between the dielectric multilayer film and the hard coat layer.
  • the film thickness of the intermediate layer-hard coat layer laminate is preferably 10 ⁇ m or more, and more preferably 16 ⁇ m or more. It is preferable that the thickness of the laminate is 10 ⁇ m or more because rainbow unevenness due to optical interference can be prevented.
  • the material for the intermediate layer is not particularly limited, and examples thereof include resins such as polyvinyl acetal resin, acrylic resin, and urethane resin.
  • the polyvinyl acetal resin is a resin obtained by acetalizing polyvinyl alcohol with at least one aldehyde.
  • Specific examples of the polyvinyl acetal include copolymer acetals such as polyvinyl acetal, polyvinyl formal, polyvinyl butyral, polyvinyl butyral containing a partially formalized part, and polyvinyl butyral acetal.
  • the said polyvinyl acetal resin may have another repeating unit.
  • These polyvinyl acetal resins may use commercially available products.
  • Examples of the commercially available products include Denkabutyral # 2000L, # 3000-1, # 3000-K, # 4000-1, # 5000-A, # 6000-C, Denka Formal # 20, # 100, # 200 (Electric Manufactured by Chemical Industry Co., Ltd.), ESREC B Series BL-1, BL-2, BL-S, BM-1, BM-2, BH-1, BX-1, BX-10, BL-1, BL-SH, Examples include BX-L, ESREC K series KS-10, ESREC KW series KW-1, KW-3, KW-10, ESREC KX series KX-1, KX-5 (manufactured by Sekisui Chemical Co., Ltd.).
  • the degree of acetalization of the polyvinyl acetal resin is preferably 5 to 65 mol%, and more preferably 15 to 50 mol% from the viewpoints of solubility in water and adhesion.
  • the degree of acetalization is 5 mol% or more, the adhesion with the hard coat layer is preferable.
  • the degree of acetalization is 65 mol% or less, the adhesion with the dielectric multilayer film is preferable.
  • the acrylic resin is not particularly limited, and examples thereof include resins having a polymer constituent component such as methacrylic acid, acrylic acid, esters or salts thereof, acrylamide, methacrylamide and the like.
  • acrylic acid; methacrylic acid; alkyl acrylate (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl Acrylate, benzyl acrylate, phenylethyl acrylate, etc.), acrylic esters such as hydroxy-containing alkyl acrylates (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.); alkyl methacrylates (methyl methacrylate, ethyl methacrylate, n-propyl me
  • the above monomers may be used alone or in combination of two or more.
  • methyl methacrylate-ethyl acrylate-ammonium acrylate-acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N-methylol acrylamide copolymer, etc. are used. It is preferable.
  • the acrylic resin may contain isocyanate as a crosslinking agent.
  • isocyanate examples include cyclic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and 4,4-diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate. And organic diisocyanate compounds.
  • a blocked isocyanate for example, product number 214 manufactured by Baxenden can be used.
  • the urethane resin is a general term for polymers having a urethane bond in the main chain, and is usually obtained by reaction of polyisocyanate and polyol.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • NDI nophthylene diisocyanate
  • TODI toluidine diisocyanate
  • HDI hexamethylene dicyanate
  • IPDI isophorone diisocyanate
  • the polyol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, hexanetriol and the like.
  • the urethane resin may be a urethane resin obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight.
  • a commercially available polyurethane resin may be used.
  • the commercial product is not particularly limited, but Superflex 150HS, Superflex 470, etc. (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-20, Hydran WLS-210, Hydran HW-161, etc. (Dic Corporation) 8UA series (Taisei Fine Chemical).
  • polyvinyl acetal resin acrylic resin, and urethane resin may be used alone or in combination of two or more.
  • the glass transition temperature (Tg) of the resin is preferably ⁇ 30 to 60 ° C., more preferably ⁇ 20 to 40 ° C.
  • a glass transition temperature (Tg) of ⁇ 30 ° C. or higher is preferable because stability is improved.
  • the glass transition temperature (Tg) is 60 ° C. or less because good adhesion can be obtained.
  • the film thickness of the intermediate layer is preferably 4.0 ⁇ m or more, more preferably 6.0 ⁇ m or more, and further preferably 6.0 to 30 ⁇ m.
  • the total film thickness of the intermediate layer-dielectric multilayer film stack is preferably 10 ⁇ m or more.
  • the refractive index of the intermediate layer is preferably a value between the refractive index of the dielectric multilayer film and the refractive index of the hard coat layer from the relationship of the refractive index with the adjacent dielectric multilayer film and the hard coat layer.
