Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
• • 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
  • B32B1/00—Layered products having a non-planar shape
• • 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
  • B32B17/10009—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 number, the constitution or treatment of glass sheets
  • B32B17/10036—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 number, the constitution or treatment of glass sheets comprising two outer glass sheets
• • 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
  • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
  • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
  • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
• • 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
  • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
  • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
  • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic 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
  • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
  • C03C27/06—Joining glass to glass by processes other than fusing
  • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/29—Laminated material
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/01—Head-up displays
  • G02B27/0101—Head-up displays characterised by optical features
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • 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
  • B32B2307/412—Transparent
• • 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
  • B32B2307/416—Reflective
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/536—Hardness
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/554—Wear resistance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/01—Head-up displays
  • G02B27/0101—Head-up displays characterised by optical features
  • G02B2027/0118—Head-up displays characterised by optical features comprising devices for improving the contrast of the display / brillance control visibility
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/01—Head-up displays
  • G02B2027/0192—Supplementary details
  • G02B2027/0194—Supplementary details with combiner of laminated type, for optical or mechanical aspects
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/26—Reflecting filters

Definitions

• the present invention relates to a reflective film, a laminate, a windshield glass, and an image display system.
• the reflective film By incorporating a reflective film into laminated glass used for automobile windshields, etc., the reflective film (laminated glass) can be used as a projection display member of a head-up display system.
• Patent Document 1 discloses the use of a reflective film including a retardation layer and a plurality of cholesteric liquid crystal layers as a projection display member of a head-up display system mounted on an automobile.
• laminated glass for automobiles has an interlayer between two glass plates.
• Patent Document 1 describes that a reflective film is provided as an intermediate film in a windshield glass having a laminated glass structure.
• An object of the present invention is to provide a reflective film that exhibits excellent curved surface followability when laminated to an object, exhibits excellent abrasion resistance after lamination, and also has excellent reflective properties.
• Another object of the present invention is to provide a windshield glass, a laminate, and an image display system.
• the present invention provides the following.
• a reflective film comprising, in this order, an adhesive layer, a reflective layer that selectively reflects light, and a hard coat layer.
• the hard coat layer is a layer formed using a curable composition for forming a hard coat layer containing a cationic polymerizable compound, The reflective film according to any one of (1) to (3), wherein the content of the cationic polymerizable compound is 5% by mass or more based on the total solid content of the curable composition for forming a hard coat layer.
• the hard coat layer is a layer formed using a curable composition for forming a hard coat layer containing inorganic particles
• the reflective film according to (5), wherein the inorganic particles have an average primary particle size of 40 nm or more.
• the reflective film according to (5) or (6), wherein the inorganic particles have an average primary particle size of 40 nm or more and less than 200 nm.
• the surface roughness Sa1 of the component having a wavelength of 2.5 ⁇ m or less on the surface of the hard coat layer opposite to the reflective layer side is 0.30 nm or more, according to any one of (1) to (7).
• reflective film The reflective film according to any one of (1) to (8), wherein the surface roughness Sa2 of the component having a wavelength of 10 ⁇ m or more on the surface of the hard coat layer opposite to the reflective layer side is 2.0 nm or less. .
• (20) comprising, in this order, a hard coat layer, a reflective layer that selectively reflects light, and a heat seal layer laminated on one side of the reflective layer; a reflective layer is formed using a composition containing a polymerizable liquid crystal compound, A reflective film in which the heat-sealing layer includes a thermoplastic resin or an elastomer.
• the heat seal layer is a layer formed using a composition containing a polymerization initiator.
• the reflective film according to (21), wherein the composition further contains a polymerizable compound.
• the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group
• a polarization conversion layer is formed using a composition containing a polymerizable liquid crystal compound,
• a reflective film in which the heat-sealing layer includes a thermoplastic resin or an elastomer.
• the reflective film according to (24), wherein the heat seal layer is a layer formed using a composition containing a polymerization initiator.
• the reflective film according to (25), wherein the composition further contains a polymerizable compound.
• the reflective film according to any one of (22), (23), and (26), wherein the content of the polymerizable compound is 5 to 80% by mass based on the solid content of the composition.
• the reflective film according to any one of (22), (23), and (26), wherein the polymerizable compound has an I/O ratio of 0.4 or more.
• the reflective film according to any one of (20) to (28), wherein the heat seal layer has a water content of 2.0% or less at 25° C. and 60% RH.
• a windshield glass comprising a glass plate and the reflective film according to any one of (20) to (28) bonded together via a heat-sealing layer.
• An image display system comprising the windshield glass according to (30) and a projector that irradiates projected image light onto the reflective film side of the windshield glass.
• a reflective film that exhibits excellent curved surface followability when laminated to an object, exhibits excellent abrasion resistance after lamination, and also has excellent reflective properties.
• a windshield glass, a laminate, and an image display system can be provided.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a windshield glass having a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention.
• FIG. 1 is a schematic diagram showing an example of a windshield glass having a reflective film of the present invention.
• a reflective film, a windshield glass, a laminate, and an image having an adhesive layer, a reflective layer, and a hard coat layer (HC layer) of the present invention in this order will be described.
• the display system will be explained in detail. Note that the figures described below are illustrative for explaining the present invention, and the present invention is not limited to the figures shown below.
• " ⁇ " indicating a numerical range includes the numerical values written on both sides.
• the range of ⁇ 1 is the range including the numerical value ⁇ 1 and the numerical value ⁇ 1 , and expressed in mathematical symbols as ⁇ 1 ⁇ 1 ⁇ 1 .
• angles such as “angle expressed in specific numerical values”, “parallel”, “perpendicular”, and “perpendicular” include error ranges generally accepted in the relevant technical field. More specifically, in this specification, parallel, perpendicular, and perpendicular mean a range of parallel ⁇ 5°, a range of perpendicular ⁇ 5°, and a range of perpendicular ⁇ 5°, respectively. Further, “same” includes the generally acceptable error range in the relevant technical field, and “overall” etc. also includes the generally acceptable error range in the relevant technical field.
• “Selective” with respect to circularly polarized light means that the amount of either the right-handed circularly polarized light component or the left-handed circularly polarized light component is greater than the amount of the other circularly polarized light component.
• the degree of circular polarization of light is preferably 0.3 or more, more preferably 0.6 or more, and even more preferably 0.8 or more. More preferably, it is substantially 1.0.
• the degree of circular polarization is expressed as
• sense regarding circularly polarized light, we mean whether it is right-handed circularly polarized light or left-handed circularly polarized light.
• the sense of circularly polarized light is that when you look at the light as if it is traveling towards you, if the tip of the electric field vector rotates clockwise as time increases, it is right-handed circularly polarized light, and if it rotates counterclockwise, it is left-handed circularly polarized light. Defined as circularly polarized light.
• sense is sometimes used to refer to the twist direction of the helix of cholesteric liquid crystal.
• the helical twist direction (sense) of the cholesteric liquid crystal is right, it reflects right-handed circularly polarized light and transmits left-handed circularly polarized light, and when the sense is left, it reflects left-handed circularly polarized light and transmits right-handed circularly polarized light.
• Visible light is electromagnetic waves with wavelengths that can be seen by the human eye, and usually indicates light in the wavelength range of 380 to 780 nm.
• Invisible light is light in a wavelength range of less than 380 nm or in a wavelength range of more than 780 nm.
• B blue
• G green
• R red
• the “visible light transmittance” is the A light source visible light transmittance defined in JIS (Japanese Industrial Standards) R 3212:2015 (Automotive safety glass test method). That is, the transmittance of each wavelength in the wavelength range of 380 to 780 nm is measured using a spectrophotometer using A light source, and the transmittance is obtained from the wavelength distribution and wavelength interval of the CIE (Commission Internationale de l'Eclairage) photopic standard luminous efficiency. This is the transmittance obtained by multiplying the transmittance at each wavelength by the weighted coefficient obtained by weighting and averaging the results.
• reflected light or “transmitted light” it is used in a meaning that includes scattered light and diffracted light.
• the polarization state of each wavelength of light can be measured using a spectroradiometer or spectrometer equipped with a circularly polarizing plate.
• the intensity of light measured through the right-handed circularly polarizing plate corresponds to I R and the intensity of light measured through the left-handed circularly polarizing plate corresponds to IL .
• measurement can also be performed by attaching a circularly polarizing plate to an illuminance meter or optical spectrometer. The ratio can be measured by attaching a right-handed circularly polarized light transmitting plate and measuring the amount of right-handed circularly polarized light, and by attaching a left-handed circularly polarized light transmitting plate and measuring the amount of left-handed circularly polarized light.
• P-polarized light means polarized light that vibrates in a direction parallel to the plane of incidence of light.
• the incident surface refers to a surface that is perpendicular to a reflective surface (such as a windshield glass surface) and that includes incident light and reflected light.
• a reflective surface such as a windshield glass surface
• the plane of vibration of the electric field vector is parallel to the plane of incidence.
• the front phase difference is a value measured using AxoScan manufactured by Axometrics. Unless otherwise specified, the measurement wavelength is 550 nm.
• a value measured using KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments Co., Ltd.) by making light with a wavelength within the visible wavelength range incident in the normal direction of the film can also be used.
• the wavelength selection filter can be replaced manually, or the measurement value can be converted using a program or the like.
• Projection image means an image based on the projection of light from the projector used, rather than the surrounding scenery such as the front.
• the projected image is observed by the viewer as a virtual image that appears above the projected image display area of the windshield glass.
• “Screen image” means an image displayed on a rendering device of a projector or an image rendered by a rendering device on an intermediate image screen or the like.
• An image is a real image, as opposed to a virtual image. Both the image and the projected image may be a monochrome image, a multicolor image of two or more colors, or a full color image.
• the reflective film of the present invention is characterized by having an adhesive layer, a reflective layer that selectively reflects light (hereinafter also simply referred to as a "reflective layer”), and a hard coat layer in this order.
• Another configuration of the reflective film of the present invention is that it has a hard coat layer, a reflective layer that selectively reflects light in wavelength, and a heat seal layer laminated on one side of the reflective layer in this order. do.
• a hard coat layer a reflective layer that selectively reflects light
• a polarization conversion layer a polarization conversion layer
• a heat seal layer laminated on one side of the polarization conversion layer are combined. It is characterized by having the following in order:
• FIG. 1 shows an example of the reflective film of the present invention.
• the reflective film 10A shown in FIG. 1 includes an adhesive layer 1, a reflective layer 2, and a hard coat layer (hereinafter also referred to as HC layer) 3 in this order.
• HC layer hard coat layer
• FIG. 6 shows another example of the reflective film of the present invention.
• the reflective film 10E shown in FIG. 6 includes a heat seal layer 12, a reflective layer 2, and an HC layer 3 in this order.
• FIG. 7 shows another example of the reflective film of the present invention.
• the reflective film 10F shown in FIG. 7 includes a heat seal layer 12, a polarization conversion layer 5, a reflective layer 2, and an HC layer 3 in this order.
• the reflective film 10F may have a retardation layer and a transparent base material, as described below.
• the polarization conversion layer 5 is placed on the side of the vehicle-inside glass plate 11.
• the windshield glass shown in FIG. 8 has a car interior glass plate 11, a heat seal layer 12, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent base material 7, and an HC layer 3 in this order.
• the reflective film of the present invention has an adhesive layer for adhering the film to the outside of the laminated glass. Having the adhesive layer allows the reflective film to be attached to the windshield.
• the material of the adhesive layer can be any material as long as it has transparency to ensure the visibility of display contents when the reflective film of the present invention is applied to the windshield, and can bond the reflective film and the windshield. is not particularly limited, and may be made of resin or elastomer (including oil-extended rubber).
• the above resins include 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA", usually containing 3% by mass or more of vinyl acetate structural units), polyolefin resin such as polyethylene, Vinyl chloride resin, polystyrene resin, vinyl ester resin (excluding EVA), saturated polyester resin, polyamide resin, fluororesin (polyvinylidene fluoride, etc.), polycarbonate resin, polyacetal resin, urethane resin, epoxy resin, (meth)acrylate resin ( (Also referred to as (meth)acrylic resin, meaning (meth)acrylic acid ester resin, etc.), unsaturated polyester resins, silicone resins, and modified resins of these resins.
• urethane resins include urethane-modified polyester resins and urethane resins.
• Elastomers include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, and blocks of conjugated dienes. Hydrogenated products of (co)polymers, hydrogenated products of block copolymers of aromatic vinyl compounds and conjugated dienes, ethylene- ⁇ -olefin copolymers, polar group-modified olefin copolymers, polar group-modified Elastomers made of olefin copolymers and metal ions and/or metal compounds, nitrile rubbers (e.g.
• thermoplastic polyolefin elastomers TPO
• thermoplastic polyurethanes TPU
• thermoplastic polyester elastomers TPEE
• thermoplastic polyamide elastomers TPAE
• diene elastomers 1,2-polybutadiene, etc.
• silicone elastomers fluorine-based elastomers.
• the weight average molecular weight of the resin or elastomer is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, from the viewpoint of the balance between solubility in a solvent and storage modulus.
• the adhesive layer contains these resins or elastomers
• these resins or elastomers alone can be used as the constituent material of the adhesive layer, but softeners, plasticizers, lubricants, crosslinking agents, crosslinking aids, and photosensitizers may also be used.
• the adhesive layer may further contain a coupling agent, an additive such as a titanium coupling agent, a polymerizable group-containing compound, or another polymer as a constituent material. That is, the adhesive layer may be constructed using a resin composition or a composition containing an elastomer.
• SK Dyne 2057 SK Dyne 2094, SK Dyne 2147, SK Dyne 1811L, SK Dyne 1478, SK Dyne 1442, SK Dyne 1435, SK Dyne 1415 (Soken Co., Ltd.
• NCF-N632, NCF-D692, NCF-F619 MO-T015, MO-5115XV (manufactured by Lintec Co., Ltd.), TD06, MK64, TI14, ME57, TX48, MJ63, MG70, MF58 (manufactured by Tomegawa Paper Mills Co., Ltd.), Panaclean PD-S1, Panaclean PD-R5 (manufactured by Panac Co., Ltd.), MHM-FWD, MHM-FWV, MHM-UVC, MHM-SI (manufactured by Nichiei Shinka Co., Ltd.), Olivine EG-655, and Olivine BPS5896 (manufactured by Toyo Ink Co., Ltd.) (trade names).
• the thickness of the adhesive layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 1 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m. If the adhesive layer is within the above range, the scratch resistance will be better, the adhesion between the windshield and the reflective film will be improved, and the curved surface followability will be better.
• the storage modulus E' of the adhesive layer at 25° C. and frequency of 1 Hz is preferably greater than 1 kPa, and from the viewpoint of adhesion to the windshield, it is preferably 4 GPa or less.
• the storage elastic modulus E' is more preferably greater than 1 KPa and less than or equal to 1 GPa, and even more preferably greater than 1 KPa and less than or equal to 100 MPa.
• the maximum value of the loss tangent (tan ⁇ ) of the adhesive layer at a frequency of 1 Hz is preferably in the temperature range of -80 to 40°C, more preferably in the range of -60 to 40°C.
• the storage modulus of the adhesive layer at 25° C. and a frequency of 1 Hz and the tan ⁇ at a frequency of 1 Hz are determined as follows.
• test piece was conditioned in advance at a temperature of 25°C and an atmosphere of 60% relative humidity for 2 hours or more.
• a master curve of tan ⁇ , storage modulus, and loss modulus with respect to frequency at 25° C. is obtained by editing the “master curve”.
• the maximum value of tan ⁇ and the frequency showing the maximum value are determined from the obtained master curve.
• the method of forming the adhesive layer is not particularly limited, and examples thereof include coating method, casting method (solventless casting method and solvent casting method), pressing method, extrusion method, injection molding method, casting method, and inflation method. It will be done. Specifically, a liquid material in which the constituent material of the adhesive layer is dissolved or dispersed in a solvent, or a melt of the components constituting the constituent material of the adhesive layer is prepared, and then this liquid material or melt is applied. Then, by removing the solvent as necessary, a reflective film including an adhesive layer can be produced.
• the constituent material of the adhesive layer is applied in the same manner as above on the release-treated surface of the release sheet that has been subjected to release treatment, and dried to form a sheet having an adhesive layer, and the adhesive layer of this sheet is used as a reflective layer. By pasting them together, an adhesive layer can be created on the reflective layer.
• a reflective layer is arrange
• the heat seal layer is a layer for physically bonding the reflective film and the glass substrate.
• the heat seal layer includes a thermoplastic resin or an elastomer.
• the thermoplastic resin is preferably one that has good affinity and adhesion with the glass substrate, such as 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA", usually 3% by mass or more of vinyl acetate).
• polyolefin resins such as polyethylene, polyvinyl chloride resins, polystyrene resins, vinyl ester resins (excluding EVA), saturated polyester resins, polyamide resins, fluororesins (polyvinylidene fluoride, etc.), polycarbonate resins, Polyacetal resin, urethane resin, epoxy resin, (meth)acrylate resin (also referred to as (meth)acrylic resin, meaning (meth)acrylic acid ester resin, etc.), unsaturated polyester resin, silicone resin, and these resins Modified resins and the like can be mentioned.
• the urethane resin include urethane-modified polyester resins and urethane resins.As the thermoplastic resin, polyvinyl butyral or ethylene-vinyl acetate copolymer is preferred.
• Polyvinyl butyral can be obtained by acetalizing polyvinyl alcohol with butyraldehyde.
• the degree of acetalization of polyvinyl butyral is not particularly limited, but is preferably 40% or more, more preferably 60% or more.
• the upper limit is not particularly limited, but is preferably 85% or less, more preferably 75% or less.
• Polyvinyl alcohol used in the synthesis of polyvinyl butyral is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol with a saponification degree of 80 to 99.8 mol% is generally used. Further, the degree of polymerization of the polyvinyl alcohol is preferably 200 to 3,000.
• Elastomers include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, and blocks of conjugated dienes.
• TPU thermoplastic polyolefin elastomers
• TPEE thermoplastic polyester
• the thermoplastic resin or elastomer may be synthesized by a known method, or a commercially available product may be used.
• commercially available elastomers include Clarity LA1114, Clarity LA2140, Clarity LA2250, Clarity LA2330, Clarity LA4285, Hyblar 5127, Hyblar 7311F, Septon 2104, and Septon 2063 (trade name, manufactured by Kuraray Co., Ltd.).
• the elastomer is preferably an acrylic block (co)polymer or a styrene block (co)polymer.
• the weight average molecular weight of the thermoplastic resin and elastomer is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, from the viewpoint of the balance between solubility in a solvent and storage modulus.
• the heat seal layer is preferably formed using a composition (heat seal layer forming composition) containing a polymerizable compound for chemically bonding with the reflective layer or the polarization conversion layer.
• the polymerizable compound is preferably one that can chemically bond with the polymerizable liquid crystal compound used to form the reflective layer or the polarization conversion layer.
• the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group
• polymerizable it is preferable that the compound also has an ethylenically unsaturated polymerizable group.
• Examples of the ethylenically unsaturated polymerizable group-containing compound include the following. However, the present invention is not limited to the exemplified compounds below.
• (meth)acrylate commercially available products, such as Aronix M-208 manufactured by Toagosei Co., Ltd.), 1,6-hexanediol di(meth)acrylate, and its epichlorohydrin-modified products, neopentyl glycol di(meth)acrylate, hydroxypivalic acid Neopentyl glycol di(meth)acrylate and its caprolactone modified product, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclo Decane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, trimethylolpropane acrylic acid/benzoic acid ester, and isocyanuric acid EO-modified di(meth)acrylate (as a commercial product, for example, manufactured by Toagose
• trimethylolpropane tri(meth)acrylate (as a commercially available product, e.g. TPMTA manufactured by Nippon Kayaku), its EO, PO, epichlorohydrin modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, and its EO, PO, epichlorohydrin-modified product, isocyanuric acid EO-modified tri(meth)acrylate (commercially available products, such as Toagosei Aronix M-315, etc.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate (2, Trifunctional (meth)acrylate compounds such as 2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, and its EO, PO, and epichlorohydrin modified products; pentaerythritol tetra(meth)acrylate (commercially available
• Two or more kinds of ethylenically unsaturated polymerizable group-containing compounds may be used in combination.
