Reflective film, multilayer body, windshield glass, and image display system

Abstract

The present invention provides: a reflective film that excels in a curved surface following property when stuck to a sticking target object, that exhibits excellent wear resistance after sticking, and that further excels in a reflection characteristic; windshield glass; a multilayer body; and an image display system. The reflective film of the present invention has an adhesive layer, a reflective layer that wavelength-selectively reflects light, and a hard coat layer, in that order.

Description

Reflective films, laminates, windshield glass, image display systems

[0001] The present invention relates to a reflective film, a laminate, a windshield glass, and an image display system.

[0002] By incorporating a reflective film into laminated glass used in automobile windshields, etc., the reflective film (laminated glass) can be used as a projection image display component in a head-up display system. For example, Patent Document 1 discloses the use of a reflective film including a retardation layer and multiple cholesteric liquid crystal layers as a projection image display component in a head-up display system mounted on an automobile. Typically, laminated glass for automobiles has an interlayer film between two glass sheets. Patent Document 1 also describes providing a reflective film on the interlayer film in a windshield glass having a laminated glass structure.

[0003] International Publication No. 2016 / 052367

[0004] In a configuration in which a reflective film is provided on an interlayer, as in Patent Document 1, there is a problem of double images occurring due to reflections from the glass plate surface and the reflective film surface. While this problem can be solved by providing a reflective film on the outer side of the laminated glass, the reflective film itself is required to have excellent abrasion resistance because it is located on the outer side of the laminated glass. Furthermore, when providing a reflective film, it is required to be able to conform to the shape of a curved surface, etc. Hereinafter, this property of conforming to a curved surface will be referred to as curved surface conformability. Furthermore, in terms of its function as a component for projected images, the reflective film itself is required to have excellent reflective properties. An object of the present invention is to provide a reflective film that exhibits excellent curved surface conformability when attached to an object, excellent abrasion resistance after attachment, and excellent reflective properties. Another object of the present invention is to provide a windshield glass, a laminate, and an image display system.

[0005] The present invention provides the following:

[0006] (1) A reflective film having, in this order, an adhesive layer, a reflective layer that wavelength-selectively reflects light, and a hard coat layer. (2) The reflective film according to (1), wherein the adhesive layer has a thickness of 1 to 30 μm. (3) The reflective film according to (1) or (2), wherein the hard coat layer has a thickness of 1 μm or more. (4) The reflective film according to any one of (1) to (3), wherein the hard coat layer is formed using a curable composition for forming a hard coat layer containing a cationically polymerizable compound, and the content of the cationically polymerizable compound is 5 mass% or more relative to the total solid content of the curable composition for forming a hard coat layer. (5) The reflective film according to any one of (1) to (4), wherein the hard coat layer is formed using a curable composition for forming a hard coat layer containing inorganic particles, and the content of the inorganic particles is 0.5 mass% or more relative to the total solid content of the curable composition for forming a hard coat layer. (6) The reflective film according to (5), wherein the average primary particle size of the inorganic particles is 40 nm or more. (7) 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. (8) The reflective film according to any one of (1) to (7), wherein the surface roughness Sa1 of components having a wavelength of 2.5 μm or less on the surface of the hard coat layer opposite the reflective layer side is 0.30 nm or more. (9) The reflective film according to any one of (1) to (8), wherein the surface roughness Sa2 of components having a wavelength of 10 μm or more on the surface of the hard coat layer opposite the reflective layer side is 2.0 nm or less. (10) The reflective film according to any one of (1) to (9), further comprising a transparent substrate. (11) The reflective film according to (10), wherein the transparent substrate is a cellulose acylate film. (12) The reflective film according to any one of (1) to (11), further comprising a retardation layer. (13) The reflective film according to (12), further comprising a polarization conversion layer, wherein the retardation layer, the reflective layer, and the polarization conversion layer are arranged in this order. (14) The reflective film according to any one of (1) to (13), further comprising a matte layer between the adhesive layer and the reflective layer. (15) The reflective film according to (14), wherein the surface of the matte layer opposite to the reflective layer has a surface roughness Sa1 of 0.30 nm or more for components with a wavelength of 2.5 μm or less.(16) A laminate comprising the reflective film according to any one of (1) to (15) and a protective film laminated on the surface of the reflective film opposite to the reflective layer side of the adhesive layer of the reflective film. (17) The laminate according to (16), in which the difference in thermal shrinkage rate at 140°C between the reflective film and the protective film is less than 1.5%. (18) A windshield glass comprising a glass plate and the reflective film according to any one of (1) to (15) laminated together via an adhesive layer. (19) An image display system comprising the windshield glass according to (18) and a projector that irradiates the reflective film side of the windshield glass with projection image light. (20) A reflective film comprising, in this order, a hard coat layer, a reflective layer that selectively reflects light in a wavelength direction, and a heat seal layer laminated on one side of the reflective layer, wherein the reflective layer is formed using a composition containing a polymerizable liquid crystal compound, and the heat seal layer contains a thermoplastic resin or an elastomer. (21) The reflective film according to (20), wherein the heat seal layer is a layer formed using a composition containing a polymerization initiator. (22) The reflective film according to (21), wherein the composition further contains a polymerizable compound. (23) The reflective film according to (22), wherein the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group, and the polymerizable compound has an ethylenically unsaturated polymerizable group. (24) A reflective film having, in this order, a hard coat layer, a reflective layer that wavelength-selectively reflects light, a polarization conversion layer, and a heat seal layer laminated on one side of the polarization conversion layer, wherein the polarization conversion layer is formed using a composition containing a polymerizable liquid crystal compound, and the heat seal layer contains a thermoplastic resin or an elastomer. (25) The reflective film according to (24), wherein the heat seal layer is a layer formed using a composition containing a polymerization initiator. (26) The reflective film according to (25), wherein the composition further contains a polymerizable compound. (27) The reflective film according to any one of (22), (23), and (26), wherein the content of the polymerizable compound is 5 to 80 mass % relative to the solid content of the composition. (28) The reflective film according to any one of (22), (23), and (26), wherein the I / O ratio of the polymerizable compound is 0.4 or more.(29) The reflective film according to any one of (20) to (28), wherein the moisture content of the heat seal layer at 25°C and 60% RH is 2.0% or less. (30) A windshield glass formed by bonding a glass plate and the reflective film according to any one of (20) to (28) via a heat seal layer. (31) An image display system comprising the windshield glass according to (30) and a projector that irradiates a projection image light onto the reflective film side of the windshield glass.

[0007] According to the present invention, it is possible to provide a reflective film that has excellent curved surface conformability when attached to an object, exhibits excellent abrasion resistance after attachment, and also has excellent reflective properties. Furthermore, according to the present invention, it is possible to provide a windshield glass, a laminate, and an image display system.

[0008] FIG. 1 is a schematic diagram showing an example of a reflective film of the present invention. FIG. 2 is a schematic diagram showing an example of a reflective film of the present invention. FIG. 3 is a schematic diagram showing an example of a reflective film of the present invention. FIG. 4 is a schematic diagram showing an example of a windshield glass having a reflective film of the present invention. FIG. 5 is a schematic diagram showing an example of a reflective film of the present invention. FIG. 6 is a schematic diagram showing an example of a windshield glass having a reflective film of the present invention. FIG. 7 is a schematic diagram showing an example of a reflective film of the present invention.

[0009] The reflective film, windshield glass, laminate, and image display system of the present invention, each having an adhesive layer, a reflective layer, and a hard coat layer (HC layer) in this order, will be described in detail below based on preferred embodiments shown in the accompanying drawings. Note that the drawings described below are merely illustrative for explaining the present invention, and the present invention is not limited to the drawings shown below. Note that, in the following, the "to" symbol indicating a range of values ​​includes the values ​​written on both sides. For example, ε １ is the number α １ ~Number β １ That is, ε １ The range of α １ and the number β １ The range includes α １ ≦ε １ ≦β １Unless otherwise specified, angles such as "angles expressed by specific numerical values," "parallel," "perpendicular," and "orthogonal" include a generally acceptable error range in the relevant technical field. More specifically, in this specification, parallel, perpendicular, and orthogonal mean a range of parallel ±5°, a range of orthogonal ±5°, and a range of perpendicular ±5°, respectively. Furthermore, "the same" includes a generally acceptable error range in the relevant technical field, and "over the entire surface" and the like also include a generally acceptable error range in the relevant technical field.

[0010] When referring to circular polarization, the term "selective" means that the amount of either the right-handed circularly polarized component or the left-handed circularly polarized component of light is greater than the other circularly polarized component. Specifically, when referring to "selective," 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. It is even more preferably substantially 1.0. Here, the degree of circular polarization is defined as the intensity of the right-handed circularly polarized component of light, expressed as I R , the intensity of the left circularly polarized component is I L When this is the case, |I R -I L | / (I R +I L ) is the value expressed as

[0011] The "sense" of circularly polarized light refers to whether it is right-handed or left-handed. The sense of circular polarization is defined as follows: when viewed as if the light is traveling toward 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.

[0012] The term "sense" is sometimes used to refer to the twist direction of the helix of cholesteric liquid crystals. When the twist direction (sense) of the helix of a cholesteric liquid crystal is right-handed, it reflects right-handed circularly polarized light and transmits left-handed circularly polarized light, and when the sense is left-handed, it reflects left-handed circularly polarized light and transmits right-handed circularly polarized light.

[0013] Unless otherwise specified, the term "light" refers to visible light and natural light (unpolarized). Visible light is electromagnetic light with wavelengths visible to the human eye, and typically refers to light in the wavelength range of 380 to 780 nm. Invisible light is light in the wavelength range of less than 380 nm or greater than 780 nm. Furthermore, although not limited thereto, within visible light, light in the wavelength range of 420 to 490 nm is blue (B) light, light in the wavelength range of 495 to 570 nm is green (G) light, and light in the wavelength range of 620 to 750 nm is red (R) light.

[0014] The "visible light transmittance" is the A-light source visible light transmittance defined in JIS (Japanese Industrial Standards) R 3212:2015 (Test Methods for Automotive Safety Glass). That is, the transmittance is determined by measuring the transmittance at each wavelength in the wavelength range of 380 to 780 nm using an A-light source with a spectrophotometer, and multiplying the transmittance at each wavelength by a weighting coefficient obtained from the wavelength distribution and wavelength interval of the CIE (Commission Internationale de l'Eclairage) photopic standard relative luminosity factor, and calculating a weighted average. When simply referring to "reflected light" or "transmitted light," this term is used to include scattered light and diffracted light.

[0015] The polarization state of each wavelength of light can be measured using a spectroradiometer or a spectrometer equipped with a circular polarizer. In this case, the intensity of light measured through a right circular polarizer is I. R , the light intensity measured through a left circular polarizer is I L It can also be measured by attaching a circular polarizer to an illuminance meter or optical spectrometer. The ratio can be calculated 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.

[0016] P-polarized light is polarized light that vibrates parallel to the plane of incidence of the light. The plane of incidence is perpendicular to the reflecting surface (such as the surface of a windshield glass) and includes both the incident and reflected light rays. In p-polarized light, the vibration plane of the electric field vector is parallel to the plane of incidence.

[0017] The front retardation is a value measured using an AxoScan manufactured by Axometrics. Unless otherwise specified, the measurement wavelength is 550 nm. The front retardation can also be a value measured using a KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) by irradiating light with a wavelength within the visible light wavelength range in the normal direction to the film. When selecting the measurement wavelength, the wavelength selection filter can be changed manually, or the measured value can be converted using a program or the like.

[0018] "Projection image" means an image based on the projection of light from the projector being used, rather than the surrounding scenery such as the view ahead. A projection image is perceived by an observer as a virtual image that appears to appear beyond the projection image display area on the windshield glass. "Screen image" means an image displayed on the projector's drawing device, or an image drawn by the drawing device on an intermediate image screen or the like. In contrast to a virtual image, a screen is a real image. Both the image and the projection image may be a monochromatic image, a multi-color image with two or more colors, or a full-color image.

[0019] The reflective film of the present invention is characterized by having an adhesive layer, a reflective layer that selectively reflects light in wavelengths (hereinafter also simply referred to as "reflective layer"), and a hard coat layer in this order.

[0020] Another configuration of the reflective film of the present invention is characterized by having, in this order, a hard coat layer, a reflective layer that selectively reflects light in wavelengths, and a heat seal layer laminated on one side of the reflective layer.

[0021] Another configuration of the reflective film of the present invention is characterized by having, in this order, a hard coat layer, a reflective layer that reflects light wavelength-selectively, a polarization conversion layer, and a heat seal layer laminated on one side of the polarization conversion layer.

[0022] An example of the reflective film of the present invention is shown in Fig. 1. The reflective film 10A shown in Fig. 1 has an adhesive layer 1, a reflective layer 2, and a hard coat layer (hereinafter also referred to as an HC layer) 3 in this order.

[0023] Another example of the reflective film of the present invention is shown in Fig. 6. The reflective film 10E shown in Fig. 6 has a heat seal layer 12, a reflective layer 2, and an HC layer 3 in this order.

[0024] Figure 7 shows another example of the reflective film of the present invention. The reflective film 10F shown in Figure 7 has 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 substrate, as described below. When such a reflective film 10F is incorporated into a windshield glass, it is arranged, for example, with the polarization conversion layer 5 facing the interior glass plate 11, as shown in Figure 8. The windshield glass shown in Figure 8 has, in this order, the interior glass plate 11, a heat seal layer 12, the polarization conversion layer 5, the reflective layer 2, a retardation layer 6, a transparent substrate 7, and an HC layer 3.

[0025] Each layer used in the reflective film of the present invention will be described below.

[0026] <Adhesive Layer> The reflective film of the present invention has an adhesive layer for adhering the film to the outside of laminated glass. The adhesive layer makes it possible to adhere the reflective film to a windshield. The adhesive layer is not particularly limited in material, as long as it has transparency that ensures visibility of the display content when the reflective film of the present invention is applied to a windshield and can adhere the reflective film to the windshield, and may be made of a resin or an elastomer (including oil-extended rubber).

[0027] Examples of the resin include polyolefin resins such as 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA," which typically contains 3% by mass or more of vinyl acetate structural units), and polyethylene, polyvinyl 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 resin, silicone resin, and modified resins of these resins. Examples of urethane resins include urethane-modified polyester resin and urethane resin.

[0028] Examples of the elastomer include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, hydrogenated products of block (co)polymers of conjugated dienes, hydrogenated products of block copolymers of aromatic vinyl compounds and conjugated dienes, ethylene-α-olefin copolymers, polar group-modified olefin copolymers, elastomers composed of polar group-modified olefin copolymers and metal ions and / or metal compounds, nitrile rubbers (e.g., acrylonitrile-butadiene rubbers), butyl rubbers, acrylic rubbers, thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), and diene elastomers (1,2-polybutadiene, etc.), silicone elastomers, and fluorine-based elastomers.

[0029] 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.

[0030] When the adhesive layer contains these resins or elastomers, the adhesive layer may be made of only these resins or elastomers, or the adhesive layer may further contain additives such as softeners, plasticizers, lubricants, crosslinking agents, crosslinking aids, photosensitizers, antioxidants, antiaging agents, heat stabilizers, flame retardants, antibacterial agents, antifungal agents, weather resistance agents, UV absorbers, tackifiers, nucleating agents, pigments, dyes, organic fillers, inorganic fillers, silane coupling agents, and titanium coupling agents, polymerizable group-containing compounds, or other polymers as constituent materials. That is, the adhesive layer may be made of a resin composition or a composition containing an elastomer.

[0031] Commercially available adhesives may be used, for example, SK Dyne 2057, SK Dyne 2094, SK Dyne 2147, SK Dyne 1811L, SK Dyne 1478, SK Dyne 1442, SK Dyne 1435, SK Dyne 1415 (all manufactured by Soken Chemical & Engineering Co., Ltd.), NCF-N632, NCF-D692, NCF-F619, MO-T015, MO-5115XV (all manufactured by Lintec Corporation), TD06, MK 64, TI14, ME57, TX48, MJ63, MG70, MF58 (all manufactured by Tomoegawa Paper Co., Ltd.), Panaclean PD-S1, Panaclean PD-R5 (all manufactured by Panac Corporation), MHM-FWD, MHM-FWV, MHM-UVC, MHM-SI (manufactured by Nichiei Shinka Co., Ltd.), Orivine EG-655, and Orivine BPS5896 (all manufactured by Toyo Ink Co., Ltd.) (all trade names).

[0032] The thickness of the adhesive layer is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 1 to 30 μm, and particularly preferably 5 to 20 μm. When the thickness of the adhesive layer is within the above range, the adhesive layer has better scratch resistance, improved adhesion between the windshield and the reflective film, and better curved surface conformability.

[0033] From the viewpoint of scratch resistance, the storage modulus E' of the adhesive layer at 25°C and a frequency of 1 Hz is preferably greater than 1 kPa, and from the viewpoint of adhesion to a windshield, it is preferably 4 GPa or less. The storage modulus E' is more preferably greater than 1 KPa and 1 GPa or less, and even more preferably greater than 1 KPa and 100 MPa or less.

[0034] The maximum value of the loss tangent (tan δ) of the adhesive layer at a frequency of 1 Hz is preferably in the temperature range of −80 to 40° C., more preferably −60 to 40° C. By setting tan δ within the above range, it is possible to achieve both good adhesion to the windshield and durability.

[0035] In the present invention, the storage modulus of the adhesive layer at 25° C. and a frequency of 1 Hz and tan δ at a frequency of 1 Hz are determined as follows.

[0036] (Sample Preparation Method) The adhesive layer is dissolved in a solvent or melted, and the resulting coating solution is applied to the release-treated surface of a release-treated release PET (polyethylene terephthalate) sheet to a dry thickness of 40 μm. The coating is then dried, and the adhesive layer is peeled off from the release PET sheet to prepare a test piece of the adhesive layer. (Measurement Method) Using a dynamic viscoelasticity measuring device (DVA-225, manufactured by ITS Japan Co., Ltd.), the test piece is pre-conditioned for at least 2 hours at a temperature of 25°C and a relative humidity of 60%. Measurements are then performed under the following conditions in the "step temperature rise / frequency dispersion" mode. Then, a master curve of tan δ, storage modulus, and loss modulus versus frequency at 25°C is obtained using the "master curve" editor. The maximum value of tan δ and the frequency at which the maximum value is obtained are determined from the obtained master curve. Sample: 5 mm x 20 mm; Grip distance: 20 mm; Set strain: 0.10%; Measurement temperature: -100 to 40°C; Heating condition: 2°C / min

[0037] (Method for forming adhesive layer) The method for forming the adhesive layer is not particularly limited, and examples thereof include a coating method, a casting method (solventless casting method and solvent casting method), a pressing method, an extrusion method, an injection molding method, a casting method, and an inflation method. In detail, 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, and thereafter, the solvent is removed as necessary, thereby making it possible to produce a reflective film including an adhesive layer.

[0038] In addition, the adhesive layer can be produced on the reflective layer by applying the constituent material of the adhesive layer to the release-treated surface of the release sheet in the same manner as above, drying the sheet, and bonding the adhesive layer of this sheet to the reflective layer. When the reflective layer is disposed on a transparent substrate, a reflective film can be formed by bonding the adhesive layer of the sheet to the side of the transparent substrate opposite to the reflective layer.

[0039] <Heat Seal Layer> The heat seal layer is a layer for physically bonding the reflective film and the glass substrate.

[0040] The heat seal layer contains a thermoplastic resin or elastomer. Thermoplastic resins with good affinity and adhesion to glass substrates are preferred, including polyolefin resins such as 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA," which typically contains 3% by mass or more of vinyl acetate structural units), and polyethylene, polyvinyl chloride resin, polystyrene resin, vinyl ester resin (excluding EVA), saturated polyester resin, polyamide resin, fluororesin (e.g., polyvinylidene fluoride), 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 resin, silicone resin, and modified resins of these resins. Urethane resins include urethane-modified polyester resins and urethane resins. Thermoplastic resins such as polyvinyl butyral and ethylene-vinyl acetate copolymer are preferred.

[0041] 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. The degree of polymerization of the polyvinyl alcohol is preferably 200 to 3000.

[0042] Examples of the elastomer include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, hydrogenated products of block (co)polymers of conjugated dienes, hydrogenated products of block copolymers of aromatic vinyl compounds and conjugated dienes, ethylene-α-olefin copolymers, polar group-modified olefin copolymers, elastomers composed of polar group-modified olefin copolymers and metal ions and / or metal compounds, nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubber, acrylic rubbers, thermoplastic elastomers such as thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), diene elastomers (1,2-polybutadiene, etc.), silicone elastomers, and fluorine-based elastomers.

[0043] The thermoplastic resin or elastomer may be synthesized by a known method, or a commercially available product may be used. Examples of commercially available elastomers include Kuralyte LA1114, Kuralyte LA2140, Kuralyte LA2250, Kuralyte LA2330, Kuralyte LA4285, Hybrar 5127, Hybrar 7311F, Septon 2104, and Septon 2063 (trade names, manufactured by Kuraray Co., Ltd.). The elastomer is preferably an acrylic block (co)polymer or a styrene block (co)polymer.

[0044] 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.

[0045] 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. For example, when the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group, the polymerizable compound also preferably has an ethylenically unsaturated polymerizable group.

[0046] Examples of the ethylenically unsaturated polymerizable group-containing compound include the following. However, the present invention is not limited to the following exemplified compounds. For example, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, triethylene glycol di(meth)acrylate, epichlorohydrin-modified ethylene glycol di(meth)acrylate (commercially available products include Denacol DA-811 manufactured by Nagase & Co., Ltd.), polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, ethylene oxide (EO), propylene oxide (PO),propylene oxide) block polyether di(meth)acrylate (commercially available products, such as the Blemmer PET series manufactured by Nippon Oil & Fats Co., Ltd.), dipropylene glycol di(meth)acrylate, bisphenol A EO addition type di(meth)acrylate (commercially available products, such as M-210 manufactured by Toagosei Co., Ltd. and NK Ester A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd.), hydrogenated bisphenol A EO addition type di(meth)acrylate (NK Ester A-HPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A PO addition type di(meth)acrylate (commercially available products, such as Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A epichlorohydrin addition type di(meth)acrylate (commercially available products, such as Ebecryl 150 manufactured by Daicel UCB Co., Ltd.), bisphenol A EO·PO addition type di(meth)acrylate (commercially available products include BP-023-PE manufactured by Toho Chemical Industry Co., Ltd.), bisphenol F Examples of bifunctional (meth)acrylate compounds include EO-added di(meth)acrylate (commercially available products include 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 products, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, trimethylolpropane acrylic acid benzoate, and isocyanuric acid EO-modified di(meth)acrylate (commercially available products include Aronix M-215 manufactured by Toagosei Co., Ltd.);

[0047] Further, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (commercially available products include, for example, TPMTA manufactured by Nippon Kayaku Co., Ltd.) and its EO, PO, or epichlorohydrin-modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products, isocyanuric acid EO-modified tri(meth)acrylate (commercially available products include, for example, Aronix M-315 manufactured by Toagosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products; Examples of such compounds include tetrafunctional (meth)acrylate compounds such as tetraerythritol tetra(meth)acrylate (commercially available products include TPMTA manufactured by Shin-Nakamura Chemical Co., Ltd.), EO, PO, and epichlorohydrin-modified products thereof, and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof; and hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof, and sorbitol hexa(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof. Two or more ethylenically unsaturated polymerizable group-containing compounds may be used in combination. In this case, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, "DPHA" (manufactured by Nippon Kayaku Co., Ltd.), or the like can be preferably used.