  • the refractive index of the intermediate layer is 1.48 to 1.58. It is preferable that
  • an infrared absorbing layer As other functional layers, an infrared absorbing layer, a heat insulating layer, an adhesive layer, a transparent resin layer, and the like may be provided as long as the object and effects of the present invention are not impaired. Among these, when attaching an infrared shielding film to a building member, a window glass, etc., it is preferable to provide an adhesive layer.
  • the material of the adhesive layer is not particularly limited, but is a dry laminating agent, a wet laminating agent, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, an adhesive such as nitrile rubber, a heat seal agent, A hot melt agent etc. are mentioned.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m from the viewpoints of the pressure-sensitive adhesive effect and the drying speed.
  • the manufacturing method of an infrared shielding film includes the process of forming a dielectric multilayer film, and the process of forming a hard-coat layer. In addition, the process of forming an intermediate
  • the method of forming the dielectric multilayer film can be roughly classified into a dry film forming method and a wet film forming method according to the above-described refractive index layer forming method.
  • an infrared shielding film can be manufactured by sequentially forming a refractive index layer by vapor-depositing two or more dielectric materials on a substrate.
  • the vapor deposition method includes physical vapor deposition and chemical vapor deposition. Of these, it is preferable to use physical vapor deposition, and it is more preferable to use vacuum vapor deposition or sputtering.
  • the vacuum deposition method is a method in which a dielectric material is heated and evaporated by resistance heating or electron gun irradiation to form a thin film on a substrate.
  • Sputtering on the other hand, generates plasma between a substrate and a target using a plasma generator, bombards the dielectric material with ions using an electric potential gradient, and strikes the dielectric material on the substrate. It is the method of forming into a film. For these methods, known methods can be referred to as appropriate.
  • a refractive index layer is formed by applying a coating solution on a substrate and drying to form a refractive index layer sequentially, applying a coating solution in layers, drying, or a combination thereof. By doing so, an infrared shielding film can be manufactured.
  • the coating solution can usually contain a solvent in addition to the water-soluble resin and / or metal oxide particles and other additives.
  • the solvent may be water, an organic solvent, or a mixed solvent thereof.
  • the component that can be contained in the coating solution can be appropriately selected depending on whether the coating solution is a coating solution for a high refractive index layer or a coating solution for a low refractive index layer.
  • a water-soluble resin first water-soluble resin and second water-soluble resin
  • metal oxide particles first metal oxide particles and second metal oxide particles
  • organic solvent examples include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether, Examples thereof include ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in admixture of two or more.
  • the solvent of the coating solution is preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and more preferably water.
  • the concentration of the water-soluble resin in the coating solution is preferably 1 to 10% by mass.
  • the concentration of the metal oxide particles is preferably 1 to 50% by mass.
  • the method for preparing the coating solution is not particularly limited, and examples thereof include a method in which a water-soluble resin, metal oxide particles added as necessary, and other additives are added and stirred and mixed.
  • the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, it may be adjusted to an appropriate viscosity using a solvent.
  • a coating solution containing metal oxide particles in the form of core / shell particles for example, titanium oxide coated with silicon-containing hydrated oxide
  • the pH is 5.0 to 7.0.
  • the coating method of the coating liquid for example, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a slide curtain coating method, a slide hopper coating method and the like are preferably used.
  • the viscosity of the coating solution at 40 to 45 ° C. is preferably 5 to 300 mPa ⁇ s, and preferably 10 to 250 mPa ⁇ s. Is more preferable.
  • the viscosity of the coating solution at 40 to 45 ° C. is preferably 5 to 1200 mPa ⁇ s, more preferably 25 to 500 mPa ⁇ s. preferable.
  • the viscosity at 15 ° C. of the coating solution is preferably 10 mPa ⁇ s or more, more preferably 15 to 30000 mPa ⁇ s, further preferably 20 to 20000 mPa ⁇ s, and 20 to 18000 mPa ⁇ s. It is particularly preferred that
  • the coating film obtained by applying the coating solution varies depending on the components of the coating solution to be used, but the refractive index layer can be formed by preferably drying at 60 to 120 ° C., preferably 80 to 95 ° C.
  • the drying temperature is preferably 30 ° C. or higher.
  • drying is preferably performed at a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 30 to 100 ° C. (preferably 10 to 50 ° C.).
  • a drying method warm air drying, infrared drying, and microwave drying are used. Specific examples of the drying method include a method of blowing warm air of 40 to 60 ° C. for 1 to 5 seconds.
  • drying may be performed by a single process or a multistage process, drying is preferably performed by a multistage process. In this case, it is more preferable that the temperature of the constant rate drying unit is smaller than the temperature of the reduction rate drying unit.