• "DPHA” manufactured by Nippon Kayaku
• a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be preferably used.
• polyester (meth)acrylate and epoxy (meth)acrylate having a weight average molecular weight of 200 or more and less than 1000 are also preferable.
• polyester (meth)acrylates include the Beam Set 700 series manufactured by Arakawa Chemical Co., Ltd., such as Beam Set 700 (6 functional), Beam Set 710 (4 functional), Beam Set 720 (3 functional), etc. It will be done.
• epoxy (meth)acrylates include the SP series manufactured by Showa Kobunshi Co., Ltd., such as SP-1506, 500, SP-1507, 480, the VR series, such as VR-77, and the product name EA- manufactured by Shin Nakamura Chemical Industry Co., Ltd. Examples include 1010/ECA, EA-11020, EA-1025, EA-6310/ECA, and the like.
• the I/O ratio (ratio of inorganic value (I value) to organic value (O value)) of a polymerizable compound (especially a compound containing an ethylenically unsaturated polymerizable group) is a factor in adhesion to the glass substrate. It is preferably 0.40 or more, more preferably 0.60 or more, and even more preferably 1.2 or more. Although the upper limit of the I/O ratio is not particularly limited, it is preferably smaller than 3.0 from the viewpoint of compatibility with the thermoplastic resin.
• the I/O ratio is calculated using the calculation method in the organic conceptual diagram.
• Organic conceptual diagrams were proposed by Fujita et al., and are an effective method for predicting various physicochemical properties from the chemical structure of organic compounds (Yoshio Koda, Organic Conceptual Diagrams - Basics and Applications, Sankyo Publishing). (1984)). Since the polarity of organic compounds depends on the number of carbon atoms and substituents, the inorganic value of other substituents is based on the case where the organic value of methylene group is 20 and the inorganic value of hydroxyl group is 100. and the organic value are determined, and the inorganic value and organic value of the organic compound are calculated. Organic compounds with large inorganicity values have high polarity, and organic compounds with large organicity values have low polarity.
• the content of the polymerizable compound is preferably 5 to 80% by mass, and 10 to 60% by mass based on the solid content in the composition. It is more preferably 15% to 50% by mass, and even more preferably 15% to 50% by mass.
• the solid content in the composition means other components in the composition excluding the solvent. Even if other components are liquid, they are calculated as solid content.
• the composition used to form the heat seal layer preferably contains a polymerization initiator from the viewpoint of adhesion to glass.
• the polymerization initiator include photopolymerization initiators.
• the photopolymerization initiator may be any photopolymerization initiator as long as it can generate radicals as active species upon irradiation with light, and any known photopolymerization initiator can be used without any limitations.
• Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy -2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer and 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] Acetophenones such as phenyl ⁇ -2-methyl-propan-1-one; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], and ethanone, 1- Oxime
• auxiliary agent for the polymerization initiator triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylamino Ethyl benzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone etc.
• the above polymerization initiators and auxiliary agents can be synthesized by known methods and are also available as commercial products.
• the content of the polymerization initiator contained in the composition used to form the heat seal layer is not particularly limited, and may be adjusted as appropriate within a range that allows the polymerization reaction of the polymerizable compound to proceed favorably.
• a polymerization initiator is included in the composition used to form the heat seal layer, the content of the polymerization initiator is 0.1 to 20 parts by mass based on 100 parts by mass of the polymerizable compound contained in the composition. is preferable, 0.5 to 10 parts by weight is more preferable, and even more preferably 1 to 10 parts by weight.
• the heat seal layer may contain inorganic particles. Since the heat seal layer contains inorganic particles, unevenness is formed on the surface of the heat seal layer, and when the heat seal layer and the HC layer are rolled into a state where they are in direct contact, friction between the heat seal layer and the HC layer is reduced. This is preferable because it can be rolled without wrinkles.
• the inorganic particles contained in the heat-sealing layer are preferably inorganic oxide particles, more preferably silica (silicon dioxide) particles, aluminum oxide particles, titanium dioxide particles, or zirconium oxide particles, and even more preferably silica particles.
• the inorganic particles consist of primary particles and form secondary particles formed by aggregation of the primary particles.
• the average primary particle diameter of the inorganic particles is not particularly limited, but is preferably 5 to 50 nm, more preferably 5 to 15 nm.
• the average secondary particle diameter of the inorganic particles is not particularly limited, but is preferably 100 to 500 nm.
• the content of inorganic particles in the heat-sealing layer is not particularly limited, but is preferably 1% by mass or more, more preferably 9% by mass or more, based on the total mass of the heat-sealing layer.
• the upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less.
• the average primary particle diameter of the inorganic particles is measured by transmission electron microscopy. Specifically, for 50 arbitrarily selected primary particles, the diameter of a circle circumscribing the primary particles is determined, and the arithmetic mean thereof is taken as the average primary particle diameter.
• the observation magnification of the transmission electron microscope is set to any magnification that allows the primary particle diameter to be determined between 500,000 times and 5,000,000 times.
• the above average secondary particle diameter is a value measured by performing true spherical fitting (refractive index 1.46) using a laser diffraction scattering particle size distribution measuring device.
• the measuring device for example, MicroTrac MT3000 manufactured by Microtrac Bell Co., Ltd. can be used.
• the heat seal layer may contain a leveling agent.
• a leveling agent By containing the leveling agent in the heat-sealing layer, the surface of the heat-sealing layer is smoothed, and visibility when integrated with a glass substrate can be improved.
• a known leveling agent can be used, such as a surfactant, and among them, a fluorine-based surfactant or a silicone-based surfactant is preferable.
• the fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
• a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving properties.
• the content of the leveling agent in the heat-sealing layer is not particularly limited, but is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.1% by mass, based on the total mass of the heat-sealing layer.
• the water contact angle of the surface of the heat seal layer opposite to the reflective layer or polarization conversion layer is not particularly limited, but from the viewpoint of better adhesion to the glass substrate, it is preferably 100° or less, more preferably 90° or less. , 70° or less is more preferable.
• the lower limit is not particularly limited, but is often 10° or more, more often 30° or more.
• the method for measuring the water contact angle is as follows. First, three different locations on the surface of the heat-sealing layer of the reflective film were measured using a contact angle meter CA-X (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) using pure water in an environment of 20°C and 65% RH.
• a droplet of .0 mm is made at the tip of the needle and brought into contact with the surface of the heat-sealing layer to form a droplet.
• the angle between the tangent to the pure water surface and the heat-sealing layer surface at the point where the heat-sealing layer surface and pure water contact, 25 seconds after the heat-sealing layer surface and pure water contact, on the side containing pure water. are measured and their average value is taken as the water contact angle of the heat seal layer.
• the heat seal layer is preferably formed by applying a composition for forming a heat seal layer.
• the composition for forming a heat seal layer is a composition that contains the above-mentioned components and is used to form a heat seal layer.
• the composition for forming a heat seal layer preferably contains a solvent from the viewpoint of coatability.
• the type of solvent is not particularly limited, and examples include water and organic solvents, with organic solvents being preferred. Examples of organic solvents include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers.
• the method of applying the composition for forming a heat seal layer is not particularly limited, and examples thereof include wire bar coating method, curtain coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, spin coating method, and dip coating method. Examples include coating methods, spray coating methods, and slide coating methods.
• the coating film obtained by coating may be subjected to a drying treatment if necessary.
• the drying treatment include heat treatment.
• the heating temperature in the heat treatment is not particularly limited, but is preferably 50 to 150°C, more preferably 60 to 140°C.
• the heating time is not particularly limited, but is preferably 0.5 to 20 minutes, more preferably 0.5 to 10 minutes.
• the surface of the formed heat-sealing layer (the surface opposite to the reflective layer or polarization conversion layer) may be subjected to surface treatment, if necessary.
• the surface of the heat-sealing layer may be subjected to hydrophilic treatment.
• the hydrophilic treatment include plasma treatment, ultraviolet irradiation treatment, corona treatment, and electron beam irradiation treatment, with corona treatment being preferred.
• the conditions for the hydrophilic treatment are appropriately selected depending on the type of treatment to be performed, and are preferably adjusted so that the water contact angle on the surface of the heat-sealing layer falls within the range described above.
• the average thickness of the heat seal layer is preferably 0.2 ⁇ m or more, more preferably 0.4 ⁇ m or more, and even more preferably 0.8 ⁇ m or more from the viewpoint of adhesion to the glass substrate, reflective layer, or polarization conversion layer.
• the upper limit is not particularly limited, but from the viewpoint of thinning the film, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less.
• the method for measuring the above average thickness is to cut the heat seal layer with a microtome, cut out a cross section, observe the cross section using a SEM (Scanning Electron Microscope), and measure the thickness at three different locations on the heat seal layer. Measure the thickness at , calculate the average value (arithmetic mean value) of the measured values, and use it as the average thickness.
• the heat seal layer may have a single layer structure or a multilayer structure of two or more layers.
• the average value of the total thickness of the heat-sealing layer may be within the above range.
• the moisture content (water content at 25° C. and 60% RH) of the heat seal layer is preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less from the viewpoint of wet heat durability. preferable.
• the lower limit is not particularly limited, and may be 0%.
• the moisture content of the heat-sealing layer was measured by scraping the heat-sealing layer and conditioning the sample in an environment of 25°C and 60% RH for 24 hours or more. VA-05'' (both manufactured by Mitsubishi Chemical Corporation) using the Karl Fischer method, and calculated by dividing the water content (g) by the sample mass (g, including water content).
• the reflective film of the present invention has a reflective layer that selectively reflects light.
• the reflective layer of the present invention has a cholesteric liquid crystal layer having a selective reflection center wavelength in a red wavelength region, a cholesteric liquid crystal layer having a selective reflection center wavelength in a green wavelength region, and a selective reflection center wavelength in a blue wavelength region. It is preferable to have a cholesteric liquid crystal layer.
• the three cholesteric liquid crystal layers have different selective reflection center wavelengths. Each cholesteric liquid crystal layer may be in direct contact with any other cholesteric liquid crystal layer.
• a cholesteric liquid crystal layer is a layer in which a liquid crystal compound is fixed in an oriented state in a helical structure of a cholesteric liquid crystal phase, and reflects light with a center wavelength of selective reflection according to the pitch of the helical structure, while reflecting light with a center wavelength of selective reflection according to the pitch of the helical structure. Transmits light in the area. Further, the cholesteric liquid crystal layer exhibits selective reflection property for either left or right circularly polarized light at a specific wavelength.
• the reflective layer preferably satisfies the following requirements (i) to (iii) from the viewpoint of visibility.
• the maximum value of natural light reflectance is more than 7% (preferably more than 20%), and the difference between the maximum value and the minimum value of natural light reflectance is 3% or more, and the total value of the wavelength band width in the region higher than the average value of the maximum value and minimum value of the natural light reflectance is 20 to 80 nm.
• the maximum value of natural light reflectance is more than 7% (preferably more than 20%), and the difference between the maximum value and the minimum value of natural light reflectance is 3% or more, and the total value of the wavelength band width in the region higher than the average value of the maximum value and minimum value of the natural light reflectance is 20 to 80 nm.
• the maximum value of natural light reflectance is more than 7% (preferably 20% or more) and is higher than the average value of the maximum value and minimum value of natural light reflectance.
• the total value of the wavelength band width is 120 nm or more.
• the reflected wavelength and reflectance can be adjusted by adjusting the selective reflection center wavelength, thickness (helical pitch number), etc. of the cholesteric liquid crystal layer.
• a cholesteric liquid crystal layer that mainly reflects light in the blue wavelength region achieves reflection that satisfies requirement (i)
• a cholesteric liquid crystal layer that reflects light in the green wavelength region achieves reflection that satisfies requirement (ii).
• the maximum value of the natural light reflectance in the range from 400 nm to less than 500 nm is preferably more than 7%, more preferably 20% or more.
• the upper limit is not particularly limited, but is often 35% or less, for example.
• the maximum value of the natural light reflectance in the range of 500 nm or more and less than 600 nm is preferably more than 7%, more preferably 20% or more.
• the upper limit is not particularly limited, but is often 35% or less, for example.
• the maximum value of the natural light reflectance in the range of 600 to 800 nm is preferably more than 7%, more preferably 20% or more.
• the upper limit is not particularly limited, but is often 35% or less, for example.
• the difference between the maximum value and the minimum value of the natural light reflectance in the range of 400 nm or more and less than 500 nm is preferably 4 to 20%, More preferably 4% to 12%.
• the difference between the maximum value and the minimum value of the natural light reflectance in the range from 500 nm to 600 nm is 4 to 20%. is preferable, and 4 to 12% is more preferable.
• the wavelength band width of the region where the reflectance is higher than the average value of the maximum value and the minimum value of the reflectance from 400 nm to less than 500 nm is set to 30 ⁇ 30 nm. 78 nm is preferred, and 35 to 75 nm is more preferred.
• the wavelength band width of the region where the reflectance is higher than the average value of the maximum value and minimum value of the reflectance from 500 nm to 600 nm is , 30 to 78 nm is preferable, and 35 to 75 nm is more preferable.
• the wavelength band width of 400 nm or more and less than 500 nm, and the wavelength band width of 500 nm or more and less than 600 nm the narrower the width, the better the transmittance, but since the wavelength band width of 600 to 800 nm is wide, If the wavelength band width is too narrow and/or the wavelength band width is 500 nm or more and less than 600 nm, there is a risk that the reflected color tone will deteriorate.
• the wavelength band width of 400 nm or more and less than 500 nm and the wavelength band width of 500 nm or more and less than 600 nm are preferably within the above ranges. Moreover, the influence of the wavelength band width in the range of 500 nm or more and less than 600 nm is greater on the transmittance.
• the wavelength band width of the region where the reflectance is higher than the average value of the maximum value and minimum value of the reflectance in the range of 600 to 800 nm is set to 120 to 200 nm. is preferred.
• the reflective layer preferably has two or more cholesteric liquid crystal layers with different selective reflection center wavelengths. Further, each cholesteric liquid crystal layer is preferably in direct contact with any other cholesteric liquid crystal layer.
• the film thickness between the layers increases, making it difficult to obtain the effect of interference of light reflected by each cholesteric liquid crystal layer.
• a configuration in which the cholesteric liquid crystal layers are in contact with each other is preferable because the wavelength band width can be narrowed by the effect of interference of light reflected by each cholesteric liquid crystal layer.
• the film thickness of each cholesteric liquid crystal layer is thinner than the wavelength of light (visible light 380 to 780 nm) because the interference effect becomes more pronounced.
• the cholesteric liquid crystal layers are not limited to a structure in which they are in direct contact with each other, but may be in a structure in which they are laminated via an adhesive layer or the like.
• each cholesteric liquid crystal layer may have at least one selective reflection center wavelength, but at least one of the cholesteric liquid crystal layers may have two or more selective reflection center wavelengths.
• a cholesteric liquid crystal layer having two or more selective reflection center wavelengths is achieved by a helical structure in which the helical pitch changes in the thickness direction.
• the total thickness of the reflective layer is preferably 0.4 to 2.0 ⁇ m, more preferably 0.6 to 1.8 ⁇ m, and even more preferably 0.8 to 1.4 ⁇ m.
• the total thickness of the reflective layer is within the above range, the natural light reflectance of the reflective layer is high, the brightness of the displayed image can be increased, and the transmittance is high.
• the material and method for manufacturing the cholesteric liquid crystal layer will be described below.
• Examples of the material used to form the cholesteric liquid crystal layer include a liquid crystal composition containing a polymerizable liquid crystal compound and a chiral agent (optically active compound).
• the liquid crystal composition may further contain a surfactant, a polymerization initiator, a solvent, and the like, if necessary.
• the above liquid crystal composition can be applied to a support, an alignment layer, a lower cholesteric liquid crystal layer, etc., and after cholesteric alignment ripening, the liquid crystal composition can be fixed by curing to form a cholesteric liquid crystal layer.
• the polymerizable liquid crystal compound may be a rod-like liquid crystal compound or a discotic liquid crystal compound, but is preferably a rod-like liquid crystal compound.
• An example of the rod-shaped polymerizable liquid crystal compound that forms the cholesteric liquid crystal layer is a rod-shaped nematic liquid crystal compound.
• Rod-shaped nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines.
• phenyldioxanes, tolans, and alkenylcyclohexylbenzonitrile are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
• a polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into a liquid crystal compound.
• the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, with an unsaturated polymerizable group being preferred and an ethylenically unsaturated polymerizable group being more preferred.
• the polymerizable group can be introduced into the molecules of the liquid crystal compound by various methods.
• the number of polymerizable groups that the polymerizable liquid crystal compound has in one molecule is preferably 1 to 6, more preferably 1 to 3.
• Examples of polymerizable liquid crystal compounds include Makromol. Chem. , Volume 190, Page 2255 (1989), Advanced Materials Volume 5, Page 107 (1993), US Patent No.
• the following mixture 1 can be mentioned.
• the content of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 80 to 99.9% by mass, and 85 to 99.5% by mass based on the solid content mass (mass excluding solvent) of the liquid crystal composition. % is more preferable, and 90 to 99% by mass is even more preferable.
• the cholesteric liquid crystal layer may have a low ⁇ n.
• the low ⁇ n cholesteric liquid crystal layer can be formed using a low ⁇ n polymerizable liquid crystal compound.
• the low ⁇ n polymerizable liquid crystal compound will be specifically explained below.
• a narrow band reflective layer can be obtained by forming a cholesteric liquid crystal phase using a low ⁇ n polymerizable liquid crystal compound and forming a fixed film.
• low ⁇ n polymerizable liquid crystal compounds include compounds described in WO2015/115390, WO2015/147243, WO2016/035873, JP2015-163596A, and JP2016-053149A.
• WO2016/047648 For a liquid crystal composition that provides a reflective layer with a small half width, reference can also be made to the description in WO2016/047648.
• liquid crystal compound is a polymerizable compound represented by the following formula (I) described in WO2016/047648.
• A represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent
• L is a single bond
• m represents an integer from 3 to 12
• Sp 1 and Sp 2 each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms.
• Q 1 and Q 2 are each independently a hydrogen atom or the following formulas Q-1 to Q It represents a polymerizable group selected from the group consisting of groups represented by -5, provided that either one of Q 1 and Q 2 represents a polymerizable group.
• the phenylene group is preferably a 1,4-phenylene group.
• the substituent is not particularly limited, and includes, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether. Examples include substituents selected from the group consisting of a group, an amide group, an amino group, a halogen atom, and a group constituted by a combination of two or more of the above-mentioned substituents.
• the phenylene group and trans-1,4-cyclohexylene group may have 1 to 4 substituents. When it has two or more substituents, the two or more substituents may be the same or different.
• the alkyl group may be either linear or branched.
• the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
• Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, Examples include 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, linear or branched heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• an alkyl group also applies to an alkoxy group containing an alkyl group.
• specific examples of the alkylene group when referring to an alkylene group include divalent groups obtained by removing one arbitrary hydrogen atom from each of the above-mentioned examples of the alkyl group.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 5 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
• Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• X 3 represents a single bond, -O-, -S-, or -N(Sp 4 -Q 4 )-, or a nitrogen atom forming a ring structure together with Q 3 and Sp 3 shows.
• Sp 3 and Sp 4 each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or one or more linear or branched alkylene groups having 1 to 20 carbon atoms.
• Q 3 and Q 4 each independently represent a hydrogen atom, a cycloalkyl group, or a cycloalkyl group in which one or more -CH 2 - is -O-, -S-, -NH-, -N(CH 3 )
• the substitution position is not particularly limited. Among these, a tetrahydrofuranyl group is preferred, and a 2-tetrahydrofuranyl group is more preferred.
• the m-1 L's may be the same or different from each other.
• Sp 1 and Sp 2 each independently represent one or more of a single bond, a straight chain or branched alkylene group having 1 to 20 carbon atoms, and a straight chain or branched alkylene group having 1 to 20 carbon atoms.
• the linking group is preferably a linking group composed of a combination of one or more groups, and is preferably a straight-chain alkylene group having 1 to 10 carbon atoms with -O- bonded to both ends.
• Q 1 and Q 2 each independently represent a hydrogen atom or a polymerizable group selected from the group consisting of the groups represented by the above formulas Q-1 to Q-5, provided that Q 1 and Q Either one of 2 represents a polymerizable group.