[0048] Also preferred as the ethylenically unsaturated polymerizable group-containing compound are polyester(meth)acrylates and epoxy(meth)acrylates having a weight-average molecular weight of 200 or more and less than 1,000. Commercially available polyester(meth)acrylates include those manufactured by Arakawa Chemical Industries Co., Ltd. under the trade name of the Beamset 700 series, such as Beamset 700 (hexafunctional), Beamset 710 (tetrafunctional), and Beamset 720 (trifunctional). Epoxy(meth)acrylates include those manufactured by Showa Polymer Co., Ltd. under the trade name of the SP series, such as SP-1506, 500, SP-1507, and 480, and those manufactured by VR series, such as VR-77, and those manufactured by Shin-Nakamura Chemical Co., Ltd. under the trade names of EA-1010 / ECA, EA-11020, EA-1025, and EA-6310 / ECA.

[0049] The I / O ratio (ratio of inorganic value (I value) to organic value (O value)) of the polymerizable compound (particularly, an ethylenically unsaturated polymerizable group-containing compound) is preferably 0.40 or more, more preferably 0.60 or more, and even more preferably 1.2 or more, from the viewpoint of adhesion to a glass substrate. There is no particular upper limit to the I / O ratio, but it is preferably less than 3.0 from the viewpoint of compatibility with a thermoplastic resin.

[0050] The I / O ratio is calculated using the calculation method in the organic conceptual diagram. The organic conceptual diagram was proposed by Fujita et al. and is an effective method for predicting various physicochemical properties from the chemical structure of an organic compound (see Koda Yoshio, Organic Conceptual Diagram - Fundamentals and Applications, Sankyo Publishing (1984)). Since the polarity of an organic compound depends on the number of carbon atoms and substituents, the inorganic and organic values ​​of other substituents are determined based on the organic value of the methylene group being 20 and the inorganic value of the hydroxyl group being 100, and the inorganic and organic values ​​of the organic compound are then calculated. Organic compounds with a high inorganic value have high polarity, and organic compounds with a high organic value have low polarity.

[0051] Specific methods for calculating the I value, O value, and I / O ratio have been published as an organic conceptual diagram calculation sheet for Excel by Homma et al., co-authors of "New Edition Organic Conceptual Diagram: Fundamentals and Applications" (http: / / www.ecosci.jp / sheet / orgs_help.html), and these calculations can be performed using this.

[0052] When the composition used to form the heat seal layer contains a polymerizable compound, the content of the polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 50% by mass, based on the solid content of the composition. By setting the polymerizable compound content in the composition used to form the heat seal layer within the above range, it is possible to achieve both adhesion to the glass substrate and adhesion to the reflective layer or polarization conversion layer. The solid content of the composition refers to the components other than the solvent in the composition. Even if the other components are in a liquid state, they are counted as solids.

[0053] The composition used to form the heat seal layer (heat seal layer-forming composition) preferably contains a polymerization initiator from the viewpoint of adhesion to glass. Examples of the polymerization initiator include a photopolymerization initiator. The photopolymerization initiator may be any one that can generate radicals as active species upon light irradiation, and known photopolymerization initiators can be used without any restrictions. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl 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]phenyl}-2-methyl-propan-1-one and other acetophenones; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and Oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime); benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride;Thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Furthermore, as an auxiliary agent for the polymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. may be used in combination. The above polymerization initiators and auxiliary agents can be synthesized by known methods or are commercially available. Commercially available radical photopolymerization initiators include Irgacure (127, 651, 184, 819, 907, 1870 (CGI-403 / Irg184=7 / 3 mixed initiator, 500, 369, 1173, 2959, 4265, 4263, etc.), OXE01) manufactured by BASF, KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.) manufactured by Nippon Kayaku, and Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer, and the like;

[0054] The content of the polymerization initiator contained in the composition used to form the heat-seal layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction of the polymerizable compound proceeds smoothly. When the composition used to form the heat-seal layer contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound contained in the composition.

[0055] The heat seal layer may contain inorganic particles. When 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 in a state where they are in direct contact with each other, friction between the heat seal layer and the HC layer can be reduced, which is preferable because the heat seal layer can be rolled without wrinkles. The inorganic particles contained in the heat seal 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.

[0056] The inorganic particles preferably consist of primary particles, with secondary particles formed by aggregation of the primary particles. The average primary particle size 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 size of the inorganic particles is not particularly limited, but is preferably 100 to 500 nm.

[0057] The content of the inorganic particles in the heat seal layer is not particularly limited, but is preferably 1% by mass or more, more preferably 9% by mass or more, relative to the total mass of the heat seal layer. The upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less.

[0058] The average primary particle diameter of inorganic particles is measured by observation with a transmission electron microscope. Specifically, the diameter of the circle circumscribing the primary particles is determined for 50 randomly selected primary particles, and the arithmetic mean is taken as the average primary particle diameter. The magnification of the transmission electron microscope is set to any magnification between 500,000 and 5,000,000 that allows the primary particle diameter to be determined. The average secondary particle diameter is a value measured by performing spherical fitting (refractive index 1.46) using a laser diffraction / scattering particle size distribution analyzer. For example, a MicroTrac MT3000 manufactured by Microtrac-Bell Corporation can be used as the measuring device.

[0059] The heat seal layer may contain a leveling agent. By including a leveling agent in the heat seal layer, the surface of the heat seal layer is smoothed, thereby improving visibility when integrated with a glass substrate. As the leveling agent, known leveling agents can be used, for example, surfactants, and among these, fluorine-based surfactants or silicone-based surfactants are preferred. The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in terms of uniformity of the thickness of the coating film and liquid saving.

[0060] The content of the leveling agent in the heat seal 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 seal layer.

[0061] The water contact angle of the surface of the heat seal layer opposite the reflective layer or polarization conversion layer is not particularly limited, but is preferably 100° or less, more preferably 90° or less, and even more preferably 70° or less, in terms of better adhesion to the glass substrate. The lower limit is not particularly limited, but is often 10° or more, and more often 30° or more. The water contact angle is measured as follows. First, at three different locations on the heat seal layer surface of the reflective film, a contact angle meter CA-X (manufactured by Kyowa Interface Science Co., Ltd.) is used to create 1.0 mm diameter droplets using pure water at the tip of a needle under an environment of 20°C and 65% RH, and these droplets are brought into contact with the surface of the heat seal layer to form droplets. 25 seconds after the heat seal layer surface comes into contact with the pure water, the angle formed by the tangent to the pure water surface and the heat seal layer surface at the point where the heat seal layer surface and the pure water come into contact is measured, and the average of these angles is taken as the water contact angle of the heat seal layer.

[0062] 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 contains the above-mentioned components and is a composition used to form a heat seal layer. From the viewpoint of coatability, the composition for forming a heat seal layer preferably contains a solvent. 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.

[0063] The method for applying the composition for forming a heat seal layer is not particularly limited, and examples thereof 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.

[0064] The coating film obtained by coating may be subjected to a drying treatment, if necessary. Examples of the drying treatment include a heat treatment. The heating temperature in the heat treatment is not particularly limited, but is preferably 50 to 150°C, and more preferably 60 to 140°C. The heating time is not particularly limited, but is preferably 0.5 to 20 minutes, and more preferably 0.5 to 10 minutes.

[0065] The surface of the formed heat seal layer (the surface opposite to the reflective layer or polarization conversion layer) may be subjected to a surface treatment as needed. For example, the surface of the heat seal layer may be subjected to a hydrophilization treatment in order to reduce the water contact angle of the surface of the heat seal layer. Examples of hydrophilization treatment include plasma treatment, ultraviolet irradiation treatment, corona treatment, and electron beam irradiation treatment, with corona treatment being preferred. The conditions for the hydrophilization treatment are appropriately selected depending on the type of treatment to be performed, and are preferably adjusted so that the water contact angle of the surface of the heat seal layer falls within the range described above.

[0066] The average thickness of the heat seal layer is preferably 0.2 μm or more, more preferably 0.4 μm or more, and even more preferably 0.8 μm 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, it is preferably 20 μm or less, more preferably 10 μm or less. The average thickness is measured by cutting the heat seal layer with a microtome to cut out a cross section, observing the cross section with an SEM (Scanning Electron Microscope), measuring the thickness at three different positions on the heat seal layer, and calculating the average (arithmetic mean) of the measured values ​​to obtain the average thickness.

[0067] The heat seal layer may have a single layer structure or a multi-layer structure of two or more layers. When the heat seal layer has a multi-layer structure, the average total thickness of the heat seal layer may be within the above range.

[0068] The moisture content of the heat seal layer (moisture content at 25°C and 60% RH) is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.5% or less, from the viewpoint of wet heat durability. The lower limit is not particularly limited, and may be 0%. The moisture content of the heat seal layer was measured by the Karl Fischer method using a moisture meter and sample drying apparatus "CA-03" and "VA-05" (both manufactured by Mitsubishi Chemical Corporation) after samples collected by scraping the heat seal layer were humidified for 24 hours or more in an environment of 25°C and 60% RH, and the moisture content (g) was calculated by dividing the moisture content by the sample mass (g, including the moisture content).

[0069] <Reflective layer that wavelength-selectively reflects light> The reflective film of the present invention has a reflective layer that wavelength-selectively reflects light. The reflective layer of the present invention preferably has a cholesteric liquid crystal layer having a selective reflection center wavelength in the red wavelength region, a cholesteric liquid crystal layer having a selective reflection center wavelength in the green wavelength region, and a cholesteric liquid crystal layer having a selective reflection center wavelength in the blue wavelength region. The three cholesteric liquid crystal layers have different selective reflection center wavelengths. Each cholesteric liquid crystal layer may be in direct contact with any of the other cholesteric liquid crystal layers.

[0070] As is well known, a cholesteric liquid crystal layer is a layer in which liquid crystal compounds are fixed in a helical oriented state of a cholesteric liquid crystal phase, and reflects light with a selective reflection center wavelength corresponding to the pitch of the helical structure and transmits light in other wavelength ranges. Furthermore, a cholesteric liquid crystal layer exhibits selective reflection for either left- or right-handed circularly polarized light at a specific wavelength.

[0071] Here, from the viewpoint of visibility, it is preferable that the reflective layer satisfy the following requirements (i) to (iii): (i) in the wavelength range of 400 nm or more and less than 500 nm, the maximum value of natural light reflectance is more than 7% (preferably more than 20%), the difference between the maximum and minimum values ​​of natural light reflectance is 3% or more, and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of natural light reflectance is 20 to 80 nm; (ii) in the wavelength range of 500 nm or more and less than 600 nm, the maximum value of natural light reflectance is more than 7% (preferably more than 20%), the difference between the maximum and minimum values ​​of natural light reflectance is 3% or more, and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of natural light reflectance is 20 to 80 nm. (iii) In the wavelength range of 600 to 800 nm, the maximum value of the natural light reflectance is more than 7% (preferably, 20% or more), and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of the natural light reflectance is 120 nm or more.

[0072] In a reflective layer having a cholesteric liquid crystal layer, the reflected wavelength and reflectance can be adjusted by the selective reflection center wavelength and thickness (helical pitch number) of the cholesteric liquid crystal layer, etc. A reflection that satisfies requirement (i) can be realized mainly by a cholesteric liquid crystal layer that reflects light in the blue wavelength region, a reflection that satisfies requirement (ii) can be realized by a cholesteric liquid crystal layer that reflects light in the green wavelength region, and a reflection that satisfies requirement (iii) can be realized by a cholesteric liquid crystal layer that reflects light in the red wavelength region.

[0073] From the viewpoint of being able to increase transmittance while improving reflected color, the maximum natural light reflectance at 400 nm or more and less than 500 nm is preferably more than 7%, more preferably 20% or more. The upper limit is not particularly limited, but is often, for example, 35% or less. Similarly, from the viewpoint of being able to increase transmittance while improving reflected color, the maximum natural light reflectance at 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, for example, 35% or less. From the viewpoint of being able to increase the brightness of a displayed image while improving reflected color, the maximum natural light reflectance at 600 to 800 nm is preferably more than 7%, more preferably 20% or more. The upper limit is not particularly limited, but is often, for example, 35% or less.

[0074] From the viewpoint of being able to increase transmittance while improving reflected color, the difference between the maximum and minimum natural light reflectance values ​​at wavelengths of 400 nm or more and less than 500 nm is preferably 4 to 20%, more preferably 4 to 12%. Similarly, from the viewpoint of being able to increase transmittance while improving reflected color, the difference between the maximum and minimum natural light reflectance values ​​at wavelengths of 500 nm or more and less than 600 nm is preferably 4 to 20%, more preferably 4 to 12%.

[0075] From the viewpoint of improving the reflected color and increasing the transmittance, the wavelength bandwidth of the region where the reflectance is higher than the average of the maximum and minimum values ​​of the reflectance between 400 nm and less than 500 nm is preferably 30 to 78 nm, more preferably 35 to 75 nm. Similarly, from the viewpoint of improving the reflected color and increasing the transmittance, the wavelength bandwidth of the region where the reflectance is higher than the average of the maximum and minimum values ​​of the reflectance between 500 nm and less than 600 nm is preferably 30 to 78 nm, more preferably 35 to 75 nm. The narrower the wavelength bandwidth between 400 nm and less than 500 nm and the narrower the wavelength bandwidth between 500 nm and less than 600 nm, the more advantageous the transmittance is. However, since the wavelength bandwidth between 600 and 800 nm is wide, if the wavelength bandwidth between 400 nm and less than 500 nm and / or the wavelength bandwidth between 500 nm and less than 600 nm is too narrow, the reflected color may deteriorate. From this point of view, it is preferable that the wavelength bandwidth from 400 nm to less than 500 nm and the wavelength bandwidth from 500 nm to less than 600 nm are within the above ranges. Furthermore, the wavelength bandwidth from 500 nm to less than 600 nm has a greater effect on the transmittance.

[0076] From the viewpoint of improving the reflected color and the front brightness of the displayed image, the wavelength bandwidth of the region where the reflectance is higher than the average value of the maximum and minimum reflectance values ​​from 600 to 800 nm is preferably 120 to 200 nm.

[0077] The reflective layer preferably has two or more cholesteric liquid crystal layers having different selective reflection center wavelengths, and each cholesteric liquid crystal layer is preferably in direct contact with any other cholesteric liquid crystal layer.

[0078] If the cholesteric liquid crystal layers are spaced apart, the thickness between the layers becomes thicker, making it difficult to obtain the effect of interference of light reflected by each cholesteric liquid crystal layer. In contrast, 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. In particular, if the thickness of each cholesteric liquid crystal layer is thinner than the wavelength of light (visible light 380 to 780 nm), the effect of interference becomes more pronounced, which is preferable.

[0079] In the present invention, when the reflective layer has two or more cholesteric liquid crystal layers, the cholesteric liquid crystal layers are not limited to a configuration in which they are in direct contact with each other, but may be laminated via an adhesive layer or the like.

[0080] Here, 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.

[0081] The total thickness of the reflective layer is preferably 0.4 to 2.0 μm, more preferably 0.6 to 1.8 μm, and even more preferably 0.8 to 1.4 μm. When the total thickness of the reflective layer is within the above range, the natural light reflectance by the reflective layer is increased, the brightness of the displayed image can be increased, and the transmittance is also increased.

[0082] (Method for Producing Cholesteric Liquid Crystal Layer) Hereinafter, materials and methods for producing a cholesteric liquid crystal layer will be described. Examples of materials used to form the above-mentioned 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, as necessary. The above-mentioned liquid crystal composition is applied to a support, an alignment layer, and a cholesteric liquid crystal layer that will serve as an underlying layer, and after cholesteric alignment aging, the liquid crystal composition is cured and fixed to form a cholesteric liquid crystal layer.

[0083] (Polymerizable Liquid Crystal Compound) The polymerizable liquid crystal compound may be a rod-shaped liquid crystal compound or a discotic liquid crystal compound, but is preferably a rod-shaped liquid crystal compound. Examples of rod-shaped polymerizable liquid crystal compounds that form a cholesteric liquid crystal layer include rod-shaped nematic liquid crystal compounds. Preferred rod-shaped nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitriles. Not only low-molecular-weight liquid crystal compounds but also polymer-molecular-weight liquid crystal compounds can be used.

[0084] A polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into a liquid crystal compound. Examples of 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 molecule 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 are described in Makromol. Chem. , Vol. 190, p. 2255 (1989), Advanced Materials Vol. 5, p. 107 (1993), U.S. Pat. No. 4,683,327, U.S. Pat. No. 5,622,648, U.S. Pat. No. 5,770,107, WO95 / 022586, WO95 / 024455, WO97 / 00600, WO98 / 023580, WO98 / 052905, JP-A Nos. 1-272551, 6-016616, 7-110469, 11-080081, and 2001-328973. Two or more polymerizable liquid crystal compounds may be used in combination. The use of two or more polymerizable liquid crystal compounds in combination can lower the alignment temperature.

[0085] A specific example of the polymerizable liquid crystal compound is the following mixture 1.

[0086]

[0087] The content of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 80 to 99.9 mass %, more preferably 85 to 99.5 mass %, and even more preferably 90 to 99 mass %, relative to the solid mass of the liquid crystal composition (mass excluding the solvent).

[0088] In order to improve the visible light transmittance, the cholesteric liquid crystal layer may have a low Δn. The low Δn cholesteric liquid crystal layer can be formed using a low Δn polymerizable liquid crystal compound. The low Δn polymerizable liquid crystal compound will be specifically described below.

[0089] (Low Δn polymerizable liquid crystal compound) A cholesteric liquid crystal phase is formed using a low Δn polymerizable liquid crystal compound, and this is fixed into a film, thereby obtaining a narrow-band reflective layer. Examples of low Δn polymerizable liquid crystal compounds include the compounds described in WO2015 / 115390, WO2015 / 147243, WO2016 / 035873, JP2015-163596A, and JP2016-053149A. For liquid crystal compositions that provide a reflective layer with a small half-width, the description in WO2016 / 047648 can also be referenced.

[0090] The liquid crystal compound is also preferably a polymerizable compound represented by the following formula (I) described in WO2016 / 047648.

[0091]

[0092] In formula (I), A represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent; L represents a linking group selected from the group consisting of a single bond, —CHO—, —OCH—, —(CH)OC(═O)—, —C(═O)O(CH)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —CH═CH—C(═O)O—, and —OC(═O)—CH═CH—; m represents an integer of 3 to 12; Sp 1 and Sp 2each independently represents a linking group selected from the group consisting of 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 in which one or more -CH2- groups are replaced with -O-, -S-, -NH-, -N(CH3)-, -C(=O)-, -OC(=O)-, or -C(=O)O-; Q 1 and Q 2 each independently represents a hydrogen atom or a polymerizable group selected from the group consisting of groups represented by the following formulas Q-1 to Q-5, 1 and Q 2 represents a polymerizable group.

[0093]

[0094] In formula (I), the phenylene group is preferably a 1,4-phenylene group. When the phenylene group and trans-1,4-cyclohexylene group are referred to as "optionally having a substituent," the substituent is not particularly limited, and examples thereof include a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an amide group, an amino group, a halogen atom, and a group formed by combining two or more of the above-mentioned substituents. In addition, examples of the substituent include the -C(=O)-X group described below. 3 -Sp 3 -Q 3 The phenylene group and the trans-1,4-cyclohexylene group may have 1 to 4 substituents. When the phenylene group and the trans-1,4-cyclohexylene group have two or more substituents, the two or more substituents may be the same or different.

[0095] The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1,1-dimethylpropyl, n-hexyl, isohexyl, linear or branched heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. The above description of the alkyl group also applies to alkoxy groups containing an alkyl group. Specific examples of the alkylene group include divalent groups obtained by removing any one hydrogen atom from each of the above alkyl group examples. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0096] The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 5 or more, and is 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.

[0097] The substituents that the phenylene group and the trans-1,4-cyclohexylene group may have include an alkyl group, an alkoxy group, and —C(═O)—X 3 -Sp 3 -Q 3 Preferred are substituents selected from the group consisting of: 3 represents a single bond, -O-, -S-, or -N(Sp 4 -Q 4 ) - or Q 3 and Sp 3 The nitrogen atom forming a ring structure with Sp is shown. 3 and Sp 4each independently represents a linking group selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or a linear or branched alkylene group having 1 to 20 carbon atoms in which one or more -CH- groups are replaced with -O-, -S-, -NH-, -N(CH)-, -C(=O)-, -OC(=O)-, or -C(=O)O-.

[0098] Q 3 and Q 4 each independently represents a hydrogen atom, a cycloalkyl group, a cycloalkyl group in which one or more -CH2- groups are substituted with -O-, -S-, -NH-, -N(CH3)-, -C(=O)-, -OC(=O)-, or -C(=O)O-, or a polymerizable group selected from the group consisting of groups represented by formulae Q-1 to Q-5.

[0099] Specific examples of cycloalkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -NH-, -N(CH3)-, -C(=O)-, -OC(=O)-, or -C(=O)O- include a tetrahydrofuranyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperidyl group, a piperazinyl group, and a morpholinyl group. The substitution position is not particularly limited. Of these, a tetrahydrofuranyl group is preferred, and a 2-tetrahydrofuranyl group is more preferred.

[0100] In formula (I), L represents a linking group selected from the group consisting of a single bond, -CHO-, -OCH-, -(CH)OC(=O)-, -C(=O)O(CH)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -CH=CH-C(=O)O-, and -OC(=O)-CH=CH-. L is preferably -C(=O)O- or -OC(=O)-. The m-1 Ls may be the same or different.

[0101] Sp 1 and Sp 2each independently represents a linking group selected from the group consisting of 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 in which one or more -CH2- groups are replaced with -O-, -S-, -NH-, -N(CH3)-, -C(=O)-, -OC(=O)-, or -C(=O)O-. 1 and Sp 2 are preferably each independently a linear alkylene group having 1 to 10 carbon atoms bonded to both terminals with linking groups selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-, or a linking group formed by combining one or more groups selected from the group consisting of -OC(=O)-, -C(=O)O-, -O-, and linear alkylene groups having 1 to 10 carbon atoms, and are preferably linear alkylene groups having 1 to 10 carbon atoms bonded to both terminals with -O-.

[0102] Q 1 and Q 2 each independently represents a hydrogen atom or a polymerizable group selected from the group consisting of groups represented by the above formulas Q-1 to Q-5, 1 and Q 2 represents a polymerizable group. The polymerizable group is preferably an acryloyl group (formula Q-1) or a methacryloyl group (formula Q-2).

[0103] In formula (I), m represents an integer of 3 to 12. m is preferably an integer of 3 to 9, more preferably an integer of 3 to 7, and even more preferably an integer of 3 to 5.

[0104] The polymerizable compound represented by formula (I) preferably contains, as A, at least one phenylene group which may have a substituent and at least one trans-1,4-cyclohexylene group which may have a substituent. The polymerizable compound represented by formula (I) preferably contains, as A, 1 to 4 trans-1,4-cyclohexylene groups which may have a substituent, more preferably 1 to 3, and even more preferably 2 or 3. The polymerizable compound represented by formula (I) also preferably contains, as A, one or more phenylene groups which may have a substituent, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 2 or 3.

[0105] In formula (I), when mc is the number obtained by dividing the number of trans-1,4-cyclohexylene groups represented by A by m, 0.1<mc<0.9 is preferred, 0.3<mc<0.8 is more preferred, and 0.5<mc<0.7 is even more preferred. It is also preferred that the liquid crystal composition contains a polymerizable compound represented by formula (I) where 0.1<mc<0.3, together with a polymerizable compound represented by formula (I) where 0.5<mc<0.7.

[0106] Specific examples of the polymerizable compound represented by formula (I) include the compounds described in paragraphs 0051 to 0058 of WO2016 / 047648, as well as compounds described in JP2013-112631A, JP2010-070543A, Japanese Patent No. 4725516, WO2015 / 115390, WO2015 / 147243, WO2016 / 035873, JP2015-163596A, and JP2016-053149A.

[0107] (Chiral Agent: Optically Active Compound) A chiral agent has the function of inducing a helical structure in a cholesteric liquid crystal phase. Chiral compounds can be selected according to the purpose, as the sense or pitch of the helix induced varies depending on the compound. The chiral agent is not particularly limited, and known compounds can be used. Examples of chiral agents include those described in 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), JP-A Nos. 2003-287623, 2002-302487, 2002-080478, 2002-080851, 2010-181852, and 2014-034581.