  • the temperature range of the constant rate drying section is preferably 30 to 60 ° C.
  • the temperature range of the decreasing rate drying section is preferably 50 to 100 ° C.
  • a setting process means the process of cooling the coating film obtained by application
  • the temperature of the cold air in the setting process is preferably 1 to 15 ° C, more preferably 5 to 10 ° C.
  • the time for which the coating film is exposed to the cold air is preferably 10 to 360 seconds, more preferably 10 to 300 seconds, and further preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • the time until the setting step is completed is preferably within 5 minutes, and more preferably within 2 minutes.
  • the set time is within 5 minutes, interlayer diffusion of the refractive index layer components (metal oxide particles, etc.) is suppressed, and the value of the refractive index difference between the high refractive index layer and the low refractive index layer can increase.
  • the set time can be controlled by adjusting the concentration of the water-soluble resin and metal oxide particles in the coating solution and adding additives such as gelatin pectin, agar, carrageenan, gellan gum and the like.
  • the set time can be controlled by appropriately adjusting the type and concentration of the water-soluble resin and the metal oxide particles added as necessary.
  • the “completion of the setting process” means a state in which the coating film component does not adhere to the finger when the finger is pressed against the surface of the coating film.
  • the hard coat layer can usually be formed by a wet film forming method in which a hard coat layer coating solution is applied and dried, followed by heating and / or irradiation with active energy rays, a dry film forming method in which vapor deposition is performed, or the like. Among these, it is preferable to carry out by a hard coat layer wet film forming method.
  • the coating liquid for hard coat layers contains a hard coat material and a solvent. If necessary, an infrared absorber, a pigment and a dye, a surfactant, inorganic particles, and the like may be included.
  • the solvent is not particularly limited, and methyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, ethyl acetate and the like can be used.
  • the concentration of the hard coat material that can be contained in the coating liquid for the hard coat layer is preferably 10 to 50% by mass, and more preferably 10 to 20% by mass.
  • the coating is not particularly limited, but can be performed by continuous coating using a die coater, gravure coater, comma coater, or the like, in addition to coating by wire bar, spin coating, dip coating.
  • the drying method is not particularly limited, and examples thereof include heating and blowing of warm air.
  • the drying temperature is not particularly limited, but is preferably 30 to 150 ° C.
  • thermosetting resin in the coating liquid for hard coat layer When the thermosetting resin in the coating liquid for hard coat layer is heated, the thermosetting resin undergoes crosslinking or the like, and can become a hard coat agent.
  • active energy ray-curable resin in the hard coat layer coating solution can be used as a hard coat agent by irradiating an active energy ray (for example, an ultraviolet lamp) to cause crosslinking or the like of the active energy ray-curable resin. .
  • the coating liquid for hard coat layer contains a polysiloxane precursor
  • drying and heating may be performed simultaneously by adjusting the temperature in the drying step.
  • the intermediate layer can usually be formed by applying and drying an intermediate layer coating solution.
  • the intermediate layer coating solution contains an intermediate layer forming monomer and a solvent. Other additives may be included as necessary.
  • the solvent is not particularly limited as long as it does not interact with the monomer.
  • the coating and drying methods are not particularly limited, and the intermediate layer can be formed by appropriately taking into account known techniques.
  • the above-described infrared shielding film can be applied to a wide range of fields.
  • a film for window pasting such as a heat ray reflecting film that gives a heat ray reflecting effect, a film for an agricultural greenhouse, etc. As, it is mainly used for the purpose of improving the weather resistance.
  • the infrared shielding film according to the present invention is suitably used for a member to be bonded to a substrate such as glass or a glass substitute resin directly or via an adhesive.
  • a substrate such as glass or a glass substitute resin directly or via an adhesive.
  • pasting to windows exposed to sunlight such as outdoor windows of buildings and automobile windows, film for window pasting that gives infrared reflection effect to suppress excessive rise in indoor temperature, film for agricultural greenhouse, etc.
  • it is mainly used for the purpose of an agricultural film provided with an infrared shielding effect for suppressing an excessive increase in the temperature in the house.
  • the infrared shielding film of the present invention is sandwiched between glasses and used as an infrared shielding film for automobiles.
  • the infrared shielding film can be sealed from outside air gas. From the viewpoint of durability, it is preferable.
  • an infrared shielding body including a base and the above-described infrared shielding film disposed on at least one surface of the base.
  • the infrared shielding film described above a pair of intermediate films sandwiching the infrared shielding film, and a pair of plate glasses sandwiching the infrared shielding film and the intermediate film.