• the polymerizable group is preferably an acryloyl group (formula Q-1) or a methacryloyl group (formula Q-2).
• m represents an integer of 3 to 12.
• m is preferably an integer of 3 to 9, more preferably 3 to 7, even more preferably 3 to 5.
• the polymerizable compound represented by formula (I) has at least one phenylene group which may have a substituent as A and a trans-1,4-cyclohexylene group which may have a substituent. It is preferable to include at least one.
• the polymerizable compound represented by formula (I) preferably contains 1 to 4 trans-1,4-cyclohexylene groups, which may have a substituent, and preferably contains 1 to 3 trans-1,4-cyclohexylene groups as A. is more preferable, and it is even more preferable to contain 2 or 3 pieces.
• the polymerizable compound represented by formula (I) preferably contains one or more phenylene groups, which may have a substituent, as A, more preferably 1 to 4, and 1 to 4. It is more preferable to contain three pieces, and it is particularly preferable to contain two or three pieces.
• examples of the polymerizable compound represented by formula (I) include compounds described in paragraphs 0051 to 0058 of WO2016/047648, as well as JP2013-112631A, JP2010-070543A, Examples include compounds described in Patent No. 4725516, WO2015/115390, WO2015/147243, WO2016/035873, JP 2015-163596, and JP 2016-053149.
• the chiral agent has the function of inducing a helical structure of the cholesteric liquid crystal phase.
• Chiral compounds may be selected depending on the purpose, since the helical sense or helical pitch induced by the compound differs depending on the compound.
• There are no particular limitations on the chiral agent and known compounds can be used. Examples of chiral agents include the Liquid Crystal Device Handbook (Chapter 3, Section 4-3, Chiral Agents for TN and STN, p. 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989), Japanese Patent Laid-Open No. 2003-287623, Examples include compounds described in JP-A Nos. 2002-302487, 2002-080478, 2002-080851, 2010-181852, and 2014-034581.
• Chiral agents generally contain asymmetric carbon atoms, but axially asymmetric compounds or planar asymmetric compounds that do not contain asymmetric carbon atoms can also be used as chiral agents.
• Axial asymmetric compounds or planar asymmetric compounds include binaphthyl, helicene, paracyclophane, and derivatives thereof.
• the chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have polymerizable groups, a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound results in repeating units derived from the polymerizable liquid crystal compound and repeating units derived from the chiral agent. repeating units can be formed.
• the polymerizable group possessed by the polymerizable chiral agent is preferably the same type of group as the polymerizable group possessed by the polymerizable liquid crystal compound. Therefore, the polymerizable group of the chiral agent is preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and preferably an ethylenically unsaturated polymerizable group. Particularly preferred. Moreover, a liquid crystal compound may be sufficient as a chiral agent.
• isosorbide derivatives As the chiral agent, isosorbide derivatives, isomannide derivatives, binaphthyl derivatives, etc. are preferable.
• isosorbide derivative commercially available products such as LC756 manufactured by BASF may be used.
• the content of the chiral agent in the liquid crystal composition is preferably 0.01 to 200 mol%, more preferably 1 to 30 mol%, based on the total molar amount of the polymerizable liquid crystal compound. Note that the content of the chiral agent in the liquid crystal composition is intended to be the concentration (% by mass) of the chiral agent relative to the total solid content in the composition.
• the cholesteric liquid crystal layer of the reflective layer included in the reflective film of the present invention may have two or more selective reflection center wavelengths.
• a cholesteric liquid crystal layer having two or more selective reflection center wavelengths is achieved by changing the pitch of the helical structure in the thickness direction.
• a cholesteric liquid crystal layer in which the pitch of the helical structure changes in the thickness direction is created by changing the thickness when forming a cholesteric liquid crystal layer using a chiral agent whose helical twisting power (HTP) changes when irradiated with light. It can be produced by changing the amount of light irradiated in the direction.
• HTP helical twisting power
• Examples of chiral agents whose HTP changes upon irradiation with light include those that undergo back isomerization, dimerization, isomerization and dimerization, etc. upon irradiation with light.
• the photoisomerizable group is preferably an isomerization site of a compound exhibiting photochromic properties, an azo group, an azoxy group, or a cinnamoyl group.
• the liquid crystal composition contains a polymerization initiator.
• the polymerization initiator used is preferably a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation.
• photopolymerization initiators include ⁇ -carbonyl compounds (described in U.S. Pat. No. 2,367,661 and U.S. Pat. No. 2,367,670), acyloin ether (described in U.S. Pat. No. 2,448,828), and ⁇ -hydrocarbons. Substituted aromatic acyloin compounds (described in U.S. Pat. No.
• an acylphosphine oxide compound or an oxime compound As the polymerization initiator contained in the liquid crystal composition, it is also preferable to use an acylphosphine oxide compound or an oxime compound.
• the acylphosphine oxide compound include commercially available IRGACURE 810 (compound name: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) manufactured by BASF Japan Co., Ltd.
• oxime compounds include IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arcles NCI-831, and Adeka Arcles NCI-930.
• the content of the photopolymerization initiator in the liquid crystal composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass, based on the content of the polymerizable liquid crystal compound.
• the liquid crystal composition may optionally contain a crosslinking agent in order to improve film strength and durability after curing.
• a crosslinking agent those that are cured by ultraviolet rays, heat, moisture, etc. can be suitably used.
• the crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose.
• crosslinking agents include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; epoxy compounds such as glycidyl(meth)acrylate and ethylene glycol diglycidyl ether; Aziridine compounds such as 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] and 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; hexamethylene diisocyanate, biuret-type isocyanate, etc.
• polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate
• epoxy compounds such as glycidyl(meth)acrylate and ethylene glycol diglycidyl ether
• Aziridine compounds such as 2,2-bishydroxymethylbutanol-tris[3-(1
• isocyanate compounds polyoxazoline compounds having an oxazoline group in the side chain; alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane.
• a known catalyst can be used depending on the reactivity of the crosslinking agent, and productivity can be improved in addition to improving membrane strength and durability. These may be used alone or in combination of two or more.
• the content of the crosslinking agent is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, based on the total solid content of the liquid crystal composition.
• (meth)acrylate is used to mean “one or both of acrylate and methacrylate.”
• the liquid crystal composition may contain an alignment control agent that contributes to stably or rapidly forming a cholesteric liquid crystal layer with planar alignment.
• alignment control agents include fluorine (meth)acrylate polymers described in paragraphs 0018 to 0043 of JP-A No. 2007-272185, and formulas ( Examples include compounds represented by I) to (IV) and compounds described in JP-A No. 2013-113913.
• the alignment control agent one type may be used alone, or two or more types may be used in combination.
• alignment control agents include alignment control agent 1 and alignment control agent 2 below.
• the content of the alignment control agent in the liquid crystal composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and 0.02 to 5% by mass, based on the total mass of the polymerizable liquid crystal compound. 1% by mass is more preferred.
• the liquid crystal composition may contain at least one kind selected from various additives such as a surfactant for adjusting the surface tension of the coating film and making the thickness uniform, and a polymerizable monomer.
• various additives such as a surfactant for adjusting the surface tension of the coating film and making the thickness uniform, and a polymerizable monomer.
• polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, coloring materials, metal oxide fine particles, etc. may be added within a range that does not reduce optical performance. It can be added with.
• the cholesteric liquid crystal layer consists of a liquid crystal composition in which a polymerizable liquid crystal compound, a polymerization initiator, a chiral agent, a surfactant, etc. added as necessary are dissolved in a solvent, a transparent base material, a retardation layer, an alignment layer, etc.
• the cholesteric liquid crystal composition is coated on the previously prepared cholesteric liquid crystal layer, etc. and dried to obtain a coating film, and this coating film is irradiated with actinic rays to polymerize the cholesteric liquid crystal composition, thereby fixing the cholesteric regularity.
• cholesteric liquid crystal layer can be formed. Note that a laminated film consisting of a plurality of cholesteric liquid crystal layers can be formed by repeatedly performing the above-described manufacturing process for cholesteric liquid crystal layers.
• the solvent used for preparing the liquid crystal composition is not particularly limited and can be appropriately selected depending on the purpose, but organic solvents are preferably used.
• the organic solvent is not particularly limited and can be selected as appropriate depending on the purpose. Examples include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers. Can be mentioned. These may be used alone or in combination of two or more. Among these, ketones are preferred in consideration of the burden on the environment.
• the method of applying the liquid crystal composition to the transparent substrate, the alignment layer, the underlying cholesteric liquid crystal layer, etc. is not particularly limited, and can be appropriately selected depending on the purpose.
• coating methods include wire bar coating, curtain coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spin coating, dip coating, spray coating, and slide coating.
• One example is the law.
• It can also be carried out by transferring a liquid crystal composition separately coated onto a support.
• the heating temperature is preferably 200°C or lower, more preferably 130°C or lower.
• This alignment treatment yields an optical thin film in which the polymerizable liquid crystal compound is twisted and oriented so that the helical axis is substantially perpendicular to the film surface.
• the liquid crystal composition can be cured by further polymerizing the oriented liquid crystal compound.
• the polymerization may be thermal polymerization or photopolymerization using light irradiation, but photopolymerization is preferred. It is preferable to use ultraviolet light for light irradiation.
• the irradiation energy is preferably 20 mJ/cm 2 to 50 J/cm 2 , more preferably 100 to 1,500 mJ/cm 2 .
• light irradiation may be performed under heating conditions or under a nitrogen atmosphere.
• the irradiation ultraviolet wavelength is preferably 350 to 430 nm.
• the polymerization reaction rate is preferably higher, preferably 70% or more, and more preferably 80% or more.
• the polymerization reaction rate can be determined by measuring the consumption rate of polymerizable functional groups by infrared absorption spectrum.
• the reflective film of the present invention has a hard coat layer (HC layer).
• the HC layer provides abrasion resistance that prevents scratches even when hard materials rub against it, scratch resistance that prevents scratches even when pushed by hard materials, and even if dirt adheres to it, it can be easily wiped off. Provides stain resistance, etc.
• the HC layer in the present invention comprises at least one compound selected from the group consisting of a polysiloxane compound having a polymerizable group in its molecule and a fluorine-containing compound having a polymerizable group in its molecule, and other than these compounds. It is preferably formed by polymerizing and curing a polymerizable compound having a polymerizable group in the molecule described below, and it is more preferable that these polymerizable groups are radically polymerizable groups.
• the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds and the polymerizable compound forming the HC layer exist in a bonded state, providing better antifouling properties.
• the compound selected from the group consisting of a polysiloxane-containing compound and a fluorine-containing compound has a polymerizable group
• the polymerizable group in the compound selected from the group consisting of a polysiloxane-containing compound and a fluorine-containing compound described below does not react. Therefore, it exists in the HC layer in a bonded state.
• the HC layer furthest from the adhesive layer may contain at least a compound selected from the group consisting of a polysiloxane compound and a fluorine-containing compound.
• a compound selected from the group consisting of a polysiloxane compound and a fluorine-containing compound Preferably, it is more preferable that only the HC layer farthest from the adhesive layer contains it.
• the HC layer furthest from the adhesive layer has at least the above-mentioned Preferably, it is a cured film of the compound, and more preferably only the HC layer furthest from the adhesive layer is a cured film of the compound.
• specific embodiments of the HC layer will be described, but the present invention is not limited to the following embodiments.
• the fluorine-containing compound in the present invention is not particularly limited as long as it can impart abrasion resistance and antifouling properties to the HC layer, and any compound having a fluorine atom in the molecule can be used.
• a fluorine-containing antifouling agent exhibiting antifouling properties is preferably used.
• the fluorine-containing compound may be a monomer, an oligomer, or a polymer.
• the fluorine-containing compound must have a substituent that contributes to bond formation or compatibility with other components (e.g., polysiloxane-containing compound, polymerizable monomer that is a component of the resin, resin) in the HC layer. is preferred.
• These substituents may be the same or different, and preferably there is a plurality of them.
• This substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any one of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability.
• Examples of preferable substituents include Examples include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among these, a radically polymerizable group is preferred, and an acryloyl group or a methacryloyl group is more preferred.
• the fluorine-containing compound may be a polymer or an oligomer with a compound that does not contain a fluorine atom.
• a fluorine-based compound represented by the following general formula (F) is preferable.
• n is 1 to 3 represents an integer of 1 to 3.
• R A represents a polymerizable unsaturated group.
• the polymerizable unsaturated group is preferably a group having an unsaturated bond (i.e., a radically polymerizable group) that can cause a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays and electron beams, and (meth) Examples include acryloyl group, (meth)acryloyloxy group, vinyl group, and allyl group, and (meth)acryloyl group, (meth)acryloyloxy group, and any hydrogen atom in these groups are substituted with a fluorine atom. groups are preferably used.
• R f represents a (per)fluoroalkyl group or a (per)fluoropolyether group.
• the (per)fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group
• the (per)fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. represents a species. From the viewpoint of antifouling properties, it is preferable that the fluorine content in R f be higher.
• the number of carbon atoms in the (per)fluoroalkyl group is preferably 1 to 20, more preferably 1 to 10.
• (Per)fluoroalkyl groups have linear structures (e.g., -CF 2 CF 3 , -CH 2 (CF 2 ) 4 H, -CH 2 (CF 2 ) 8 CF 3 , and -CH 2 CH 2 (CF 2 ) 4 H), branched structures (for example, -CH(CF 3 ) 2 , -CH 2 CF(CF 3 ) 2 , -CH(CH 3 )CF 2 CF 3 , and -CH(CH 3 ) (CF 2 ) 5 CF 2 H), an alicyclic structure (preferably a 5-membered or 6-membered ring, for example, a perfluorocyclohexyl group and a perfluorocyclopentyl group, or substituted with these groups) (alkyl group) may also be used.
• the (per)fluoropolyether group refers to the case where the (per)fluoroalkyl group has an ether bond, and may be a monovalent or divalent or more valent group.
• the fluoropolyether group include -CH 2 OCH 2 CF 2 CF 3 , -CH 2 CH 2 OCH 2 C 4 F 8 H, -CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , -CH 2 CH
• Examples include 2 OCF 2 CF 2 OCF 2 CF 2 H, and a fluorocycloalkyl group having 4 or more fluorine atoms and having 4 to 20 carbon atoms.
• examples of the perfluoropolyether group include -(CF 2 O) p -(CF 2 CF 2 O) q -, -[CF(CF 3 )CF 2 O] p -[CF(CF 3 )]
• Examples include q -, -(CF 2 CF 2 CF 2 O) p -, and -(CF 2 CF 2 O) p -.
• the above p and q each independently represent an integer of 0 to 20. However, p+q is an integer of 1 or more.
• the total of p and q is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23.
• the above-mentioned fluorine-containing antifouling agent preferably has a perfluoropolyether group represented by -(CF 2 O) p -(CF 2 CF 2 O) q - from the viewpoint of having excellent antifouling properties.
• the fluorine-containing antifouling agent preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.
• W represents a single bond or a connecting group.
• W include alkylene groups, arylene groups, heteroalkylene groups, and linking groups that are combinations of these groups. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or a combination of these groups.
• a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or a combination of these groups.
• an ethylene group is preferable, and an ethylene group bonded to a carbonylimino group is more preferable.
• the fluorine atom content of the fluorine-containing antifouling agent is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.
• fluorine-containing antifouling agents examples include R-2020, M-2020, R-3833, M-3833 manufactured by Daikin Chemical Industries, Ltd., and Optool DAC (all trade names) manufactured by Dainippon Ink Co., Ltd. Examples include Megafac F-171, F-172, F-179A, RS-78, RS-90, Defensor MCF-300 and MCF-323 (all trade names).
• the product of n and m (n ⁇ m) is preferably 2 or more, and more preferably 4 or more.
• Preferred specific examples of the embodiment in which n and m are both 1 in the general formula (F) include compounds represented by the following general formulas (F-1) to (F-3).
• R f2 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms
• R 11 represents a hydrogen atom or a methyl group
• R 21 represents a single bond or an alkylene group
• R 22 represents a single bond or a divalent linking group
• p is an integer representing the degree of polymerization
• the degree of polymerization p is greater than or equal to k (k is an integer of 3 or more).
• R 22 represents a divalent linking group
• examples of this divalent linking group include those similar to the above-mentioned W.
• telomer type (meth)acrylate containing a fluorine atom in general formula (F-1) examples include (meth)acrylic acid moieties or fully fluorinated alkyl ester derivatives.
• the compound represented by the general formula (F-1) above may be synthesized by the general formula (F-1) depending on the telomerization conditions and the separation conditions of the reaction mixture.
• a plurality of fluorine-containing (meth)acrylic acid esters in which p of the group R f2 (CF 2 CF 2 ) p R 22 CH 2 CH 2 R 21 O- is k, k+1, k+2, etc. May include.
• F-2 F(CF 2 ) q -CH 2 -CHX-CH 2 Y
• q represents an integer from 1 to 20
• X and Y represent a (meth)acryloyloxy group or a hydroxyl group, and at least one of X and Y represents a (meth)acryloyloxy group.
• the fluorine-containing (meth)acrylic acid ester represented by the general formula (F-2) has a fluoroalkyl group having 1 to 20 carbon atoms and a trifluoromethyl group (-CF 3 ) at the end. Even in a small amount of fluorine-containing (meth)acrylic acid ester, trifluoromethyl groups are effectively oriented on the surface.
• q is preferably 6 to 20, more preferably 8 to 10.
• Fluorine-containing (meth)acrylic esters having a fluoroalkyl group having 8 to 10 carbon atoms have an excellent coefficient of friction compared to fluorine-containing (meth)acrylic esters having fluoroalkyl groups with other chain lengths. It exhibits a reduction effect and has excellent abrasion resistance.
• the fluorine-containing (meth)acrylic acid ester represented by the general formula (F-2) includes 1-(meth)acryloyloxy-2-hydroxy-4,4,5,5,6,6,7 , 7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane, 2-(meth)acryloyloxy-1-hydroxy-4, 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane, and 1 ,2-bis(meth)acryloyloxy4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13 - Heneicosafluorotridecane.
• Fluorine atom-containing monofunctional (meth)acrylate represented by the above general formula (F-3) is produced by reacting a fluorine atom-containing alcohol compound represented by the following general formula (FG-3) with (meth)acrylic acid halide. It can be obtained by
• fluorine atom-containing alcohol compound represented by the above general formula (FG-3) include 1H,1H-perfluoro-3,6-dioxaheptan-1-ol, 1H,1H-perfluoro-3,6- Dioxaoctan-1-ol, 1H,1H-perfluoro-3,6-dioxadecane-1-ol, 1H,1H-perfluoro-3,6,9-trioxadecan-1-ol, 1H,1H-perfluoro- 3,6,9-trioxaundecan-1-ol, 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol, 1H,1H-perfluoro-3,6,9,12-tetra Oxatridecan-1-ol, 1H,1H-perfluoro-3,6,9,12-tetraoxatetradecan-1-ol, 1H,1H-perfluoro
• the (meth)acrylic acid halide to be reacted with the fluorine atom-containing alcohol compound represented by the above general formula (FG-3) includes (meth)acrylic acid fluoride, (meth)acrylic acid chloride, (meth)acrylic acid chloride, and (meth)acrylic acid halide.
• examples include bromide and (meth)acrylic acid iodide. From the viewpoint of availability, (meth)acrylic acid chloride is preferred.
• the fluorine-containing polyether compound represented by the above general formula (F-3)' may have a plurality of polymerizable unsaturated groups.
• the fluorine-containing polyether compound represented by the general formula (F-3)' above contains six or more fluorine-containing polyether chains represented by the general formula (FG-3)' as repeating units in the R f3 group. It is important that the material is resistant to scratches, and this can impart abrasion resistance. More specifically, it may be a mixture containing 6 or more repeating units of the fluorine-containing polyether chain, and when used in the form of a mixture, a fluorine-containing unsaturated compound containing less than 6 repeating units and a fluorine-containing unsaturated compound containing less than 6 repeating units may be used.
• the fluorine-containing polyether chain represented by the general formula (FG-3)' is preferably 6 or more, more preferably 10 or more, even more preferably 18 or more, and particularly preferably 20 or more.