[0108] Chiral agents generally contain an asymmetric carbon atom, but axially asymmetric or planarly asymmetric compounds without an asymmetric carbon atom can also be used as chiral agents. Examples of axially asymmetric or planarly 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 a polymerizable group, a polymer having a repeating unit derived from the polymerizable liquid crystal compound and a repeating unit derived from the chiral agent can be formed by polymerization of the polymerizable chiral agent and the polymerizable liquid crystal compound. In this embodiment, the polymerizable group of the polymerizable chiral agent is preferably the same type of group as the polymerizable group of 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 particularly preferably an ethylenically unsaturated polymerizable group. The chiral agent may also be a liquid crystal compound.

[0109] The chiral dopant is preferably an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative. Commercially available isosorbide derivatives, such as LC756 manufactured by BASF, may be used. The content of the chiral dopant 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. The content of the chiral dopant in the liquid crystal composition refers to the concentration (% by mass) of the chiral dopant relative to the total solid content in the composition.

[0110] As described above, the cholesteric liquid crystal layer of the reflective layer of 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 can be achieved by changing the pitch of the helical structure in the thickness direction. A cholesteric liquid crystal layer whose pitch of the helical structure changes in the thickness direction can be produced by changing the amount of light irradiation in the thickness direction when forming the cholesteric liquid crystal layer using a chiral agent whose helical twisting power (HTP) changes when irradiated with light.

[0111] Chiral agents whose HTP changes upon irradiation with light include those that undergo back-isomerization, dimerization, isomerization and dimerization, etc. When the chiral agent has a photoisomerizable group, the photoisomerizable group is preferably an isomerization site of a compound exhibiting photochromic properties, an azo group, an azoxy group, or a cinnamoyl group. Specific examples of the compound include compounds described in JP-A-2002-080478, JP-A-2002-080851, JP-A-2002-179668, JP-A-2002-179669, JP-A-2002-179670, JP-A-2002-179681, JP-A-2002-179682, JP-A-2002-338575, JP-A-2002-338668, JP-A-2003-313189, and JP-A-2003-313292.

[0112] (Polymerization Initiator) The liquid crystal composition preferably contains a polymerization initiator. In an embodiment in which the polymerization reaction is caused to proceed by ultraviolet irradiation, the polymerization initiator used is preferably a photopolymerization initiator capable of initiating the polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds (described in U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No. 2,722,512), polynuclear quinone compounds (described in U.S. Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (described in JP-A-60-105667 and U.S. Pat. No. 4,239,850), and acylphosphites. Benzene oxide compounds (JP-B No. 63-040799, JP-B No. 5-029234, JP-A No. 10-095788, JP-A No. 10-029997, JP-A No. 2001-233842, JP-A No. 2000-080068, JP-A No. 2006-342166, JP-A No. 2013-114249, JP-A No. 2014 Examples of such compounds include those described in JP-A-137466, JP 4223071, JP 2010-262028, and JP-T-2014-500852, oxime compounds (described in JP 2000-066385 and JP 4454067), and oxadiazole compounds (described in U.S. Pat. No. 4,212,970). For example, the description in paragraphs 0500 to 0547 of JP 2012-208494 can also be referred to.

[0113] As the polymerization initiator contained in the liquid crystal composition, it is also preferable to use an acylphosphine oxide compound or an oxime compound. Examples of the acylphosphine oxide compound include the commercially available product IRGACURE 810 (compound name: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) manufactured by BASF Japan Ltd. Examples of the oxime compound include commercially available products such as IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-831, ADEKA ARCLES NCI-930 (manufactured by ADEKA), and ADEKA ARCLES NCI-831 (manufactured by ADEKA). Only one type of polymerization initiator may be used, or two or more types may be used in combination. 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.

[0114] (Crosslinking Agent) The liquid crystal composition may optionally contain a crosslinking agent in order to improve the film strength and durability after curing. As the crosslinking agent, those that are cured by ultraviolet light, heat, moisture, etc. can be suitably used. The crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. Examples of 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; isocyanate compounds such as hexamethylene diisocyanate and biuret-type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; and alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane. Furthermore, known catalysts can be used depending on the reactivity of the crosslinking agent, which can improve productivity in addition to improving film 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. By setting the content of the crosslinking agent to 3% by mass or more, the effect of improving the crosslinking density can be obtained, and by setting the content of the crosslinking agent to 20% by mass or less, a decrease in the stability of the cholesteric liquid crystal layer can be prevented. Note that "(meth)acrylate" is used to mean "either one or both of acrylate and methacrylate."

[0115] (Alignment Control Agent) The liquid crystal composition may contain an alignment control agent that contributes to stably or quickly forming a cholesteric liquid crystal layer with planar alignment. Examples of alignment control agents include fluorine (meth)acrylate polymers described in paragraphs

[0018] to

[0043] of JP-A No. 2007-272185, compounds represented by formulas (I) to (IV) described in paragraphs

[0031] to

[0034] of JP-A No. 2012-203237, and compounds described in JP-A No. 2013-113913. Note that one type of alignment control agent may be used alone, or two or more types may be used in combination.

[0116] Specific examples of compounds that can be used as alignment control agents include the following alignment control agent 1 and alignment control agent 2.

[0117]

[0118]

[0119] 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 even more preferably 0.02 to 1% by mass, based on the total mass of the polymerizable liquid crystal compound.

[0120] (Other Additives) The liquid crystal composition may further contain at least one 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, etc. Furthermore, if necessary, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, metal oxide fine particles, etc. may be further added to the liquid crystal composition within a range that does not deteriorate the optical performance.

[0121] The cholesteric liquid crystal layer can be formed by applying a liquid crystal composition prepared by dissolving a polymerizable liquid crystal compound and a polymerization initiator, and optionally a chiral agent, a surfactant, etc., in a solvent onto a transparent substrate, a retardation layer, an alignment layer, or a previously prepared cholesteric liquid crystal layer, etc., and drying the composition to obtain a coating film, which is then irradiated with actinic rays to polymerize the cholesteric liquid crystal composition, thereby forming a cholesteric liquid crystal layer with fixed cholesteric regularity. Note that a laminate film consisting of multiple cholesteric liquid crystal layers can be formed by repeatedly performing the above-mentioned manufacturing process for the cholesteric liquid crystal layer.

[0122] (Solvent) 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 appropriately selected depending on the purpose, and examples thereof include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers. These may be used alone or in combination of two or more. Among these, ketones are preferred when considering the environmental impact.

[0123] (Coating, Alignment, Polymerization) The method of applying the liquid crystal composition to the transparent substrate, alignment layer, and underlying cholesteric liquid crystal layer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the coating method 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. Alternatively, the liquid crystal composition can be applied to a support and transferred onto the support. The applied liquid crystal composition is heated to align the liquid crystal molecules. The heating temperature is preferably 200°C or lower, more preferably 130°C or lower. This alignment treatment results in an optical thin film in which the polymerizable liquid crystal compound is twisted and aligned so that its helical axis is substantially perpendicular to the film surface.

[0124] The aligned liquid crystal compound can be further polymerized to harden the liquid crystal composition. The polymerization may be either thermal polymerization or photopolymerization using light irradiation, but photopolymerization is preferred. The light irradiation is preferably performed using ultraviolet light. The irradiation energy is 20 mJ / cm. 2 ~50 J / cm 2 is preferred, and 100 to 1,500 mJ / cm 2 is more preferable. In order to promote the photopolymerization reaction, light irradiation may be carried out under heated conditions or in a nitrogen atmosphere. The wavelength of the irradiated ultraviolet light is preferably 350 to 430 nm. From the viewpoint of stability, a higher polymerization reaction rate is preferable, 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 using infrared absorption spectroscopy.

[0125] <Hard Coat Layer (HC Layer)> The reflective film of the present invention has a hard coat layer (HC layer). The HC layer provides abrasion resistance that makes it difficult to scratch even when rubbed with a hard substance, scratch resistance that makes it difficult to scratch even when pressed with a hard substance, and antifouling properties that allow dirt to be easily wiped off even if dirt adheres to the film.

[0126] The HC layer in the present invention is preferably obtained by polymerizing and curing at least one compound selected from the group consisting of polysiloxane-containing compounds having polymerizable groups in their molecules and fluorine-containing compounds having polymerizable groups in their molecules, and the polymerizable compound other than these compounds that has polymerizable groups in its molecule as described below, and more preferably these polymerizable groups are radical polymerizable groups.Therefore, in the HC layer, the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds and the polymerizable compound that forms the HC layer exist in a bonded state, and can provide better antifouling properties.When the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds has polymerizable group, the polymerizable group in the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds described below will react and form bond and exist in the HC layer.

[0127] In addition, when the HC layer is a laminated structure of two or more layers as described later, it is preferable that the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds is at least contained in the HC layer farthest from the adhesive layer, and more preferably only contained in the HC layer farthest from the adhesive layer.When using at least one compound selected from the group consisting of polysiloxane-containing compounds with polymerizable groups in the molecule and fluorine-containing compounds with polymerizable groups in the molecule, it is preferable that the HC layer farthest from the adhesive layer is at least the cured film of the compound, and more preferably only the HC layer farthest from the adhesive layer is the cured film of the compound.Hereinafter, the specific embodiment of the HC layer will be described, but the present invention is not limited to the following embodiment.

[0128] (Fluorine-containing compound) In the present invention, the fluorine-containing compound is not particularly limited as long as it can impart abrasion resistance and antifouling properties to the HC layer, and a compound having a fluorine atom in the molecule can be used.As the fluorine-containing compound, a fluorine-containing antifouling agent that exhibits the properties of an antifouling agent is preferably used.

[0129] In the present invention, the fluorine-containing compound may be any of a monomer, an oligomer, and a polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with other components (for example, polysiloxane-containing compounds, polymerizable monomers that are constituent components of resins, resins) in the HC layer. The substituents may be the same or different, and it is preferable that there are a plurality of them. The substituent is preferably a polymerizable group, and may be any polymerizable reactive group that exhibits any of radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, and addition polymerization. Preferred examples of the substituent 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 them, a radical 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.

[0130] The fluorine-containing antifouling agent is preferably a fluorine-based compound represented by the following general formula (F): ｆ )-[(W)-(R Ａ ) ｎ ] ｍ (In the formula, R ｆ represents a (per)fluoroalkyl group or a (per)fluoropolyether group, W represents a single bond or a linking group, R Ａ represents a polymerizable unsaturated group. n represents an integer of 1 to 3. m represents an integer of 1 to 3.

[0131] In general formula (F), R Ａ represents a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having an unsaturated bond that can undergo a radical polymerization reaction when irradiated with active energy rays such as ultraviolet rays and electron beams (i.e., a radically polymerizable group), and examples thereof include a (meth)acryloyl group, a (meth)acryloyloxy group, a vinyl group, and an allyl group. Of these groups, a (meth)acryloyl group, a (meth)acryloyloxy group, and groups in which any hydrogen atom is substituted with a fluorine atom are preferably used.

[0132] In general formula (F), R ｆ represents a (per)fluoroalkyl group or a (per)fluoropolyether group. Here, the (per)fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per)fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. From the viewpoint of antifouling properties, R ｆ The higher the fluorine content in the polymer, the more preferable.

[0133] The number of carbon atoms in the (per)fluoroalkyl group is preferably 1 to 20, more preferably 1 to 10. The (per)fluoroalkyl group has a linear structure (for example, —CF ２ CF ３ , -CH ２ (CF ２ ) ４ H, —CH ２ (CF ２ ) ８ CF ３ , and -CH２ CH ２ (CF ２ ) ４ H), but also branched structures (e.g., —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) or an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these groups).

[0134] The (per)fluoropolyether group refers to a (per)fluoroalkyl group having an ether bond, and may be a monovalent or divalent or higher valent group. Examples of 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 ２ OCF ２ CF ２ OCF ２ CF ２ H, and a fluorocycloalkyl group having 4 to 20 carbon atoms and 4 or more fluorine 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 )] ｑ -, - (CF ２ CF ２ CF ２ O) ｐ -, and -(CF ２ CF ２ O) ｐ The above-mentioned p and q each independently represent an integer of 0 to 20, provided that 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. From the viewpoint of excellent antifouling properties, the above-mentioned fluorine-containing antifouling agent is preferably -(CF ２ O) ｐ -(CF ２ CF ２ O) ｑ It is preferable that the hydroxyl group has a perfluoropolyether group represented by the formula:

[0135] In the present invention, the fluorine-containing antifouling agent preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.

[0136] In general formula (F), W represents a single bond or a linking group. Examples of W include alkylene groups, arylene groups, and heteroalkylene groups, as well as linking groups formed by combining these groups. These linking groups may further have functional groups such as oxy groups, carbonyl groups, carbonyloxy groups, carbonylimino groups, and sulfonamide groups, as well as functional groups formed by combining these groups. W is preferably an ethylene group, and more preferably an ethylene group bonded to a carbonylimino group.

[0137] 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.

[0138] Examples of preferred fluorine-containing antifouling agents include R-2020, M-2020, R-3833, M-3833 and Optool DAC (all trade names) manufactured by Daikin Chemical Industries, Ltd., and Megafac F-171, F-172, F-179A, RS-78, RS-90, Defensa MCF-300 and MCF-323 (all trade names) manufactured by Dainippon Ink Co., Ltd.

[0139] In light of abrasion resistance, in general formula (F), the product of n and m (n×m) is preferably 2 or greater, and more preferably 4 or greater.

[0140] In general formula (F), preferred specific examples of the embodiment in which n and m are simultaneously 1 include compounds represented by the following general formulae (F-1) to (F-3).

[0141] General formula (F-1): R ｆ２ (CF ２ CF ２ ) ｐ R ２２ CH ２ CH ２ R ２１ OCOCR １１ =CH ２

[0142] (In the formula, R ｆ２ represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms, and 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, and the degree of polymerization p is k or more (k is an integer of 3 or more).

[0143] R ２２ When represents a divalent linking group, examples of this divalent linking group include the same as those for W described above.

[0144] Examples of the fluorine atom-containing telomer type (meth)acrylate in the general formula (F-1) include partially or completely fluorinated alkyl ester derivatives of (meth)acrylic acid.

[0145] When the compound represented by the general formula (F-1) is synthesized by telomerization, the R group of the general formula (F-1) may be formed depending on the telomerization conditions and the separation conditions of the reaction mixture. ｆ２ (CF ２ CF ２ ) ｐ R ２２ CH ２ CH ２ R ２１ The compound may contain a plurality of fluorine-containing (meth)acrylic acid esters in which p in O- is k, k+1, k+2, . . .

[0146] General formula (F-2): F(CF ２ ) ｑ -CH ２ -CHX-CH ２ Y (wherein q represents an integer of 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).

[0147] The fluorine-containing (meth)acrylic acid ester represented by the general formula (F-2) has a trifluoromethyl group (—CF ３ Even a small amount of this fluorine-containing (meth)acrylic acid ester effectively orients the trifluoromethyl groups on the surface.

[0148] In view of abrasion resistance and ease of production of the compound, q is preferably 6 to 20, more preferably 8 to 10. A fluorine-containing (meth)acrylic acid ester having a fluoroalkyl group having 8 to 10 carbon atoms exhibits a superior effect of reducing the friction coefficient and is excellent in abrasion resistance, even compared with fluorine-containing (meth)acrylic acid esters having fluoroalkyl groups of other chain lengths.

[0149] Specific examples of the fluorine-containing (meth)acrylic acid ester represented by the general formula (F-2) include 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, Examples of suitable hydroxy groups include 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)acryloyloxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane. Of these, 1-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 is preferred.

[0150] General formula (F-3): F(CF ２ ) ｒ O (CF ２ CF ２ O) ｓ CF ２ CH ２ OCOCR ３ =CH ２ (In the formula, R ３ represents a hydrogen atom or a methyl group, s represents an integer of 1 to 20, and r represents an integer of 1 to 4.

[0151] The fluorine atom-containing monofunctional (meth)acrylate represented by the above general formula (F-3) can be obtained by reacting a fluorine atom-containing alcohol compound represented by the following general formula (FG-3) with a (meth)acrylic acid halide.

[0152] General formula (FG-3): F(CF ２ ) ｒ O (CF ２ CF ２ O) ｓ CF ２ CH ２ OH (In general formula (FG-3), s represents an integer of 1 to 20, and r represents an integer of 1 to 4.)

[0153] Specific examples of the fluorine atom-containing alcohol compound represented by the 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-dioxadecan-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-tetraoxatridecan-1-ol, 1H,1H-perfluoro-3,6,9,12-tetraoxatetradecan-1-ol, and 1H,1H-perfluoro-3,6,9,12-tetraoxatetradecan-1-ol. Oxahexadecan-1-ol, 1H,1H-perfluoro-3,6,9,12,15-pentaoxahexadecan-1-ol, 1H,1H-perfluoro-3,6,9,12,15-pentaoxaheptadecan-1-ol, 1H,1H-perfluoro-3,6,9,12,15-pentaoxanonadecan-1-ol, 1H,1H-perfluoro-3,6,9,12,15,1 8-hexaoxaicosan-1-ol, 1H,1H-perfluoro-3,6,9,12,15,18-hexaoxadocosan-1-ol, 1H,1H-perfluoro-3,6,9,12,15,18,21-heptaoxatricosan-1-ol, and 1H,1H-perfluoro-3,6,9,12,15,18,21-heptaoxapentacosan-1-ol.These are commercially available products, and specific examples thereof include 1H,1H-perfluoro-3,6-dioxaheptan-1-ol (trade name "C5GOL", manufactured by Exflo Corporation), 1H,1H-perfluoro-3,6,9-trioxadecan-1-ol (trade name "C7GOL", manufactured by Exflo Corporation), 1H,1H-perfluoro-3,6-dioxadecan-1-ol (trade name "C8GOL", manufactured by Exflo Corporation), 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol (trade name "C10GOL", manufactured by Exflo Corporation), and 1H,1H-perfluoro-3,6,9,12-tetraoxahexadecan-1-ol (trade name "C12GOL", manufactured by Exflo Corporation). Of these, 1H,1H-perfluoro-3,6,9,12-tetraoxatridecan-1-ol is preferred.

[0154] Examples of the (meth)acrylic acid halide to be reacted with the fluorine atom-containing alcohol compound represented by general formula (FG-3) include (meth)acrylic acid fluoride, (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide. From the viewpoint of availability, etc., (meth)acrylic acid chloride is preferred.

[0155] Preferable specific examples of the compound represented by general formula (F-3) are shown below, but the compound is not limited to these. Preferable specific examples represented by general formula (F-3) are also described in JP-A-2007-264221.

[0156] (b-1): F ９ C ４ O.C. ２ F ４ O.C. ２ F ４ OCF ２ CH ２ OCOCH=CH ２ (b-2): F ９ C ４ O.C. ２ F ４ O.C. ２ F ４ OCF ２ CH ２ OCOC (CH３ ) = CH ２

[0157] Furthermore, apart from the compound represented by formula (F-3), a compound represented by the following formula (F-3)' is also preferred.

[0158] General formula (F-3)': R ｆ３ - [(O) ｃ (O=C) ｂ (CX ４ X ５ ) ａ -CX ３ =CX １ X ２ ] (In the formula, X １ and X ２ represents H or F, and X ３ are H, F, and CH ３ or CF ３ represents X ４ and X ５ is H, F, or CF ３ a, b, and c represent 0 or 1; R ｆ３ represents a fluorine-containing organic group containing an ether bond and having 18 to 200 carbon atoms.) The compound represented by the general formula (F-3)' is ｆ３ In the group, the general formula (FG-3)': -(CX ６ ２ CF ２ CF ２ O)-(wherein, X ６ is a fluorine-containing unsaturated compound having six or more repeating units represented by F or H).

[0159] Examples of the fluorine-containing polyether compound represented by the above general formula (F-3)' include compounds represented by the general formula (c-1): ｆ３ -[(O) (O=C) ｂ -CX ３ =CX １ X ２ ] General formula (c-2) R ｆ３ -[(O)(O=C)-CX ３ =CX １ X ２ ] General formula (c-3) R ｆ３ - [(O) ｃ (O=C)-CF=CH ２(The definitions of the respective symbols in formulae (c-1) to (c-3) are the same as in formula (FG-3)'.) As the polymerizable unsaturated group of the above fluorine-containing polyether compound, those having the following structure can be preferably used.

[0160] The fluorine-containing polyether compound represented by the general formula (F-3)' may have a plurality of polymerizable unsaturated groups. ２ Compounds having the structure shown below are preferred in that they have particularly high polymerization (curing) reactivity and can efficiently produce cured products.

[0161] The fluorine-containing polyether compound represented by the general formula (F-3)′ is R ｆ３ It is important that the group contains 6 or more repeating units of the fluorine-containing polyether chain represented by general formula (FG-3)', thereby imparting abrasion resistance. More specifically, a mixture containing 6 or more repeating units of the fluorine-containing polyether chain may be used, and when used in the form of a mixture, it is preferable to use a mixture in which the abundance ratio of fluorine-containing unsaturated compounds having 6 or more repeating units of the polyether chain is highest in the distribution of the fluorine-containing unsaturated compounds having less than 6 repeating units and the fluorine-containing unsaturated compounds having 6 or more repeating units. The number of repeating units of the fluorine-containing polyether chain represented by 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. This reduces the coefficient of dynamic friction and improves abrasion resistance. Furthermore, the fluorine-containing polyether chain R ｆ３ It may be at the end of the group or in the chain.

[0162] R ｆ３ Specifically, the group is represented by the general formula (c-4): R ４ - (CX ６ ２ CF ２ CF ２ O) ｔ - (R ５ ) ｅ - (in the formula, X ６ is X in the fluorine-containing polyether chain represented by formula (FG-3)' ６is synonymous with 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 of 6 to 66, and e represents 0 or 1. ｆ３ The group is a divalent or higher organic group R ５ and further has R at the end. ４ R is a fluorine-containing organic group having the formula ５ may be any organic group capable of bonding the fluorine-containing polyether chain represented by general formula (FG-3)' to a reactive carbon-carbon double bond. Examples thereof 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 a low refractive index.

[0163] As specific examples of the fluorine-containing polyether compound represented by the general formula (F-3)′, compounds such as those described in the republished patent publication WO 2003 / 022906 are preferably used. ２ =CF-COO-CH ２ CF ２ CF ２ -(OCF ２ CF ２ CF ２ ) ７ -OC ３ F ７ is preferred.

[0164] In general formula (F), examples of embodiments in which n and m are not 1 at the same time include compounds represented by general formulas (F-4) and (F-5).

[0165] General formula (F-4): (R ｆ１ )-[(W)-(R Ａ ) ｎ ] ｍ (In general formula (F-4), R ｆ１represents a (per)fluoroalkyl group or a (per)fluoropolyether group, W represents a linking group, R Ａ represents a polymerizable unsaturated group. n represents an integer of 1 to 3, and m represents an integer of 1 to 3, provided that n and m are not simultaneously 1.) From the viewpoint of achieving excellent water and oil repellency and excellent sustainability of the water and oil repellency (soil-resistant durability), it is preferable that n is 2 to 3 and m is 1 to 3, more preferably that n is 2 to 3 and m is 2 to 3, and even more preferably that n is 3 and m is 2 to 3.

[0166] R ｆ１ R can be monovalent to trivalent. ｆ１ When is monovalent, the terminal group is (C ｎ F ２ｎ＋１ ) -, (C ｎ F ２ｎ＋１ O) -, (XC ｎ F ２ｎ O) -, (XC ｎ F ２ｎ＋１ )-(wherein X is a hydrogen atom, a chlorine atom, or a bromine atom, and n is an integer of 1 to 10). 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 preferred.

[0167] 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.

[0168] R ｆ１When 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 O.C. 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.

[0169] Here, the average values ​​of p, q, r, and s in the formula are 0 to 50. Among these, 3 to 30 is preferable, 3 to 20 is more preferable, and 4 to 15 is even more preferable. t is an integer of 2 to 6. Preferable specific examples and synthesis methods of the compound represented by general formula (F-4) are described in WO 2005 / 113690.