  • a heat ray reflective laminated glass is provided.
  • the infrared shielding body of the present invention means an embodiment in which the infrared shielding film of the present invention is provided on at least one surface of the substrate.
  • the infrared shielding film of the present invention is provided on a plurality of surfaces of the substrate.
  • a plurality of substrates may be provided on the substrate.
  • the laminated glass has a structure in which an infrared shielding film is sandwiched between two sheet glasses using two interlayer films.
  • the substrate include, for example, glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy
  • examples thereof include resins, melamine resins, phenol resins, diallyl phthalate resins, polyimide resins, urethane resins, polyvinyl acetate resins, polyvinyl alcohol resins, styrene resins, vinyl chloride resins, metal plates, ceramics, and cloths.
  • the type of the resin may be any of a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin, or two or more of these may be used in combination.
  • the substrate may be in various forms such as a film, plate, sphere, cube, and cuboid.
  • an infrared shielding body in which the infrared shielding film of the present invention is provided on a plate-like ceramic substrate or glass substrate is preferable.
  • the film thickness of the substrate is not particularly limited, but is preferably 0.1 mm to 5 cm.
  • the glass substrate are preferably, for example, float plate glass and polished plate glass described in JIS R 3202: 2011.
  • the glass thickness is preferably 0.01 mm to 20 mm.
  • an adhesive layer such as an adhesive (adhesive) is coated on the infrared shielding film, and the substrate is interposed via the adhesive layer.
  • adhesive layer such as an adhesive (adhesive) is coated on the infrared shielding film, and the substrate is interposed via the adhesive layer.
  • the method of affixing to is used suitably.
  • Examples of the adhesive applicable to the present invention include an adhesive mainly composed of a photocurable or thermosetting resin.
  • the adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive.
  • an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost.
  • solvent-based and emulsion-based acrylic adhesives are preferable, and solvent-based acrylic adhesives are more preferable because the peel strength can be easily controlled.
  • solvent-based acrylic adhesive are preferable, and solvent-based acrylic adhesives are more preferable because the peel strength can be easily controlled.
  • the adhesive layer for bonding the infrared shielding film of the present invention and the substrate is preferably installed so that the infrared shielding film is on the sunlight (heat ray) incident surface side. Further, it is preferable to sandwich the infrared shielding film of the present invention between a window glass and a substrate because it can be sealed from surrounding gas such as moisture and has excellent durability. Even if the infrared shielding film of the present invention is installed outdoors or on the outside of a vehicle (for external application), it is preferable because of environmental durability.
  • polyvinyl butyral resin or ethylene-vinyl acetate copolymer resin may be used as the adhesive.
  • specific examples thereof include plastic polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.), ethylene-vinyl acetate copolymer (manufactured by DuPont, Takeda Pharmaceutical Co., Ltd., duramin), modified ethylene-acetic acid Vinyl copolymer (manufactured by Tosoh Corporation, Mersen G).
  • laminated glass As for laminated glass, the same glass as described above can be used.
  • plate glass inorganic glass and organic glass, such as the above-mentioned glass base
  • substrate are mentioned.
  • the inorganic glass is not particularly limited, and examples thereof include various types of inorganic glass such as float plate glass, polished plate glass, mold plate glass, netted plate glass, wire-containing plate glass, heat ray absorbing plate glass, and colored plate glass.
  • examples of the organic glass include glass plates made of resins such as polycarbonates, polystyrenes, and polymethyl methacrylates. These organic glass plates may be a laminate formed by laminating a plurality of sheet-shaped ones made of the resin. Regarding the color, not only the transparent glass plate but also glass plates of various colors such as general-purpose green, brown and blue used for vehicles and the like can be used.
  • the same type of plate glass may be used, or two or more types may be used in combination.
  • the thickness of the plate glass is preferably about 1 to 10 mm in consideration of the strength and the transmittance of infrared light in the visible light region.
  • the curved plate glass preferably has a radius of curvature of 0.5 to 2.0 m. If the radius of curvature of the plate glass is within this range, the infrared shielding film can follow the curved shape of the glass.
  • any film can be used as long as it has a bonding performance for bonding the infrared shielding film and the glass.
  • interlayer film examples include a polyvinyl butyral resin that can also be used as an adhesive or an ethylene-vinyl acetate copolymer resin.
  • the intermediate film may be composed of a single layer of the resin film or may be used in a state where two or more layers are laminated.
  • the two intermediate films may be made of the same type of resin, or may be made of different types of resin.
