Cured film and laminate, and methods for producing the same

Abstract

To provide a cured film and a laminate, excellent in delustering properties and scratch resistance; and to provide a method for producing the cured film and the laminate.SOLUTION: Provided is a cured film formed by irradiating an active energy ray-curable composition with active energy rays, and in the cured film, the active energy ray-curable composition includes a polymer (A) having an unsaturated double bond and polyfunctional (meth)acrylate (B) at a main chain or a side chain, and has a wrinkle-like uneven structure on a surface thereof. Provided is a method for producing the cured film, in which the active energy ray-curable composition including the polymer (A) having the unsaturated double bond at the main chain or the side chain or a cured product of the polymer (A) is irradiated with vacuum ultraviolet rays. Provided is a laminate having the cured film on a base material. Provided is a method for producing the laminate, in which the active energy ray-curable composition including the polymer (A) having the unsaturated double bond and the polyfunctional (meth)acrylate (B) at the main chain or the side chain is laminated on the base material, and is cured by irradiation with the vacuum ultraviolet rays.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cured film and a laminate, and to a method for producing the same. [Background technology]

[0002] In order to impart a matte finish to building materials such as wallpaper, display components, decorative films, and other components, fine irregularities are sometimes imparted to the surface of the substrate. In addition, these components are sometimes required to have antistatic properties. Patent Document 1 discloses a method of forming fine irregularities on the surface of a biaxially oriented thermoplastic resin film used in a magnetic recording medium by irradiating the surface with excimer laser light. Patent Document 2 discloses a method for forming irregularities on the surface of a film having a hard coat layer used in an anti-reflection film, in which a film having a hard coat layer containing a hard coat resin and inorganic fine particles is irradiated with excimer light to decompose the hard coat resin portion of the surface layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 4-305430 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-224920 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the method described in Patent Document 1 can only obtain a specific uneven structure that does not provide a sufficient matte effect. Moreover, since the unevenness is formed directly on the biaxially oriented thermoplastic resin film, it is difficult to apply it to display applications that require various surface properties such as scratch resistance and antistatic properties. In the method described in Patent Document 2, only the hard coat resin of the hard coat layer is decomposed to expose inorganic fine particles on the surface, which makes the particles more likely to fall off and may impair visibility when used in displays, etc. Another problem is that the surface uneven structure is limited by the shape and distribution of the particles. An object of the present invention is to provide a cured film and a laminate that are excellent in matte properties and scratch resistance, and a method for producing such a cured film and a laminate. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] A cured film obtained by irradiating an active energy ray-curable composition with active energy rays, wherein the active energy ray-curable composition contains a polymer (A) having an unsaturated double bond in a main chain or a side chain and a polyfunctional (meth)acrylate (B), and the cured film has a wrinkled uneven structure on the surface. [2] The cured film according to [1] above, wherein the polymer (A) is a (meth)acrylic acid ester copolymer (A1). [3] The cured film according to [1] or [2] above, wherein the active energy ray-curable composition is substantially free of particles. [4] The cured film according to any one of [1] to [3] above, wherein the concave-convex structure has a mean length of roughness curve elements (RSm) according to JIS B0601:2013 of 1 to 50 μm and an arithmetic mean height (Sa) defined in ISO25178 of 0.1 to 5 μm. [5] The cured film according to any one of the above [1] to [4], wherein the average value (θa) of the local tilt angles in the concave-convex structure is 2° or more. [6] The cured film according to any one of the above [1] to [5], which has a 60° gloss of 50 or less. [7] The method for producing a cured film according to any one of the above [1] to [6], comprising irradiating an active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth)acrylate (B) with vacuum ultraviolet light. [8] A laminate having the cured film according to any one of [1] to [6] above on a substrate. [9] The laminate according to [8] above, wherein the substrate is a film.

[10] A method for producing a laminate according to [8] or [9], comprising: laminating an active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth)acrylate (B) on a substrate; and curing the composition by irradiating it with vacuum ultraviolet light. [Effects of the Invention]

[0006] The cured film and laminate of the present invention have excellent matte properties and scratch resistance. According to the method for producing a cured film and a laminate of the present invention, a cured film and a laminate having excellent matte properties and scratch resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. "(meth)acrylic" is a general term for acrylic and methacrylic. The symbol "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower and upper limits.