• the fluorine-containing polyether chain may be present at the end of the R f3 group or within the chain.
• the R f3 group has the general formula (c-4): R 4 -(CX 6 2 CF 2 CF 2 O) t -(R 5 ) e - (wherein, X 6 has the same meaning as X 6 in the fluorine-containing polyether chain represented by formula (FG-3)') , R 4 represents a hydrogen atom, a halogen atom, an alkyl group, a fluorine-containing alkyl group, an alkyl group containing an ether bond, or a fluorine-containing alkyl group containing an ether bond, R 5 represents a divalent or higher organic group, t represents an integer from 6 to 66, and e represents 0 or 1.) A group represented by is preferred.
• the R f3 group is a fluorine-containing organic group that is bonded to a reactive carbon-carbon double bond via a divalent or higher-valent organic group R 5 and further has R 4 at the terminal.
• R 5 may be any organic group as long as it can bond the fluorine-containing polyether chain represented by the general formula (FG-3)' to a reactive carbon-carbon double bond. Examples include an alkylene group, a fluorine-containing alkylene group, an alkylene group containing an ether bond, and a fluorine-containing alkylene group containing an ether bond. Among these, a fluorine-containing alkylene group or a fluorine-containing alkylene group containing an ether bond is preferred in terms of transparency and low refractive index.
• fluorine-containing polyether compound represented by the general formula (F-3)' compounds listed in Republished Patent No. WO 2003/022906 are preferably used.
• CH 2 CF-COO-CH 2 CF 2 CF 2 -(OCF 2 CF 2 CF 2 ) 7 -OC 3 F 7 is preferred.
• Examples of embodiments in which n and m are not 1 at the same time in general formula (F) include compounds represented by general formula (F-4) and general formula (F-5).
• n is Represents an integer from 1 to 3
• m represents an integer from 1 to 3
• n and m are never 1 at the same time.
• R f1 can be monovalent to trivalent.
• the terminal groups are (C n F 2n+1 )-, (C n F 2n+1 O)-, (XC n F 2n O)-, (XC n F 2n+1 )- (wherein X is It is preferably a hydrogen atom, a chlorine atom, or a bromine atom, and n is an integer of 1 to 10).
• CF 3 O(C 2 F 4 O) p CF 2 ⁇ , C 3 F 7 O(CF 2 CF 2 CF 2 O) p CF 2 CF 2 ⁇ , C 3 F 7 O(CF(CF 3 ) CF 2 O) p CF(CF 3 )- or F(CF(CF 3 )CF 2 O) p CF(CF 3 )- is preferable.
• the average value of p is 0 to 50, preferably 3 to 30, more preferably 3 to 20, and even more preferably 4 to 15.
• R f1 is divalent, -(CF 2 O) q (C 2 F 4 O) r CF 2 -, -(CF 2 ) 3 O(C 4 F 8 O) r (CF 2 ) 3 -, -CF 2 O (C 2 F 4 O) r CF 2 -, -C 2 F 4 O (C 3 F 6 O) r C 2 F 4 -, -CF (CF 3 ) (OCF 2 CF (CF 3 ) ) s OC t F 2t O(CF(CF 3 )CF 2 O) r CF(CF 3 )- or -(CF(CF 3 )CF 2 O) p CF(CF 3 )- is preferred.
• the average value of p, q, r, and s in the formula is 0 to 50.
• the number is preferably 3 to 30, more preferably 3 to 20, and even more preferably 4 to 15.
• t is an integer from 2 to 6.
• Preferred specific examples and synthesis methods of the compound represented by general formula (F-4) are described in International Publication No. 2005/113690.
• F(CF(CF 3 )CF 2 O) p CF(CF 3 )- with an average value of p of 6 to 7 is referred to as "HFPO-"
• -HFPO- F(CF(CF 3 )CF 2 O) p CF(CF 3 )- with an average value of p of 6 to 7
• -HFPO- indicates a specific compound of general formula (F-4), but is limited to these. It's not a thing.
• the compound whose polymerizable unsaturated group is a (meth)acryloyloxy group may have a plurality of (meth)acryloyloxy groups. Because the fluorine-containing antifouling agent has multiple (meth)acryloyloxy groups, it forms a three-dimensional network structure when cured, has a high glass transition temperature, and has low transferability of the antifouling agent. Durability against repeated wiping of dirt can be improved. Furthermore, an HC layer with excellent heat resistance, weather resistance, etc. can be obtained.
• Specific examples of the compound represented by the above general formula (F-5) include di(meth)acrylic acid-2,2,2-trifluoroethylethylene glycol, di(meth)acrylic acid-2,2,3 , 3,3-pentafluoropropylethylene glycol, di(meth)acrylic acid-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di(meth)acrylic acid-2,2,3 , 3,4,4,5,5,5-nonafluoropentylethylene glycol, di(meth)acrylic acid-2,2,3,3,4,4,5,5,6,6,6-undeca Fluorohexylethylene glycol, di(meth)acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di(meth)acrylic acid Acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di
• di(meth)acrylic acid esters can be prepared by known methods such as those listed in JP-A-6-306326.
• diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol is preferred. used.
• the compound whose polymerizable unsaturated group is a (meth)acryloyloxy group is a compound having a plurality of (per)fluoroalkyl groups or (per)fluoropolyether groups in one molecule. There may be.
• the weight average molecular weight (Mw) of a fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, such as gel permeation chromatography (GPC).
• Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and even more preferably 400 or more and less than 25,000. If it is more than the above lower limit, the surface migration property of the antifouling agent in the HC layer increases, which is preferable.
• the fluorine-containing compound may have a multimodal weight average molecular weight.
• the fluorine-containing compound may be included in the curable composition for forming an HC layer.
• the content of the fluorine-containing compound in the curable composition for HC layer formation is preferably 0.01 to 5% by mass, and 0.1 to 5% by mass, based on the total solid content in the curable composition for HC layer formation. It is more preferably 0.5-5% by weight, particularly preferably 0.5-2% by weight. When the amount added is at least the above upper limit, the coefficient of friction can be reduced and the abrasion resistance can be further improved.
• the amount added in the curable composition for forming the HC layer that forms the HC layer containing the fluorine-containing compound or the polysiloxane compound means.
• the solid content in the curable composition for forming an HC layer means components other than the solvent in the curable composition for forming an HC layer. Even if the component is liquid, it is considered solid.
• the polysiloxane-containing compound in the present invention is not particularly limited, and includes compounds having a polysiloxane structure in the molecule.
• the polysiloxane structure possessed by the polysiloxane-containing compound may be linear, branched, or cyclic.
• a polysiloxane antifouling agent exhibiting antifouling properties is preferably used.
• the polysiloxane antifouling agent is a compound represented by the following general formula (F-6).
• R a R A b SiO (4-ab)/2 (In the formula, R represents a hydrogen atom, methyl group, ethyl group, propyl group, or phenyl group, R A represents an organic group containing a polymerizable unsaturated group, and 0 ⁇ a, 0 ⁇ b, a+b ⁇ 4 )
• a is preferably from 1 to 2.75, more preferably from 1 to 2.5; when it is 1 or more, the synthesis of the compound becomes industrially easy; when it is 2.75 or less, it improves curability and antifouling properties. It becomes easier to balance both.
• Examples of the polymerizable unsaturated group in R A include the same polymerizable unsaturated groups (i.e., radically polymerizable groups) as R A in the above general formula (F), such as (meth)acryloyl group, (meth)acryloyl Preferred are oxy groups and groups in which any hydrogen atom in these groups is substituted with a fluorine atom. Also in the polysiloxane antifouling agent, from the viewpoint of film strength, it is preferable to have a plurality of polymerizable unsaturated groups in one molecule.
• the polysiloxane antifouling material is preferably polydimethylsiloxane having a plurality of polymerizable unsaturated groups in one molecule.
• Preferred examples of polysiloxane antifouling agents include those having a substituent at the end and/or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units.
• the compound chain containing dimethylsilyloxy as a repeating unit may contain structural units other than dimethylsilyloxy.
• These substituents may be the same or different, and preferably there is a plurality of them.
• This substituent is preferably a polymerizable group, and may be any polymerizable group exhibiting any one of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability.
• substituents examples include (meth)acryloyl group, ((meth)acryloyloxy) group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, and carboxyl group. group, and a group containing an amino group and the like.
• radically polymerizable groups are preferred, and (meth)acryloyloxy groups are particularly preferred from the viewpoint of improving stain resistance.
• the number of substituents in the compound is preferably 100 to 10,000 g/mol, more preferably 100 to 3,000 g/mol, and 100 to 2,000 g/mol in terms of functional group equivalents. is more preferred, and 100 to 1000 g/mol is particularly preferred.
• the functional group equivalent to the above-mentioned lower limit value, it does not become more compatible with the polymerizable compound (resin component when forming the HC layer) in the curable composition for HC layer formation, and the stain resistance is improved. This is preferable because the surface migration property of the agent in the HC layer becomes high. It is preferable to set the functional group equivalent to the above upper limit value or less because it is possible to improve the film hardness and improve the antifouling property.
• R A is preferably an organic group containing a (meth)acryloyl group, and more preferably the bond to the Si atom is a Si--O--C bond for ease of industrial synthesis.
• b is preferably 0.4 to 0.8, more preferably 0.6 to 0.8; when it is at least the above lower limit, the curability improves, and when it is below the above upper limit, the antifouling property improves. .
• a+b is preferably 3 to 3.7, more preferably 3 to 3.5. If it is more than the above lower limit, the compound is likely to be unevenly distributed on the surface of the HC layer, and if it is less than the above upper limit, both curability and antifouling properties can be improved.
• the polysiloxane antifouling agent preferably has 3 or more Si atoms in one molecule, and more preferably 3 to 40 Si atoms. When there are three or more Si atoms, uneven distribution of the compound on the surface of the HC layer is promoted, making it easier to obtain sufficient antifouling properties.
• Polysiloxane antifouling agents can be produced using known methods such as those listed in JP-A No. 2007-145884.
• additives having a polysiloxane structure include polysiloxanes (for example, "KF-96-10CS", “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE"), “X-22-164”, “X-22-164A”, “X-22-164AS”, “X-22-164B”, “X-22-164C”, “X-22-5002”, “X -22-173B”, “X-22-174D”, “X-22-167B”, “X-22-161AS” (product names), manufactured by Shin-Etsu Chemical Co., Ltd.; “AK-5”, “AK-30”, “AK-32” (product name), manufactured by Toagosei Co., Ltd.; “Silaplane FM0725”, “Siraplane FM0721” (product name), manufactured by Chisso Corporation; “DMS-” Preferred are "
• the weight average molecular weight of the polysiloxane-containing compound is preferably 300 or more, more preferably 300 to 100,000, and even more preferably 300 to 30,000.
• the weight average molecular weight of the polysiloxane-containing compound is 300 or more, uneven distribution of the polysiloxane-containing compound on the surface of the HC layer is promoted, and the abrasion resistance and hardness are further improved.
• the content of the polysiloxane-containing compound in the curable composition for HC layer formation is preferably 0.01 to 5% by mass, and 0.1 to 5% by mass, based on the total solid content in the curable composition for HC layer formation. It is more preferably 5% by weight, even more preferably 0.5-5% by weight, particularly preferably 0.5-2% by weight.
• the amount added is at least the above lower limit, the antifouling properties can be further improved.
• the polysiloxane compound that is insufficiently mixed with the polymerizable compound (resin component when forming the HC layer) in the curable composition for HC layer formation may be present on the surface.
• the HC layer has a laminated structure of two or more layers as described below, it means the amount added in the curable composition for forming the HC layer that forms the HC layer containing the polysiloxane compound.
• the HC layer used in the present invention can be obtained by irradiating the curable composition for forming an HC layer with active energy rays and curing it.
• active energy ray refers to ionizing radiation, and includes X-rays, ultraviolet rays, visible light, infrared rays, electron beams, alpha rays, beta rays, gamma rays, and the like.
• the HC layer-forming curable composition used to form the HC layer contains at least one component (hereinafter also referred to as "active energy ray-curable component") that has the property of being cured by irradiation with active energy rays. .
• the active energy ray-curable component is preferably at least one polymerizable compound selected from the group consisting of radically polymerizable compounds and cationic polymerizable compounds.
• a "polymerizable compound” is a compound which has a polymeric group in a molecule, and the polymeric group should just be one or more in 1 molecule.
• the polymerizable group is a group that can participate in a polymerization reaction, and specific examples include groups included in various polymerizable compounds described below. Further, examples of the polymerization reaction include various polymerization reactions such as radical polymerization, cationic polymerization, and anionic polymerization. Further, the HC layer in the present invention includes at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in the molecule and fluorine-containing compounds having a polymerizable group in the molecule, and compounds other than these compounds.
• the curable composition for forming an HC layer containing a polymerizable compound having a polymerizable group in its molecule is irradiated with active energy rays to be polymerized and cured.
• the polymerizable group possessed by the polysiloxane-containing compound, the fluorine-containing compound, and the polymerizable compound is a radically polymerizable group.
• the HC layer used in the present invention may have a one-layer structure or a laminated structure of two or more layers, and preferably has a one-layer structure or a laminated structure of two or more layers as detailed below.
• a preferred embodiment of the curable composition for forming an HC layer for forming a one-layer structure HC layer includes, as a first embodiment, two or more ethylenically unsaturated groups in one molecule.
• examples include curable compositions for forming an HC layer containing at least one polymerizable compound having the following properties.
• the ethylenically unsaturated group refers to a functional group containing an ethylenically unsaturated double bond.
• a curable composition for forming an HC layer includes at least one radically polymerizable compound and at least one cationically polymerizable compound.
• the curable composition for forming an HC layer according to the first embodiment will be explained below.
• the polymerizable compound having two or more ethylenically unsaturated groups in one molecule contained in the curable composition for forming an HC layer of the first aspect is an ester of polyhydric alcohol and (meth)acrylic acid [
• the number of ethylenically unsaturated groups contained in the polymerizable compound having two or more ethylenically unsaturated groups in one molecule is not particularly limited, but is preferably from 2 to 10, more preferably from 2 to 6, and from 4 to 6. 6 is more preferred, and 5 to 6 are particularly preferred.
• Polymerization of a polymerizable compound having an ethylenically unsaturated group can be carried out by irradiation with active energy rays in the presence of a radical photopolymerization initiator.
• a radical photopolymerization initiator the radical photopolymerization initiator described below is preferably applied.
• the content ratio of the radical photopolymerization initiator to the polymerizable compound having an ethylenically unsaturated group in the curable composition for forming an HC layer the content ratio of the radical photopolymerization initiator to the radical polymerizable compound described below Descriptions of quantitative ratios are preferably applied.
• the curable composition for forming an HC layer of the second aspect preferably contains at least one radically polymerizable compound and at least one cationically polymerizable compound.
• a curable composition for forming an HC layer may be mentioned.
• the curable composition for forming an HC layer contains a radical photopolymerization initiator and a cationic photopolymerization initiator.
• a curable composition for forming an HC layer may be mentioned. In the following, this aspect will be referred to as the second aspect (1).
• the above radically polymerizable compound preferably contains two or more radically polymerizable groups in one molecule and one or more urethane bonds in one molecule.
• a) it contains an alicyclic epoxy group and an ethylenically unsaturated group, and the number of alicyclic epoxy groups contained in one molecule is one;
• a curable composition for forming an HC layer may be mentioned.
• this aspect will be referred to as the second aspect (2).
• the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) preferably has a structure derived from a) above, when the total solid content of the HC layer is 100% by mass. 5 to 70% by mass of the structure derived from b) above, 25 to 80% by mass of the structure derived from b) above, 0.1 to 10% by mass of c) above, and 0.1 to 10% by mass of d) above.
• the curable composition for forming an HC layer of the second aspect (2) has the above-mentioned a) when the total solid content of the curable composition for forming an HC layer is 100% by mass. It is preferably contained in an amount of 15 to 70% by mass.
• the term "alicyclic epoxy group” refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
• the curable composition for forming an HC layer of the second aspect contains at least one radically polymerizable compound and at least one cationically polymerizable compound.
• the radically polymerizable compound in the second aspect (1) contains two or more radically polymerizable groups in one molecule selected from the group consisting of an acryloyl group and a methacryloyl group.
• the above-mentioned radically polymerizable compound may preferably contain, for example, 2 to 10, and more preferably 2 to 6, radically polymerizable groups selected from the group consisting of acryloyl and methacryloyl groups in one molecule. , more preferably 4 to 6 pieces, particularly preferably 5 to 6 pieces.
• a radically polymerizable compound having a molecular weight of 200 or more and less than 1,000 is preferable.
• “molecular weight” shall refer to the weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) for a multimer.
• GPC device HLC-8120 (manufactured by Tosoh Corporation)
• Eluent Tetrahydrofuran
• the curable composition for forming an HC layer of the second aspect (1) contains a radically polymerizable compound containing two or more radically polymerizable groups in one molecule selected from the group consisting of an acryloyl group and a methacryloyl group. In addition, it may contain one or more radically polymerizable compounds other than such radically polymerizable compounds.
• radically polymerizable compounds include the following.
• the present invention is not limited to the exemplified compounds below.
• (meth)acrylate commercially available products, such as Aronix M-208 manufactured by Toagosei Co., Ltd.), 1,6-hexanediol di(meth)acrylate, and its epichlorohydrin-modified products, neopentyl glycol di(meth)acrylate, hydroxypivalic acid Neopentyl glycol di(meth)acrylate and its caprolactone modified product, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclo Decane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, trimethylolpropane acrylic acid/benzoic acid ester, and isocyanuric acid EO-modified di(meth)acrylate (as a commercial product, for example, manufactured by Toagose
• trimethylolpropane tri(meth)acrylate (as a commercially available product, e.g. TPMTA manufactured by Nippon Kayaku), its EO, PO, epichlorohydrin modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, and its EO, PO, epichlorohydrin modified product, isocyanuric acid EO modified tri(meth)acrylate (commercially available products, such as Toagosei Aronix M-315, etc.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate (2, Trifunctional (meth)acrylate compounds such as 2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, and its EO, PO, and epichlorohydrin modified products; pentaerythritol tetra(meth)acrylate (commercially available)
• Two or more radically polymerizable compounds may be used in combination.
• "DPHA” manufactured by Nippon Kayaku
• a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be preferably used.
• polyester (meth)acrylate and epoxy (meth)acrylate having a weight average molecular weight of 200 or more and less than 1000 are also preferable.
• polyester (meth)acrylates include the Beam Set 700 series manufactured by Arakawa Chemical Co., Ltd., such as Beam Set 700 (6 functional), Beam Set 710 (4 functional), Beam Set 720 (3 functional), etc. It will be done.
• epoxy (meth)acrylates include the SP series manufactured by Showa Kobunshi Co., Ltd., such as SP-1506, 500, SP-1507, 480, the VR series, such as VR-77, and the product name EA- manufactured by Shin Nakamura Chemical Industry Co., Ltd. Examples include 1010/ECA, EA-11020, EA-1025, EA-6310/ECA, and the like.
• the curable composition for forming an HC layer according to the second aspect (2) which is a preferred aspect of the second aspect, contains b) a radically polymerizable compound containing three or more ethylenically unsaturated groups in one molecule.
• a radically polymerizable compound containing three or more ethylenically unsaturated groups in one molecule includes.
• Component b) includes esters of polyhydric alcohols and (meth)acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, and (meth)acrylamide.
• radically polymerizable compounds containing three or more radically polymerizable groups in one molecule selected from the group consisting of acryloyl groups and methacryloyl groups are preferred.
• Specific examples include compounds that are esters of polyhydric alcohols and (meth)acrylic acid and have three or more ethylenically unsaturated groups in one molecule.
• resins containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule are also preferred.
• resins containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule include polyester resins, polyether resins, acrylic resins, epoxy resins, and urethane resins. , alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polymers such as polyfunctional compounds such as polyhydric alcohols.
• radically polymerizable compounds containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule include the examples shown in paragraph 0096 of JP-A No. 2007-256844. Examples include compounds. Further, specific examples of radically polymerizable compounds containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule include KAYARAD DPHA, DPHA-2C, and PET manufactured by Nippon Kayaku.