  • the intermediate film preferably contains heat ray shielding fine particles having an average particle diameter of 0.2 ⁇ m or less having heat ray shielding absorption ability from the viewpoint of the heat ray shielding effect.
  • heat ray shielding fine particles having an average particle diameter of 0.2 ⁇ m or less having heat ray shielding absorption ability from the viewpoint of the heat ray shielding effect.
  • the functional fine particles include Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo metals, oxidation
  • ATO antimony-doped tin oxide
  • ITO indium tin oxide
  • the average particle size of the heat ray-shielding fine particles is 0.2 ⁇ m or less because the heat ray shielding effect can be secured while suppressing the reflection of visible light, and haze deterioration due to scattering does not occur and transparency can be secured. Is preferable, and it is more preferable that it is 0.15 micrometer or less.
  • the lower limit of the average particle diameter is not particularly limited, but is preferably 0.10 ⁇ m or more.
  • the average particle size is determined by observing particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope, measuring the particle size of 1,000 arbitrary particles, and calculating the simple average value (number average). As required.
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the content of the heat ray shielding fine particles is not particularly limited, but is preferably 0.5 to 10% by mass with respect to the total mass of the intermediate film from the viewpoint of the heat ray shielding effect, and preferably 0.5 to More preferably, it is 5 mass%.
  • the film thickness of the intermediate layer is usually about 0.1 to 2 mm.
  • a coating solution for a low refractive index layer was prepared. Specifically, 430 parts of colloidal silica (10% by mass) (Snowtex OXS; manufactured by Nissan Chemical Industries, Ltd.), 150 parts of boric acid aqueous solution (3% by mass), 85 parts of water, 300 parts of polyvinyl alcohol (4% by mass) (JP-45; degree of polymerization: 4500; degree of saponification: 88 mol%; manufactured by Nihon Acetate Bipoval Co., Ltd.), 3 parts of surfactant (5% by mass) (softazoline LSB-R; river Were added in this order at 45 ° C. And it finished to 1000 parts with pure water, and prepared the coating liquid for low refractive index layers.
  • a coating solution for a high refractive index layer was prepared. Specifically, a dispersion of silica-modified titanium oxide particles was prepared in advance, and a solvent or the like was added thereto.
  • a dispersion of silica-modified titanium oxide particles was prepared as follows.
  • An aqueous titanium sulfate solution was thermally hydrolyzed by a known method to obtain titanium oxide hydrate.
  • the obtained titanium oxide hydrate was suspended in water to obtain 10 L of an aqueous suspension (TiO 2 concentration: 100 g / L).
  • To this was added 30 L of an aqueous sodium hydroxide solution (concentration: 10 mol / L) with stirring, the temperature was raised to 90 ° C., and the mixture was aged for 5 hours.
  • the obtained solution was neutralized with hydrochloric acid, filtered and washed with water to obtain a base-treated titanium compound.
  • the base-treated titanium compound was suspended in pure water and stirred so that the TiO 2 concentration was 20 g / L. Under stirring, it was added citric acid in an amount of 0.4 mol% with respect to TiO 2 weight. The temperature was raised to 95 ° C., concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the liquid temperature was maintained, followed by stirring for 3 hours.
  • the pH and zeta potential of the obtained mixed solution were measured, the pH was 1.4 and the zeta potential was +40 mV.
  • the particle size was measured with Zetasizer Nano (manufactured by Malvern), the volume average particle size was 35 nm and the monodispersity was 16%.
  • a solvent or the like was added to the silica-modified titanium oxide particle sol aqueous dispersion prepared in this way to prepare a coating solution for a high refractive index layer.
  • a polyethylene terephthalate film (A4300, double-sided easy-adhesion layer, thickness: 50 ⁇ m, length: 200 m ⁇ width 210 mm, refractive index: 1.58, manufactured by Toyobo Co., Ltd.) was prepared as a substrate.
  • a 9-layer multilayer coating was performed on the back surface of the 9-layer multilayer coated product (a substrate surface (back surface) opposite to the 9-layer multilayer coated substrate surface).
  • the formed high refractive index layer had a refractive index of 1.95, and the low refractive index layer had a refractive index of 1.45.
  • the intermediate layer coating solution is applied and dried using a wire bar so that the dry film thickness is 6.0 ⁇ m. Formed.
  • the refractive index of the intermediate layer was 1.49.
  • [Hard coat layer] (Coating solution 1 for hard coat layer) Cellulax CX-Z410K (infrared doped zinc oxide (AZO) methyl isobutyl ketone dispersion sol, manufactured by Nissan Chemical Industries, Ltd.), pentaerythritol triacrylate (manufactured by Daicel-Cytech), and methyl ethyl ketone as a solvent.