[0170] In the following, F(CF(CF ３ )CF ２ O) ｐ CF (CF ３ )-, those with an average value of p of 6 to 7 are described as "HFPO-", and -(CF(CF ３ )CF ２ O) ｐ CF (CF３ )--wherein the average value of p is 6 to 7 is expressed as "-HFPO--", and specific compounds of general formula (F-4) are shown, but are not limited to these.

[0171] (d-1): HFPO-CONH-C-(CH ２ OCOCH=CH ２ ) ２ CH ２ CH ３ (d-2): HFPO-CONH-C-(CH ２ OCOCH=CH ２ ) ２ H (d-3): HFPO-CONH-C ３ H ６ NHCH ３ 1:1 Michael addition polymer of trimethylolpropane triacrylate (d-4): (CH ２ =CHCOOCH ２ ) ２ HC-CONH-HFPO-CONH-(CH ２ OCOCH=CH ２ ) ２ H (d-5): (CH ２ =CHCOOCH ２ ) ３ -C-CONH-HFPO-CONH-C-(CH ２ OCOCH=CH ２ ) ３

[0172] Furthermore, as the compound represented by general formula (F-4), a compound represented by the following general formula (F-5) can also be used.

[0173] General formula (F-5): CH ２ =CX １ -COO-CHY-CH ２ -OCO-CX ２ =CH ２ (X in the formula １ and X ２ represents a hydrogen atom or a methyl group, and Y represents a fluoroalkyl group having 2 to 20 carbon atoms and 3 or more fluorine atoms, or a fluorocycloalkyl group having 4 to 20 carbon atoms and 4 or more fluorine atoms.

[0174] In the present invention, the compound in which the polymerizable unsaturated group is a (meth)acryloyloxy group may have a plurality of (meth)acryloyloxy groups. When the fluorine-containing antifouling agent has a plurality of (meth)acryloyloxy groups, it forms a three-dimensional network structure when cured, which results in a high glass transition temperature, low transferability of the antifouling agent, and improved durability against repeated wiping of stains. Furthermore, it is possible to obtain an HC layer with excellent heat resistance, weather resistance, etc.

[0175] Specific examples of the compound represented by the general formula (F-5) include 2,2,2-trifluoroethylethylene glycol di(meth)acrylate, 2,2,3,3,3-pentafluoropropylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,5,5,5-pentafluoropropylethylene glycol di(meth)acrylate, 5,5,6,6,6-undecafluorohexylethylene glycol, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol di(meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol di(meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecylethylene glycol di(meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecylethylene glycol di(meth)acrylate, 2-trifluoromethyl methyl ester Preferred examples of di(meth)acrylates include 3-methyl-3,3,3-trifluoropropylethylene glycol di(meth)acrylate, 3-trifluoromethyl-4,4,4-trifluorobutylethylene glycol di(meth)acrylate, 1-methyl-2,2,3,3,3-pentafluoropropylethylene glycol di(meth)acrylate, and 1-methyl-2,2,3,3,4,4,4-heptafluorobutylethylene glycol di(meth)acrylate, and these can be used alone or in combination. Such di(meth)acrylates can be prepared by known methods such as those described in JP-A-6-306326.In the present invention, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol diacrylate is preferably used.

[0176] In the present invention, the compound in which the polymerizable unsaturated group is a (meth)acryloyloxy group may be a compound having a plurality of (per)fluoroalkyl groups or (per)fluoropolyether groups in one molecule.

[0177] The weight-average molecular weight (Mw) of the fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC). The 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 equal to or greater than the above lower limit, the surface migration of the antifouling agent in the HC layer is enhanced, which is preferable. If it is less than the above upper limit, the surface migration of the fluorine-containing compound is not hindered during the process of applying and curing the HC layer-forming curable composition described below, which makes it easier for the fluorine-containing compound to be unevenly distributed on the HC layer surface, and improves abrasion resistance and film hardness, which is preferable. In addition, the fluorine-containing compound may have a multimodal weight-average molecular weight.

[0178] As described below, when forming an HC layer, it is preferable to use a curable composition for forming an HC layer. The fluorine-containing compound may be contained in the curable composition for forming an HC layer. The content of the fluorine-containing compound in the curable composition for forming an HC layer is preferably 0.01 to 5 mass%, more preferably 0.1 to 5 mass%, even more preferably 0.5 to 5 mass%, and particularly preferably 0.5 to 2 mass%, relative to the total solids content in the curable composition for forming an HC layer. When the amount added is equal to or greater than the above upper limit, the coefficient of friction can be reduced, and abrasion resistance is further improved. Furthermore, when the amount added is equal to or less than the above lower limit, fluorine-containing compounds that are insufficiently mixed with the polymerizable compound in the curable composition for forming the HC layer (the resin component when forming the HC layer) do not precipitate on the surface, which is preferable because whitening of the HC layer or the generation of white powder on the surface is suppressed. Note that when the HC layer has a laminate structure of two or more layers, as described below, this refers to the amount added in the curable composition for forming an HC layer that forms an HC layer containing a fluorine-containing compound or a polysiloxane compound. The solid content in the curable composition for forming an HC layer means the components other than the solvent in the curable composition for forming an HC layer. Even if the components are in a liquid state, they are considered to be solids.

[0179] (Polysiloxane-containing compound) The polysiloxane-containing compound in the present invention is not particularly limited, and examples thereof include compounds having a polysiloxane structure in the molecule. The polysiloxane structure of the polysiloxane-containing compound may be any of linear, branched, and cyclic. As the polysiloxane-containing compound, a polysiloxane antifouling agent exhibiting the properties of an antifouling agent is preferably used.

[0180] The polysiloxane antifouling agent is preferably a compound represented by the following general formula (F-6).

[0181] General formula (F-6): R ａ R Ａ ｂ SiO （４－ａ－ｂ）／２ (wherein R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group; R Ａ represents an organic group containing a polymerizable unsaturated group, and 0<a, 0<b, a+b<4.

[0182] a is preferably 1 to 2.75, more preferably 1 to 2.5. When a is 1 or more, the compound can be easily synthesized industrially, and when a is 2.75 or less, both curability and antifouling properties can be easily achieved.

[0183] R Ａ As the polymerizable unsaturated group in the general formula (F), R Ａ Examples of suitable polymerizable unsaturated groups (i.e., radically polymerizable groups) include those listed above, and preferred are (meth)acryloyl groups, (meth)acryloyloxy groups, and groups in which any hydrogen atom in these groups has been substituted with a fluorine atom. From the viewpoint of film strength, it is also preferred that the polysiloxane antifouling agent has a plurality of polymerizable unsaturated groups in one molecule. The polysiloxane antifouling agent is preferably a polydimethylsiloxane having a plurality of polymerizable unsaturated groups in one molecule.

[0184] Preferred examples of polysiloxane antifouling agents include those having a substituent at the end and / or side chain of a compound chain containing multiple 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 are multiple substituents. This substituent is preferably a polymerizable group, and may be any of radically polymerizable, cationic polymerizable, anionic polymerizable, condensation polymerizable, and addition polymerizable. Preferred examples of the substituent include groups containing a (meth)acryloyl group, a ((meth)acryloyloxy) group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a fluoroalkyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Of these, radically polymerizable groups are preferred, and a (meth)acryloyloxy group is particularly preferred from the viewpoint of improving antifouling properties. Furthermore, from the viewpoint of achieving both film strength and antifouling properties, the number of the above-mentioned substituents in the compound is preferably 100 to 10,000 g / mol in terms of functional group equivalent, more preferably 100 to 3,000 g / mol, even more preferably 100 to 2,000 g / mol, and particularly preferably 100 to 1,000 g / mol. By making the functional group equivalent equal to or greater than the above-mentioned lower limit, the compound is not more compatible with the polymerizable compound in the curable composition for forming the HC layer (the resin component when forming the HC layer), which is preferable because it increases the surface migration of the antifouling agent in the HC layer. By making the functional group equivalent equal to or less than the above-mentioned upper limit, it is preferable because it can improve film hardness and antifouling properties.

[0185] R Ａ As for b, an organic group containing a (meth)acryloyl group is preferred, and from the viewpoint of ease of industrial synthesis, it is more preferred that the bond to the Si atom be an Si—O—C bond. b is preferably 0.4 to 0.8, more preferably 0.6 to 0.8, and when b is equal to or greater than the lower limit, curability is improved, and when it is equal to or less than the upper limit, antifouling properties are improved.

[0186] Furthermore, a+b is preferably 3 to 3.7, and more preferably 3 to 3.5. If it is equal to or greater than the lower limit, the compound is likely to be unevenly distributed on the surface of the HC layer, whereas if it is equal to or less than the upper limit, both curability and antifouling properties can be improved.

[0187] 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 3 or more Si atoms, the compound is more likely to be unevenly distributed on the HC layer surface, making it easier to obtain sufficient antifouling properties.

[0188] The polysiloxane antifouling agent can be produced by a known method such as that described in JP-A-2007-145884. Examples of additives having a polysiloxane structure include polysiloxanes (e.g., "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-22-167 ... Preferred are "AK-2-161AS" (trade name), all manufactured by Shin-Etsu Chemical Co., Ltd.; "AK-5", "AK-30", and "AK-32" (trade names), all manufactured by Toagosei Co., Ltd.; "Silaplane FM0725" and "Silaplane FM0721" (trade names), all manufactured by Chisso Corporation; "DMS-U22", "RMS-033", and "UMS-182" (trade names), all manufactured by Gelest; and "Acrit 8SS-723" (trade name), all manufactured by Taisei Fine Chemical Co., Ltd.). Also preferred are the polysiloxane compounds described in Tables 2 and 3 of JP-A No. 2003-112383.

[0189] 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. When 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.

[0190] The content of the polysiloxane-containing compound in the HC layer-forming curable composition is preferably 0.01 to 5 mass%, more preferably 0.1 to 5 mass%, even more preferably 0.5 to 5 mass%, and particularly preferably 0.5 to 2 mass%, relative to the total solids content of the HC layer-forming curable composition. When the amount added is equal to or greater than the above-mentioned lower limit, the antifouling properties can be further improved. Furthermore, when the amount added is equal to or less than the above-mentioned upper limit, the polysiloxane-containing compound that is insufficiently mixed with the polymerizable compound in the HC layer-forming curable composition (the resin component used to form the HC layer) does not precipitate on the surface, which is preferable because it prevents the HC layer from whitening or the formation of white powder on the surface. Note that when the HC layer has a laminate structure of two or more layers, as described below, this refers to the amount added in the HC layer-forming curable composition that forms the HC layer containing the polysiloxane compound.

[0191] The HC layer used in the present invention can be obtained by irradiating the curable composition for forming the HC layer with active energy rays and curing it. In this specification, the term "active energy rays" refers to ionizing radiation, and includes X-rays, ultraviolet rays, visible light, infrared rays, electron beams, α rays, β rays, γ rays, etc.

[0192] The curable composition for forming the HC layer used to form the HC layer contains at least one component that has the property of being cured by irradiation with active energy rays (hereinafter also referred to as "active energy ray-curable component"). The active energy ray-curable component is preferably at least one polymerizable compound selected from the group consisting of radically polymerizable compounds and cationically polymerizable compounds. In this specification, a "polymerizable compound" refers to a compound having a polymerizable group in its molecule, and the number of such polymerizable groups may be at least one per molecule. The polymerizable group is a group that can participate in a polymerization reaction, and specific examples include groups contained in the various polymerizable compounds described below. Examples of polymerization reactions include various polymerization reactions such as radical polymerization, cationic polymerization, and anionic polymerization. The HC layer of the present invention is preferably obtained by irradiating a curable composition for forming the HC layer, which contains at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in their molecules and fluorine-containing compounds having a polymerizable group in their molecules, and a polymerizable compound other than these compounds having a polymerizable group in their molecules, with active energy rays to polymerize and cure the composition. In this case, the polymerizable groups possessed by the polysiloxane-containing compound, the fluorine-containing compound, and the polymerizable compound are preferably radically polymerizable groups. The HC layer used in the present invention may have a single-layer structure or a laminated structure of two or more layers, and an HC layer having a single-layer structure or a laminated structure of two or more layers, which will be described in detail below, is preferred.

[0193] 1) Single-Layer Structure A preferred embodiment of the curable composition for forming a single-layer HC layer is a curable composition for forming a HC layer containing at least one polymerizable compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group refers to a functional group containing an ethylenically unsaturated double bond. A second embodiment is a curable composition for forming a HC layer containing at least one radically polymerizable compound and at least one cationically polymerizable compound.

[0194] The curable composition for forming an HC layer of the first embodiment will be described below. Examples of 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 embodiment include esters of polyhydric alcohols and (meth)acrylic acid [for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Examples of the ethylenically unsaturated polymerizable compound include ethylene oxide-modified esters of the above esters, polyethylene oxide-modified esters, and caprolactone-modified esters of the above esters, vinyl benzene and its derivatives (e.g., 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfones (e.g., divinyl sulfone), acrylamides (e.g., methylenebisacrylamide), and methacrylamide. The number of ethylenically unsaturated groups contained in the polymerizable compound having two or more ethylenically unsaturated groups per molecule is not particularly limited, but is preferably 2 to 10, more preferably 2 to 6, even more preferably 4 to 6, and particularly preferably 5 to 6.

[0195] The polymerization of the 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.As the radical photopolymerization initiator, the radical photopolymerization initiator described later is preferably used.In addition, with regard to 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 later is preferably used.

[0196] Next, the curable composition for forming an HC layer of the second embodiment will be described. The curable composition for forming an HC layer of the second embodiment preferably contains at least one radical polymerizable compound and at least one cationic polymerizable compound. A preferred embodiment includes a curable composition for forming an HC layer comprising: a radical polymerizable compound containing two or more radical polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule; and a cationic polymerizable compound.

[0197] The curable composition for forming the HC layer preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. A preferred embodiment of the second aspect is a curable composition for forming the HC layer, which comprises: a radical polymerizable compound containing two or more radical polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule; a cationic polymerizable compound; a radical photopolymerization initiator; and a cationic photopolymerization initiator. Hereinafter, this embodiment will be referred to as the second aspect (1).

[0198] In the second aspect (1), the radically polymerizable compound preferably contains two or more radically polymerizable groups in one molecule and one or more urethane bonds in one molecule.

[0199] Another preferred embodiment of the second embodiment is a curable composition for forming an HC layer, comprising: a) a cationically polymerizable compound containing an alicyclic epoxy group and an ethylenically unsaturated group, wherein the compound contains one alicyclic epoxy group and one ethylenically unsaturated group per molecule, and has a molecular weight of 300 or less; b) a radically polymerizable compound containing three or more ethylenically unsaturated groups per molecule; c) a radical polymerization initiator; and d) a cationic polymerization initiator. Hereinafter, this embodiment will be referred to as Second Aspect (2). The HC layer obtained by curing the curable composition for forming an HC layer of Second Aspect (2) can preferably contain, relative to the total solids content of the HC layer being 100% by mass, 5 to 70% by mass of the structure derived from a), 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). In one embodiment, the curable composition for forming an HC layer of the second embodiment (2) preferably contains 15 to 70 mass% of the above-mentioned a) when the total solid content of the curable composition for forming an HC layer is taken as 100 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.

[0200] Hereinafter, various components that can be contained in the curable composition for forming an HC layer according to the second embodiment, preferably the second embodiment (1) or the second embodiment (2), will be described in more detail.

[0201] -Radical Polymerizable Compound- The curable composition for forming an HC layer of the second embodiment contains at least one radically polymerizable compound and at least one cationically polymerizable compound. The radically polymerizable compound in the second embodiment (1) contains two or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups per molecule. The radically polymerizable compound may contain, for example, preferably 2 to 10 radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups per molecule, more preferably 2 to 6 radically polymerizable groups, even more preferably 4 to 6 radically polymerizable groups, and particularly preferably 5 to 6 radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups.

[0202] The radical polymerizable compound is preferably a radical polymerizable compound having a molecular weight of 200 or more but less than 1,000. In this specification, the term "molecular weight" refers to the weight average molecular weight of a polymer measured in terms of polystyrene by gel permeation chromatography (GPC). Specific measurement conditions for the weight average molecular weight include the following: GPC apparatus: HLC-8120 (manufactured by Tosoh Corporation) Column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, inner diameter 7.8 mm x column length 30.0 cm) Eluent: tetrahydrofuran

[0203] Furthermore, the curable composition for forming an HC layer of the second aspect (1) may contain, in addition to a radical polymerizable compound containing two or more radical polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule, one or more radical polymerizable compounds other than the radical polymerizable compound.

[0204] Examples of radical polymerizable compounds include the following. However, the present invention is not limited to the following exemplified compounds. For example, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, triethylene glycol di(meth)acrylate, epichlorohydrin-modified ethylene glycol di(meth)acrylate (commercially available products include Denacol DA-811 manufactured by Nagase & Co., Ltd.), polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, ethylene oxide (EO), propylene oxide (PO),propylene oxide) block polyether di(meth)acrylate (commercially available products, such as the Blemmer PET series manufactured by Nippon Oil & Fats Co., Ltd.), dipropylene glycol di(meth)acrylate, bisphenol A EO addition type di(meth)acrylate (commercially available products, such as M-210 manufactured by Toagosei Co., Ltd. and NK Ester A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd.), hydrogenated bisphenol A EO addition type di(meth)acrylate (NK Ester A-HPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A PO addition type di(meth)acrylate (commercially available products, such as Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A epichlorohydrin addition type di(meth)acrylate (commercially available products, such as Ebecryl 150 manufactured by Daicel UCB Co., Ltd.), bisphenol A EO·PO addition type di(meth)acrylate (commercially available products include BP-023-PE manufactured by Toho Chemical Industry Co., Ltd.), bisphenol F Examples of bifunctional (meth)acrylate compounds include EO-added di(meth)acrylate (commercially available products include 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 products, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, trimethylolpropane acrylic acid benzoate, and isocyanuric acid EO-modified di(meth)acrylate (commercially available products include Aronix M-215 manufactured by Toagosei Co., Ltd.);

[0205] Further, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (commercially available products include, for example, TPMTA manufactured by Nippon Kayaku Co., Ltd.) and its EO, PO, or epichlorohydrin-modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products, isocyanuric acid EO-modified tri(meth)acrylate (commercially available products include, for example, Aronix M-315 manufactured by Toagosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products; Examples of such compounds include tetrafunctional (meth)acrylate compounds such as tetraerythritol tetra(meth)acrylate (commercially available products include TPMTA manufactured by Shin-Nakamura Chemical Co., Ltd.), EO-, PO-, or epichlorohydrin-modified products thereof, and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate and EO-, PO-, epichlorohydrin-, fatty acid-, or alkyl-modified products thereof; and hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate and EO-, PO-, epichlorohydrin-, fatty acid-, or alkyl-modified products thereof, and sorbitol hexa(meth)acrylate and EO-, PO-, epichlorohydrin-, fatty acid-, or alkyl-modified products thereof. Two or more radically polymerizable compounds may be used in combination. In this case, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, "DPHA" (manufactured by Nippon Kayaku Co., Ltd.), or the like can be preferably used.

[0206] Also preferred as the radical polymerizable compound are polyester(meth)acrylates and epoxy(meth)acrylates having a weight-average molecular weight of 200 or more and less than 1,000. Commercially available polyester(meth)acrylates include the Beamset 700 series (trade name) manufactured by Arakawa Chemical Industries, Ltd., such as Beamset 700 (hexafunctional), Beamset 710 (tetrafunctional), and Beamset 720 (trifunctional). Epoxy(meth)acrylates include the SP series (trade name) manufactured by Showa Polymer Co., Ltd., such as SP-1506, 500, SP-1507, and 480, and the VR series (trade name) VR-77, and Shin-Nakamura Chemical Co., Ltd., such as EA-1010 / ECA, EA-11020, EA-1025, and EA-6310 / ECA.

[0207] The curable composition for forming an HC layer according to the second aspect (2), which is a preferred embodiment of the second aspect, includes b) a radically polymerizable compound containing three or more ethylenically unsaturated groups per molecule. The b) compound containing three or more ethylenically unsaturated groups per molecule is hereinafter also referred to as "component b" (component b). Examples of component b) include esters of polyhydric alcohols and (meth)acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, and (meth)acrylamide. Among these, radically polymerizable compounds containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups per molecule are preferred. Specific examples include esters of polyhydric alcohols and (meth)acrylic acid, which contain three or more ethylenically unsaturated groups per molecule. More specifically, for example, (di)pentaerythritol tetra(meth)acrylate, (di)pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO-modified phosphate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, (di)pentaerythritol Examples of the (di)pentaerythritol include tripentaerythritol(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone-modified tris(acryloxyethyl)isocyanurate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, 1,2,4-cyclohexane tetra(meth)acrylate, and pentaglycerol triacrylate. Note that the above-mentioned "(di)pentaerythritol" is used to mean either or both of pentaerythritol and dipentaerythritol.

[0208] Furthermore, a resin containing three or more radical polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule is also preferred. Examples of the resin containing three or more radical 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, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, and polymers of polyfunctional compounds such as polyhydric alcohols.

[0209] 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 the exemplary compounds shown in paragraph 0096 of JP-A-2007-256844. Furthermore, 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 esters of polyols and (meth)acrylic acid, such as KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, and GPO-303 manufactured by Nippon Kayaku, and V#400 and V#36095D manufactured by Osaka Organic Chemical Industry Co., Ltd. In addition, Shiko 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 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UL-503LN (manufactured by Kyoei Co., Ltd.) Daicel Chemical Industries, Ltd.), Unidic 17-806, Unidic 17-813, Unidic V-4030, Unidic V-4000BA (Dainippon Ink & Chemicals, Inc.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (Daicel UCB), Hi-Corp AU-2010, Hi-Corp AU-2020 (Tokushiki Co., Ltd.), Aronix M-1960 (Toa Goh Co., Ltd.) and tri- or higher functional urethane acrylate compounds such as Artresin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, and HDP-4T (manufactured by Toagosei Co., Ltd.), and tri- or higher functional polyester compounds such as Aronix M-8100, M-8030, and M-9050 (manufactured by Daicel Cytec Co., Ltd.), and KBM-8307 (manufactured by Daicel Cytec Co., Ltd.).As component b), only one type may be used, or two or more types having different structures may be used in combination.

[0210] As described above, the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) can preferably contain 5 to 70 mass% of the structure derived from a) above, 25 to 80 mass% of the structure derived from b) above, 0.1 to 10 mass% of c) above, and 0.1 to 10 mass% of d) above, when the total solid content of the HC layer is taken as 100 mass%. The structure derived from b) is preferably contained in an amount of 40 to 75 mass%, more preferably 60 to 75 mass%, when the total solid content of the HC layer is taken as 100 mass%. Furthermore, the curable composition for forming an HC layer of the second aspect (2) preferably contains 40 to 75 mass%, more preferably 50 to 75 mass%, of component b) when the total solid content of the curable composition for forming an HC layer is taken as 100 mass%.

[0211] -Cationically Polymerizable Compound- The curable composition for forming an HC layer according to the second embodiment preferably contains at least one radically polymerizable compound and at least one cationically polymerizable compound. Any cationically polymerizable compound having a polymerizable group capable of cation polymerization (cationically polymerizable group) can be used without any limitations. Furthermore, 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 per molecule, or a polyfunctional compound containing two or more cationically polymerizable groups per molecule. The number of cationically polymerizable groups contained in the polyfunctional compound is not particularly limited, but may be, for example, 2 to 6 per molecule. Furthermore, the two or more cationically polymerizable groups contained in one molecule of the polyfunctional compound may be the same, or may be two or more different in structure.