• UV-1400B UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV- 7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV- 3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (Nippon Gosei), UL- 503LN (manufactured by Kyoeisha Chemical), Unidic 17-806, 17-813, V-4030, Unidic V-4000BA (manufactured by Dainippon Ink Chemical), EB-1290K, EB-220, EB-5129, EB- 1830, EB-4358 (manufactured by Daicel
• the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) preferably contains the components derived from a) above, when the total solid content of the HC layer is 100% by mass. It can contain 5 to 70% by mass of the structure derived from b), 25 to 80% by mass of the structure derived from b), 0.1 to 10% by mass of c), and 0.1 to 10% by mass of d).
• the structure derived from b) preferably contains 40 to 75% by mass, more preferably 60 to 75% by mass, when the total solid content of the HC layer is 100% by mass.
• the curable composition for forming an HC layer of the second aspect (2) contains 40 to 75% by weight of component b) when the total solid content of the curable composition for forming an HC layer is 100% by weight. %, more preferably 50 to 75% by mass.
• the curable composition for forming an HC layer of the second aspect preferably contains at least one radically polymerizable compound and at least one cationically polymerizable compound.
• the cationically polymerizable compound any compound having a cationically polymerizable polymerizable group (cationically polymerizable group) can be used without any restriction. Further, the number of cationically polymerizable groups contained in one molecule is at least one.
• the cationically polymerizable compound may be a monofunctional compound containing one cationically polymerizable group in one molecule, or a polyfunctional compound containing two or more cationically polymerizable groups.
• the number of cationically polymerizable groups contained in the polyfunctional compound is not particularly limited, but is, for example, 2 to 6 in one molecule. Further, two or more cationically polymerizable groups contained in one molecule of the polyfunctional compound may be the same or may be two or more types having different structures.
• the cationically polymerizable compound preferably has one or more radically polymerizable groups in one molecule together with the cationically polymerizable group.
• the radically polymerizable group that such a cationically polymerizable compound has the above description of the radically polymerizable compound can be referred to.
• it is an ethylenically unsaturated group
• the ethylenically unsaturated group is more preferably a radically polymerizable group selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group.
• the number of radically polymerizable groups in one molecule of the cationically polymerizable compound having a radically polymerizable group is at least 1, preferably 1 to 3, and more preferably 1.
• the cationic polymerizable group include oxygen-containing heterocyclic groups and vinyl ether groups.
• the cationically polymerizable compound may contain one or more oxygen-containing heterocyclic groups and one or more vinyl ether groups in one molecule.
• the oxygen-containing heterocycle may be a single ring or a fused ring. Moreover, those having a bicyclo skeleton are also preferable.
• the oxygen-containing heterocycle may be a non-aromatic ring or an aromatic ring, and is preferably a non-aromatic ring. Specific examples of monocycles include epoxy rings, tetrahydrofuran rings, and oxetane rings. Further, examples of those having a bicyclo skeleton include an oxabicyclo ring. Note that the cationically polymerizable group containing an oxygen-containing heterocycle is included in the cationically polymerizable compound as a monovalent substituent or as a polyvalent substituent having a valence of two or more.
• the above-mentioned condensed ring is a condensation of two or more oxygen-containing heterocycles, or a condensation of one or more oxygen-containing heterocycles with one or more ring structures other than the oxygen-containing heterocycle.
• Ring structures other than the above-mentioned oxygen-containing heterocycles include, but are not limited to, cycloalkane rings such as cyclohexane rings.
• oxygen-containing heterocycle Specific examples of the oxygen-containing heterocycle are shown below. However, the present invention is not limited to the specific examples below.
• the cationically polymerizable compound may contain a partial structure other than the cationically polymerizable group.
• a partial structure is not particularly limited, and may be a linear structure, a branched structure, or a cyclic structure. These partial structures may contain one or more heteroatoms such as oxygen atoms and nitrogen atoms.
• a preferred embodiment of the cationically polymerizable compound includes a compound containing a cyclic structure (compound containing a cyclic structure) as the cationically polymerizable group or as a partial structure other than the cationically polymerizable group.
• the number of cyclic structures contained in the cyclic structure-containing compound is, for example, one in one molecule, and may be two or more.
• the number of cyclic structures contained in the cyclic structure-containing compound is, for example, 1 to 5 in one molecule, but is not particularly limited.
• a compound containing two or more cyclic structures in one molecule may contain the same cyclic structure, or may contain two or more types of cyclic structures with different structures.
• cyclic structure contained in the above-mentioned cyclic structure-containing compound is an oxygen-containing heterocycle. The details are as described above.
• Cationic polymerizability determined by dividing the molecular weight (hereinafter referred to as "B") by the number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound (hereinafter referred to as "C")
• the cationically polymerizable group equivalent is preferably 50 or more.
• the cationically polymerizable group contained in the cationically polymerizable compound for which the cationically polymerizable group equivalent is determined can be an epoxy group (epoxy ring). That is, in one embodiment, the cationically polymerizable compound is an epoxy ring-containing compound.
• the epoxy ring-containing compound is determined by dividing the molecular weight by the number of epoxy rings contained in one molecule, from the viewpoint of improving the adhesion between the HC layer obtained by curing the curable composition for HC layer formation and the resin film.
• the epoxy group equivalent is preferably less than 150, and more preferably 120 or less from the viewpoint of better wear resistance.
• the epoxy group equivalent of the epoxy ring-containing compound is, for example, 50 or more.
• the molecular weight of the cationically polymerizable compound is preferably 500 or less, more preferably 300 or less.
• a cationic polymerizable compound having a molecular weight within the above range tends to easily penetrate into the transparent substrate described below, and can contribute to improving the adhesion between the HC layer obtained by curing the curable composition for forming an HC layer and the transparent substrate. It is assumed that.
• the curable composition for forming an HC layer according to the second aspect (2) contains a) an alicyclic epoxy group and an ethylenically unsaturated group, and the number of alicyclic epoxy groups contained in one molecule is 1. and contains a cationically polymerizable compound in which the number of ethylenically unsaturated groups contained in one molecule is one and the molecular weight is 300 or less.
• component a) the above a) will be referred to as "component a)".
• the number of alicyclic epoxy groups and ethylenically unsaturated groups in one molecule is preferably one each.
• the molecular weight of component a) is 300 or less, preferably 210 or less, and more preferably 200 or less.
• a preferred embodiment of component a) is a compound represented by the following general formula (1).
• R represents a monocyclic hydrocarbon or a bridged hydrocarbon
• L represents a single bond or a divalent linking group
• Q represents an ethylenically unsaturated group.
• R in general formula (1) is a monocyclic hydrocarbon
• the monocyclic hydrocarbon is preferably an alicyclic hydrocarbon, and more preferably an alicyclic group having 4 to 10 carbon atoms. , more preferably an alicyclic group having 5 to 7 carbon atoms, and particularly preferably an alicyclic group having 6 carbon atoms.
• Preferred specific examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, with a cyclohexyl group being preferred.
• R in general formula (1) is a bridged hydrocarbon
• the bridged hydrocarbon is preferably a bicyclic bridged hydrocarbon (bicyclo ring) or a tricyclic bridge hydrocarbon (tricyclo ring).
• Specific examples include bridged hydrocarbons having 5 to 20 carbon atoms, such as norbornyl group, bornyl group, isobornyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, Examples include a tricyclopentanyl group, an adamantyl group, and an adamantyl group substituted with a lower alkyl group (eg, having 1 to 6 carbon atoms).
• the divalent linking group is preferably a divalent aliphatic hydrocarbon group.
• the number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1.
• the divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, even more preferably a linear alkylene group.
• component a) examples include various compounds exemplified in paragraph 0015 of JP-A-10-017614, compounds represented by the following general formula (1A) or (1B), and 1,2-epoxy -4-vinylcyclohexane and the like. Among these, compounds represented by the following general formula (1A) or (1B) are more preferred. In addition, as for the compound represented by the following general formula (1A), its isomer is also preferable.
• R 1 represents a hydrogen atom or a methyl group
• L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.
• the divalent aliphatic hydrocarbon group represented by L 2 in general formulas (1A) and (1B) has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon number.
• the divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, even more preferably a linear alkylene group.
• the HC layer obtained by curing the curable composition for forming an HC layer according to the second aspect (2) preferably has a structure derived from a) of 15 to 10% when the total solid content of the HC layer is 100% by mass.
• the content is preferably 70% by mass, more preferably 18 to 50% by mass, and even more preferably 22 to 40% by mass.
• the curable composition for forming an HC layer according to the second aspect (2) contains component a) in an amount of 15 to 70% by mass when the total solid content of the curable composition for forming an HC layer is 100% by mass. %, more preferably 18 to 50% by weight, even more preferably 22 to 40% by weight.
• cyclic structure contained in the above-mentioned cyclic structure-containing compound is an alicyclic structure.
• the alicyclic structure include a cyclo ring, a dicyclo ring, and a tricyclo ring structure, and specific examples include a dicyclopentanyl ring and a cyclohexane ring.
• the cationically polymerizable compound described above can be synthesized by a known method. It is also possible to obtain it as a commercial product.
• cationically polymerizable compounds containing an oxygen-containing heterocycle as a cationically polymerizable group include 3,4-epoxycyclohexylmethyl methacrylate (commercial products such as Cyclomer M100 manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl -3',4'-epoxycyclohexane carboxylate (for example, commercially available products such as Union Carbide's UVR6105, UVR6110 and Daicel Chemical's Celoxide 2021), bis(3,4-epoxycyclohexylmethyl)adipate (for example, Union Carbide's UVR6128) ), vinylcyclohexene monoepoxide (for example, Celloxide 2000 manufactured by Daicel Chemical), ⁇ -caprolactone-modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate (for example, Celloxide 2081 manufactured by Daicel Chemical
• Daicel Chemical Celloxide 3000 7,7'-dioxa-3,3'-bis[bicyclo[ 4.1.0]heptane] (for example, Celoxide 8000 manufactured by Daicel Chemical), 3-ethyl-3-hydroxymethyloxetane, 1,4bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3 -ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane and di[1-ethyl(3-oxetanyl)]methyl ether.
• cationically polymerizable compounds containing a vinyl ether group as a cationically polymerizable group include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexane.
• Examples include dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and pentaerythritol tetravinyl ether.
• the cationically polymerizable compound containing a vinyl ether group those having an alicyclic structure are also preferable.
• JP-A-8-143806, JP-A-8-283320, JP-A-2000-186079, JP-A-2000-327672, JP-A-2004-315778, and , JP-A-2005-29632, etc. can also be used.
• Exemplary compounds B-1 to B-14 are shown below as specific examples of cationically polymerizable compounds, but the present invention is not limited to the following specific examples.
• preferred embodiments of the curable composition for forming an HC layer include the following embodiments. It is more preferable that one or more of the following aspects are satisfied, and even more preferable that two or more of the following aspects are satisfied. Note that it is also preferable that one cationically polymerizable compound satisfies a plurality of aspects.
• the cationically polymerizable compound includes a cationically polymerizable compound having a cationically polymerizable group equivalent of less than 150.
• an epoxy group-containing compound having an epoxy group equivalent of less than 150 is included.
• the cationically polymerizable compound contains an ethylenically unsaturated group.
• the content of the cationically polymerizable compound in the curable composition for forming an HC layer is preferably 10 parts by mass or more, and 15 parts by mass, based on 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound. The above is more preferable, and 20 parts by mass or more is even more preferable. Further, the content of the cationically polymerizable compound in the curable composition for forming an HC layer is preferably 50 parts by mass or less based on 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound.
• the content of the cationic polymerizable compound in the curable composition for forming an HC layer is 0.05 parts by mass based on 100 parts by mass of the total content of the radical polymerizable compound and the cationic polymerizable compound.
• the amount is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, and even more preferably at least 1 part by mass.
• the content of the cationically polymerizable compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound.
• the content of the cationically polymerizable compound in the curable composition for forming an HC layer is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the curable composition for forming an HC layer.
• the upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 25% by mass or less.
• a compound having both a cationically polymerizable group and a radically polymerizable group is classified as a cationically polymerizable compound, and the content thereof in the curable composition for forming an HC layer is defined.
• the curable composition for forming an HC layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
• the curable composition for forming an HC layer containing a radically polymerizable compound preferably contains a radical photopolymerization initiator, and the curable composition for forming an HC layer containing a cationic polymerizable compound preferably contains a cationic photopolymerization initiator. It is preferable. Note that one type of radical photopolymerization initiator may be used, or two or more types with different structures may be used in combination. The same holds true for cationic photopolymerization initiators. Each photopolymerization initiator will be explained below.
• the radical photopolymerization initiator may be anything that can generate radicals as active species upon irradiation with light, and any known radical photopolymerization initiator may be used without any restrictions. can. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy -2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer and 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] Acetophenones such
• auxiliary agents for radical photopolymerization initiators triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4- Diisopropylthioxanthone or the like may be used in combination.
• radical photopolymerization initiator and auxiliary agent can be synthesized by known methods, and can also be obtained as commercial products.
• the content of the radical photopolymerization initiator in the above-mentioned curable composition for forming an HC layer may be adjusted as appropriate within a range that allows the polymerization reaction (radical polymerization) of the radically polymerizable compound to proceed favorably, and is not particularly limited. do not have.
• the amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1 to 10 parts by weight based on 100 parts by weight of the radically polymerizable compound contained in the curable composition for forming an HC layer. More preferred.
• Cationic photopolymerization initiator may be anything that can generate cations as active species upon irradiation with light, and any known cationic photopolymerization initiator may be used without any restrictions. can. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (eg, diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts.
• cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, JP-A-8-283320
• Examples of cationic polymerization catalysts include those exemplified in paragraph 0020 of .
• the cationic photopolymerization initiator can be synthesized by a known method and is also available as a commercially available product.
• Commercially available products include, for example, Nippon Soda CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102.
• PHOTOINITIATOR 2047 manufactured by Rhodia
• a diazonium salt, an iodonium salt, a sulfonium salt, or an iminium salt is preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, etc. Furthermore, from the viewpoint of weather resistance, iodonium salts are preferred.
• iodonium salt-based cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Kasei, BBI-102 manufactured by Midori Chemical, WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., WPI-124 manufactured by Wako Pure Chemical Industries, Ltd. Examples include WPI-169 manufactured by Wako Pure Chemical Industries, WPI-170 manufactured by Wako Pure Chemical Industries, and DTBPI-PFBS manufactured by Toyo Gosei.
• the content of the cationic photopolymerization initiator in the above-mentioned curable composition for forming an HC layer may be adjusted as appropriate within a range that allows the polymerization reaction (cationic polymerization) of the cationic polymerizable compound to proceed favorably, and is not particularly limited. do not have. It is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and even more preferably 2 to 100 parts by weight, per 100 parts by weight of the cationic polymerizable compound.
• photopolymerization initiators include photopolymerization initiators described in paragraphs 0052 to 0055 of JP-A No. 2009-204725, and the contents of this publication are incorporated into the present invention.
• the curable composition for forming an HC layer contains at least one component having a property of being cured by irradiation with active energy rays and a compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds, and optionally at least one component. It is preferable to include a polymerization initiator. Their details are as described above. Next, various components that can be optionally included in the curable composition for forming an HC layer will be explained.
• the curable composition for forming an HC layer can contain inorganic particles having an average primary particle size of less than 2 ⁇ m. From the viewpoint of improving the hardness of a front plate having an HC layer obtained by curing the curable composition for forming an HC layer (and further improving the hardness of a liquid crystal panel having this front plate), the curable composition for forming an HC layer and this composition
• the hardened HC layer preferably contains inorganic particles having an average primary particle size of less than 2 ⁇ m.
• the average primary particle size of the inorganic particles is preferably 5 nm to 1 ⁇ m, more preferably 5 to 200 nm, and even more preferably 40 nm or more and less than 200 nm.
• the particles were observed using a transmission electron microscope (magnification of 500,000 to 2,000,000 times), and 100 randomly selected particles (primary particles) were observed. , the average value of these particle sizes is taken as the average primary particle size.
• examples of the inorganic particles include silica particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. Among these, silica particles are preferred.
• the surface of the inorganic particles is preferably treated with a surface modifier containing an organic segment in order to increase the affinity with the organic component contained in the curable composition for forming an HC layer.
• the surface modifier preferably has a functional group that can form a bond with the inorganic particles or be adsorbed to the inorganic particles and a functional group that has a high affinity with the organic component in the same molecule.
• Examples of surface modifiers having functional groups that can bind or adsorb to inorganic particles include silane surface modifiers, metal alkoxide surface modifiers such as aluminum, titanium, and zirconium, and phosphoric acid groups, sulfuric acid groups, and sulfonic acid groups.
• a surface modifier having an anionic group such as a group and an anionic group such as a carboxylic acid group is preferred.
• the functional group having high affinity with the organic component include a functional group having the same hydrophilic and hydrophobic properties as the organic component, and a functional group capable of chemically bonding with the organic component.
• functional groups that can chemically bond to organic components are preferred, and ethylenically unsaturated groups or ring-opening polymerizable groups are more preferred.
• inorganic particles having an ethylenically unsaturated group on the surface are preferable as the above-mentioned inorganic particles.
• a preferred surface modifier for inorganic particles is a metal alkoxide surface modifier or a polymerizable compound having an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule.
• Specific examples of the surface modifier include the following exemplified compounds S-1 to S-8.
• S-1 H 2 C C(X)COOC 3 H 6 Si(OCH 3 ) 3
• S-2 H 2 C C(X) COOC 2 H 4 OTi(OC 2 H 5 ) 3
• H 2 C C(X)COOC 2 H 4 OSO 3 H
• S-6 H 2 C C(X)COO(C 5 H 10 COO) 2 H
• S-7 H 2 C C(X)COOC 5 H 10 COOH S-8 CH 2 CH (O) CH 2 OC 3 H 6 Si(OCH 3 ) 3
• X represents a hydrogen atom or a methyl group
• the surface modification of inorganic particles with a surface modifier is preferably performed in a solution.
• a surface modifier is also present, or after the inorganic particles are mechanically dispersed, a surface modifier is added and stirred, or the inorganic particles are mechanically dispersed.
• Surface modification may be performed before (if necessary, heating is performed after drying, or pH (power of hydrogen) is changed), and then dispersion may be performed.
• the solvent for dissolving the surface modifier highly polar organic solvents are preferred. Specific examples include known solvents such as alcohols, ketones, and esters.
• the content of the inorganic particles is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, when the total solid content of the curable composition for HC layer formation is 100% by mass. .
• the lower limit of the above content is not particularly limited and may be 0% by mass (the HC layer does not need to contain inorganic particles), but if it is included, it is 0.5% by mass. It is preferably at least 1% by mass, more preferably at least 1% by mass, even more preferably at least 7% by mass.
• the shape of the primary particles of the inorganic particles may be either spherical or non-spherical, and the primary particles of the inorganic particles are preferably spherical. In order to further improve the hardness, it is more preferable that 2 to 10 spherical inorganic particles (primary particles) are present as higher-order particles such as non-spherical secondary particles or higher.
• inorganic particles include ELCOM V-8802 (spherical silica particles with an average primary particle size of 15 nm manufactured by JGC Catalysts & Chemicals), ELCOM V-8803 (unshaped silica particles manufactured by JGC Catalysts & Chemicals), and MiBK-SD ( (Spherical silica particles with an average primary particle size of 10-20 nm manufactured by Nissan Chemical Industries), MEK-AC-2140Z (Spherical silica particles with an average primary particle size of 10-20 nm manufactured by Nissan Chemical Industries), MEK-AC-4130 (Spherical silica particles with an average primary particle size of 10-20 nm manufactured by Nissan Chemical Industries) MiBK-SD-L (spherical silica particles with an average primary particle size of 40 to 50 nm manufactured by Nissan Chemical), MEK-ST-L (average primary particle size manufactured by Nissan Chemical) MEK-AC-5140Z (spherical silica particles with an average primary particle size of 85
• MEK-AC-2140Z manufactured by Nissan Chemical Industries is preferred from the viewpoint of further improving hardness, and RX-300, MEK-ST-ZL and MEK-AC-5140Z are preferred from the viewpoint of imparting surface irregularities. From the viewpoint of both visibility, MEK-ST-ZL and MEK-AC-5140Z are more preferred.