  • AZO infrared doped zinc oxide
  • a fluorosurfactant Megafax F-552, manufactured by DIC Corporation
  • the hard coat layer coating solution 1 is applied using a wire bar so that the dry film thickness is 6.0 ⁇ m, and dried at a drying section temperature of 90 ° C. By doing so, a coating film was formed.
  • the coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer.
  • the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm 2 and the irradiation amount was 0.5 J / cm 2 .
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was obtained.
  • the refractive index of the hard coat layer was 1.59.
  • the transmittance of the visible light region was measured using a spectrophotometer U-4100 (manufactured by Shimadzu Corporation). * a * b * were measured value and b * values of a * in the color system, the value of a * of -4.1, b * values was 3.3.
  • Example 2 In the same manner as in Example 1, a second film comprising a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer was obtained.
  • the hard coat layer coating solution 2 is applied using a wire bar so that the dry film thickness is 4.0 ⁇ m, and dried at a drying section temperature of 90 ° C. By doing so, a coating film was formed.
  • the coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer.
  • the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm 2 and the irradiation amount was 0.5 J / cm 2 .
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was obtained.
  • the refractive index of the hard coat layer was 1.59.
  • Example 3 Except that 0.001% by mass of Savinyl Blue RS (manufactured by CLARIANT) with respect to the mass of AZO was added to the coating solution 1 for hard coat layer of Example 1, except that the coating solution for hard coat layer was used.
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 4 Except that 0.008% by mass of Savinyl Blue RS (manufactured by CLARIANT) with respect to the mass of AZO was added to the coating solution 1 for hard coat layer of Example 1, except that the coating solution for hard coat layer was used.
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 5 Except for using the hard coat layer coating solution obtained by adding 0.01% by weight of Savinyl Blue RS (manufactured by CLARIANT) to the hard coat layer coating solution 1 of Example 1 in the same manner as in Example 1, an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • Savinyl Blue RS manufactured by CLARIANT
  • the refractive index of the hard coat layer was 1.59.
  • Example 6 In the coating liquid 1 for hard coat layer of Example 1, 0.002% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 7 In the hard coat layer coating solution 1 of Example 1, 0.005% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 8> In the hard coat layer coating solution 1 of Example 1, 0.007% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 9 In the same manner as in Example 1, a second film comprising a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer was obtained.
  • [Hard coat layer] (Coating liquid 3 for hard coat layer) Infrared absorbent (gallium-doped zinc oxide (GZO) methyl ethyl ketone dispersion sol, manufactured by Hakusui Tech Co., Ltd.), pentaerythritol triacrylate (Daicel Cytec Co., Ltd.) and solvent methyl ethyl ketone are mixed, and then a fluorosurfactant (mega 0.1 wt% of Fax F-552 (manufactured by DIC Corporation) was added to prepare a coating liquid 3 for hard coat layer. Under the present circumstances, it adjusted so that the total solid content of the coating liquid 3 for hard-coat layers might be 37 mass%. Moreover, it adjusted so that the density
  • GZO gallium-doped zinc oxide
  • the hard coat layer coating solution 3 is applied using a wire bar so that the dry film thickness is 7 ⁇ m, and dried at a drying section temperature of 90 ° C. A coating film was formed.
  • the coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer.
  • the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm 2 and the irradiation amount was 0.5 J / cm 2 .
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was obtained.
  • the refractive index of the hard coat layer was 1.58.
  • Example 10 [Dielectric multilayer film] Based on the description in paragraphs “0046” to “0049” of JP-T-2008-528313, coPEN / PETG is alternately laminated on the base material used in Example 1 by resin extrusion (coextrusion method). A dielectric multilayer film was formed. At this time, the total number of refractive index layers including the coPEN layer and the PETG layer is 50 layers.
  • the film thickness of the formed low refractive index layer was 170 nm for each layer
  • the film thickness of the high refractive index layer was 170 nm for each layer.
  • the refractive index of the high refractive index layer was 1.64
  • the refractive index of the low refractive index layer was 1.57.
  • the refractive index of the intermediate layer was 1.49.
  • a hard coat layer is formed on the intermediate layer of the fourth film produced as described above in the same manner as in Example 1, and consists of a base material-dielectric multilayer film (50 layers laminated) -intermediate layer-hard coat layer. An infrared shielding film was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 11 In the same manner as in Example 10, a fourth film composed of a base material-dielectric multilayer film (laminated 50 layers) -intermediate layer was obtained.