[0212] In one embodiment, the cationically polymerizable compound preferably has one or more radically polymerizable groups in one molecule in addition to the cationically polymerizable group. For the radically polymerizable group possessed by such a cationically polymerizable compound, the above description of the radically polymerizable compound can be referred to. The ethylenically unsaturated group is preferably an ethylenically unsaturated group, and 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 one, preferably one to three, and more preferably one.

[0213] The cationically polymerizable group preferably includes an oxygen-containing heterocyclic group and a vinyl ether group. The cationically polymerizable compound may contain one or more oxygen-containing heterocyclic groups and one or more vinyl ether groups in one molecule.

[0214] The oxygen-containing heterocycle may be a monocycle or a fused ring. Those having a bicyclo skeleton are also preferred. The oxygen-containing heterocycle may be a non-aromatic ring or an aromatic ring, and a non-aromatic ring is preferred. Specific examples of monocycles include an epoxy ring, a tetrahydrofuran ring, and an oxetane ring. Those having a bicyclo skeleton include an oxabicyclo ring. The cationically polymerizable group containing an oxygen-containing heterocycle is contained in the cationically polymerizable compound as a monovalent substituent or as a divalent or higher polyvalent substituent. The fused ring may be a ring formed by condensing two or more oxygen-containing heterocycles, or a ring formed by condensing one or more oxygen-containing heterocycles with one or more ring structures other than the oxygen-containing heterocycle. Examples of ring structures other than the oxygen-containing heterocycle include, but are not limited to, cycloalkane rings such as a cyclohexane ring.

[0215] Specific examples of oxygen-containing heterocycles are shown below, but the present invention is not limited to these examples.

[0216]

[0217] The cationically polymerizable compound may contain a partial structure other than the cationically polymerizable group. Such 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.

[0218] A preferred embodiment of the cationically polymerizable compound is a compound containing a cyclic structure as the cationically polymerizable group or as a partial structure other than the cationically polymerizable group (cyclic structure-containing compound). The cyclic structure contained in the cyclic structure-containing compound may be, for example, one or two or more cyclic structures per molecule. The number of cyclic structures contained in the cyclic structure-containing compound is, for example, 1 to 5 per molecule, but is not particularly limited. A compound containing two or more cyclic structures per molecule may contain the same cyclic structure, or may contain two or more cyclic structures with different structures.

[0219] An example of the cyclic structure contained in the cyclic structure-containing compound is an oxygen-containing heterocycle, the details of which are as described above.

[0220] The cationic polymerizable group equivalent (= B / C), calculated by dividing the molecular weight (hereinafter referred to as "B") by the number of cationic polymerizable groups (hereinafter referred to as "C") contained in one molecule of the cationic polymerizable compound, is, for example, 300 or less. From the viewpoint of improving adhesion between the HC layer obtained by curing the curable composition for forming an HC layer and the resin film, it is preferably less than 150, and from the viewpoint of better abrasion resistance, it is more preferably 120 or less. On the other hand, from the viewpoint of the moisture absorption of the HC layer obtained by curing the curable composition for forming an HC layer, the cationic polymerizable group equivalent is preferably 50 or more. In addition, in one embodiment, the cationic polymerizable group contained in the cationic polymerizable compound for which the cationic polymerizable group equivalent is to be calculated can be an epoxy group (epoxy ring). That is, in one embodiment, the cationic polymerizable compound is an epoxy ring-containing compound. From the viewpoint of improving adhesion between the resin film and the HC layer obtained by curing the curable composition for forming an HC layer, the epoxy ring-containing compound preferably has an epoxy group equivalent, calculated by dividing the molecular weight by the number of epoxy rings contained in one molecule, of less than 150, and from the viewpoint of better abrasion resistance, more preferably 120 or less. The epoxy group equivalent of the epoxy ring-containing compound is, for example, 50 or more.

[0221] The molecular weight of the cationically polymerizable compound is preferably not more than 500, and more preferably not more than 300. A cationically polymerizable compound having a molecular weight within the above range tends to easily penetrate into the transparent substrate described below, and is presumed to be able to contribute to improving the adhesion between the HC layer obtained by curing the HC layer-forming curable composition and the transparent substrate.

[0222] The curable composition for forming an HC layer of the second aspect (2) includes a) a cationically polymerizable compound containing an alicyclic epoxy group and an ethylenically unsaturated group, wherein the number of the alicyclic epoxy group and the number of the ethylenically unsaturated group contained in one molecule are one, and the molecular weight is 300 or less. Hereinafter, the above a) will be referred to as "component a)."

[0223] Examples of the ethylenically unsaturated group include radical polymerizable groups including an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group, and among these, an acryloyl group, a methacryloyl group, or a C(O)OCH═CH ２ The number of alicyclic epoxy groups and ethylenically unsaturated groups in one molecule is preferably one each, and more preferably an acryloyl group or a methacryloyl group.

[0224] The molecular weight of component a) is 300 or less, preferably 210 or less, and more preferably 200 or less.

[0225] A preferred embodiment of component a) is a compound represented by the following general formula (1).

[0226]

[0227] In general formula (1), R represents a monocyclic hydrocarbon or a crosslinked hydrocarbon, L represents a single bond or a divalent linking group, and Q represents an ethylenically unsaturated group.

[0228] When R in general formula (1) is a monocyclic hydrocarbon, the monocyclic hydrocarbon is preferably an alicyclic hydrocarbon, more preferably an alicyclic group having 4 to 10 carbon atoms, even 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.

[0229] When R in general formula (1) is a bridged hydrocarbon, the bridged hydrocarbon is preferably a bicyclic bridged hydrocarbon (bicyclo ring) or a tricyclic bridged hydrocarbon (tricyclo ring). Specific examples include bridged hydrocarbons having 5 to 20 carbon atoms, such as norbornyl, bornyl, isobornyl, tricyclodecyl, dicyclopentenyl, dicyclopentanyl, tricyclopentenyl, tricyclopentanyl, adamantyl, and adamantyl groups substituted with a lower (e.g., 1 to 6 carbon atoms) alkyl group.

[0230] When L represents a divalent linking group, the divalent linking group is preferably a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom. The divalent aliphatic hydrocarbon group is preferably a linear, branched, or cyclic alkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group.

[0231] Q includes ethylenically unsaturated groups such as acryloyl, methacryloyl, vinyl, styryl, and allyl groups, and particularly, acryloyl, methacryloyl, or C(O)OCH=CH ２ is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0232] Specific examples of component a) include the various compounds exemplified in paragraph 0015 of JP-A No. 10-017614, compounds represented by the following general formula (1A) or (1B), and 1,2-epoxy-4-vinylcyclohexane. Of these, compounds represented by the following general formula (1A) or (1B) are more preferred. Note that isomers of the compound represented by the following general formula (1A) are also preferred.

[0233]

[0234]

[0235] In general formulas (1A) and (1B), R １ represents a hydrogen atom or a methyl group, L ２ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0236] L in general formulas (1A) and (1B) ２ The number of carbon atoms in the divalent aliphatic hydrocarbon group represented by the formula (I) is 1 to 6, preferably 1 to 3, and more preferably 1. As the divalent aliphatic hydrocarbon group, a linear, branched, or cyclic alkylene group is preferred, a linear or branched alkylene group is more preferred, and a linear alkylene group is even more preferred.

[0237] The HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) preferably contains 15 to 70 mass %, more preferably 18 to 50 mass %, and even more preferably 22 to 40 mass % of the structure derived from a) above, when the total solid content of the HC layer is taken as 100 mass %. Furthermore, the curable composition for forming an HC layer of the second aspect (2) preferably contains 15 to 70 mass %, more preferably 18 to 50 mass %, and even more preferably 22 to 40 mass % of component a) when the total solid content of the curable composition for forming an HC layer is taken as 100 mass %.

[0238] Another example of the cyclic structure contained in the cyclic structure-containing compound is an alicyclic structure, such as a cyclo ring, a dicyclo ring, or a tricyclo ring, and specific examples thereof include a dicyclopentanyl ring or a cyclohexane ring.

[0239] The cationically polymerizable compounds described above can be synthesized by known methods, and are also available as commercial products.

[0240] Specific examples of the cationically polymerizable compound containing an oxygen-containing heterocycle as a cationically polymerizable group include 3,4-epoxycyclohexylmethyl methacrylate (commercially available products such as Cyclomer M100 manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (commercially available products such as UVR6105 and UVR6110 manufactured by Union Carbide and Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd.), bis(3,4-epoxycyclohexylmethyl)adipate (for example, UVR6128 manufactured by Union Carbide), vinylcyclohexene monoepoxide (for example, Celloxide 2000 manufactured by Daicel Chemical Industries, Ltd.), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl 3', Examples of such methyl esters include 4'-epoxycyclohexane carboxylate (e.g., Celloxide 2081 manufactured by Daicel Chemical Industries, Ltd.), 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4,1,0]heptane (e.g., Celloxide 3000 manufactured by Daicel Chemical Industries, Ltd.), 7,7'-dioxa-3,3'-bis[bicyclo[4.1.0]heptane] (e.g., Celloxide 8000 manufactured by Daicel Chemical Industries, Ltd.), 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(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.

[0241] Specific examples of cationically polymerizable compounds containing a vinyl ether group as the cationically polymerizable group include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and pentaerythritol tetravinyl ether. Cationic polymerizable compounds containing a vinyl ether group are also preferably those having an alicyclic structure.

[0242] Furthermore, as the cationically polymerizable compound, compounds exemplified in 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 can also be used.

[0243] Specific examples of the cationically polymerizable compound include compounds B-1 to B-14, but the present invention is not limited to these examples.

[0244]

[0245]

[0246]

[0247] Furthermore, from the viewpoint of improving adhesion between the HC layer obtained by curing the curable composition for forming an HC layer and the resin film, the following aspects can be mentioned as preferred aspects of the curable composition for forming an HC layer. It is more preferable that one or more of the following aspects are satisfied, and even more preferable that two or more are satisfied. It is also preferable that one cationically polymerizable compound satisfies multiple aspects. (1) The cationically polymerizable compound includes a cationically polymerizable compound having a cationically polymerizable group equivalent of less than 150. Preferably, the cationically polymerizable compound includes an epoxy group-containing compound having an epoxy group equivalent of less than 150. (2) The cationically polymerizable compound includes an ethylenically unsaturated group.

[0248] The content of the cationically polymerizable compound in the curable composition for forming an HC layer is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, per 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 50 parts by mass or less, per 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 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound. Meanwhile, the content of the cationically polymerizable compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, per 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound. In addition, the content of the cationically polymerizable compound in the curable composition for forming the 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 the HC layer.The upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 25% by mass or less.In this specification, a compound having both a cationically polymerizable group and a radically polymerizable group is classified as a cationically polymerizable compound, and the content in the curable composition for forming the HC layer is specified.

[0249] (Polymerization initiator) 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 radical 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. Only one type of radical photopolymerization initiator may be used, or two or more types with different structures may be used in combination. This also applies to cationic photopolymerization initiators. Each photopolymerization initiator will be explained in turn below.

[0250] (i) Radical Photopolymerization Initiator The radical photopolymerization initiator may be any one that can generate radicals as active species upon irradiation with light, and known radical photopolymerization initiators can be used without any limitations. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl 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-methyl acetophenones such as 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); benzoyl benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2 benzophenones such as (4-benzoylbenzyl)trimethylammonium bromide and (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride;Examples of the photopolymerization initiator include acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Furthermore, examples of the photopolymerization initiator aids that may be used in combination include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. The above radical photopolymerization initiators and auxiliaries can be synthesized by known methods and are also available as commercial products. Preferred examples of commercially available radical photopolymerization initiators include Irgacure (127, 651, 184, 819, 907, 1870 (CGI-403 / Irg184=7 / 3 mixed initiator, 500, 369, 1173, 2959, 4265, 4263, etc.), OXE01) manufactured by BASF, KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.) manufactured by Nippon Kayaku, and Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer;

[0251] The content of the radical photopolymerization initiator in the curable composition for forming an HC layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds satisfactorily. The content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound contained in the curable composition for forming an HC layer.

[0252] (ii) Cationic Photopolymerization Initiator The cationic photopolymerization initiator may be any one capable of generating cations as active species upon irradiation with light, and known cationic photopolymerization initiators can be used without any limitations. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (e.g., diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts. More specific examples include cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs

[0050] to

[0053] of JP-A-8-143806, and those exemplified as cationic polymerization catalysts in paragraph

[0020] of JP-A-8-283320. Cationic photopolymerization initiators can be synthesized by known methods and are also commercially available. Examples of commercially available products include CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102 manufactured by Nippon Soda; PHOTOINITIATOR 2047 manufactured by Rhodia; UVI-6974 and UVI-6990 manufactured by Union Carbide; and CPI-10P manufactured by San-Apro.

[0253] As the cationic photopolymerization initiator, a diazonium salt, an iodonium salt, a sulfonium salt, or an iminium salt is preferred from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, etc. Furthermore, an iodonium salt is preferred from the viewpoint of weather resistance.

[0254] Specific commercially available examples of iodonium salt-based cationic photopolymerization initiators include B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Industry Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., WPI-124 manufactured by Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Synthetic Chemical Industry Co., Ltd.

[0255] Specific examples of iodonium salt compounds that can be used as cationic photopolymerization initiators include the following compounds PAG-1 and PAG-2.

[0256]

[0257]

[0258] The content of the cationic photopolymerization initiator in the curable composition for forming the HC layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds satisfactorily. The content is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and even more preferably 2 to 100 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound.

[0259] Other photopolymerization initiators include those described in paragraphs 0052 to 0055 of JP-A-2009-204725, the contents of which are incorporated herein by reference.

[0260] -Components that may be optionally contained in the curable composition for forming an HC layer- The curable composition for forming an HC layer contains at least one component that has the 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 may optionally contain, and preferably contains, at least one polymerization initiator. Details of these are as described above. Next, various components that may optionally be contained in the curable composition for forming an HC layer will be described.

[0261] (i) Inorganic Particles The HC layer-forming curable composition may contain inorganic particles having an average primary particle size of less than 2 μm. From the viewpoint of improving the hardness of a front panel having an HC layer obtained by curing the HC layer-forming curable composition (and further improving the hardness of a liquid crystal panel having this front panel), the HC layer-forming curable composition and the HC layer obtained by curing this composition preferably contain inorganic particles having an average primary particle size of less than 2 μm. The average primary particle size of the inorganic particles is preferably 5 nm to 1 μm, more preferably 5 to 200 nm, and even more preferably 40 nm or more but less than 200 nm. The average primary particle size of the inorganic particles and the matte particles described below is determined by observing the particles with a transmission electron microscope (magnification: 500,000 to 2,000,000 times), observing 100 randomly selected particles (primary particles), and averaging the particle sizes of these particles to determine the average primary particle size.

[0262] Examples of the inorganic particles include silica particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles, with silica particles being preferred.

[0263] The inorganic particles are preferably surface-treated with a surface modifier containing an organic segment to enhance their affinity with the organic components contained in the curable composition for forming an HC layer. Surface modifiers preferably contain, in the same molecule, a functional group capable of bonding with or adsorbing to the inorganic particles and a functional group having high affinity with the organic component. Preferred surface modifiers having functional groups capable of bonding with or adsorbing to the inorganic particles include silane-based surface modifiers, metal alkoxide surface modifiers such as aluminum, titanium, and zirconium, and surface modifiers having anionic groups such as phosphate groups, sulfate groups, sulfonate groups, and carboxylate groups. Functional groups with high affinity with the organic component include functional groups with similar hydrophilicity to the organic component and functional groups capable of chemically bonding with the organic component. Among these, functional groups capable of chemically bonding with the organic component are preferred, with ethylenically unsaturated groups or ring-opening polymerizable groups being more preferred. Among these, inorganic particles having ethylenically unsaturated groups on their surfaces are preferred.

[0264] The 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. These surface modifiers chemically bond the inorganic particles and the organic component, thereby increasing the crosslink density of the HC layer and thereby improving scratch resistance.

[0265] Specific examples of the surface modifier include the following exemplary 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 ) ３S-3H ２ C=C(X)COOC ２ H ４ OCOC ５ H １０ OPO (OH) ２ S-4 (H ２ C=C(X)COOC ２ H ４ OCOC ５ H １０ O) ２ POOH S-5 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 O.C. ３ H ６ Si(OCH ３ ) ３ (X represents a hydrogen atom or a methyl group)

[0266] The surface modification of inorganic particles with a surface modifier is preferably carried out in a solution. When the inorganic particles are mechanically dispersed, the surface modifier may be present together, or the inorganic particles may be mechanically dispersed and then the surface modifier may be added and stirred, or the inorganic particles may be surface-modified before being mechanically dispersed (if necessary, heated, dried, then heated, or pH (power of hydrogen) may be changed), and then dispersed. A highly polar organic solvent is preferred as the solvent for dissolving the surface modifier. Specific examples include known solvents such as alcohols, ketones, and esters.

[0267] The content of inorganic particles is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, when the total solid content of the curable composition for forming an HC layer is taken as 100% by mass. The lower limit of the content is not particularly limited and may be 0% by mass (no inorganic particles may be contained in the HC layer). However, if inorganic particles are contained, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 7% by mass or more. The shape of the primary particles of the inorganic particles may be either spherical or non-spherical. The primary particles of the inorganic particles are preferably spherical, and from the viewpoint of further improving hardness, it is more preferable that the primary particles of the inorganic particles are present in the HC layer obtained by curing the curable composition for forming an HC layer as higher-order particles of non-spherical secondary particles or higher, in which 2 to 10 spherical inorganic particles (primary particles) are linked together.

[0268] Specific examples of inorganic particles include ELCOM V-8802 (spherical silica particles having an average primary particle size of 15 nm, manufactured by JGC Catalysts and Chemicals), ELCOM V-8803 (irregular shaped silica particles, manufactured by JGC Catalysts and Chemicals), MiBK-SD (spherical silica particles having an average primary particle size of 10 to 20 nm, manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-2140Z (spherical silica particles having an average primary particle size of 10 to 20 nm, manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-4130 (spherical silica particles having an average primary particle size of 45 nm, manufactured by Nissan Chemical Industries, Ltd.), and MiBK-SD-L (spherical silica particles having an average primary particle size of 40 to 50 nm, manufactured by Nissan Chemical Industries, Ltd.). Examples of suitable silica particles include MEK-AC-2140Z (spherical silica particles having an average primary particle size of 85 nm, manufactured by Nissan Chemical Industries, Ltd.), MEK-ST-L (spherical silica particles having an average primary particle size of 40 to 50 nm, manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-5140Z (spherical silica particles having an average primary particle size of 85 nm, manufactured by Nissan Chemical Industries, Ltd.), MEK-ST-ZL (spherical silica particles having an average primary particle size of 85 nm, manufactured by Nissan Chemical Industries, Ltd.), and RX-300 (spherical silica particles having an average primary particle size of 7 nm, manufactured by Nippon Aerosil Co., Ltd.). Among these, MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd. 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, and MEK-ST-ZL and MEK-AC-5140Z are more preferred from the viewpoint of achieving both surface irregularities and visibility.

[0269] (ii) Matte Particles The curable composition for forming an HC layer may also contain matte particles. Matte particles refer to particles having an average primary particle size of 2 μm 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 μm, more preferably 4 to 14 μm, and even more preferably 6 to 10 μm.

[0270] Specific examples of matte particles include silica particles and TiO ２ and organic particles such as crosslinked acrylic particles, crosslinked acrylic-styrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, the matte particles are preferably organic particles, and crosslinked acrylic particles, crosslinked acrylic-styrene particles, or crosslinked styrene particles are more preferred.

[0271] The content of matte particles per unit volume in the HC layer obtained by curing the curable composition for forming the HC layer is 0.10 g / cm ３ More than this is preferred, and 0.10 to 0.40 g / cm ３ More preferably, 0.10 to 0.30 g / cm ３ is more preferred.

[0272] (iii) Ultraviolet Absorber (UV Absorber) The curable composition for forming an HC layer may contain an ultraviolet absorber. Examples of ultraviolet absorbers include benzotriazole compounds and triazine compounds. Here, the benzotriazole compound is a compound having a benzotriazole ring. Specific examples include the various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. The triazine compound is a compound having a triazine ring. Specific examples include the various triazine-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. The content of the ultraviolet absorber in the curable composition for forming an HC layer is preferably 0.1 to 10% by mass, based on the total solids content of the curable composition for forming an HC layer being 100% by mass. For more information on ultraviolet absorbers, see paragraph 0032 of JP-A-2013-111835. In this specification, ultraviolet light refers to light having a central emission wavelength in the wavelength band of 200 to 380 nm.

[0273] (iv) Leveling Agent The curable composition for forming an HC layer can contain a leveling agent. As the leveling agent, a fluorine-containing polymer is preferably used. For example, the fluoroaliphatic group-containing polymer described in Japanese Patent No. 5175831 can be mentioned. In addition, a fluoroaliphatic group-containing polymer in which the content of the fluoroaliphatic group-containing monomer represented by general formula (1) constituting the fluoroaliphatic group-containing polymer is 50 mass% or less of the total polymerized units can also be used as the leveling agent.

[0274] When the HC layer-forming curable composition contains a leveling agent, the content of the leveling agent is preferably 0.01 to 7 mass%, more preferably 0.05 to 5 mass%, and even more preferably 0.1 to 2 mass%, based on the solid content of the HC layer-forming curable composition. The HC layer-forming curable composition may contain only one type of leveling agent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably in the above range.

[0275] (v) Solvent The curable composition for forming an HC layer preferably contains a solvent. The solvent is preferably an organic solvent, and one or more organic solvents can be mixed in any ratio. Specific examples of 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; 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; and diacetone alcohol. Among these, it is preferable to use a mixture of cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl acetate, and methyl acetate in any ratio.

[0276] The amount of solvent in the HC layer-forming curable composition can be adjusted as appropriate within a range that ensures the coating suitability of the composition. The solvent content is preferably 50 to 500 parts by mass, more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator. The solid content of the HC-forming curable composition is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 65 to 75% by mass, relative to the total mass of the HC-forming curable composition.

[0277] (vi) Other Components In addition to the above components, the curable composition for forming an HC layer can contain one or more known additives in any amount. Examples of additives include surface conditioners, polymerization inhibitors, polyrotaxanes, etc. For details, see, for example, paragraphs 0032 to 0034 of JP 2012-229412 A. However, the additives are not limited to these, and various additives that can generally be added to curable compositions for forming an HC layer can be used.

[0278] The curable composition for forming the HC layer can be prepared by mixing the above-described various components simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known mixer or the like can be used for preparation.

[0279] (Thickness of HC Layer) The thickness of the HC layer is preferably 1 μm or more, more preferably 1 to 100 μm, even more preferably 1 to 20 μm, particularly preferably 3 to 20 μm, and most preferably 5 to 20 μm. The thickness of the HC layer is measured by cutting the HC layer with a microtome to cut out a cross section, staining it overnight with an approximately 3% by mass aqueous solution of osmium tetroxide, cutting out the surface again, and observing the cross section using a scanning electron microscope (SEM).

[0280] The surface roughness Sa1 of the component with a wavelength of 2.5 μm 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 particularly preferably 0.50 nm or more. There is no particular upper limit, but it is often 3.0 nm or less, and more often 2.0 nm or less. When the surface roughness Sa1 is within the above range, when the reflective film is rolled in a state where the reflective layer and the HC layer are in direct contact with each other at the semi-finished product stage of the reflective film (a laminate stage including a reflective layer and an HC layer and no adhesive layer), the friction between the reflective layer and the HC layer can be reduced, so that the film can be rolled up without wrinkles, which is preferable.

[0281] The surface roughness Sa2 of the component with a wavelength of 10 μm 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. The lower limit is not particularly limited, but is often 0.5 nm or more. By having the surface roughness Sa2 in the above range, the visibility of the reflective film can be improved, which is preferable.