• the curable composition for forming an HC layer can also contain mat particles.
• the matte particles are particles having an average primary particle size of 2 ⁇ m or more, and may be inorganic particles, organic particles, or particles of an inorganic/organic composite material.
• the shape of the matte particles may be either spherical or non-spherical.
• the average primary particle size of the matte particles is preferably 2 to 20 ⁇ m, more preferably 4 to 14 ⁇ m, and even more preferably 6 to 10 ⁇ m.
• matte particles include inorganic particles such as silica particles and TiO 2 particles, and organic particles such as crosslinked acrylic particles, crosslinked acrylic-styrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles.
• the matte particles are organic particles, and crosslinked acrylic particles, crosslinked acrylic-styrene particles, or crosslinked styrene particles are more preferable.
• the content of matte particles per unit volume in the HC layer obtained by curing the curable composition for HC layer formation is preferably 0.10 g/cm 3 or more, more preferably 0.10 to 0.40 g/cm 3 , and .10 to 0.30 g/cm 3 is more preferable.
• UV absorber The curable composition for forming an HC layer can contain an ultraviolet absorber.
• the ultraviolet absorber include benzotriazole compounds and triazine compounds.
• the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835.
• a triazine compound is a compound having a triazine ring, and specific examples include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP-A No. 2013-111835.
• the content of the ultraviolet absorber in the curable composition for HC layer formation is preferably 0.1 to 10% by mass, when the total solid content of the curable composition for HC layer formation is 100% by mass.
• paragraph 0032 of JP-A No. 2013-111835 can also be referred to.
• ultraviolet light in this specification refers to light having an emission center wavelength in a wavelength band of 200 to 380 nm.
• the curable composition for forming an HC layer can contain a leveling agent.
• a leveling agent a fluorine-containing polymer is preferably used.
• the fluoroaliphatic group-containing polymer described in Japanese Patent No. 5175831 may be mentioned.
• a fluoroaliphatic group-containing polymer in which the content of the fluoroaliphatic group-containing monomer represented by general formula (1), which constitutes the fluoroaliphatic group-containing polymer, is 50% by mass or less of the total polymerized units can be used as a leveling agent. It can also be used.
• the content of the leveling agent is preferably from 0.01 to 7% by mass, and from 0.05 to 5% by mass based on the solid content of the curable composition for forming an HC layer. It is more preferably 0.1% to 2% by mass, and even more preferably 0.1 to 2% by mass.
• the curable composition for forming an HC layer may contain only one type of leveling agent, or may contain two or more types of leveling agents. When two or more types are contained, it is preferable that the total amount falls within the above range.
• the curable composition for forming an HC layer contains a solvent.
• the solvent is preferably an organic solvent, and one or more organic solvents may be used in any proportion.
• organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; and cellosolves such as ethyl cellosolve.
• aromatics such as toluene and xylene
• glycol ethers such as propylene glycol monomethyl ether
• acetate esters such as methyl acetate, ethyl acetate, and butyl acetate
• diacetone alcohol and the like.
• the amount of solvent in the curable composition for forming an HC layer can be adjusted as appropriate within a range that ensures coating suitability of the composition.
• the content of the solvent is preferably 50 to 500 parts by weight, more preferably 80 to 200 parts by weight, based on 100 parts by weight of the total amount of the polymerizable compound and photopolymerization initiator.
• the solid content of the curable composition for HC formation is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and more preferably 65 to 75% by mass, based on the total mass of the curable composition for HC formation. % is more preferable.
• the curable composition for forming an HC layer can contain one or more types of known additives in arbitrary amounts.
• additives include surface conditioners, polymerization inhibitors, polyrotaxanes, and the like.
• paragraphs 0032 to 0034 of JP-A No. 2012-229412 can be referred to.
• the additives are not limited to these, and various additives that can be generally added to the curable composition for forming an HC layer can be used.
• the curable composition for forming an HC layer can be prepared by mixing the various components described above simultaneously or sequentially in any order.
• the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
• the thickness of the HC layer is preferably 1 ⁇ m or more, more preferably 1 to 100 ⁇ m, even more preferably 1 to 20 ⁇ m, particularly preferably 3 to 20 ⁇ m, and most preferably 5 to 20 ⁇ m.
• the thickness of the HC layer was determined by cutting the HC layer with a microtome, cutting out a cross section, staining it with an approximately 3% by mass osmium tetroxide aqueous solution overnight, cutting out the surface again, and measuring the cross section with an SEM (Scanning Electron Microscope). Observe using an electron microscope).
• the surface roughness Sa1 of the component with a wavelength of 2.5 ⁇ m or less on the surface of the HC layer opposite to the reflective layer side is preferably 0.30 nm or more, more preferably 0.40 nm or more, even more preferably 0.45 nm or more, and 0. Particularly preferred is .50 nm or more.
• the upper limit is not particularly limited, but is often 3.0 nm or less, more often 2.0 nm or less.
• the reflective layer and the HC layer are rolled into a roll in such a state that they are in contact with each other, it is possible to reduce the friction between the reflective layer and the HC layer, which is preferable since the reflective layer and the HC layer can be rolled without wrinkles.
• the surface roughness Sa2 of the component having a wavelength of 10 ⁇ m or more on the surface of the HC layer opposite to the reflective layer side is preferably 2.0 nm or less, more preferably 1.5 nm or less, and even more preferably 1.2 nm or less. Although the lower limit is not particularly limited, it is often 0.5 nm or more. It is preferable that the surface roughness Sa2 falls within the above range, as this can improve the visibility of the reflective film.
• the surface roughness of the HC layer surface was measured using a surface profile measurement system [VertScan (registered trademark) R5500G, manufactured by Hitachi High-Tech Science Co., Ltd.] under the following conditions. Measure the shape and read the image data. ⁇ Measurement mode: Wave mode ⁇ Completion: Yes ⁇ Baseline correction: Yes
• FFT fast Fourier transformed
• the surface roughness Sa of the acquired image data was defined as the surface roughness Sa2 of the component having a wavelength of 10 ⁇ m or more.
• the HC layer can be formed by applying a curable composition for forming an HC layer and irradiating the composition with active energy rays. Coating can be performed by known coating methods such as dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, and gravure coating.
• the HC layer can also be formed as a HC layer with a laminated structure of two or more layers (for example, about 2 to 5 layers) by simultaneously or sequentially applying two or more compositions having different compositions.
• the HC layer can be formed by irradiating the applied curable composition for forming an HC layer with active energy rays.
• the curable composition for forming an HC layer contains a radically polymerizable compound, a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator
• the polymerization reaction of the radically polymerizable compound and the cationic polymerizable compound The polymerization can be initiated and progressed by the action of a radical photopolymerization initiator and a cationic photopolymerization initiator, respectively.
• the wavelength of the irradiated light may be determined depending on the type of polymerizable compound and polymerization initiator used.
• Light sources for light irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and LEDs (Light Emitting) that emit light in the wavelength band of 150 to 450 nm. Diode). Further, the amount of light irradiation is preferably 30 to 3000 mJ/cm 2 , more preferably 100 to 1500 mJ/cm 2 . If necessary, drying treatment may be performed before and/or after the light irradiation. The drying process can be performed by blowing hot air, placing in a heating furnace, transporting in a heating furnace, etc.
• the heating temperature is not particularly limited as long as it is set to a temperature that allows the solvent to be removed by drying.
• the heating temperature refers to the temperature of hot air or the ambient temperature in the heating furnace.
• the reflective film may have layers other than the above-described adhesive layer, reflective layer, and HC layer.
• the reflective film 10B includes an adhesive layer 1, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent base material 7, and an HC layer 3 in this order.
• a protective film 4 is arranged on the side of the adhesive layer 1 of the reflective film 10B opposite to the reflective layer 2 side, and a laminate including the reflective film 10B and the protective film 4 is formed.
• the reflective film 10C has the adhesive layer 1, the transparent base material 7, the polarization conversion layer 5, the reflective layer 2, the retardation layer 6, and the HC layer 3 in this order.
• a protective film 4 is disposed on the side of the adhesive layer 1 of the reflective film 10C opposite to the reflective layer 2 side, and a laminate including the reflective film 10C and the protective film 4 is formed.
• the reflective film 10D includes an adhesive layer 1, a matte layer 8, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent base material 7, and an HC layer 3 in this order.
• a protective film 4 is disposed on the opposite side of the reflective layer 2 of the adhesive layer 1 of the reflective film 10D, and a laminate including the reflective film 10C and the protective film 4 is formed.
• the reflective film 10B and the reflective film 10C are made of the same material except that the order of lamination is different.
• the members constituting the reflective film 10B, the reflective film 10C, and the reflective film 10D, and the protective film will be described in detail.
• the adhesive layer 1, reflective layer 2, and HC layer 3 in the reflective film 10B, reflective film 10C, and reflective film 10D are the same as the adhesive layer, reflective layer, and HC layer described above, respectively, so the explanation will be omitted. omitted.
• the polarization conversion layer is a layer in which a helical alignment structure of a liquid crystal compound is fixed, and the pitch number x of the helical alignment structure and the film thickness y (unit: ⁇ m) of the polarization conversion layer are expressed by the following relational expressions (a) to (c). It is preferable that it satisfies all of the following. 0.1 ⁇ x ⁇ 1.0... Formula (a) 0.5 ⁇ y ⁇ 3.0... Formula (b) 3000 ⁇ (1560 ⁇ y)/x ⁇ 50000... Formula (c) Note that one pitch of the helical structure of the liquid crystal compound corresponds to one turn of the spiral of the liquid crystal compound. That is, the pitch number is 1 when the director of the helically aligned liquid crystal compound (in the case of a rod-shaped liquid crystal, the long axis direction) is rotated by 360 degrees.
• the polarization conversion layer When the polarization conversion layer has a helical structure of a liquid crystal compound, it exhibits optical rotation and birefringence for visible light having a shorter wavelength than the reflection peak wavelength in the infrared region. Therefore, polarization in the visible range can be controlled.
• the pitch number x of the helical orientation structure of the polarization conversion layer and the film thickness y of the polarization conversion layer within the above ranges, the polarization conversion layer can optically compensate for visible light or straight lines incident on the reflective film.
• a function of converting polarized light (p-polarized light) into circularly polarized light can be provided.
• the polarization conversion layer exhibits optical rotation and birefringence with respect to visible light because the liquid crystal compound has a helical structure that satisfies the relational expressions (a) to (c).
• the pitch P of the helical structure of the polarization conversion layer is set to a length corresponding to the pitch P of the cholesteric liquid crystal layer whose selective reflection center wavelength is in the long wavelength infrared region, it is possible to Shows high optical rotation and birefringence.
• Relational expression (a) is "0.1 ⁇ x ⁇ 1.0.” It is preferable that the pitch number x of the helical structure is 0.1 or more because sufficient optical rotation and birefringence can be obtained. Further, when the pitch number x of the helical structure is 1.0 or less, optical rotation and birefringence are sufficient, and desired elliptically polarized light is easily obtained.
• the relational expression (b) is "0.5 ⁇ y ⁇ 3.0.”
• the thickness y of the polarization conversion layer is 0.5 ⁇ m or more, sufficient optical rotation and birefringence can be obtained.
• the thickness y of the polarization conversion layer is 3.0 ⁇ m or less, optical rotation and birefringence are sufficient, and desired circularly polarized light is easily obtained.
• the relational expression (c) is "3000 ⁇ (1560 ⁇ y)/x ⁇ 50000.”
• (1560xy)/x is 3000 or more, desired polarized light can be easily obtained.
• (1560xy)/x is 50,000 or less, desired polarized light can be easily obtained.
• the pitch number x of the helical structure of the polarization conversion layer is more preferably 0.1 to 0.8, and the film thickness y is more preferably 0.6 to 2.6 ⁇ m. Further, “(1560 ⁇ y)/x” is more preferably 5000 to 13000.
• the polarization conversion layer has a long pitch P of a helical structure and a small number of pitches x. Specifically, it is preferable that the polarization conversion layer has a spiral pitch P equal to the pitch P of a cholesteric liquid crystal layer whose selective reflection center wavelength is in the long wavelength infrared region, and a small pitch number x. More specifically, it is preferable that the polarization conversion layer has a helical pitch P equal to the pitch P of a cholesteric liquid crystal layer with a selective reflection center wavelength of 3000 to 10000 nm, and a small number of pitches x. In such a polarization conversion layer, since the selective reflection center wavelength corresponding to the pitch P is much longer wavelength than visible light, it more suitably exhibits the above-mentioned optical rotation and birefringence with respect to visible light.
• Such a polarization conversion layer can basically be formed in the same manner as a known cholesteric liquid crystal layer.
• the liquid crystal compound used should be adjusted so that the pitch number x and the film thickness y [ ⁇ m] of the helical structure in the polarization conversion layer satisfy all of the relational expressions (a) to (c). It is preferable to adjust the chiral agent used, the amount of chiral agent added, the film thickness, etc.
• a retardation layer changes the state of incident polarized light by adding a phase difference (optical path difference) to two orthogonal polarized light components.
• the front retardation of the retardation layer may be a retardation that can be optically compensated.
• the retardation layer preferably has a front retardation of 50 to 160 nm at a wavelength of 550 nm.
• the angle of the slow axis is 10 to 50° or - The angle is preferably 50° to -10°.
• the retardation layer converts linearly polarized light into circularly polarized light
• the retardation layer has a front retardation of ⁇ /4, and the front retardation is 3 ⁇ /4. It may be composed of something that gives 4.
• the angle of the slow axis may be arranged so as to change the incident linearly polarized light into circularly polarized light.
• the front retardation of the retardation layer at a wavelength of 550 nm is preferably in the range of 100 to 450 nm, more preferably in the range of 120 to 200 nm or 300 to 400 nm.
• the direction of the slow axis of the retardation layer is determined by the direction of incidence of projected light for displaying a projected image when the reflective film is used in a head-up display system, and the direction of the helical direction of the cholesteric liquid crystal layer constituting the reflective layer. It is preferable to decide according to the sense of
• the retardation layer is not particularly limited and can be appropriately selected depending on the purpose.
• the retardation layer include a stretched polycarbonate film, a stretched norbornene-based polymer film, a transparent film containing and oriented inorganic particles having birefringence such as strontium carbonate, and an inorganic dielectric material on a support.
• examples include a thin film obtained by obliquely vapor-depositing a polymerizable liquid crystal compound, a film in which a polymerizable liquid crystal compound is uniaxially oriented and the orientation is fixed, and a film in which a liquid crystal compound is uniaxially oriented and the orientation is fixed.
• a film in which a polymerizable liquid crystal compound is uniaxially aligned and fixed in orientation is preferably exemplified as a retardation layer.
• a retardation layer can be formed by coating a liquid crystal composition containing a polymerizable liquid crystal compound on the surface of a transparent substrate, a temporary support, or an alignment layer, and then converting the polymerizable liquid crystal compound in the liquid crystal composition into a liquid crystal. After being formed into a nematic orientation in a state, it can be fixed by curing. Formation of the retardation layer in this case can be performed in the same manner as the formation of the cholesteric liquid crystal layer described above, except that no chiral agent is added to the liquid crystal composition.
• the heating temperature is preferably 50 to 120°C, more preferably 60 to 100°C.
• a retardation layer is formed by applying a composition containing a polymeric liquid crystal compound onto the surface of a transparent substrate, temporary support, or alignment layer to form a nematic alignment in a liquid crystal state, and then fixing the alignment by cooling. It may also be a layer obtained by
• the thickness of the retardation layer is not particularly limited, and is preferably 0.2 to 300 ⁇ m, more preferably 0.5 to 150 ⁇ m, and even more preferably 1.0 to 80 ⁇ m.
• the thickness of the retardation layer formed from the liquid crystal composition is not particularly limited, and is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 5.0 ⁇ m, and even more preferably 0.7 to 2.0 ⁇ m.
• the slow axis of the retardation layer is set, for example, at an angle ⁇ with respect to the axis of the retardation layer in an arbitrary direction.
• the direction of the slow axis can be set, for example, by rubbing the alignment film that is the lower layer of the retardation layer.
• the reflective film may be in the form of a thin film, a sheet, or the like.
• the reflective film may be in the form of a roll or the like as a thin film before being used in the windshield glass.
• Transparent substrates can also be used as substrates in forming reflective layers or HC layers.
• the transparent substrate used for forming the reflective layer or HC layer may be a temporary support that is peeled off after forming the reflective layer or HC layer. Therefore, the finished reflective film and windshield glass may not include a transparent substrate. Note that when the completed reflective film or windshield glass includes a transparent base material rather than being peeled off as a temporary support, the transparent base material is preferably transparent in the visible light region.
• the material of the transparent base material is not particularly limited.
• the transparent substrate include polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and plastic films such as silicones.
• PET polyethylene terephthalate
• acrylic resins acrylic resins
• epoxy resins epoxy resins
• polyurethanes polyamides
• polyolefins polyolefins
• cellulose derivatives cellulose derivatives
• plastic films such as silicones.
• glass in addition to the above-mentioned plastic film, glass may be used.
• cellulose acylate film is preferred.
• the thickness of the transparent base material may be about 5.0 to 1000 ⁇ m, preferably 10 to 250 ⁇ m, more preferably 15 to 90 ⁇ m, and even more preferably 40 to 80 ⁇ m.
• the transparent base material may be formed into a film by any method, such as a melt film forming method and a solution film forming method.
• the melt film forming method consists of a melting process in which the resin is melted using an extruder, a process in which the molten resin is extruded into a sheet form from a die, and a process in which it is formed into a film form. It is preferable to include. Depending on the material of the resin, a filtration step for the molten resin may be provided after the melting step, or cooling may be performed when extruding into a sheet. A specific solution film forming method will be described below, but the present invention is not limited thereto.
• the method for manufacturing the transparent base material described above includes a melting process in which the resin is melted using an extruder, a filtration process in which the molten resin is filtered through a filtration device equipped with a filter, and the filtered resin is extruded into a sheet form from a die. , a film forming step of forming an unstretched transparent base material by cooling and solidifying the film by bringing it into close contact with a cooling drum; and a stretching step of uniaxially or biaxially stretching the unstretched transparent base material. preferable.
• a transparent base material can be manufactured.
• the pore diameter of the filter used in the process of filtering the molten resin is 1 ⁇ m or less, foreign substances can be sufficiently removed.
• the method for forming a transparent substrate can include the following steps.
• the method for manufacturing the transparent substrate described above includes a melting step of melting the resin using an extruder. It is preferable that the resin or the mixture of the resin and the additive be dried to a water content of 200 ppm or less, and then introduced into a single-screw (single-screw) or twin-screw extruder and melted. At this time, it is also preferable to melt the resin in nitrogen or vacuum in order to suppress decomposition of the resin.
• the extruder is preferably a uniaxial kneading extruder. Furthermore, it is also preferable to use a gear pump in order to increase the precision of feeding the molten resin (melt).
• the method for manufacturing a transparent substrate includes a filtration step of filtering the molten resin through a filtration device equipped with a filter, and the pore size of the filter used in the filtration step is preferably 1 ⁇ m or less. In the filtration process, only one set or two or more sets of filtration devices having filters having pore diameters in this range may be installed in the filtration process.
• the above-mentioned method for producing a transparent substrate includes a film forming step of extruding the filtered resin into a sheet from a die, placing it in close contact with a cooling drum, and cooling and solidifying it to form an unstretched transparent substrate.
• a layer containing an ultraviolet absorber and a layer not containing an ultraviolet absorber may be laminated. More preferably, a three-layer structure with a layer containing an ultraviolet absorber as an inner layer is preferable because the polarizer is not affected by ultraviolet rays. This is preferable in that deterioration can be suppressed and bleeding out of the ultraviolet absorber can be suppressed.
• the thickness of the inner layer of the obtained transparent substrate is preferably 50 to 99%, more preferably 60 to 99%, and 70 to 99% of the thickness of all layers. % is more preferable.
• Such stacking can be performed using a feedblock die and a multi-manifold die.
• the temperature of the resin extruded from the die is preferably 280 to 320°C, more preferably 285 to 310°C. It is preferable that the temperature of the resin extruded from the die in the melting step is 280° C. or higher, since this reduces the amount of unmelted raw material resin and suppresses the generation of foreign matter. It is preferable that the temperature of the resin extruded from the die in the melting step is 320° C. or lower, since decomposition of the resin can be reduced and generation of foreign matter can be suppressed.