  • [Hard coat layer] (Coating solution 4 for hard coat layer) Infrared absorber (antimony-doped tin oxide (ATO) methyl isobutyl ketone dispersion sol, manufactured by ANP), pentaerythritol triacrylate (manufactured by Daicel Cytec), and methyl ethyl ketone as a solvent are mixed, and then a fluorosurfactant 0.1% by mass (Megafax F-552, manufactured by DIC Corporation) was added. And the coating liquid 4 for hard-coat layers was prepared by adding 0.004 mass% Savinyl Blue RS (made by CLARIANT) with respect to the mass of AZO. Under the present circumstances, it adjusted so that the total solid content of the coating liquid 4 for hard-coat layers might be 30 mass%. Moreover, it adjusted so that the density
  • ATO antimony-doped tin oxide
  • a hard coat layer was formed on the intermediate layer of the fourth film by the same method as in Example 2 using the coating liquid 4 for hard coat layer.
  • an infrared shielding film composed of a base material-dielectric multilayer film (50 layers laminated) -intermediate layer-hard coat layer was obtained.
  • the refractive index of the hard coat layer was 1.59.
  • Example 1 A base material-dielectric multilayer film (50 layers) was prepared in the same manner as in Example 11 except that Savinyl Blue RS (manufactured by CLARIANT) was not added to the coating liquid 4 for hard coat layer of Example 11. An infrared shielding film comprising a laminate) -intermediate layer-hard coat layer was produced.
  • Savinyl Blue RS manufactured by CLARIANT
  • the refractive index of the hard coat layer was 1.59.
  • the refractive index of the hard coat layer was 1.59.
  • a hard coat layer is formed on the base material used in Example 1 by using the hard coat layer coating solution 5 in the same manner as in Example 9 to produce an infrared shielding film composed of the base material and the hard coat layer. did.
  • the refractive index of the hard coat layer was 1.58.
  • Example 4 Similar to Example 1 except that the hard coat layer coating solution 1 of Example 1 with 0.004% by mass of cadmium red added to the mass of AZO was used. In this way, an infrared shielding film comprising a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 5 Similar to Example 1 except that the hard coat layer coating solution 1 of Example 1 was added with 0.001% by mass of cadmium red based on the mass of AZO. In this way, an infrared shielding film comprising a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 1 is the same as Example 1 except that the hard coat layer coating solution 1 is obtained by adding 0.01% by weight of a phthalocyanine pigment to the AZO weight to the hard coat layer coating solution 1 of Example 1.
  • an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • Example 7 Except for using hard coat layer coating solution in which 0.01% by mass of cobalt green was added to the AZO mass to hard coat layer coating solution 1 of Example 1, the same as Example 1 was used. In this way, an infrared shielding film comprising a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.
  • the refractive index of the hard coat layer was 1.59.
  • the transmittance and reflectance were measured by irradiating light having a wavelength of 250 nm to 2500 nm from the opposite direction to the surface of the infrared shielding film on which the hard coat layer was formed.
  • the solar radiation acquisition rate (Tts) was calculated
  • a spectrophotometer U-4100 manufactured by Shimadzu Corporation was used for measurement of transmittance and reflectance.
  • Tts The value of solar radiation acquisition rate (Tts) is less than 55%
  • O The value of solar radiation acquisition rate (Tts) is 55% or more and less than 57%
  • ⁇ The value of solar radiation acquisition rate (Tts) is 57% or more
  • 59 The value of solar radiation acquisition rate (Tts) is 59% or more.
  • a three-wavelength fluorescent lamp (white light, FHF32EXNH-10P Mellow Line 32W, manufactured by Toshiba Corporation) is turned on from the surface on which the hard coat layer is formed in an environment of 25 ° C. and 55% RH. Irradiated. At this time, the color tone of the infrared shielding film was visually observed while sequentially changing the observation angle of the infrared shielding film, and the color tone change was evaluated according to the following criteria.
  • the infrared shielding films according to the examples have excellent heat shielding performance.
  • the infrared shielding films according to the examples show good results in the color tone change depending on the observation angle, and since the reflection intensity ratio is close to 1, regular reflectances of 5 degrees and 60 degrees with respect to the normal of the film surface There was no difference. That is, it turns out that the infrared shielding film which concerns on an Example has low angle dependence of a color tone.
  • the infrared shielding film according to the comparative example has not realized both the heat shielding performance and the reduction of the angle dependency of the color tone.
  • the angle dependency of the color tone is low, but it is understood that the heat shielding performance is insufficient.