[0282] 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 Corporation) to measure the uneven shape in a 128 μm × 128 μm area on the HC layer surface and read the image data under the following conditions: Measurement mode: Wave mode Interpolation: Yes Baseline correction: Yes

[0283] The obtained image data was subjected to a fast Fourier transform (FFT), and when the wavelength was 2.5 μm, image data was obtained by extracting components with a frequency of 1 / wavelength = 1 / 2.5 (1 / μm) = 1000 / 2.5 (1 / mm) = 400 (1 / mm) or more using a high pass filter, and the surface roughness Sa of the obtained image data was taken as the surface roughness Sa1 of components of 2.5 μm or less.

[0284] Similarly, for a wavelength of 10 μm, image data was obtained by extracting components of frequency = 1 / wavelength = 1 / 10 (1 / μm) = 1000 / 10 (1 / mm) = 100 (1 / mm) or less using low-pass filtering, and the surface roughness Sa of the obtained image data was taken as the surface roughness Sa2 of components with wavelengths of 10 μm or more.

[0285] (Method of Forming HC Layer) An HC layer can be formed by applying a curable composition for forming an HC layer and irradiating it 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 an HC layer with a laminate structure of two or more layers (for example, about two to five layers) by simultaneously or sequentially applying two or more compositions with different compositions.

[0286] The HC layer can be formed by irradiating the applied HC layer-forming curable composition with active energy rays. For example, when the HC layer-forming curable composition contains a radical polymerizable compound, a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator, the polymerization reactions of the radical polymerizable compound and the cationic polymerizable compound can be initiated and progressed by the action of the radical photopolymerization initiator and the cationic photopolymerization initiator, respectively. The wavelength of the irradiated light may be determined depending on the type of polymerizable compound and polymerization initiator used. Examples of 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 diodes) that emit light in the 150 to 450 nm wavelength band. The light irradiation dose is 30 to 3,000 mJ / cm. ２is preferred, and 100 to 1500 mJ / cm ２ is more preferable. A drying treatment may be carried out as necessary either before or after light irradiation, or both. The drying treatment can be carried out by blowing hot air, placing the composition in a heating furnace, transporting the composition in the heating furnace, or the like. When the curable composition for forming an HC layer contains a solvent, the heating temperature is not particularly limited as long as it is set to a temperature at which the solvent can be dried and removed. Here, the heating temperature refers to the temperature of the hot air or the atmospheric temperature in the heating furnace.

[0287] The reflective film may have layers other than the above-mentioned adhesive layer, reflective layer, and HC layer. For example, in the example shown in FIG. 2, the reflective film 10B has an adhesive layer 1, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent substrate 7, and an HC layer 3, in this order. A protective film 4 is arranged on the side of the reflective film 10B opposite the reflective layer 2 side of the adhesive layer 1, forming a laminate including the reflective film 10B and the protective film 4. In addition, in the example shown in FIG. 3, the reflective film 10C has an adhesive layer 1, a transparent substrate 7, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, and an HC layer 3, in this order. A protective film 4 is arranged on the side of the reflective film 10C opposite the reflective layer 2 side of the adhesive layer 1, forming a laminate including the reflective film 10C and the protective film 4. In the example shown in FIG. 4 , the reflective film 10D has an adhesive layer 1, a matte layer 8, a polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent substrate 7, and an HC layer 3, in this order. A protective film 4 is disposed on the side of the adhesive layer 1 of the reflective film 10D opposite the reflective layer 2, forming a laminate including the reflective film 10C and the protective film 4. The reflective films 10B and 10C use the same materials except for the lamination order. Below, the materials constituting the reflective films 10B, 10C, and 10D, as well as the protective film, are described in detail. The adhesive layer 1, reflective layer 2, and HC layer 3 in the reflective films 10B, 10C, and 10D are the same as the adhesive layer, reflective layer, and HC layer described above, respectively, and therefore will not be described here.

[0288] <Polarization conversion layer> The polarization conversion layer is a layer in which the helical orientation structure of a liquid crystal compound is fixed, and it is preferable that the pitch number x of the helical orientation structure and the film thickness y (unit: μm) of the polarization conversion layer satisfy all of the following relational expressions (a) to (c): 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 helix of the liquid crystal compound. In other words, a pitch number of 1 is defined as a state in which the director of the helically oriented liquid crystal compound (the long axis direction in the case of rod-shaped liquid crystal) has rotated 360°.

[0289] When the polarization conversion layer has a helical structure of a liquid crystal compound, it exhibits optical rotation and birefringence for visible light, which has a wavelength shorter than the reflection peak wavelength in the infrared region. Therefore, it is possible to control polarization in the visible region. By setting 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-mentioned ranges, it is possible to impart the polarization conversion layer with the function of optically compensating for visible light or the function of converting linearly polarized light (p-polarized light) incident on the reflective film into circularly polarized light.

[0290] The polarization conversion layer exhibits optical rotation and birefringence for visible light because the liquid crystal compound has a helical structure that satisfies the relational expressions (a) to (c). In particular, by setting the pitch P of the helical structure of the polarization conversion layer 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, the polarization conversion layer exhibits high optical rotation and birefringence for short-wavelength visible light.

[0291] The relational expression (a) satisfies "0.1≦x≦1.0." When the pitch number x of the helical structure is 0.1 or more, sufficient optical rotation and birefringence are obtained, which is preferable. When the pitch number x of the helical structure is 1.0 or less, sufficient optical rotation and birefringence are obtained, making it easy to obtain the desired elliptically polarized light.

[0292] The relational expression (b) is "0.5≦y≦3.0". When the thickness y of the polarization conversion layer is 0.5 μm or more, sufficient optical rotation and birefringence are obtained. When the thickness y of the polarization conversion layer is 3.0 μm or less, the optical rotation and birefringence are sufficient, making it easy to obtain the desired circularly polarized light.

[0293] The relational expression (c) is "3000≦(1560×y) / x≦50000". When "(1560×y) / x" is 3000 or more, the desired polarization is easily obtained. When "(1560×y) / x" is 50000 or less, the desired polarization is easily obtained.

[0294] In the present invention, the pitch number x of the helical structure of the polarization conversion layer is more preferably 0.1 to 0.8, the film thickness y is more preferably 0.6 to 2.6 μm, and "(1560×y) / x" is more preferably 5000 to 13000.

[0295] That is, it is preferable that the polarization conversion layer has a long pitch P of the helical structure and a small pitch number x. Specifically, it is preferable that the polarization conversion layer has a helical pitch P equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection center wavelength 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 equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection center wavelength of 3,000 to 10,000 nm and a small pitch number x. Such a polarization conversion layer more suitably exhibits the optical rotation and birefringence for visible light described above, because the selective reflection center wavelength corresponding to the pitch P is much longer than that of visible light.

[0296] Such a polarization conversion layer can be formed in the same manner as a known cholesteric liquid crystal layer, but when forming the polarization conversion layer, it is preferable to adjust the liquid crystal compound to be used, the chiral agent to be used, the amount of chiral agent added, the film thickness, etc. so that the pitch number x of the helical structure and the film thickness y [μm] of the polarization conversion layer satisfy all of the relational expressions (a) to (c).

[0297] <Retardation Layer> The retardation layer imparts a phase difference (optical path difference) to two orthogonal polarized light components, thereby changing the state of incident polarized light.

[0298] When the retardation layer is disposed on the glass plate side facing the vehicle interior and provides optical compensation, the front retardation of the retardation layer may be a retardation that can provide optical compensation. In this case, the front retardation of the retardation layer at a wavelength of 550 nm is preferably 50 to 160 nm. Furthermore, when the direction corresponding to the vertically upward direction of the surface of the first glass plate when the windshield glass having the reflective film is mounted on a vehicle is defined as 0°, the angle of the slow axis is preferably 10 to 50° or -50 to -10°.

[0299] In addition, when the retardation layer converts linearly polarized light into circularly polarized light, the retardation layer is preferably configured to give a front retardation of λ / 4, and may be configured to give a front retardation of 3λ / 4. The angle of the slow axis may be arranged so as to be oriented in a direction that converts incident linearly polarized light into circularly polarized light.

[0300] In this case, the retardation layer preferably has a front retardation at a wavelength of 550 nm in the range of 100 to 450 nm, more preferably in the range of 120 to 200 nm or 300 to 400 nm. In addition, the direction of the slow axis of the retardation layer is preferably determined depending on the incident direction of projection light for projecting an image when the reflective film is used in a head-up display system and the sense of the helix of the cholesteric liquid crystal layer constituting the reflective layer.

[0301] The retardation layer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the retardation layer include a stretched polycarbonate film, a stretched norbornene polymer film, a transparent film containing and oriented inorganic particles having birefringence such as strontium carbonate, a thin film obtained by obliquely depositing an inorganic dielectric on a support, a film in which a polymerizable liquid crystal compound is uniaxially aligned and fixed, and a film in which a liquid crystal compound is uniaxially aligned and fixed.

[0302] Among these, a film in which a polymerizable liquid crystal compound is uniaxially aligned and fixed is a suitable example of a retardation layer. For example, such a retardation layer can be formed by applying a liquid crystal composition containing a polymerizable liquid crystal compound to a transparent substrate, a temporary support, or the surface of an alignment layer, forming the polymerizable liquid crystal compound in the liquid crystal composition into a nematic alignment in a liquid crystal state, and then fixing the alignment by curing. In this case, the formation of the retardation layer 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. However, during nematic alignment after application of the liquid crystal composition, the heating temperature is preferably 50 to 120°C, more preferably 60 to 100°C.

[0303] The retardation layer may be a layer obtained by applying a composition containing a polymer liquid crystal compound to the surface of a transparent substrate, a temporary support, an alignment layer, or the like, forming a nematic alignment in a liquid crystal state, and then fixing the alignment by cooling.

[0304] The thickness of the retardation layer is not particularly limited, but is preferably 0.2 to 300 μm, more preferably 0.5 to 150 μm, and even more preferably 1.0 to 80 μm. The thickness of the retardation layer formed from the liquid crystal composition is not particularly limited, but is preferably 0.2 to 10 μm, more preferably 0.5 to 5.0 μm, and even more preferably 0.7 to 2.0 μm.

[0305] The retardation layer has a slow axis tilted at an angle α with respect to an axis of the retardation layer in any direction. The direction of the slow axis can be set by, for example, rubbing an alignment film that is an underlying layer of the retardation layer.

[0306] The reflective film may be in the form of a thin film, a sheet, etc. The reflective film may be in the form of a roll or the like as a thin film before being used in a windshield glass.

[0307] <Transparent substrate> Transparent substrate can also be used as the substrate when forming reflective layer or HC layer.The transparent substrate used for forming reflective layer or HC layer can be a temporary support that is peeled off after forming reflective layer or HC layer.Therefore, the completed reflective film and windshield glass do not need to contain a transparent substrate.In addition, when the completed reflective film or windshield glass contains a transparent substrate, rather than being peeled off as a temporary support, it is preferable that the transparent substrate is transparent in the visible light region.

[0308] The material of the transparent substrate is not particularly limited. Examples of the transparent substrate include plastic films such as polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and silicones. In addition to the above-mentioned plastic films, glass may also be used as the temporary support. A cellulose acylate film is preferred as the transparent substrate.

[0309] The thickness of the transparent substrate may be about 5.0 to 1000 μm, preferably 10 to 250 μm, more preferably 15 to 90 μm, and even more preferably 40 to 80 μm.

[0310] The transparent substrate may be formed into a film by any method, for example, a melt casting method or a solution casting method.

[0311] (Melt film-forming method, smoothing) When a transparent substrate is formed into a film by a melt film-forming method, the melt film-forming method preferably includes a melting step of melting a resin in an extruder, a step of extruding the molten resin into a sheet form from a die, and a step of forming the resin into a film. Depending on the resin material, a filtering step of the molten resin may be provided after the melting step, or the resin may be cooled when extruded into a sheet form. Specific melt film-forming methods will be described below, but the present invention is not limited thereto.

[0312] The method for producing the transparent substrate preferably includes a melting step of melting the resin in an extruder, a filtering step of filtering the molten resin through a filtering device equipped with a filter, a film forming step of extruding the filtered resin into a sheet form through a die and bringing it into close contact with a cooling drum to cool and solidify it, thereby forming an unstretched transparent substrate, and a stretching step of uniaxially or biaxially stretching the unstretched transparent substrate. This configuration allows the transparent substrate to be produced. If the pore size of the filter used in the filtering step of the molten resin is 1 μm or less, foreign matter can be sufficiently removed. As a result, the surface roughness of the resulting transparent substrate in the film width direction can be controlled. Specifically, the method for forming the transparent substrate includes the following steps.

[0313] [Melting Step] The method for producing the transparent substrate includes a melting step in which the resin is melted in an extruder. The resin or a mixture of the resin and additives is preferably dried to a moisture content of 200 ppm or less, and then introduced into a single-screw (single-screw) or twin-screw extruder and melted. To prevent decomposition of the resin, melting in nitrogen or vacuum is also preferred. Detailed conditions can be determined by reference to paragraphs 0051-0052 of Japanese Patent No. 4962661 (paragraphs 0085-0086 of US 2013 / 0100378), and the methods can be carried out according to these publications, the contents of which are incorporated herein by reference. The extruder is preferably a single-screw kneading extruder. Furthermore, it is also preferable to use a gear pump to increase the delivery accuracy of the molten resin (melt).

[0314] [Filtration step] The method for producing the transparent substrate includes a filtration step of passing 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 μm or less. Only one set of filtration devices having filters with such pore sizes may be installed in the filtration step, or two or more sets may be installed.

[0315] [Film Forming Step] The method for producing the transparent substrate includes a film forming step in which the filtered resin is extruded into a sheet form through a die and brought into close contact with a cooling drum to be cooled and solidified to form an unstretched transparent substrate.

[0316] When the melted (and kneaded) and filtered resin (resin-containing melt) is extruded through a die into a sheet, it may be extruded as a single layer or as a multilayer. When extruding a multilayer, for example, a layer containing an ultraviolet absorber and a layer not containing an ultraviolet absorber may be laminated. A three-layer structure with an ultraviolet absorber-containing layer as the inner layer is more preferable in terms of suppressing deterioration of the polarizer due to ultraviolet rays and suppressing bleed-out of the ultraviolet absorber. When a transparent substrate is produced by extruding a multilayer, the thickness of the inner layer of the resulting transparent substrate relative to the thickness of all layers is preferably 50 to 99%, more preferably 60 to 99%, and even more preferably 70 to 99%. Such lamination can be performed using a feedblock die and a multi-manifold die.

[0317] According to paragraph 0059 of JP 2009-269301 A, it is preferable to extrude a resin (a melt containing a resin) extruded into a sheet form from a die onto a cooling drum (a casting drum), cool and solidify it, and obtain an unstretched transparent substrate (raw sheet).

[0318] In the above-mentioned method for producing a transparent substrate, 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 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 this reduces the decomposition of the resin and suppresses the generation of foreign matter. The temperature of the resin extruded from the die can be measured non-contact on the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, emissivity 0.95).

[0319] In the method for producing the transparent substrate, it is preferable to use an electrostatically applied electrode when the resin is brought into close contact with the cooling drum in the film forming step, which allows the resin to be tightly adhered to the cooling drum without roughening the film surface.

[0320] In the method for producing the transparent substrate, the temperature of the resin when it is brought into close contact with the cooling drum (at the point where the molten resin extruded from the die first comes into contact with the cooling drum) is preferably 280°C or higher. This increases the electrical conductivity of the resin, allowing it to be tightly adhered to the cooling drum by applying static electricity, and suppressing roughness of the film surface. The temperature of the resin when it is 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, emissivity 0.95).

[0321] [Stretching Step] The method for producing the transparent substrate includes a stretching step of uniaxially or biaxially stretching the unstretched transparent substrate. In the longitudinal stretching step (stretching in the same direction as the film transport direction), the transparent substrate is preheated and then stretched in the transport direction with a group of rollers having different peripheral speeds (i.e., different transport speeds) while the transparent substrate is still heated.

[0322] 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 even more preferably Tg or higher and Tg+30°C or lower, relative to the glass transition temperature (Tg) of the transparent substrate. The stretching temperature in the longitudinal stretching step is preferably Tg or higher and Tg+60°C or lower, more preferably Tg+2°C or higher and Tg+40°C or lower, and even 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, and more preferably 1.1 to 2 times.

[0323] In addition to or instead of the longitudinal stretching step, the transparent substrate is stretched transversely in the width direction by a transverse stretching step (a step of stretching in a direction perpendicular to the film conveying direction). In the transverse stretching step, for example, a tenter can be suitably used, and the transparent substrate is stretched transversely while both widthwise ends thereof are held by clips by the tenter. This transverse stretching can increase the tensile modulus of the transparent substrate in the optical film.

[0324] The transverse stretching is preferably carried out using a tenter, and the stretching temperature is preferably from Tg to Tg + 60°C, more preferably from Tg + 2°C to Tg + 40°C, and even more preferably from Tg + 4°C to Tg + 30°C, relative to the glass transition temperature (Tg) of the transparent substrate. 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 the longitudinal and transverse directions after the transverse stretching.

[0325] Furthermore, it is preferable that the variation in thickness in both the width direction and the length direction depending on the location be 10% or less, more preferably 8% or less, even more preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.

[0326] The thickness variation can be calculated as follows.

[0327] A 10 m (meter) sample of the stretched transparent substrate is taken, and 20% of each end in the width direction of the film is removed. 50 samples are taken at equal intervals in both the width direction and the length direction from the center of the film, and the thickness is measured.

[0328] Average thickness in the width direction Th ＴＤ－ａｖ , maximum value Th ＴＤ－ｍａｘ , and the minimum value Th ＴＤ－ｍｉｎ , (Th ＴＤ－ｍａｘ -Th ＴＤ－ｍｉｎ ) ÷ Th ＴＤ－ａｖ ×100 [%] is the thickness variation in the width direction.

[0329] In addition, the average thickness in the longitudinal direction Th ＭＤ－ａｖ , maximum value Th ＭＤ－ｍａｘ , and the minimum value Th ＭＤ－ｍｉｎ , (Th ＭＤ－ｍａｘ -Th ＭＤ－ｍｉｎ ) ÷ Th ＭＤ－ａｖ ×100 [%] is the thickness variation in the longitudinal direction.

[0330] The stretching step can improve the thickness accuracy of the transparent substrate.

[0331] The stretched transparent substrate can be wound into a roll in a winding process. At this time, the winding tension of the transparent substrate is 0.02 kg / mm ２ It is preferable to do the following:

[0332] Regarding other detailed conditions, the contents described in paragraphs 0134 to 0148 of JP 2015-224267 A regarding the melt film-forming process and the contents described in JP 2007-137028 A regarding the stretching process can be incorporated into this specification in accordance with the present invention.

[0333] (Solution Casting Method, Smoothing) When a transparent substrate is formed into a film by a solution casting method, it is preferable to include the steps of casting a dope solution on a casting band to form a cast film, drying the cast film, and stretching the cast film. Specifically, it is preferable to form the film by the method described in Japanese Patent No. 4,889,335. In the present invention, it is preferable to adopt the following method. For example, there is a method described in Japanese Patent Laid-Open No. 11-123732, in which the drying speed of the cast film is set to 300% by mass / min (=5% by mass / s) or less in terms of the solvent content on a dry basis, and gentle drying is performed. Furthermore, there is a method described in Japanese Patent Laid-Open No. 2003-276037, in which, in a co-casting method for a multilayered cast film having a core layer as an intermediate layer and skin layers (outer layers) on both surfaces thereof, the viscosity of the dope forming the core layer is increased to ensure the strength of the cast film, and the viscosity of the dope forming the outer layer is decreased. Furthermore, there are also preferred methods such as a method in which the casting film is rapidly dried to form a film on the surface of the casting film, and the surface condition is smoothed by the leveling effect of the formed film, and a method in which the casting film is stretched.

[0334] The transparent substrate may be thermally shrunk. This is particularly preferable when the reflective film is to be conformed to a curved glass surface, since thermal shrinkage of the transparent substrate causes the reflective film to shrink and wrinkles to be suppressed. When conforming the reflective film to a curved glass surface, it is preferable to apply an application liquid to the surface of the curved glass and then perform a process of conforming the reflective film to the curved glass. The application liquid may be a liquid obtained by dissolving a surfactant in distilled water, ion-exchanged water, or tap water. The surfactant contributes to improving the wettability of the application liquid to the surface of the substrate (e.g., glass) and adjusting the evaporation time. Examples of surfactants include ester-type surfactants such as glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters; ether-type surfactants such as alkyl polyethylene glycols and polyoxyethylene alkylphenyl ethers; and nonionic surfactants such as alkyl glycosides. The concentration of the surfactant in the application liquid is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass.

[0335] When a flat reflective film is sandwiched between curved glass, it is believed that wrinkles caused by excess film can be eliminated by shrinking the reflective film, which includes a transparent substrate. Generally, transparent substrates are stretched during manufacturing, resulting in residual stress due to the stretching. Therefore, this residual stress can be utilized to cause thermal shrinkage by heating during conforming to the curved surface. It is believed that this thermal shrinkage can eliminate wrinkles that occur when conforming to the curved glass. Furthermore, wrinkles tend to occur in areas of the glass with greater curvature near the periphery of the curved glass, but are less likely to occur in areas with less curvature. In contrast, a reflective film using a thermally shrinkable transparent substrate effectively suppresses wrinkles in areas of greater curvature. The mechanism of action is believed to be that in areas of greater curvature, the film has the freedom to expand in the thickness direction, resulting in film shrinkage in the surface direction, while in areas of less curvature, the film has the limited freedom to expand in the thickness direction, resulting in almost no film shrinkage in the surface direction. The temperature at which the transparent substrate thermally shrinks varies depending on the material used to form the transparent substrate, but shrinkage is preferably in the range of 80 to 200°C, and more preferably in the range of 100 to 140°C, which is the heating temperature using a heat gun in a typical curved surface conforming process. Heating to shrink the transparent substrate may be applied to the entire curved glass, or may be applied locally to areas with high curvature that 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. Under heating conditions using a heat gun or the like in the curved surface conforming process, the transparent substrate preferably has a heat shrinkage rate of 0.01 to 5.0% in the direction where the heat shrinkage rate is greatest and in the direction perpendicular to that direction, respectively, of 0.05 to 3.0%, more preferably 0.2 to 2.0%. When the heat shrinkage rate is 0.01% or more, wrinkles are less likely to occur when the substrate conforms to a curved surface. Furthermore, when the heat shrinkage rate is 5.0% or less, bubbles are less likely to occur when the substrate conforms to a curved surface. The heat shrinkage rate can be appropriately adjusted by adjusting the stretching conditions when producing the transparent substrate.

[0336] The thermal shrinkage rate is measured as follows. Two reference lines are marked in advance in the width direction at a distance of 100 mm on a sample piece of film cut to a width of 30 mm and a length of 120 mm. The sample piece is left to stand in a heating oven at 140°C for 45 minutes under no tension, and then the sample piece is cooled to room temperature, and the distance between the two reference lines is measured. The measured distance after treatment is defined as A [mm]. The value [%] calculated from the distance of 100 mm before treatment and the distance A mm after treatment using the formula "100 x (100 - A) / 100" is defined as the thermal shrinkage rate of the sample piece.

[0337] <Protective film layer of adhesive layer> It is preferable to provide a peelable protective film layer on one side of the adhesive layer. By providing such a protective film layer, it is possible to prevent damage to the adhesive layer of the reflective film before use and adhesion of dust, dirt, etc., and the protective film layer can be peeled off when used.

[0338] A release layer can be provided between the protective film layer and the adhesive layer to facilitate peeling of the protective film layer. The method for providing such a release layer is not particularly limited, and for example, the release layer 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 thereof include silicone-based coating agents, inorganic-based coating agents, fluorine-based coating agents, and organic-inorganic hybrid coating agents.

[0339] When a release layer is used, a laminate including 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. In this case, the release layer may be provided on the surface of the adhesive layer instead of the surface of the protective film layer.