• the temperature of the resin extruded from the die can be measured without contacting the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used with an emissivity of 0.95).
• an electrostatic charge applying electrode when bringing the resin into close contact with the cooling drum in the film forming process. This allows the resin to be strongly adhered to the cooling drum so that the film surface does not become rough.
• the temperature of the resin is preferably 280° C. or higher when the resin is brought into close contact with the cooling drum (at the point where the molten resin extruded from the die first contacts the cooling drum). This increases the electrical conductivity of the resin, allows it to be strongly adhered to the cooling drum by electrostatic application, and suppresses roughening of the film surface.
• the temperature of the resin when brought into close contact with the cooling drum can be measured without contacting the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used with an emissivity of 0.95).
• the above-mentioned method for producing a transparent base material includes a stretching step of uniaxially or biaxially stretching an unstretched transparent base material.
• the longitudinal stretching process the process of stretching in the same direction as the film transport direction
• the transparent base material is heated, and there is a difference in circumferential speed (i.e., different transport speeds). It is stretched in the transport direction by a group of rollers.
• the preheating temperature in the longitudinal stretching step is preferably Tg-40°C or higher and Tg+60°C or lower, more preferably Tg-20°C or higher and Tg+40°C or lower, and Tg or higher and Tg+30°C or lower relative to the glass transition temperature (Tg) of the transparent substrate. More preferred.
• the stretching temperature in the longitudinal stretching step is preferably Tg+2°C or higher and Tg+40°C or lower, still more preferably Tg+5°C or higher and Tg+30°C or lower.
• the stretching ratio in the longitudinal direction is preferably 1.0 to 2.5 times, more preferably 1.1 to 2 times.
• the transparent base material is laterally stretched in the width direction by a lateral stretching step (a step of stretching in a direction perpendicular to the film transport direction).
• a lateral stretching step for example, a tenter can be suitably used, and the tenter grips both ends of the transparent base material in the width direction with clips and stretches the transparent base material in the lateral direction. This lateral stretching can increase the tensile modulus of the transparent base material in the optical film.
• the lateral stretching is preferably carried out using a tenter, and the preferred stretching temperature is preferably Tg or higher and Tg + 60°C or lower, more preferably Tg + 2°C or higher and Tg + 40°C or lower, with respect to the glass transition temperature (Tg) of the transparent substrate. More preferably Tg+4°C or higher and Tg+30°C or lower.
• the stretching ratio is preferably 1.0 to 5.0 times, more preferably 1.1 to 4.0 times. It is also preferable to relax the transparent substrate in either or both of the vertical and horizontal directions after the horizontal stretching.
• the variation in thickness depending on the location in both the width direction and the longitudinal direction is kept to 10% or less, more preferably 8% or less, even more preferably 6% or less, and 4% or less. It is particularly preferred that the content be 2% or less.
• the variation in thickness can be determined as follows.
• Th TD-av thickness average value Th TD-av in the width direction, the maximum value Th TD-max , and the minimum value Th TD-min , (Th TD-max - Th TD-min ) ⁇ Th TD-av ⁇ 100 [%] is the variation in thickness in the width direction.
• the average thickness Th MD-av in the longitudinal direction, the maximum value Th MD-max , and the minimum value Th MD-min are determined, (Th MD-max - Th MD-min ) ⁇ Th MD-av ⁇ 100 [%] is the variation in thickness in the longitudinal direction.
• the transparent base material after stretching can be wound up into a roll in a winding process.
• the winding tension of the transparent base material is preferably 0.02 kg/mm 2 or less.
• a dope solution forming a core layer is used.
• a method of increasing the viscosity of the dope to ensure the strength of the cast film and lowering the viscosity of the dope forming the outer layer are used.
• preferred methods include a method in which the cast membrane is rapidly dried to form a film on the surface of the cast film, and the surface shape is smoothed by the leveling effect of the formed film, and a method in which the cast film is stretched. .
• the transparent base material may be shrunk by heat.
• the reflective film when the reflective film is made to follow curved glass, it is preferable that the reflective film shrinks due to heat shrinkage of the transparent base material, thereby suppressing wrinkles.
• the application liquid a liquid obtained by dissolving a surfactant in distilled water, ion-exchanged water, or tap water can be used.
• the surfactant contributes to improving the wettability of the application liquid to the surface of the object to be laminated (eg, glass), adjusting the evaporation time, and the like.
• ester type surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester
• ether type surfactants such as alkyl polyethylene glycol and polyoxyethylene alkylphenyl ether
• nonionic surfactants such as alkyl glycosides.
• concentration of the surfactant in the application liquid is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass.
• a reflective film using a heat-shrinkable transparent base material has the effect of effectively suppressing the occurrence of wrinkles in the highly curved portions of the glass.
• the film In areas where the curvature of the glass is large, the film has a degree of freedom to expand in the thickness direction, causing film contraction in the plane direction, and in areas where the curvature of the glass is small, the degree of freedom for the film to expand in the thickness direction is small, causing film contraction in the plane direction.
• a possible mechanism of action is that almost no film shrinkage occurs.
• the temperature at which the transparent base material is thermally shrunk varies depending on the material forming the transparent base material, but it is preferable that the transparent base material shrinks within a range of 80 to 200°C, and the heat treatment temperature with a heat gun in a general curved surface following process is It is more preferable to shrink within a certain range of 100 to 140°C.
• the heating for shrinking the transparent substrate may be applied to the entire curved glass, or may be applied locally to areas that have a high curvature and are prone to wrinkles.
• the amount of shrinkage of the transparent substrate required to suppress wrinkles in the reflective film varies depending on the curvature and dimensions of the glass.
• the transparent base material has a heat shrinkage rate of 0.01 to 5.0% in the direction where the heat shrinkage rate is maximum and in the direction perpendicular to the direction under heating conditions using a heat gun or the like in the curved surface following process. It is preferably 0.05 to 3.0%, and even more preferably 0.2 to 2.0%.
• the heat shrinkage rate is 0.01% or more, wrinkles are less likely to occur when following a curved surface.
• the thermal shrinkage rate is 5.0% or less, bubbles are less likely to be generated when following a curved surface.
• the heat shrinkage rate can be adjusted as appropriate by adjusting the stretching conditions when manufacturing the transparent base material.
• the heat shrinkage rate was measured as follows. Two reference lines are placed in advance in the width direction of a sample piece of film cut out to a width of 30 mm and a length of 120 mm so as to have an interval of 100 mm. After leaving the sample piece in a heating oven at 140° C. for 45 minutes under no tension, the sample piece is cooled to room temperature, and the distance between the two reference lines is measured. The post-processing interval measured at this time is defined as A [mm].
• the thermal shrinkage rate of the sample piece is the numerical value [%] calculated from the pre-treatment interval 100 mm and the post-treatment interval Amm using the formula "100 x (100-A)/100".
• ⁇ Protective film layer of adhesive layer> It is preferable to provide a removable protective film layer on one side of the adhesive layer. By having such a protective film layer, it is possible to prevent the adhesive layer of the reflective film before use from being damaged and from adhering to dust, dirt, etc., and the protective film layer can be peeled off at the time of use.
• a release layer can be provided between the protective film layer and the adhesive layer to facilitate peeling off the protective film layer.
• the method for providing such a release layer is not particularly limited, and, for example, it can be provided by applying a release coating agent to the surface of at least one of the protective film layer and the adhesive layer.
• the type of release coating agent is not particularly limited, and examples include silicone coating agents, inorganic coating agents, fluorine coating agents, and organic-inorganic hybrid coating agents.
• a laminate containing a reflective film and a protective film can be obtained by providing the release layer on the surface of the protective film layer and then laminating it on the surface of the adhesive layer.
• the release layer may be provided not on the surface of the protective film layer but on the surface of the adhesive layer.
• the difference in thermal shrinkage rate between the protective film layer and the reflective film layer is small.
• the difference in thermal shrinkage rate under heating conditions using a heat gun or the like in the curved surface following process is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.6% or less.
• the difference in thermal shrinkage rate at 140° C. between the reflective film and the protective film is less than 1.5%.
• the difference between the heat shrinkage rate of the reflective film at 140°C and the heat shrinkage rate of the protective film at 140°C is preferably smaller than 1.5%, more preferably 1.0% or less, and 0.6%.
• the following are more preferable.
• the lower limit is not particularly limited, and may be 0%.
• the reflective film of the present invention preferably reflects linearly polarized light.
• the projected image light is preferably p-polarized light, that is, linearly polarized light, in order to suppress reflection on the surface of the windshield glass.
• the reflective layer has a cholesteric liquid crystal layer and reflects circularly polarized light. Therefore, the reflective film of the present invention preferably has a layer that converts linearly polarized light incident on the reflective film into circularly polarized light. Examples of the layer that converts the polarization state of light include the above-mentioned polarization conversion layer and retardation layer.
• the polarization conversion layer exhibits optical rotation and birefringence with respect to visible light, and converts the polarization state of incident light.
• the polarization conversion layer is preferably made of a layer in which a birefringent material such as a liquid crystal compound is oriented with a twist amount of 360° or less.
• the retardation layer changes the state of incident polarized light by adding a phase difference (optical path difference) to two orthogonal polarized light components.
• the retardation layer is a layer in which birefringent materials such as liquid crystal compounds are aligned in the same direction, and does not have optical rotation.
• the reflective film has a polarization conversion layer or a retardation layer on the light incident side of the reflective layer
• linearly polarized light incident on the reflective film is converted to circularly polarized light
• the reflective layer reflects the circularly polarized light.
• the polarization conversion layer or the retardation layer may convert the reflected circularly polarized light into linearly polarized light and emit the linearly polarized light.
• the reflective film 10D has the polarization conversion layer 5 on one side of the reflective layer 2, and the retardation layer 6 on the other side.
• the polarization conversion layer 5 is placed on the car-inside glass plate 11 side.
• the windshield glass shown in FIG. 5 includes a car interior glass plate 11, an adhesive layer 1, a matte layer 8, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent base material 7, and an HC layer 3 in this order. It has.
• the polarization conversion layer has a function of converting projected p-polarized light (linearly polarized light) into circularly polarized light reflected by the cholesteric liquid crystal layer of the reflective layer.
• the retardation layer has a function of optically compensating for light incident from outside the windshield glass. For example, the polarization state of s-polarized light incident from the outside of the windshield glass changes when it passes through a polarization conversion layer, and a p-polarized light component is mixed therein. Since polarized sunglasses cut out s-polarized light, this p-polarized light component passes through the polarized sunglasses.
• the function of polarized sunglasses that cuts out the glare of reflected light whose main component is s-polarized light is impaired, which poses a problem that may impede driving.
• the suitability for polarized sunglasses can be improved by providing a structure including a retardation layer and optically compensating with the retardation layer.
• the reflective film 10D has a configuration in which the polarization conversion layer 5 is placed on the side of the vehicle interior glass plate 11, but the configuration is not limited thereto.
• the reflective film 10D may be arranged such that the retardation layer 6 is on the vehicle-inside glass plate 11 side.
• the retardation layer 6 has a function of converting the projected p-polarized light (linearly polarized light) into circularly polarized light reflected by the cholesteric liquid crystal layer of the reflective layer 2.
• the polarization conversion layer 5 has a function of optically compensating for light incident from the outside of the windshield glass, and by optically compensating with the polarization conversion layer 5, suitability for polarized sunglasses can be improved.
• the reflective film of the present invention may have a configuration in which the reflective layer 2 has polarization conversion layers on both sides, or may have a configuration in which it has retardation layers on both sides.
• the polarization conversion layer or retardation layer disposed on the inside glass plate has a function of converting the projected p-polarized light (linearly polarized light) into circularly polarized light reflected by the cholesteric liquid crystal layer of the reflective layer. do it.
• the polarization conversion layer or the retardation layer disposed on the outside of the vehicle may have a function of optically compensating for light incident from outside the windshield glass.
• the polarization conversion layer and the retardation layer are as described above.
• the reflective film of the present invention may have a matte layer on the opposite side of the reflective layer from the hard coat layer.
• the reflective film may have a matte layer between the adhesive layer and the reflective layer.
• the matte layer is a layer having unevenness.
• the matte layer and the HC layer can come into direct contact with each other when the reflective film is a semi-finished product (at the stage of a laminate that includes a matte layer, a reflective layer, and an HC layer but does not have an adhesive layer).
• the matte layer can be provided on the opposite side of the retardation layer or polarization conversion layer from the hard coat layer.
• the matte layer can be obtained by irradiating the curable composition for forming a matte layer with active energy rays and curing it.
• the curable composition for forming a matte layer used for forming the matte layer contains two or more ethylenically unsaturated groups in one molecule in order to ensure adhesion with the reflective layer, retardation layer, and polarization conversion layer. It is preferable to contain a polymerizable compound and a radical photopolymerization initiator, and it is preferable to contain particles in order to provide unevenness. Moreover, it is also preferable that the curable composition for forming a matte layer contains a solvent or a leveling agent.
• the thickness of the matte layer is preferably 10 nm or more, more preferably 10 nm to 1 ⁇ m, and even more preferably 30 nm to 1 ⁇ m.
• the thickness of the matte layer was determined by cutting the matte layer with a microtome, cutting out a cross section, staining it with an approximately 3% by mass osmium tetroxide aqueous solution overnight, cutting out the surface again, and measuring the cross section with an SEM (Scanning Electron Microscope). Observe using an electron microscope).
• the surface roughness Sa1 of the component having a wavelength of 2.5 ⁇ m or less on the surface of the matte layer opposite to the reflective layer side is preferably 0.30 nm or more, more preferably 0.40 nm or more, even more preferably 0.45 nm or more, and 0. Particularly preferred is .50 nm or more.
• composition for forming reflective layer ⁇ Preparation of composition for forming reflective layer, composition for forming retardation layer, and composition for forming polarization conversion layer>
• the components were mixed according to the formulation shown in Table 3 below, and filtered through a polypropylene filter with a pore size of 10 ⁇ m to form reflective layer forming compositions BG1, R1, IR1, retardation layer forming composition A1, and polarization conversion layer forming composition.
• Composition TW-1 was prepared. The amount of each component shown in Table 3 is expressed in parts by mass.
• the mixture 1, the alignment control agent 1, and the alignment control agent 2 are the compounds mentioned above.
• composition for forming matte layer Each component was mixed according to the formulation shown in Table 4 below, and filtered through a polypropylene filter with a pore size of 10 ⁇ m to prepare matte layer forming compositions M-1 to M-3.
• the amount of each component shown in Table 4 is expressed in parts by mass.
• a cellulose acylate film on which an alignment film was formed was used as a transparent base material.
• a cellulose acylate film with a thickness of 40 ⁇ m was produced using the same production method as in Example 20 of International Publication No. 2014/112575. Note that UV-531 manufactured by Teimori Kako Co., Ltd. was added to this cellulose acylate film as an ultraviolet absorber. The amount added was 3 phr (per hundred resin).
• the produced cellulose acylate film was passed through a dielectric heating roll at a temperature of 60°C to raise the surface temperature of the film to 40°C, and then an alkaline solution having the composition shown below was applied to one side of the film using a bar coater. The sample was applied at a coating amount of 14 mL/m 2 using a 110° C.
• cellulose acylate films prepared with adjusted film thicknesses of 25 ⁇ m, 60 ⁇ m, and 80 ⁇ m were prepared, and treated in the same manner as above to produce cellulose acylate films 2, 3, and 4. .
• a cellulose acylate film prepared by adjusting the film thickness to 40 ⁇ m and adjusting the stretching conditions to increase the residual stress was prepared, and subjected to the same treatment as above to form cellulose acylate film 5. Created.
• a coating solution for forming an alignment film having the composition shown below was applied at 24 mL/m 2 using a wire bar coater, and then heated at 100°C. It was dried with warm air for 120 seconds to obtain an alignment film with a thickness of 0.5 ⁇ m.
• composition of coating liquid for forming alignment film ⁇ ⁇ Modified polyvinyl alcohol shown below 28 parts by mass ⁇ Citric acid ester (AS3, manufactured by Sankyo Kagaku Co., Ltd.) 1.2 parts by mass ⁇ Photoinitiator (Irgacure 2959, manufactured by BASF) 0.84 parts by mass ⁇ Glutaraldehyde 2.8 Parts by mass/Water 699 parts by mass/Methanol 226 parts by mass ⁇
• ⁇ Preparation of reflective film> The alignment film prepared above was subjected to rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), rotation speed: 1000 rpm (revolutions) in a direction rotated 45 degrees clockwise with respect to the long side direction of the support per minute), conveyance speed: 10 m/min, number of times: 1 reciprocation).
• the reflection layer forming composition IR1 was applied to the surface of the alignment film rubbed above at room temperature using a wire bar so that the thickness of the dry film after drying was 0.4 ⁇ m to obtain a coating layer. . After drying the coating layer at room temperature for 30 seconds, it was heated in an atmosphere of 85° C. for 2 minutes. After that, in an environment with an oxygen concentration of 1000 ppm or less, ultraviolet rays were irradiated at 60 °C with a Fusion D bulb (90 mW/cm lamp) at 60% output for 6 to 12 seconds to fix the cholesteric liquid crystal phase. A cholesteric liquid crystal layer IR1 having a thickness of 0.4 ⁇ m was obtained.
• a cholesteric liquid crystal layer BG1 having a thickness of 0.34 ⁇ m was laminated on the surface of the obtained cholesteric liquid crystal layer IR1 by repeating the same process using the reflective layer forming composition BG1.
• a cholesteric liquid crystal layer R1 having a thickness of 0.20 ⁇ m was laminated on the surface of the obtained cholesteric liquid crystal layer BG1 by repeating the same process using the reflective layer forming composition R1. In this way, a film A1 having a reflective layer consisting of three cholesteric liquid crystal layers was obtained.
• a curable composition for forming an HC layer HC-1 is applied to the surface of the cellulose acylate film 1 opposite to the reflective layer in the film A1 produced above and cured to form an HC1 layer with a thickness of 6 ⁇ m.
• the coating and curing methods were as follows.
• the curable composition for forming an HC layer was applied by the die coating method using a slot die described in Example 1 of JP-A No. 2006-122889 at a conveyance speed of 30 m/min, and then coated at an ambient temperature of 60° C. for 60 seconds. Dry.
• NCF-D692 Adhesive layer thickness 15 ⁇ m, manufactured by Lintec Corporation
• the reflective film of Example 1 having the structure of HC layer/transparent base material/reflective layer/adhesive layer/protective film was produced by laminating them together. Note that the above NCF-D692 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of NCF-D692.
• Examples 2 to 13 The reflections of Examples 2 to 13 were prepared in the same manner as in Example 1, except that the curable compositions for HC layer formation HC-2 to HC-13 were used instead of the curable composition for HC layer formation HC-1. A film was produced.
• Example 14 A reflective film of Example 14 was produced in the same manner as Example 2 except that the thickness of the first HC layer was 12 ⁇ m.
• Example 15 A reflective film of Example 15 was produced in the same manner as Example 2 except that the thickness of the first HC layer was 3 ⁇ m.
• Example 16> The curable composition for HC layer formation HC-14 was used instead of the curable composition for HC layer formation HC-2, and the ultraviolet irradiation conditions for curing were as follows: illuminance 20 mW/cm 2 and irradiation amount 30 mJ/cm 2
• the first HC layer was formed in the same manner as in Example 14 except for the following steps.
• a curable composition for forming an HC layer, HC-15 was applied onto the surface of the first HC layer formed above and cured to form a second HC layer with a thickness of 4 ⁇ m.
• the coating and curing methods were as follows.
• the curable composition for forming an HC layer was applied by the die coating method using a slot die described in Example 1 of JP-A-2006-122889 at a conveyance speed of 30 m/min, and then coated at an ambient temperature of 60° C. for 150 seconds. Dry. After that, under a nitrogen purge, ultraviolet rays were irradiated with an illumination intensity of 150 mW/cm 2 and an irradiation amount of 600 mJ/cm 2 using a 160 W/cm air-cooled metal halide lamp (manufactured by Eye Graphics) at an oxygen concentration of approximately 0.1 volume %. After forming a second HC layer, winding was performed to obtain a film HC2 having a reflective layer and an HC layer.