[0008] [Cured film] The cured film of the present invention (hereinafter simply referred to as "cured film") is obtained by irradiating an active energy ray-curable composition with active energy rays, and has a wrinkled uneven structure (non-smooth structure) on the surface. The cured film has a matte finish, making it suitable as an anti-glare film. The active energy ray-curable composition contains a polymer (A) having an unsaturated double bond in the main chain or side chain and a polyfunctional (meth)acrylate (B), and therefore the cured film contains the polymer (A) and the polyfunctional (meth)acrylate (B) in a crosslinked state.

[0009] (average length of roughness curve element) The average length of the roughness curve element in the uneven structure of the cured film is the average length of the roughness curve element (RSm, hereinafter simply referred to as "RSm") according to JIS B0601:2013. The evaluation length used to calculate RSm was 236.87 μm. RSm is preferably 1 to 50 μm or more, more preferably 2 to 40 μm, even more preferably 3 to 35 μm, particularly preferably 4 to 30 μm, and most preferably 5 to 25 μm. When within the above range, excellent matte properties are achieved, resulting in excellent visibility when used in displays, etc.

[0010] (arithmetic mean height) The arithmetic mean height of the uneven structure of the cured film is the arithmetic mean height (Sa, hereinafter simply referred to as "Sa") defined in ISO 25178. The evaluation area when calculating Sa is 177.60 μm × 236.87 μm. Sa is preferably 0.1 to 5 μm or more, more preferably 0.2 to 3 μm, even more preferably 0.3 to 2 μm, and particularly preferably 0.3 to 1.5 μm. When Sa is in the above range, excellent matte properties are achieved, and excellent visibility is achieved when used in displays, etc.

[0011] (Average value of the slope angle of the uneven structure) The average value of the local inclination angle (θa, hereinafter also simply referred to as "θa") in the concave-convex structure of the cured film can be measured by the method described in the Examples below. The evaluation length for calculating θa was 236.87 μm. θa is preferably 2° or more, more preferably 4° or more, even more preferably 7° or more, particularly preferably 10° or more, and most preferably 15° or more, and the upper limit may be 90°. The higher the inclination angle, the better the matte properties.

[0012] (Thickness) From the viewpoint of improving matte properties, the thickness of the cured film (concave-convex layer) is preferably in the range of 0.1 to 100 μm, more preferably 0.2 to 20 μm, still more preferably 0.3 to 10 μm, and particularly preferably 0.3 to 7 μm. The thickness of the cured film indicates the maximum thickness of the concave-convex layer, and is determined by cross-sectional observation using an electron microscope.

[0013] (gross) The 60° gloss (60° specular gloss) of the surface of the cured film, measured by the method described in the Examples below, is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less, and most preferably 11 or less, with the lower the value the better. The smaller the 60° gloss value, the better the matte properties. Similarly, the 20° gloss is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, particularly preferably 2 or less, and most preferably 1 or less, with the lower the better. The smaller the 20° gloss value, the better the matte properties.

[0014] (Pencil hardness) The pencil hardness of the cured film, measured by the method described in the examples below, is preferably F or more, more preferably H or more, and even more preferably 2H or more. When the hardness is in the above range, the film has excellent scratch resistance and is suitable for applications where visibility is important, such as displays.

[0015] [Method for producing cured film and laminate] The cured film of the present invention and the laminate of the present invention having the same (hereinafter simply referred to as "laminate") can be produced, for example, by a method of laminating a coating film of a curable composition on a substrate and irradiating the coating film with active energy rays from the surface side (the side opposite to the substrate) to form a cured film on the surface of the substrate. By irradiating the surface side of a coating film of a curable composition with active energy rays, the surface side of the coating film cures first to form a cured coating. When the interior of the coating film subsequently cures, the cured coating on the surface that cured first buckles, forming a cured film with a wrinkled uneven structure on the surface.

[0016] (Curable composition) The curable composition used to form the cured film contains a polymer (A) having an unsaturated double bond in the main chain or a side chain (hereinafter referred to as polymer (A)) and a polyfunctional (meth)acrylate (B). The curable composition may further contain a monofunctional active energy ray-curable compound, a compound not curable with active energy ray, an organic solvent, a photopolymerization initiator, and other components, as necessary.