[0340] When a protective film layer is provided on the reflective film of the present invention (on the adhesive layer), it is preferable that the difference in thermal shrinkage between the protective film layer and the reflective film layer is small. Specifically, the difference in thermal shrinkage under heating conditions using a heat gun or the like in the curved surface conforming process is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.6% or less. By setting the difference in thermal shrinkage between the protective film layer and the reflective film layer within the above range, deformation of the reflective film when heated using a heat gun or the like to conform to curved glass can be suppressed. More specifically, the difference in thermal shrinkage between the reflective film and the protective film at 140°C is preferably less than 1.5%. In other words, the difference between the thermal shrinkage of the reflective film at 140°C and the thermal shrinkage of the protective film at 140°C is preferably less than 1.5%, more preferably 1.0% or less, and even more preferably 0.6% or less. The lower limit is not particularly limited, and an example is 0%.

[0341] The reflective film of the present invention preferably reflects linearly polarized light. When the reflective film is incorporated into a windshield glass and used as a combiner for a head-up display, the projected image light is preferably p-polarized, i.e., linearly polarized light, in order to suppress reflection on the surface of the windshield glass. On the other hand, in the present invention, 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 layers that convert the polarization state of light include the polarization conversion layer and retardation layer described above.

[0342] As described above, the polarization conversion layer exhibits optical rotation and birefringence for visible light and converts the polarization state of incident light. In the present invention, the polarization conversion layer is preferably composed of a layer in which a birefringent material such as a liquid crystal compound is oriented with a twist of 360° or less. As described above, the retardation layer imparts a phase difference (optical path difference) to two orthogonal polarized light components to change the state of incident polarized light. In the present invention, the retardation layer is a layer in which a birefringent material such as a liquid crystal compound is oriented in the same direction and does not have optical rotation.

[0343] By configuring the reflective film to have a polarization conversion layer or a retardation layer on the side of the reflective layer where light is incident, linearly polarized light incident on the reflective film can be converted into circularly polarized light, the reflective layer can reflect the circularly polarized light, and the polarization conversion layer or retardation layer can convert the reflected circularly polarized light into linearly polarized light before it is emitted.

[0344] As described above, in the example shown in Fig. 4, 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. When such a reflective film 10D is incorporated into a windshield glass, for example, it is arranged so that the polarization conversion layer 5 faces the interior glass plate 11, as shown in Fig. 5. The windshield glass shown in Fig. 5 has, in this order, the interior glass plate 11, an adhesive layer 1, a matte layer 8, the polarization conversion layer 5, a reflective layer 2, a retardation layer 6, a transparent substrate 7, and an HC layer 3.

[0345] In this case, the polarization conversion layer functions to convert projected p-polarized light (linearly polarized light) into circularly polarized light reflected by the cholesteric liquid crystal layer of the reflective layer. Meanwhile, the retardation layer functions to provide optical compensation for light entering from outside the windshield glass. For example, s-polarized light entering from outside the windshield glass changes its polarization state as it passes through the polarization conversion layer, resulting in the inclusion of p-polarized light components. Polarized sunglasses filter out s-polarized light, so this p-polarized light component passes through the polarized sunglasses. This impairs the polarized sunglasses' ability to filter out glare from reflected light, which is primarily s-polarized light, resulting in driving problems. In response to this problem, the inclusion of a retardation layer and the optical compensation provided by the retardation layer can improve the suitability for polarized sunglasses.

[0346] 5, the reflective film 10D is configured so that the polarization conversion layer 5 faces the vehicle interior glass plate 11, but the configuration is not limited thereto. The reflective film 10D may also be configured so that the retardation layer 6 faces the vehicle interior glass plate 11.

[0347] In this case, the retardation layer 6 has the function of converting projected p-polarized light (linearly polarized light) into circularly polarized light that is reflected by the cholesteric liquid crystal layer of the reflective layer 2. On the other hand, the polarization conversion layer 5 has the function of optically compensating for light that enters from outside the windshield glass, and optical compensation by the polarization conversion layer 5 can improve suitability for polarized sunglasses.

[0348] Furthermore, the reflective film of the present invention may have a configuration in which polarization conversion layers are provided on both sides of the reflective layer 2, or a configuration in which retardation layers are provided on both sides. In this case, the polarization conversion layer or retardation layer provided on the vehicle interior glass plate may have 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. On the other hand, the polarization conversion layer or retardation layer provided on the vehicle exterior side may have a function of optically compensating for light incident from outside the windshield glass. The polarization conversion layer and retardation layer are as described above.

[0349] <Matte Layer> The reflective film of the present invention may also have a matte layer on the side opposite the hard coat layer of the reflective layer. In particular, the reflective film may have a matte layer between the adhesive layer and the reflective layer. The matte layer is a layer having irregularities. By providing a matte layer, when the reflective film is rolled in a state where the matte layer and the HC layer are in direct contact with each other at the stage of a semi-finished product (a laminate including a matte layer, a reflective layer, and an HC layer, and no adhesive layer), the friction between the matte layer and the HC layer can be reduced, which is preferable because it can be rolled up without wrinkles. In a configuration having a retardation layer or a polarization conversion layer on the reflective layer, the matte layer can be provided on the side opposite the hard coat layer of the retardation layer or the polarization conversion layer.

[0350] The matte layer can be obtained by irradiating a curable composition for forming a matte layer with active energy rays and curing it. The curable composition for forming a matte layer used to form the matte layer preferably contains a polymerizable compound having two or more ethylenically unsaturated groups in one molecule and a radical photopolymerization initiator in order to ensure adhesion with the reflective layer, the retardation layer, and the polarization conversion layer, and preferably contains particles to impart unevenness. In addition, the curable composition for forming a matte layer also preferably contains a solvent or a leveling agent.

[0351] (Thickness of Matte Layer) The thickness of the matte layer is preferably 10 nm or more, more preferably 10 nm to 1 μm, and even more preferably 30 nm to 1 μm. The thickness of the matte layer is measured by cutting the matte layer with a microtome to cut out a cross section, staining it overnight with an approximately 3% by mass aqueous solution of osmium tetroxide, cutting out the surface again, and observing the cross section using a SEM (Scanning Electron Microscope).

[0352] The surface roughness Sa1 of components with wavelengths of 2.5 μm 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 particularly preferably 0.50 nm or more. When the surface roughness Sa1 is in the above range, when the reflective film is rolled in a state where the matte layer and the HC layer are in direct contact with each other at the stage of a semi-finished product of the reflective film (at the stage of a laminate including the matte layer and the HC layer and having no adhesive layer), friction between the matte layer and the HC layer can be reduced, and thus the film can be rolled up without wrinkles, which is preferable.

[0353] The present invention will be explained in more detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples, comparative examples, and preparation examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

[0354] <Preparation of curable compositions for forming HC layer> Each component was mixed according to the formulation shown in Tables 1 and 2 below, and filtered through a polypropylene filter with a pore size of 10 μm to prepare curable compositions for forming HC layer HC-1 to HC-26. The blending amount of each component shown in Tables 1 and 2 is expressed in parts by mass.

[0355]

[0356]

[0357] The units of values ​​in Tables 1 and 2 are mass %. Details of each compound listed in Tables 1 and 2 are shown below. PAG-1 and PAG-2 are the compounds described above.

[0358] <Leveling Agent> P-112: Leveling agent, compound P-112 described in paragraph 0053 of Japanese Patent No. 5175831

[0359] <Preparation of reflective layer-forming composition, retardation layer-forming composition, and polarization conversion layer-forming composition> The components were mixed according to the formulations shown in Table 3 below and filtered through a polypropylene filter with a pore size of 10 μm to prepare reflective layer-forming compositions BG1, R1, and IR1, retardation layer-forming composition A1, and polarization conversion layer-forming composition TW-1. The blending amount of each component shown in Table 3 is expressed in parts by mass. Note that mixture 1, alignment control agent 1, and alignment control agent 2 are the compounds described above.

[0360]

[0361] <Preparation of Matte Layer-Forming Composition> The components were mixed according to the formulation shown in Table 4 below, and filtered through a polypropylene filter having a pore size of 10 μm to prepare matte layer-forming compositions M-1 to M-3. The blending amount of each component shown in Table 4 is expressed in parts by mass.

[0362]

[0363] The cellulose acylate film on which the alignment film was formed was used as a transparent substrate.

[0364] <Saponification of Cellulose Acylate Film> A cellulose acylate film with a thickness of 40 μm was prepared by the same preparation method as in Example 20 of WO 2014 / 112575. UV-531 manufactured by Teisei Kako Co., Ltd. was added to this cellulose acylate film as an ultraviolet absorber. The amount added was 3 phr (per hundred resin). The prepared 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 in an amount of 14 mL / m. 2 The coating was then allowed to stand for 10 seconds under a steam-type far-infrared heater (manufactured by Noritake Co., Ltd.) heated to 110°C. Next, pure water was applied at a rate of 3 mL / m using the same bar coater. 2 The resulting film was then washed with water using a fountain coater and drained with an air knife three times, and then allowed to remain in a drying zone at 70°C for 5 seconds to dry, thereby producing saponified cellulose acylate film 1. Cellulose acylate films having thicknesses of 25 μm, 60 μm, and 80 μm were prepared and subjected to the same treatment as above to produce cellulose acylate films 2, 3, and 4. Cellulose acylate films having thicknesses of 40 μm and stretching conditions adjusted so as to increase residual stress were also prepared and subjected to the same treatment as above to produce cellulose acylate film 5.

[0365] --------------------------------------------------- Composition of alkaline solution --------------------------------------------------- Potassium hydroxide 4.7 parts by mass Water 15.7 parts by mass Isopropanol 64.8 parts by mass Surfactant (C 16 H 33 O(CHCHO) 10H) 1.0 part by mass Propylene glycol 14.9 parts by mass

[0366] <Formation of Alignment Film> A coating solution for forming an alignment film having the composition shown below was applied to the saponified surface of the saponified cellulose acylate film 1 (transparent substrate) obtained above at a rate of 24 mL / m using a wire bar coater. 2 The coating was dried with hot air at 100° C. for 120 seconds to obtain an alignment film having a thickness of 0.5 μm.

[0367] -------------------------------------------------- Composition of coating liquid for forming alignment film -------------------------------------------------- Modified polyvinyl alcohol shown below: 28 parts by mass Citrate ester (AS3, manufactured by Sankyo Chemical 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 --------------------------------------------------

[0368] (Modified polyvinyl alcohol)

[0369]

[0370] <Preparation of Reflective Film> The alignment film prepared above was subjected to a rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), rotation speed: 1000 rpm (revolutions per minute), conveying speed: 10 m / min, number of strokes: 1 round trip) in a direction rotated 45° clockwise with respect to the long side direction of the support.

[0371] The reflective layer-forming composition IR1 was applied to the rubbed alignment film surface at room temperature using a wire bar to a dry film thickness of 0.4 μm, yielding a coating layer. The coating layer was dried at room temperature for 30 seconds and then heated in an 85°C atmosphere for 2 minutes. Subsequently, in an environment with an oxygen concentration of 1000 ppm or less, ultraviolet light was irradiated at 60% output for 6 to 12 seconds using a Fusion D-bulb (90 mW / cm lamp) at 60°C to fix the cholesteric liquid crystal phase, yielding a 0.4 μm-thick cholesteric liquid crystal layer IR1. Next, the same process was repeated on the surface of the obtained cholesteric liquid crystal layer IR1 using the reflective layer-forming composition BG1, resulting in a 0.34 μm-thick cholesteric liquid crystal layer BG1. Next, the same process was repeated on the surface of the obtained cholesteric liquid crystal layer BG1 using the reflective layer-forming composition R1, resulting in a 0.20 μm-thick cholesteric liquid crystal layer R1. In this way, a film A1 having a reflective layer composed of three cholesteric liquid crystal layers was obtained. The transmission spectrum of the film A1 was measured using a spectrophotometer (V-670, manufactured by JASCO Corporation), and the transmission spectrum had selective reflection center wavelengths of 515 nm, 685 nm, and 775 nm.

[0372] The HC layer-forming curable composition HC-1 was applied to the surface of the cellulose acylate film 1 in the film A1 prepared above, opposite the reflective layer, and cured to form an HC1 layer with a thickness of 6 μm. Specifically, the application and curing methods were as follows. The HC layer-forming curable composition was applied at a conveying speed of 30 m / min by the die coating method using a slot die described in Example 1 of JP-A-2006-122889, and dried at an atmospheric temperature of 60°C for 60 seconds. Thereafter, the HC1 layer was further coated with an air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.) at an oxygen concentration of about 0.1% by volume and an illuminance of 150 mW / cm. ２ , irradiation amount 600mJ / cm ２ The applied HC layer-forming curable composition was cured by irradiation with ultraviolet light of 1000 kJ / cm 2 , thereby forming a first HC layer, and a film HC1 having a reflective layer and an HC layer was obtained.

[0373] An adhesive layer was applied to the reflective layer side of the film HC1 produced above. After peeling off the light release film of NCF-D692 (adhesive layer thickness 15 μm, manufactured by Lintec Corporation), the exposed adhesive layer and the reflective layer of film HC1 were attached to each other with a rubber roller under a load of 2 kg, thereby producing a reflective film of Example 1 having a configuration of HC layer / transparent substrate / reflective layer / adhesive layer / protective film. Note that the 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.

[0374] <Examples 2 to 13> Reflective films of Examples 2 to 13 were produced in the same manner as in Example 1, except that the curable compositions HC-2 to HC-13 for forming an HC layer were used instead of the curable composition HC-1 for forming an HC layer.

[0375] Example 14 A reflective film of Example 14 was produced in the same manner as in Example 2, except that the thickness of the first HC layer was set to 12 μm.

[0376] Example 15 A reflective film of Example 15 was produced in the same manner as in Example 2, except that the thickness of the first HC layer was set to 3 μm.

[0377] Example 16: The curable composition for forming an HC layer, HC-14, was used instead of the curable composition for forming an HC layer, and the ultraviolet irradiation conditions during curing were set at an illuminance of 20 mW / cm ２ , irradiation amount 30mJ / cm ２ A first HC layer was formed in the same manner as in Example 14, except that the following was used: HC layer-forming curable composition HC-15 was applied onto the surface of the first HC layer formed above, and cured to form a second HC layer with a film thickness of 4 μm. Specifically, the application and curing methods were as follows: The HC layer-forming curable composition was applied by the die coating method using a slot die described in Example 1 of JP-A-2006-122889 at a conveying speed of 30 m / min, and dried at an atmospheric temperature of 60°C for 150 seconds. Thereafter, under a nitrogen purge, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% by volume and an illuminance of 150 mW / cm was used. ２, irradiation amount 600mJ / cm ２ After the second HC layer was formed by irradiating the film with ultraviolet rays of 1000 kJ / cm, the film was taken up to obtain a film HC2 having a reflective layer and an HC layer.

[0378] An adhesive layer was provided on the reflective layer side of the film HC2 produced above. After peeling off the light release film NCF-D692 (adhesive layer thickness 15 μm, manufactured by Lintec Corporation), the exposed adhesive layer and the reflective layer of film HC1 were attached to each other with a rubber roller under a load of 2 kg, thereby producing a reflective film of Example 16 having a configuration of HC layer / transparent substrate / reflective layer / adhesive layer / protective film.

[0379] 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 set to 0.84 μm.

[0380] Example 18 A reflective film of Example 18 was produced in the same manner as in Example 2, except that the thickness of the cholesteric liquid crystal layer R1 was set to 0.36 μm.

[0381] Example 19 A reflective film of Example 19 was produced in the same manner as in Example 18, except that NCF-D692 (adhesive layer thickness: 10 μm, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above-mentioned 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.

[0382] 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 μm, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above-mentioned 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.

[0383] 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 μm, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above-mentioned 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.

[0384] 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 μm, manufactured by Lintec Corporation) was used as the adhesive layer. Note that the above-mentioned 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.

[0385] Example 23 A reflective film of Example 23 was produced in the same manner as in Example 18, except that Panaclean PD-S1 (adhesive layer thickness: 5 μm, manufactured by Panac Corporation) was used as the adhesive layer. Note that 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.

[0386] Example 24 A reflective film of Example 24 was produced in the same manner as in Example 18, except that MF-58 (adhesive layer thickness: 12 μm, manufactured by Tomoegawa Paper Co., Ltd.) was used as the adhesive layer. Note that 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.

[0387] Example 25 A reflective film of Example 25 was produced in the same manner as in Example 18, except that MHM-UVC (adhesive layer thickness: 15 μm, 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 MHM-UVC.

[0388] Example 26 A reflective film of Example 26 was produced in the same manner as in Example 18, except that SK Dyne 2057 (adhesive layer thickness: 25 μm, manufactured by Soken Chemical & Engineering Co., Ltd.) was used as the adhesive layer. Note that the 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.

[0389] Example 27 A reflective film of Example 27 was produced in the same manner as in Example 18, except that cellulose acylate film 2 (thickness: 25 μm) was used as the transparent substrate.

[0390] 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 μm) was used as the transparent substrate.

[0391] Example 29 A reflective film of Example 29 was produced in the same manner as in Example 18, except that Cellulose Acylate Film 4 (thickness: 80 μm) was used as the transparent substrate.

[0392] Example 30 A reflective film of Example 30 was produced in the same manner as in Example 18, except that Cellulose Acylate Film 5 (thickness: 40 μm) was used as the transparent substrate.

[0393] Example 31 A reflective film of Example 31 was produced in the same manner as in Example 24, except that a composition A1 for forming a retardation layer was applied to a rubbed alignment film surface using a wire bar, dried, and then cured under the following conditions, and a composition IR1 for forming a reflective layer was applied onto the cured retardation layer A1.

[0394] <Curing Conditions for Composition A1 for Forming Retardation Layer> After applying and drying the composition A1 for forming a retardation layer, the composition was placed on a hot plate at 50°C and heated with an electrodeless lamp "D bulb" (60 mW / cm) manufactured by Fusion UV Systems in an environment with an oxygen concentration of 1000 ppm or less. 2) for 6 seconds to form a retardation layer. This resulted in a retardation layer having a thickness adjusted to achieve a desired front retardation, i.e., a desired retardation. The retardation of the prepared retardation layer at 550 nm was measured using an AxoScan manufactured by Axometrics, and was found to be 126 nm.

[0395] Example 32 A reflective film of Example 32 was produced in the same manner as Example 31, except that a polarization conversion layer TW1 was applied to the cholesteric liquid crystal layer R1 to a thickness of 0.8 μm. The polarization conversion layer TW1 was formed by applying the polarization conversion layer-forming composition TW1 to the cholesteric liquid crystal layer R1 at room temperature using a wire bar, drying the coating at room temperature for 30 seconds, and then heating it in an 85°C atmosphere for 2 minutes. The film was then irradiated with ultraviolet light at 60% output for 6 to 12 seconds using a Fusion D bulb (90 mW / cm lamp) at 60°C in an environment with an oxygen concentration of 1000 ppm or less.

[0396] <Examples 33 to 42> The reflective films of Examples 33 to 42 were produced in the same manner as in Example 24, except that the curable compositions HC-16 to HC-25 for forming HC layers were used instead of the curable composition HC-2 for forming HC layers.

[0397] Example 43: The curable composition for forming an HC layer, HC-14, was used instead of the curable composition for forming an HC layer, and the ultraviolet irradiation conditions during curing were changed to an illuminance of 20 mW / cm. ２ , irradiation amount 30mJ / cm ２ A first HC layer was formed in the same manner as in Example 24, except that the first HC layer was formed as described above. A curable composition for forming an HC layer, HC-26, was applied to the surface of the first HC layer formed above and cured to form a second HC layer having a film thickness of 0.2 μm. An adhesive layer was also provided in the same manner as in Example 24, to produce a reflective film of Example 43.

[0398] Examples 44 to 46 Reflective films having a polarization conversion layer were produced in the same manner as in Example 32, except that HC-17 was used as the HC-forming composition. Each of matte layer-forming compositions M-1 to M-3 was applied to the surface of the polarization conversion layer of the reflective film, and cured to form a matte layer with a film thickness of 60 nm. Specifically, the application and curing methods were as follows. The matte layer-forming curable composition was applied at a conveying speed of 30 m / min by the die coating method using a slot die described in Example 1 of JP-A 2006-122889, and dried at an atmospheric temperature of 45°C for 60 seconds. Thereafter, under a nitrogen purge, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% by volume and an illuminance of 150 mW / cm was used. ２ , irradiation amount 300mJ / cm ２ The applied curable composition for forming a matte layer was cured by irradiation with ultraviolet light of 1000 kJ / cm, thereby forming a matte layer, and the reflective films of Examples 44 to 46 having the matte layer were obtained.

[0399] 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.

[0400] Comparative Example 2 A reflective film of Comparative Example 2 was produced in the same manner as in Example 1, except that no reflective layer was provided.

[0401] Comparative Example 3 A reflective film of Comparative Example 3 was produced in the same manner as in Example 1, except that no adhesive layer was provided.

[0402] The reflective film prepared above was subjected to the following tests. The test results are summarized in Table 3 below.

[0403] [Test Example 1] Pencil Hardness Pencil hardness evaluation was performed according to JIS (JIS is Japanese Industrial Standards) K5400. The protective film was peeled off from the adhesive layer of the reflective film, and a glass plate (manufactured by Corning, trade name: Eagle XG, thickness 1 mm) and the reflective film prepared above were bonded to the glass plate with the adhesive layer side of the reflective film facing each other, while applying a load of 2 kg with a rubber roller to prepare a laminate of the reflective film and the glass plate. After conditioning the laminate at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, five different points on the surface of the HC layer were scratched with a load of 750 gf using a test pencil H to 9H specified in JIS S 6006. Thereafter, among the hardnesses of the pencils where scratches were observed visually in 0 to 2 places, the highest pencil hardness was taken as the evaluation result.

[0404] [Test Example 2] Abrasion Resistance The protective film was peeled off from the adhesive layer of the reflective film, and the reflective film prepared above was attached to a glass plate (manufactured by Corning, product name: Eagle XG, thickness 1 mm) with the adhesive layer sides of the glass plate and the reflective film facing each other, while applying a load of 2 kg with a rubber roller to prepare a laminate of the reflective film and the glass plate. After conditioning the laminate at a temperature of 25 ° C and a relative humidity of 60% for 2 hours, the haze (HA) before the abrasion test was measured using a haze meter (NDH2000N, manufactured by Nippon Denshoku Co., Ltd.). Using a Taber abrasion tester (rotary abrasion tester, manufactured by Toyo Seiki Co., Ltd.), the surface of the HC layer was subjected to 100 cycles of testing at a rotation speed of 72 rpm under a CS-10F abrasion wheel and a load of 500 gf. For the laminate after the test, the haze (HB) of the test portion was measured. The Δ haze (HB-HA) before and after the test was calculated and evaluated according to the following criteria.

[0405] <Δ haze before and after abrasion resistance test> A: 1% or less. B: More than 1% and 2.5% or less. C: More than 2.5% and 4% or less. D: More than 4%. A to C are within the acceptable range.

[0406] [Test Example 3] Reflection Spectrum The protective film was peeled off from the adhesive layer of the reflective film, and the reflective film prepared above was bonded to a glass plate (manufactured by Corning Incorporated, product name: Eagle XG, thickness 1 mm) with the adhesive layer sides of the reflective film facing each other, while applying a load of 2 kg with a rubber roller, to produce a laminate of the reflective film and the glass plate. A Kakukiri Miel (manufactured by Tomoegawa Paper Co., Ltd.) was bonded to the glass plate side of the laminate, and P-polarized and S-polarized light were incident from a direction of 5° relative to the normal direction of the reflective film surface using a spectrophotometer (manufactured by JASCO Corporation, V-670), and the reflection spectra from 400 to 1000 nm were measured, respectively. The average value (average reflection spectrum) of the measured P-polarized and S-polarized reflection spectra was calculated.

[0407] The average value of the reflectance when P-polarized light and the reflectance when S-polarized light are incident is synonymous with the reflectance when unpolarized light (natural light) is incident. In other words, 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.