  • Comparative Examples 4 to 7 it can be seen that although the thermal insulation performance is obtained by the dielectric multilayer film, the angle dependency of the color tone is high.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

Le problème posé par l'invention est de fournir un film de protection infrarouge qui présente des performances de protection thermique supérieures et dans lequel la dépendance angulaire couleur-tonalité est réduite. La solution selon l'invention porte sur un film de protection infrarouge contenant une couche de revêtement dur et un film multicouche diélectrique, qui contient une couche à fort indice de réfraction et une couche à faible indice de réfraction et présentant des coordonnées de couleur L*a*b telles que a* est a*≦-3,5 et b* est -12≦b*≦5.
PCT/JP2014/064782 2013-06-14 2014-06-03 Film de protection infrarouge, corps de protection infrarouge l'utilisant et verre stratifié réfléchissant les rayons thermiques WO2014199872A1 (fr)

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WO2017094453A1 (fr) * 2015-11-30 2017-06-08 コニカミノルタ株式会社 Verre feuilleté
WO2017154276A1 (fr) * 2016-03-08 2017-09-14 住友理工株式会社 Stratifié transmettant la lumière et procédé pour produire un stratifié transmettant la lumière
WO2017217230A1 (fr) * 2016-06-15 2017-12-21 日本化薬株式会社 Feuille de protection contre les infrarouges, film intermédiaire pour verre feuilleté de protection contre les infrarouges, et verre feuilleté de protection contre les infrarouges et procédé pour leur fabrication
JP2018054760A (ja) * 2016-09-27 2018-04-05 株式会社日本触媒 光選択吸収樹脂積層体
CN108367540A (zh) * 2016-03-08 2018-08-03 住友理工株式会社 光透过性层叠体及光透过性层叠体的制造方法
JP2019155621A (ja) * 2018-03-08 2019-09-19 東レ株式会社 積層体
JP2020132454A (ja) * 2019-02-15 2020-08-31 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス
JP2020132453A (ja) * 2019-02-15 2020-08-31 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス
JP2020530134A (ja) * 2017-08-07 2020-10-15 エヴェリックス インコーポレイテッド 超薄型薄膜光干渉フィルタ

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WO2017094453A1 (fr) * 2015-11-30 2017-06-08 コニカミノルタ株式会社 Verre feuilleté
WO2017154276A1 (fr) * 2016-03-08 2017-09-14 住友理工株式会社 Stratifié transmettant la lumière et procédé pour produire un stratifié transmettant la lumière
CN108367540A (zh) * 2016-03-08 2018-08-03 住友理工株式会社 光透过性层叠体及光透过性层叠体的制造方法
EP3427942A4 (fr) * 2016-03-08 2019-03-27 Sumitomo Riko Company Limited Stratifié transmettant la lumière et procédé pour produire un stratifié transmettant la lumière
EP3474048A4 (fr) * 2016-06-15 2020-01-22 Nippon Kayaku Kabushiki Kaisha Feuille de protection contre les infrarouges, film intermédiaire pour verre feuilleté de protection contre les infrarouges, et verre feuilleté de protection contre les infrarouges et procédé pour leur fabrication
WO2017217230A1 (fr) * 2016-06-15 2017-12-21 日本化薬株式会社 Feuille de protection contre les infrarouges, film intermédiaire pour verre feuilleté de protection contre les infrarouges, et verre feuilleté de protection contre les infrarouges et procédé pour leur fabrication
JP2017223827A (ja) * 2016-06-15 2017-12-21 日本化薬株式会社 赤外線遮蔽シート、赤外線遮蔽合わせガラス用中間膜並びに赤外線遮蔽合わせガラス及びその製造方法
CN109313297A (zh) * 2016-06-15 2019-02-05 日本化药株式会社 红外线屏蔽片、红外线屏蔽夹层玻璃用中间膜以及红外线屏蔽夹层玻璃及其制造方法
JP2018054760A (ja) * 2016-09-27 2018-04-05 株式会社日本触媒 光選択吸収樹脂積層体
JP2020530134A (ja) * 2017-08-07 2020-10-15 エヴェリックス インコーポレイテッド 超薄型薄膜光干渉フィルタ
US11906765B2 (en) 2017-08-07 2024-02-20 Everix, Inc. Ultra-thin thin-film optical interference filters
JP2019155621A (ja) * 2018-03-08 2019-09-19 東レ株式会社 積層体
JP7087470B2 (ja) 2018-03-08 2022-06-21 東レ株式会社 積層体
JP2020132454A (ja) * 2019-02-15 2020-08-31 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス
JP2020132453A (ja) * 2019-02-15 2020-08-31 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス
JP7188859B2 (ja) 2019-02-15 2022-12-13 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス

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