[0017] (Polymer (A)) The polymer (A) is not particularly limited, and conventionally known polymers having an unsaturated double bond can be used. Examples of such polymers include (meth)acrylic acid ester copolymers having an unsaturated double bond, reactive urethane resins having an unsaturated double bond, reactive epoxy resins having an unsaturated double bond, allyl resins having an unsaturated double bond, and polyester resins having an unsaturated double bond. Among these, (meth)acrylic acid ester copolymers (A1) having an unsaturated double bond are preferred from the viewpoint of improving curability and scratch resistance.

[0018] The unsaturated double bond refers to a functional group having a carbon-carbon double bond. Examples include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, an allyl group, and a vinyl ether group. The polymer having an unsaturated double bond may contain only one of the functional groups, or may contain two or more of them. Among these, a (meth)acryloyl group is preferred, and an acryloyl group is particularly preferred, because of its excellent curability with active energy rays.

[0019] The double bond equivalent of the polymer (A) is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, even more preferably 0.5 to 5.0 mmol / g, and particularly preferably 0.8 to 4.5 mmol / g. Using a double bond equivalent within this range not only improves the adhesion of the cured film to the substrate, scratch resistance, and hardness, but also tends to reduce wrinkle-like irregularities, resulting in a cured film with low RSm and Sa and excellent matte properties. The double bond amount refers to the (meth)acryloyl group concentration in the acrylic resin, i.e., the amount of (meth)acryloyl groups introduced.

[0020] The weight average molecular weight of the polymer (A) is preferably 800 to 120000, more preferably 2000 to 80000, still more preferably 5000 to 60000, and particularly preferably 10000 to 50000. When the molecular weight of the polymer having an unsaturated double bond is within this range, the scratch resistance of the cured film is improved and the curability is also good, which is preferable.

[0021] The glass transition temperature of the polymer (A) is preferably −20 to 180° C., more preferably 0 to 120° C., even more preferably 10 to 110° C., particularly preferably 20 to 100° C., and most preferably 30 to 90° C. When the glass transition temperature of the polymer having an unsaturated double bond is within this range, the scratch resistance of the cured film is improved and the curability is also good, which is preferable.

[0022] Among the polymers (A), a (meth)acrylic acid ester copolymer (A1) having an unsaturated double bond (hereinafter referred to as copolymer (A1)) is preferred because it is easy to adjust the molecular weight, double bond equivalent, and glass transition temperature of the polymer, control the uneven shape, and provide good antiglare properties, scratch resistance, and curability.

[0023] (Copolymer (A1)) Commercially available copolymers (A1) include those available under the trade names of Hitachi Chemical Co., Ltd. (Hitaloid 7975, Hitaloid 7988, and Hitaloid 7975D), and those available under the trade names of DIC Corporation (Unidic V-6840, Unidic V-6841, Unidic WHV-649, and Unidic EKS-675). These copolymers can also be produced by homopolymerizing or copolymerizing monomers and then introducing (meth)acryloyl groups. The method for producing a (meth)acryloyl group-containing (meth)acrylic acid ester copolymer will be described in detail later.

[0024] When producing copolymer (A1), methods for introducing an unsaturated double bond include reacting an acrylic resin having an epoxy group with a compound having an unsaturated double bond and a carboxyl group (Method 1), reacting an acrylic resin having a carboxyl group with a compound having an unsaturated double bond and an epoxy group (Method 2), reacting an acrylic resin having a hydroxyl group with a compound having an unsaturated double bond and a carboxyl group (Method 3), reacting an acrylic resin having a carboxyl group with a compound having an unsaturated double bond and a hydroxyl group (Method 4), reacting an acrylic resin having an isocyanate group with a compound having an unsaturated double bond and a hydroxyl group (Method 5), and reacting an acrylic resin having a hydroxyl group with a compound having an unsaturated double bond and an isocyanate group (Method 6). These methods may also be used in combination. Hereinafter, radically polymerizable monomers having an unsaturated double bond may be referred to as "monomers."

[0025] In the above-mentioned method 1, examples of the monomer having an epoxy group used to obtain the (meth)acrylic acid ester copolymer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

[0026] Examples of compounds having an unsaturated double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride, and an adduct of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid and an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. Note that the compounds having a double bond and a carboxyl group may be used alone or in combination of two or more.

[0027] In the method 2, examples of the monomer having a carboxyl group used to obtain a (meth)acrylic acid ester copolymer having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may be used alone or in combination of two or more.

[0028] In the method 2, examples of the compound having an unsaturated double bond and an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These compounds may be used alone or in combination of two or more.