• An adhesive layer was applied to the reflective layer side of the film HC2 produced above. After peeling off the light release film of NCF-D692 (adhesive layer thickness 15 ⁇ m, manufactured by Lintec Corporation), the exposed adhesive layer was brought into contact with the reflective layer of film HC1 while applying a load of 2 kg with a rubber roller.
• a reflective film of Example 16 having a structure of HC layer/transparent base material/reflective layer/adhesive layer/protective film was produced by laminating.
• Example 17 A reflective film of Example 17 was produced in the same manner as in Example 2 except that the thickness of the cholesteric liquid crystal layer BG1 was 0.84 ⁇ m.
• Example 18 A reflective film of Example 18 was produced in the same manner as Example 2 except that the thickness of the cholesteric liquid crystal layer R1 was 0.36 ⁇ m.
• Example 19 A reflective film of Example 19 was produced in the same manner as Example 18, except that NCF-D692 (adhesive layer thickness: 10 ⁇ m, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above NCF-D692 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of NCF-D692.
• NCF-D692 adheresive layer thickness: 10 ⁇ m, manufactured by Lintec Corporation
• Example 20 A reflective film of Example 20 was produced in the same manner as in Example 18, except that NCF-D692 (adhesive layer thickness: 5 ⁇ m, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above NCF-D692 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of NCF-D692.
• NCF-D692 adheresive layer thickness: 5 ⁇ m, manufactured by Lintec Corporation
• Example 21 A reflective film of Example 21 was produced in the same manner as in Example 18, except that NCF-D692 (adhesive layer thickness: 20 ⁇ m, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above NCF-D692 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of NCF-D692.
• NCF-D692 adheresive layer thickness: 20 ⁇ m, manufactured by Lintec Corporation
• Example 22 A reflective film of Example 22 was produced in the same manner as in Example 18, except that NCF-D692 (adhesive layer thickness: 25 ⁇ m, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above NCF-D692 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of NCF-D692.
• NCF-D692 adheresive layer thickness: 25 ⁇ m, manufactured by Lintec Corporation
• Example 23 A reflective film of Example 23 was produced in the same manner as Example 18, except that Panaclean PD-S1 (adhesive layer thickness: 5 ⁇ m, manufactured by Panac Co., Ltd.) was used as the adhesive layer.
• the Panaclean PD-S1 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of PD-S1.
• Example 24 A reflective film of Example 24 was produced in the same manner as Example 18, except that MF-58 (adhesive layer thickness: 12 ⁇ m, manufactured by Tomoekawa Paper Manufacturing Co., Ltd.) was used as the adhesive layer. Note that the above MF-58 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of MF-58.
• MF-58 adheresive layer thickness: 12 ⁇ m, manufactured by Tomoekawa Paper Manufacturing Co., Ltd.
• Example 25 A reflective film of Example 25 was produced in the same manner as Example 18, except that MHM-UVC (adhesive layer thickness: 15 ⁇ m, manufactured by Nichiei Shinka Co., Ltd.) was used as the adhesive layer. Note that the MHM-UVC has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of the MHM-UVC.
• MHM-UVC adheresive layer thickness: 15 ⁇ m, manufactured by Nichiei Shinka Co., Ltd.
• Example 26 A reflective film of Example 26 was produced in the same manner as Example 18, except that SK Dyne 2057 (adhesive layer thickness: 25 ⁇ m, manufactured by Soken Kagaku Co., Ltd.) was used as the adhesive layer. Note that SK Dyne 2057 has a light release film, an adhesive layer, and a heavy release film, and the protective film in the reflective film corresponds to the heavy release film of SK Dyne 2057.
• Example 27 A reflective film of Example 27 was produced in the same manner as Example 18 except that cellulose acylate film 2 (thickness: 25 ⁇ m) was used as the transparent base material.
• Example 28 A reflective film of Example 28 was produced in the same manner as in Example 18, except that cellulose acylate film 3 (thickness: 60 ⁇ m) was used as the transparent base material.
• Example 29 A reflective film of Example 29 was produced in the same manner as Example 18 except that cellulose acylate film 4 (thickness: 80 ⁇ m) was used as the transparent base material.
• Example 30 A reflective film of Example 30 was produced in the same manner as Example 18 except that cellulose acylate film 5 (thickness: 40 ⁇ m) was used as the transparent base material.
• Example 31 The retardation layer forming composition A1 is applied to the rubbed alignment film surface using a wire bar, dried, and then cured under the following conditions to form a reflective layer on the cured retardation layer A1.
• a reflective film of Example 31 was produced in the same manner as Example 24, except that the composition IR1 was applied.
• composition A1 ⁇ Curing conditions for retardation layer forming composition A1> After applying and drying the composition A1 for forming a retardation layer, it was placed on a hot plate at 50°C, and in an environment with an oxygen concentration of 1000 ppm or less, an electrodeless lamp "D Bulb” manufactured by Fusion UV Systems (60 mW/cm 2 ) for 6 seconds to form a retardation layer. In this way, a retardation layer whose thickness was adjusted to have a desired front retardation, that is, a desired retardation, was obtained. The retardation of the produced retardation layer at 550 nm was measured using AxoScan manufactured by Axometrics, and was found to be 126 nm.
• Example 32 A reflective film of Example 32 was produced in the same manner as Example 31, except that the polarization conversion layer TW1 was provided on the cholesteric liquid crystal layer R1 to a thickness of 0.8 ⁇ m.
• the polarization conversion layer TW1 is formed by coating the polarization conversion layer forming composition TW1 on the cholesteric liquid crystal layer R1 at room temperature using a wire bar, drying the coating layer at room temperature for 30 seconds, and drying it in an atmosphere of 85°C. Heat for 2 minutes. Thereafter, in an environment with an oxygen concentration of 1000 ppm or less, ultraviolet rays were irradiated at 60° C. using a Fusion D bulb (90 mW/cm lamp) at 60% output for 6 to 12 seconds to form a polarization conversion layer.
• a Fusion D bulb 90 mW/cm lamp
• Examples 33 to 42 The reflections of Examples 33 to 42 were prepared in the same manner as in Example 24, except that the curable compositions for HC layer formation HC-16 to HC-25 were used instead of the curable composition for HC layer formation HC-2. A film was produced.
• Example 43 The curable composition for HC layer formation HC-14 was used instead of the curable composition for HC layer formation HC-2, and the ultraviolet irradiation conditions for curing were as follows: illuminance 20 mW/cm 2 and irradiation amount 30 mJ/cm 2
• the first HC layer was formed in the same manner as in Example 24 except for the following steps.
• a curable composition for forming an HC layer HC-26 was applied and cured to form a second HC layer with a thickness of 0.2 ⁇ m.
• a reflective film of Example 43 was produced by applying the adhesive layer in the same manner as in Example 24.
• Examples 44 to 46> A reflective film having a polarization conversion layer was produced in the same manner as in Example 32, except that HC-17 was used as the HC forming composition. Matte layer forming compositions M-1 to M-3 were each applied onto the surface of the polarization conversion layer of the reflective film and cured to form a matte layer with a thickness of 60 nm. Specifically, the coating and curing methods were as follows. The curable composition for forming a matte layer was applied by the die coating method using a slot die described in Example 1 of JP-A No. 2006-122889 at a conveyance speed of 30 m/min, and then coated at an ambient temperature of 45° C. for 60 seconds. Dry.
• Comparative example 1 A reflective film of Comparative Example 1 was produced in the same manner as in Example 1 except that the HC layer was not provided.
• Comparative example 2 A reflective film of Comparative Example 2 was produced in the same manner as Example 1 except that no reflective layer was provided.
• Comparative example 3 A reflective film of Comparative Example 3 was produced in the same manner as Example 1 except that no adhesive layer was provided.
• Pencil Hardness Pencil hardness was evaluated according to JIS (JIS stands for Japanese Industrial Standards) K5400. Peel off the protective film from the adhesive layer of the reflective film, and place a glass plate (manufactured by Corning, product name: Eagle A laminate of the reflective film and the glass plate was produced by laminating the reflective film and the glass plate while applying a load of 2 kg using a rubber roller. After conditioning the laminate for 2 hours at a temperature of 25°C and a relative humidity of 60%, five different locations on the surface of the HC layer were tested under a load of 750 gf using a test pencil of H to 9H specified in JIS S 6006. I scratched it. After that, among the hardnesses of pencils with 0 to 2 visually observed scratches, the pencil hardness with the highest hardness was used as the evaluation result.
• JIS JIS stands for Japanese Industrial Standards
• a Taber abrasion tester (rotary abrasion tester, manufactured by Toyo Seiki Co., Ltd.), the surface of the HC layer was tested for 100 cycles at a rotation speed of 72 rpm with a CS-10F abrasion wheel and a load of 500 gf. After the test, the haze (HB) of the test portion of the laminate was measured. The ⁇ haze (HB-HA) before and after the test was calculated and evaluated based on the following criteria.
• A 1% or less.
• B greater than 1% and less than 2.5%.
• C greater than 2.5% and less than 4%.
• D greater than 4%.
• a to C is an acceptable range.
• the average value of the reflectance when P-polarized light is incident and the reflectance when S-polarized light is incident is the same as the reflectance when unpolarized light (natural light) is incident. That is, the average value of the reflection spectrum of P-polarized light and the reflection spectrum of S-polarized light is synonymous with the reflection spectrum when natural light is incident.
• a to B is an acceptable range.
• the above-prepared application liquid was sprayed onto the convex side of a curved glass measuring 330 mm wide x 260 mm long, with a curvature of 330 mm, R1750 mm in the longitudinal direction, 260 mm and R1250 mm in the transverse direction.
• the reflective film produced above was cut out to a size of 330 mm x 260 mm and pasted so that the hard coat layer side of the reflective film was in contact with the convex side of the curved glass.
• the reflective film was adsorbed to the convex side of the curved glass due to the surface tension of the application solution, but a portion of the reflective film did not come into contact with the curved glass and remained as wrinkles.
• a squeegee was used while applying hot air to the wrinkled portion of the reflective film using a heat gun (Heating Gun 882, manufactured by Hakko Co., Ltd.), and the wrinkled portion of the reflective film was shrunk to follow the surface of the curved glass.
• Heating Gun 882 manufactured by Hakko Co., Ltd.
• A It will slip even if you put a 150g weight on it.
• B It will slip even if you put a 100g weight on it, but it will not slip if you put a 150g weight on it.
• C It will slip even if you put a 50g weight on it, but it will not slip if you put a 100g weight on it.
• D It will not slip when a 50g weight is placed on it.
• A No blur is visible around the point light source in the reflected image.
• B The area around the point light source in the reflected image appears blurred.
• C The area around the point light source in the reflected image appears strongly blurred.
• the reflective films of Examples 23 to 26 and 31 to 46 were able to follow curved surfaces without problems (evaluation A).
• the reflective film of Example 30 was applied with hot air from a heat gun when forming a curved surface, the reflective film curled toward the laminate film, but it could be formed by applying hot air while pressing with a squeegee, and the curved surface could be followed (rating B ).
• the reflective films of Examples 1 to 22, 27 to 29 and Comparative Examples 1 to 2 were exposed to hot air from a heat gun during curved surface molding, the reflective films curled toward the laminate film and were significantly deformed, but they could be pressed down with multiple squeegees. It was possible to mold the material and follow the curved surface (rating: C).
• the reflective film of Comparative Example 3 the reflective film and the curved glass peeled off during drying during curved surface following, and the curved surface could not be followed (rating D).
• the "HC layer Sa1” column represents the surface roughness Sa1 (nm) of the component having a wavelength of 2.5 ⁇ m or less on the surface of the hard coat layer opposite to the reflective layer side.
• the "HC layer Sa2” column represents the surface roughness Sa2 (nm) of the component having a wavelength of 10 ⁇ m or more on the surface of the hard coat layer opposite to the reflective layer side.
• the “Matte layer Sa1” column represents the surface roughness Sa1 (nm) of the component having a wavelength of 2.5 ⁇ m or less on the surface of the matte layer opposite to the reflective layer side.
• the reflective film of the present invention exhibited the desired effects.
• the content of the cationic polymerizable compound is 50 parts by mass or less based on 100 parts by mass of the total content of the radical polymerizable compound and the cationic polymerizable compound. In some cases, better abrasion resistance and pencil hardness were observed. From the comparison of Examples 2, 4, and 5, it was found that when the number of radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in the radically polymerizable compound is 4 or more (preferably 5 or more), the wear resistance is improved. It was confirmed that the pencil hardness was better.
• Example 201 The heat seal layer forming composition HS-1 was applied to the surface of the reflective layer of the reflective film of Example 18 using a wire bar so that the film thickness after drying was 0.8 ⁇ m, and then heated to 120°C. A drying process was performed for 1 minute to form a heat seal layer. Then, under a nitrogen purge, ultraviolet rays were irradiated with an illuminance of 150 mW/cm 2 and an irradiation amount of 300 mJ/cm 2 using a 160 W/cm air-cooled metal halide lamp (manufactured by Eye Graphics) at an oxygen concentration of approximately 0.1 volume %. The applied curable composition for forming a heat seal layer was cured to produce a reflective film of Example 201.
• Example 202 A reflective film of Example 202 was produced in the same manner as in Example 201, except that the heat seal layer forming composition HS-1 was applied to the surface of the polarization conversion layer of the reflective film of Example 32.
• Example 224 A reflective film of Example 224 was prepared in the same manner as Example 206, except that the heat seal layer forming composition HS-5 was applied so that the film thickness after drying was 0.4 ⁇ m.
• Example 225 A reflective film of Example 225 was prepared in the same manner as Example 206, except that the heat seal layer forming composition HS-5 was applied so that the film thickness after drying was 0.2 ⁇ m.
• Example 226 A reflective film of Example 226 was prepared in the same manner as Example 206, except that the heat seal layer forming composition HS-5 was applied so that the film thickness after drying was 10.0 ⁇ m.
• Comparative example 201 A reflective film of Comparative Example 201 was produced in the same manner as Example 201 except that HS30 was used as the composition for forming a heat seal layer.
• Test Example 7 Abrasion resistance of heat-sealing layer-applied product
• the reflective films obtained in 201 to 233 and Comparative Example 201 were placed on a glass plate (manufactured by Corning, product name: Eagle XG, thickness 1 mm). It was placed in the center of the glass plate with the surface on the heat seal layer side serving as the contact surface.
• Example 201 when the reflective film of Example 201 is used, a laminate having a glass substrate, a heat seal layer, a selective reflection layer, a support, and a hard coat layer in this order is formed, and Examples 202 to 233 Using this reflective film, a laminate including a glass substrate, a heat seal layer, a polarization conversion layer, a selective reflection layer, a retardation layer, a support, and a hard coat layer in this order was formed.
• the haze (HA) before the abrasion test was measured using a haze meter (NDH2000N, manufactured by Nippon Denshoku Co., Ltd.).
• a Taber abrasion tester rotary abrasion tester, manufactured by Toyo Seiki Co., Ltd.
• the surface of the hard coat layer was tested for 100 cycles at a rotation speed of 72 rpm with a CS-10F abrasion wheel and a load of 500 gf.
• the haze (HB) of the test portion of the laminate was measured.
• the ⁇ haze (HB-HA) before and after the test was calculated and evaluated based on the following criteria.
• A 1% or less.
• B greater than 1% and less than 2.5%.
• C greater than 2.5% and less than 4%.
• D greater than 4%.
• a to C is an acceptable range.
• Example 201 when the reflective film of Example 201 is used, a laminate having a glass substrate, a heat seal layer, a selective reflection layer, a support, and a hard coat layer in this order is formed, and Examples 202 to 233 Using this reflective film, a laminate including a glass substrate, a heat seal layer, a polarization conversion layer, a selective reflection layer, a retardation layer, a support, and a hard coat layer in this order was formed.
• a PVB film (intermediate film) manufactured by Sekisui Chemical Co., Ltd. with the same size and thickness as the glass plate and 0.76 mm is placed on top of this laminate, and a glass plate (2 mm thick, float glass) is placed on top of this. Placed.
• a Kukkiri Miere (manufactured by Tomoekawa Paper Manufacturing Co., Ltd.) was pasted on the glass plate side of the above glass sample, and using a spectrophotometer (manufactured by JASCO Corporation, V-670), P-polarized light and S-polarized light were incident from a direction of 5°, and the reflection spectra of 400 to 1000 nm were measured. The average value (average reflection spectrum) of the measured reflection spectra of P-polarized light and S-polarized light was determined.
• a to B is an acceptable range.
• Example 201 when the reflective film of Example 201 is used, a laminate having a glass substrate, a heat seal layer, a selective reflection layer, a support, and a hard coat layer in this order is formed, and Examples 202 to 233 Using this reflective film, a laminate including a glass substrate, a heat seal layer, a polarization conversion layer, a selective reflection layer, a retardation layer, a support, and a hard coat layer in this order was formed.
• a PVB film (intermediate film) manufactured by Sekisui Chemical Co., Ltd., measuring 260 mm long x 330 mm wide and 0.76 mm thick, is placed, and on top of that, a PVB film (interlayer film) of 260 mm long x 330 mm wide and 0.76 mm thick is placed.
• a curved glass substrate (second glass substrate) having a size of 330 mm and a thickness of 2 mm was placed.
• the above laminated glass was peeled between the PVB film and the hard coat layer, and the resulting laminate including the first glass substrate and the heat seal layer was prepared as a glass sample for evaluation of curved surface conformability.
• the curved surface followability of the reflective film including the heat seal layer with respect to the first glass substrate which is a curved glass substrate in the glass sample for use, was evaluated based on the following criteria.
• A The curved surface could be followed without any problem.
• B Part of the reflective film peeled off from the glass, but it was able to follow the curved surface.
• C The reflective film peeled off and could not follow the curved surface.
• a to B is an acceptable range.
• A It will slip even if you put a 150g weight on it.
• B It will slip even if you put a 100g weight on it, but it will not slip if you put a 150g weight on it.
• C It will slip even if you put a 50g weight on it, but it will not slip if you put a 100g weight on it.
• D It will not slip when a 50g weight is placed on it.
• Test Example 11 Visibility of heat-sealing layer-applied product Regarding the glass sample prepared in Test Example 9, light was applied from the glass plate side with a point light source in a dark room, and the reflected image of the point light source visually recognized on the glass plate is shown below. It was evaluated based on the following criteria.
• a laminate including a glass substrate, a heat seal layer, a polarization conversion layer, a selective reflection layer, a retardation layer, a support, and a hard coat layer in this order was formed using the following.
• a PVB film intermediate film made by Sekisui Chemical Co., Ltd., measuring 150 mm long x 25 mm wide and 0.76 mm thick, is placed, and on top of that, a flat glass plate measuring 80 mm long x 50 mm wide and 2 mm thick is placed.
• a substrate (second glass substrate) was placed.
• the glass sample for evaluation of curved surface followability produced above (the above-mentioned laminate including the first glass substrate and the reflective film including the heat-sealing layer) was conditioned for 80 hours in an environment of 90°C and 80% RH. After that, the humidity was controlled in an environment of 25° C. and 60% RH for 24 hours. The glass sample after humidity conditioning was observed, and the adhesion of the reflective film to the first glass substrate was evaluated based on the following criteria. Evaluation Criteria A: The reflective film has not peeled off from the glass. B: Part of the reflective film has peeled off from the glass.
• the reflective film of the present invention exhibited the desired effects.
• the effect is more excellent when the I/O ratio of the ethylenically unsaturated polymerizable group-containing compound is 0.60 or more (preferably 1.2 or more).
• the content of the polymerizable compound contained in the heat seal layer is 10 to 60% by mass (preferably 15 to 50% by mass) based on the total mass of the heat seal layer. %), it was confirmed that the effect was better.
• the effect is more excellent when the average thickness of the heat seal layer is 0.4 ⁇ m or more (preferably 0.8 ⁇ m or more).
• Adhesive layer 2 Reflective layer 3 Hard coat layer (HC layer) 4 Protective film 5 Polarization conversion layer 6 Retardation layer 7 Transparent base material 8 Matte layer 10A, 10B, 10C, 10D, 10E, 10F Reflective film 11 Car interior glass 12 Heat seal layer

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