[0408] From the calculated average values ​​of the reflection spectra of P-polarized light and S-polarized light, the following were calculated: - the maximum value R1 of natural light reflectance in the wavelength band of 400 nm or more and less than 500 nm; - the maximum value R2 of natural light reflectance in the wavelength band of 500 nm or more and less than 600 nm; and - the maximum value R3 of natural light reflectance in the wavelength band of 600 nm to 800 nm, and evaluated according to the following criteria.

[0409] A: Maximum values ​​R1, R2, and R3 are all greater than 20%. B: Maximum values ​​R1, R2, and R3 are all greater than 7%, and any one of them is 20% or less. C: Any one of maximum values ​​R1, R2, and R3 is 7% or less. A to B are the allowable ranges.

[0410] Test Example 4: Curved surface conformability <Preparation of working liquid> A working liquid having the composition shown below was prepared.

[0411] ------------------------------------------------------------------ Composition of application liquid ------------------------------------------------------------------ Film application liquid (3M) 10 parts by weight Water 500 parts by weight ------------------------------------------------------------------

[0412] <Curved Surface Forming of Reflective Film> The above-prepared application liquid was sprayed onto the convex side of a curved glass panel measuring 330 mm wide x 260 mm long, with a curvature of 1750 mm radius in the longitudinal direction (330 mm) and 1250 mm radius in the transverse direction (260 mm). The above-prepared reflective film was cut into a 330 mm x 260 mm piece and attached so that the hard coat layer of the reflective film contacted the convex side of the curved glass panel. The reflective film adhered to the convex side of the curved glass panel due to the surface tension of the application liquid, but a portion of the reflective film remained wrinkled and did not contact the curved glass panel. A squeegee was used to apply hot air to the wrinkled portion of the reflective film while applying hot air from a heat gun (Hakko Heating Gun 882) to shrink that portion of the reflective film and allow it to conform to the surface of the curved glass panel. The temperature of the hot air from the heat gun was measured with a thermocouple using a Memory HiLogger (LR8450, HIOKI Corporation), and was found to be 120-140°C.

[0413] <Curved surface conformance of reflective film> The protective film was peeled off from the adhesive layer of the reflective film, and the application liquid was sprayed onto the concave side of the curved glass and the surface of the adhesive layer of the reflective film formed into a curved surface as described above, and then the adhesive layer of the reflective film was adhered to the concave surface of the curved glass so that it faced the curved glass. The application liquid was scraped out with a squeegee while the reflective film and the curved glass were brought into close contact, and the film was dried at room temperature for 12 hours, and then evaluated according to the following criteria.

[0414] A: The film was able to follow the curved surface without any problems. B: Part of the film deformed when forming or following the curved surface, but the film was able to follow the curved surface. C: The film deformed significantly when forming or following the curved surface, but the film was able to follow the curved surface. D: The film was unable to form or follow the curved surface. A to C are within the acceptable range.

[0415] [Test Example 5] Slipperiness In the procedure of each example and comparative example, before providing an adhesive layer, a film having a reflective layer and an HC layer was cut into two pieces of 100 mm x 100 mm, and the reflective layer and the HC layer were laminated so that they were in contact with each other.A weight of φ30 mm was placed on the laminated film, and the feel when the two films were slid against each other was evaluated according to the following criteria.In addition, for films without a reflective layer or an HC layer, the reflective layer was laminated so that they were in contact with the transparent substrate, or the HC layer was laminated so that they were in contact with each other, and the same evaluation was carried out.In addition, for films having a matte layer on the reflective layer, the matte layer was laminated so that they were in contact with the HC layer, and the same evaluation was carried out.

[0416] A: It still slides even when a 150g weight is placed on it. B: It still slides even when a 100g weight is placed on it, but it doesn't slide when a 150g weight is placed on it. C: It still slides even when a 50g weight is placed on it, but it doesn't slide when a 100g weight is placed on it. D: It doesn't slide when a 50g weight is placed on it.

[0417] [Test Example 6] Visibility The protective film was peeled off from the adhesive layer of the reflective film, and the reflective film prepared above was placed on a glass plate (manufactured by Corning, product name: Eagle XG, thickness 1 mm) with the adhesive layer sides of the glass plate and the reflective film facing each other, and a load of 2 kg was applied with a rubber roller to form a laminate of the reflective film and the glass plate. The laminate prepared above was irradiated with light from a point light source from the glass plate side in a dark room, and the reflected image of the point light source visible on the glass plate was evaluated according to the following criteria.

[0418] A: No blurring 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.

[0419] The reflective films of Examples 23 to 26 and 31 to 46 were able to conform to curved surfaces without any problems (Rating A). The reflective film of Example 30 was deformed by curling toward the laminated film when hot air from a heat gun was applied during curved surface molding. However, by applying hot air while holding down the film with a squeegee, the film was able to conform to the curved surface (Rating B). The reflective films of Examples 1 to 22, 27 to 29 and Comparative Examples 1 and 2 were deformed significantly by curling toward the laminated film when hot air from a heat gun was applied during curved surface molding. However, by holding down the film with multiple squeegees, the film was able to conform to the curved surface (Rating C). The reflective film of Comparative Example 3 peeled off from the curved glass during drying during curved surface molding, and was unable to conform to the curved surface (Rating D). In the table below, the "HC layer Sa1" column indicates the surface roughness Sa1 (nm) of components with wavelengths of 2.5 μm or less on the surface of the hard coat layer opposite the reflective layer side. The column "HC layer Sa2" indicates the surface roughness Sa2 (nm) of components with wavelengths of 10 μm or more on the surface of the hard coat layer opposite the reflective layer side. The column "Matte layer Sa1" indicates the surface roughness Sa1 (nm) of components with wavelengths of 2.5 μm or less on the surface of the matte layer opposite the reflective layer side.

[0420]

[0421]

[0422]

[0423]

[0424] As shown in the table above, it was confirmed that the reflective film of the present invention exhibits the desired effects. A comparison between Examples 1 and 2 confirmed that superior abrasion resistance and pencil hardness were achieved when the content of the cationically polymerizable compound was 50 parts by mass or less per 100 parts by mass of the total content of the radically polymerizable compound and the cationically polymerizable compound. A comparison between Examples 2, 4, and 5 confirmed that superior abrasion resistance and pencil hardness were achieved when the radically polymerizable compound contained four or more (preferably five or more) radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups. A comparison between Examples 2, 6, and 7 confirmed that superior abrasion resistance and pencil hardness were achieved when the cationically polymerizable compound contained both cationically polymerizable groups and radically polymerizable groups. A comparison between Examples 6 and 7 confirmed that superior abrasion resistance and pencil hardness were achieved when the cationically polymerizable compound had a cationically polymerizable group equivalent of 120 or less. Comparison of Examples 10 and 12 with other Examples confirmed that the pencil hardness was superior when inorganic particles having ethylenically unsaturated groups on the surface were used. Comparison of Examples 14 to 16 confirmed that the pencil hardness was superior when the HC layer had a film thickness of 5 to 20 μm. As shown in Examples 18 to 22, it was confirmed that the pencil hardness was superior when the adhesive layer had a thickness of 5 to 20 μm. As shown in Examples 18 and 27 to 30, it was confirmed that the pencil hardness was superior when the transparent substrate had a thickness of 40 to 80 μm. Comparison of Examples 23 to 26 with other Examples confirmed that the curved surface conformability was superior when the difference in thermal shrinkage between the protective film layer and the reflective film layer was 1.0% or less.

[0425] <Preparation of curable composition for forming heat-seal layer> Each component was mixed according to the formulation shown in the table below, and filtered through a polypropylene filter with a pore size of 10 μm to prepare curable compositions for forming heat-seal layers HS-1 to HC-30. The blending amount of each component shown in Table 9 is expressed in parts by mass.

[0426]

[0427]

[0428] Example 201 The heat-sealable 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 would be 0.8 μm, and then the film was dried at 120° C. for 1 minute to form a heat-sealable layer. Thereafter, the film was further dried under nitrogen purge using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) at an oxygen concentration of about 0.1% by volume and an illuminance of 150 mW / cm. ２ , irradiation amount 300mJ / cm ２ The applied curable composition for forming a heat seal layer was cured by irradiation with ultraviolet light of 1000 kJ / cm 2 , thereby preparing a reflective film of Example 201.

[0429] Example 202 A reflective film of Example 202 was produced in the same manner as in Example 201, except that the heat-sealable layer-forming composition HS-1 was applied to the surface of the polarization conversion layer of the reflective film of Example 32.

[0430] Examples 203 to 223 and 227 to 233 Reflective films of Examples 203 to 223 and 227 to 233 were prepared in the same manner as in Example 202, except that HS2 to HS29 were used as the heat seal layer-forming compositions.

[0431] Example 224 A reflective film of Example 224 was produced in the same manner as in Example 206, except that the heat-sealable layer-forming composition HS-5 was applied so that the film thickness after drying would be 0.4 μm.

[0432] Example 225 A reflective film of Example 225 was produced in the same manner as in Example 206, except that the heat-sealable layer-forming composition HS-5 was applied so that the film thickness after drying would be 0.2 μm.

[0433] Example 226 A reflective film of Example 226 was produced in the same manner as in Example 206, except that the heat-sealable layer-forming composition HS-5 was applied so that the film thickness after drying would be 10.0 μm.

[0434] Comparative Example 201 A reflective film of Comparative Example 201 was produced in the same manner as in Example 201, except that HS30 was used as the composition for forming a heat seal layer.

[0435] The reflective film prepared above was subjected to the following tests. The test results are summarized in Table 10 below.

[0436] Test Example 7: Abrasion Resistance of Products with Heat Seal Layers The reflective films obtained in Examples 201 to 233 and Comparative Example 201 were placed on a glass plate (manufactured by Corning Incorporated, trade name: Eagle XG, thickness 1 mm) in the center of the glass plate, with the surface on the heat seal layer side as the contact surface. When the reflective film of Example 201 was used, a laminate having a glass substrate, heat seal layer, selective reflection layer, support, and hard coat layer in this order was formed. When the reflective film of Examples 202 to 233 was used, a laminate having a glass substrate, heat seal layer, polarization conversion layer, selective reflection layer, retardation layer, support, and hard coat layer in this order was formed. A PVB film (interlayer) manufactured by Sekisui Chemical Co., Ltd., with the same size as the glass plate and a thickness of 0.76 mm, was placed on top of this laminate. A glass plate (manufactured by Corning Incorporated, trade name: Eagle XG, thickness 1 mm) was then placed on top of this. This was held at 115°C and 10 kPa (0.1 atm) for 1 hour, and then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, yielding a laminated glass. The laminated glass was peeled between the PVB film and the hard coat layer to obtain a glass sample for abrasion resistance testing. The glass sample was conditioned at a temperature of 25°C and a relative humidity of 60% for 2 hours, and then the haze (HA) before the abrasion test was measured using a haze meter (NDH2000N, manufactured by Nippon Denshoku Co., Ltd.). Using a Taber abrasion tester (rotary abrasion tester, manufactured by Toyo Seiki Co., Ltd.), the surface of the hard coat layer was subjected to 100 cycles of testing using a CS-10F abrasion wheel at a rotation speed of 72 rpm under a load of 500 gf. The haze (HB) of the test portion of the laminate after testing was measured. The Δ haze (HB-HA) before and after the test was calculated and evaluated according to the following criteria.

[0437] <Δ haze before and after abrasion resistance test> A: 1% or less. B: More than 1% and 2.5% or less. C: More than 2.5% and 4% or less. D: More than 4%. A to C are within the acceptable range.

[0438] Test Example 8 Reflection Spectra of Products with Heat Seal Layers The reflective films obtained in Examples 201 to 233 and Comparative Example 201 were placed on a glass plate (thickness 2 mm, float glass) in the center of the glass plate, with the surface on the heat seal layer side as the contact surface. When the reflective film of Example 201 was 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, was formed. When the reflective film of Examples 202 to 233 was used, a laminate having 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 (interlayer) manufactured by Sekisui Chemical Co., Ltd., with the same size as the glass plate and a thickness of 0.76 mm, was placed on top of this laminate, and a glass plate (thickness 2 mm, float glass) was placed on top of that. This was held at 115°C and 10 kPa (0.1 atm) for 1 hour, and then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, yielding a laminated glass. The laminated glass was peeled between the PVB film and the hard coat layer to obtain a glass sample for measuring reflection spectra. A clear Miel (manufactured by Tomoegawa Paper Co., Ltd.) was attached to the glass plate side of the glass sample, and P-polarized and S-polarized light were incident from a direction 5° relative to the normal direction of the reflective film surface using a spectrophotometer (manufactured by JASCO Corporation, V-670), and the reflection spectra from 400 to 1000 nm were measured. The average value (average reflection spectrum) of the measured P-polarized and S-polarized reflection spectra was calculated.

[0439] From the calculated average values ​​of the reflection spectra of P-polarized light and S-polarized light, the following were calculated: - the maximum value R1 of natural light reflectance in the wavelength band of 400 nm or more and less than 500 nm; - the maximum value R2 of natural light reflectance in the wavelength band of 500 nm or more and less than 600 nm; and - the maximum value R3 of natural light reflectance in the wavelength band of 600 nm to 800 nm, and evaluated according to the following criteria.

[0440] A: Maximum values ​​R1, R2, and R3 are all greater than 20%. B: Maximum values ​​R1, R2, and R3 are all greater than 7%, and any one of them is 20% or less. C: Any one of maximum values ​​R1, R2, and R3 is 7% or less. A to B are the allowable ranges.

[0441] Test Example 9: Curved surface conformability of product with heat seal layer Preparation of laminated glass The reflective films obtained in Examples 201 to 233 and Comparative Example 201, each measuring 260 mm in length and 330 mm in width, and 2 mm in thickness, were placed on a curved glass substrate (first glass substrate) measuring 260 mm in length, 330 mm in width, and 2 mm in thickness, at the center of the glass substrate, with the surface on the heat seal layer side as the contact surface. As a result, when the reflective film of Example 201 was used, a laminate having the glass substrate, heat seal layer, selective reflection layer, support, and hard coat layer in this order was formed, and when the reflective films of Examples 202 to 233 were used, a laminate having the glass substrate, heat seal layer, polarization conversion layer, selective reflection layer, retardation layer, support, and hard coat layer in this order was formed. A 260 mm x 330 mm x 0.76 mm thick PVB film (interlayer) manufactured by Sekisui Chemical Co., Ltd. was placed on top of this laminate (on top of the hard coat layer), and a 260 mm x 330 mm x 2 mm thick curved glass substrate (second glass substrate) was placed on top of that. This was then held at 115°C and 10 kPa (0.1 atm) for 1 hour, and then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, yielding a laminated glass. The 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 curved surface conformability evaluation. The curved surface conformability of the reflective film including the heat seal layer relative to the first glass substrate, which was the curved glass substrate in the glass sample for curved surface conformability evaluation, was evaluated according to the following criteria.

[0442] A: Able to follow the curved surface without any problems. B: Part of the reflective film peeled off from the glass, but the curved surface could be followed. C: The reflective film peeled off, and the curved surface could not be followed. A to B are within the acceptable range.

[0443] [Test Example 10] Slipperiness of product with heat seal layer In each example and comparative example, a film having a heat seal layer and an HC layer was cut into two pieces measuring 100 mm x 100 mm, and the heat seal layer and the HC layer were laminated so that they were in contact with each other. A weight of φ30 mm was placed on the laminated film, and the feel when the two films were slid against each other was evaluated according to the following criteria. In addition, for films without a heat seal layer, the reflective layer and the HC layer were laminated so that they were in contact with each other, and the same evaluation was performed.

[0444] A: It still slides even when a 150g weight is placed on it. B: It still slides even when a 100g weight is placed on it, but it doesn't slide when a 150g weight is placed on it. C: It still slides even when a 50g weight is placed on it, but it doesn't slide when a 100g weight is placed on it. D: It doesn't slide when a 50g weight is placed on it.

[0445] [Test Example 11] Visibility of product with heat seal layer For the glass sample prepared in Test Example 9, light was applied from a point light source from the glass plate side in a dark room, and the reflected image of the point light source visible on the glass plate was evaluated according to the following criteria.

[0446] A: No blurring is visible around the point light source in the reflected image. B: The area around the point light source in the reflected image is blurred. C: The area around the point light source in the reflected image is strongly blurred. D: The reflective film peeled off during curved surface molding, making it impossible to evaluate.

[0447] [Test Example 12: Peelability] <Preparation of Laminated Glass> A reflective film obtained in Examples 201 to 233 and Comparative Example 201, measuring 150 mm in length and 25 mm in width, was placed on a flat glass substrate measuring 80 mm in length, 50 mm in width, and 2 mm in thickness, at the center of the glass substrate, with the surface of the heat seal layer serving as the contact surface. When the reflective film of Example 201 was 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, was formed. When the reflective film of Examples 202 to 233 was used, a laminate having 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 (interlayer) manufactured by Sekisui Chemical Co., Ltd., measuring 150 mm in length, 25 mm in width, and 0.76 mm in thickness was placed on top of this laminate, and a flat glass substrate (second glass substrate) measuring 80 mm in length, 50 mm in width, and 2 mm in thickness was placed on top of that. This was held at 115°C and 10 kPa (0.1 atm) for 1 hour, and then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove bubbles, yielding a laminated glass. The laminated glass was peeled between the PVB film and the hard coat layer to obtain a glass sample for peel strength testing.

[0448] [Peeling property; evaluation of peel strength] The reflective film portion of the glass sample for peeling property test prepared above was gripped with the arm of a Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.), and peeled while maintaining an angle of 90° between the reflective film portion and the flat glass, and the peel strength was measured and evaluated according to the following criteria. Evaluation criteria A: 4.0 N / 25 mm or more B: 2.5 N / 25 mm or more, less than 4.0 N / 25 mm C: 1.0 N / 25 mm or more, less than 2.5 N / 25 mm D: Less than 1.0 N / 25 mm

[0449] [Humidity and Heat Durability] The glass sample for evaluating curved surface conformability prepared above (the above-described laminate including the first glass substrate and the reflective film including the heat seal layer) was conditioned for 80 hours in an environment of 90°C and 80% RH, and then conditioned for 24 hours in an environment of 25°C and 60% RH. The glass sample after conditioned humidity was observed, and the adhesion of the reflective film to the first glass substrate was evaluated according to the following criteria. Evaluation criteria A: The reflective film was not peeled off from the glass. B: The reflective film was partially peeled off from the glass.

[0450]

[0451] As shown in Table 10, it was confirmed that the reflective film of the present invention exhibits the desired effects. In particular, a comparison of Examples 205 and 210 to 213 confirmed that the effect was even better when the I / O ratio of the ethylenically unsaturated polymerizable group-containing compound was 0.60 or more (preferably 1.2 or more). Furthermore, a comparison of Examples 201 and 203 to 209 confirmed that the effect was even better when the content of the polymerizable compound in the heat-seal layer was 10 to 60% by mass (preferably 15 to 50% by mass) relative to the total mass of the heat-seal layer. Furthermore, a comparison of Examples 223 to 225 confirmed that the effect was even better when the average thickness of the heat-seal layer was 0.4 μm or more (preferably 0.8 μm or more).

[0452] REFERENCE SIGNS LIST 1 adhesive layer 2 reflective layer 3 hard coat layer (HC layer) 4 protective film 5 polarization conversion layer 6 retardation layer 7 transparent substrate 8 matte layer 10A, 10B, 10C, 10D, 10E, 10F reflective film 11 vehicle interior glass 12 heat seal layer

Claims

1. The optical film has a hard coat layer, a reflective layer that selectively reflects light of a wavelength, and a heat seal layer laminated on one side of the reflective layer, in this order; the reflective layer is formed using a composition containing a polymerizable liquid crystal compound, A reflective film, wherein the heat seal layer comprises a thermoplastic resin or an elastomer.

2. The reflective film according to claim 1 , wherein the heat seal layer is a layer formed using a composition containing a polymerization initiator.

3. The reflective film of claim 2 , wherein the composition further comprises a polymerizable compound.

4. the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group, The reflective film according to claim 3 , wherein the polymerizable compound has an ethylenically unsaturated polymerizable group.

5. The optical film has, in this order, a hard coat layer, a reflective layer that selectively reflects light in a wavelength direction, a polarization conversion layer, and a heat seal layer laminated on one side of the polarization conversion layer, the polarization conversion layer is formed using a composition containing a polymerizable liquid crystal compound, A reflective film, wherein the heat seal layer comprises a thermoplastic resin or an elastomer.

6. The reflective film according to claim 5 , wherein the heat seal layer is a layer formed using a composition containing a polymerization initiator.

7. The reflective film of claim 6 , wherein the composition further comprises a polymerizable compound.

8. The reflective film according to any one of claims 3, 4 and 7, wherein the content of the polymerizable compound is 5 to 80 mass % based on the solid content of the composition.

9. The reflective film according to claim 3 , wherein the I / O ratio of the polymerizable compound is 0.4 or more.

10. The reflective film according to any one of claims 1 to 7, wherein the heat seal layer has a moisture content of 2.0% or less at 25°C and 60% RH.

11. A windshield glass comprising the glass plate and the reflective film according to any one of claims 1 to 7 bonded together via the heat seal layer.

12. 12. An image display system comprising: the windshield glass according to claim 11; and a projector that irradiates a projection image light onto the reflective film side of the windshield glass.

13. The reflective film has, in this order, an adhesive layer, a reflective layer that selectively reflects light of a wavelength, and a hard coat layer.

14. The reflective film according to claim 13, wherein the adhesive layer has a thickness of 1 to 30 μm.

15. The reflective film according to claim 13 , wherein the hard coat layer has a thickness of 1 μm or more.

16. the hard coat layer is a layer formed using a curable composition for forming a hard coat layer, the curable composition containing a cationic polymerizable compound; The reflective film according to claim 13, wherein the content of the cationically polymerizable compound is 5 mass % or more based on the total solid content of the curable composition for forming a hard coat layer.

17. the hard coat layer is a layer formed using a curable composition for forming a hard coat layer, the curable composition containing inorganic particles; The reflective film according to claim 13 , wherein the content of the inorganic particles is 0.5% by mass or more based on the total solid content of the curable composition for forming a hard coat layer.

18. The reflective film according to claim 17 , wherein the inorganic particles have an average primary particle size of 40 nm or more.

19. The reflective film according to claim 17 , wherein the inorganic particles have an average primary particle size of 40 nm or more and less than 200 nm.

20. The reflective film according to claim 13 , wherein the surface roughness Sa1 of the hard coat layer on the surface opposite to the reflective layer side is 0.30 nm or more for components having a wavelength of 2.5 μm or less.

21. The reflective film according to claim 13 , wherein the surface roughness Sa2 of the hard coat layer on the surface opposite to the reflective layer side for components having a wavelength of 10 μm or more is 2.0 nm or less.

22. The reflective film of claim 13 further comprising a transparent substrate.

23. The reflective film according to claim 22 , wherein the transparent substrate is a cellulose acylate film.

24. The reflective film according to claim 13 , further comprising a retardation layer.

25. Further comprising a polarization conversion layer, The reflective film according to claim 24 , wherein the retardation layer, the reflective layer, and the polarization conversion layer are arranged in this order.

26. The reflective film according to claim 13 , further comprising a matte layer between the adhesive layer and the reflective layer.

27. The reflective film according to claim 26 , wherein the surface roughness Sa1 of the matte layer on the surface opposite to the reflective layer side is 0.30 nm or more for components having a wavelength of 2.5 μm or less.

28. The reflective film according to any one of claims 13 to 27, A laminate comprising a protective film laminated on the surface of the reflective film opposite to the reflective layer side of the adhesive layer.

29. The laminate according to claim 28 , wherein the difference in heat shrinkage rate between the reflective film and the protective film at 140° C. is less than 1.5%.

30. A windshield glass comprising a glass plate and the reflective film according to any one of claims 13 to 27 bonded together via the adhesive layer.

31. 31. An image display system comprising: the windshield glass according to claim 30; and a projector that irradiates a projection image light onto the reflective film side of the windshield glass.