[0029] In the method 3, examples of the vinyl monomer having a hydroxyl group used to obtain the (meth)acrylic acid ester copolymer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. These may be used alone or in combination of two or more.

[0030] In the method 3, the same compounds as those in the method 1 can be used as the compound having an unsaturated double bond and a carboxyl group.

[0031] In the above method 4, the same (meth)acrylic acid ester copolymer having a carboxyl group as in the above method 2 can be used.

[0032] In the method 4, examples of the compound having an unsaturated double bond and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. These may be used alone or in combination of two or more.

[0033] In the above-mentioned method 5, examples of the vinyl monomer having an isocyanate group used to obtain a (meth)acrylic acid ester copolymer having an isocyanate group include isocyanate ethyl (meth)acrylate.

[0034] In the above method 5, the compound having an unsaturated double bond and a hydroxyl group may be, for example, the same compounds as those listed in the above method 4.

[0035] In the method 6, the same compounds as those in the method 3 can be used as the (meth)acrylic acid ester copolymer having a hydroxyl group.

[0036] In the method 6, an example of the compound having an unsaturated double bond and an isocyanate group is isocyanate ethyl (meth)acrylate. These may be used alone or in combination of two or more.

[0037] Among the above methods, method 1 is preferred from the viewpoints of cost and productivity. In method 1, the unsaturated double bond is introduced by a ring-opening addition reaction between the epoxy group of the (meth)acrylic acid ester copolymer having an epoxy group and the carboxyl group of the compound having an unsaturated double bond and a carboxyl group.

[0038] In the method 1, the ratio of the compound having an unsaturated double bond and a carboxyl group to the epoxy groups in the (meth)acrylic acid ester copolymer having an epoxy group is preferably 10 to 150 mol %, more preferably 30 to 130 mol %, and even more preferably 50 to 110 mol %. Using the compound in this range is preferable from the viewpoints of allowing the reaction to proceed just right and reducing the amount of raw material residue. Furthermore, copolymers of (meth)acrylates other than those mentioned above or other monomers, such as the above-mentioned (meth)acrylic acid ester copolymers having an epoxy group, may also be used. The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

[0039] Examples of monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate, methoxy(poly)ethylene glycol (poly)propylene glycol (meth)acrylate, octoxy(poly)ethylene glycol (meth)acrylate, octoxy(poly)propylene glycol ( Examples of the monomer include (meth)acrylates such as (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, and stearoxy(poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl(meth)acrylamide, n-butyl(meth)acrylamide, i-butyl(meth)acrylamide, t-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, and N,N-dihydroxyethyl(meth)acrylamide; and styrene-based monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These monomers may be used alone or in combination of two or more.

[0040] The (meth)acrylic acid ester copolymer can be produced by radical polymerization using the above-mentioned raw material monomers. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0041] Examples of organic solvents used in radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

[0042] Examples of radical polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total of the raw material monomers.

[0043] In addition, during radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the (meth)acrylic acid ester copolymer. Examples of the chain transfer agent include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenediaminetetraacetic acid)-2-methylpropanol, methyl-3-mercaptopropionate ... Examples of thiol compounds include (oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

[0044] The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1.0 to 15 parts by weight, per 100 parts by weight of the total of the vinyl monomers as raw materials.

[0045] The reaction time for the radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours, and the reaction temperature is preferably 40 to 120°C, more preferably 50 to 100°C.

[0046] To react a compound having a double bond and a carboxyl group with a (meth)acrylic acid ester copolymer, the compound having a double bond and a carboxyl group is added to the (meth)acrylic acid ester copolymer obtained as described above, and the reaction is carried out in the presence of one or more catalysts, such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, or triethylamine, typically at a temperature of 90 to 140°C, preferably 100 to 120°C, for typically 3 to 9 hours. The catalyst is preferably used in an amount of approximately 0.5 to 3 parts by weight per 100 parts by weight of the combined raw materials (meth)acrylic acid ester polymer and the compound having a double bond and a carboxyl group. This reaction may be carried out immediately after the polymerization reaction to produce the (meth)acrylic acid ester copolymer, or by separating the acrylic resin from the reaction system and then adding the compound having a double bond and a carboxyl group.

[0047] The double bond content in the (meth)acrylic acid ester copolymer is preferably in the range of 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, even more preferably 0.5 to 5.0 mmol / g, and particularly preferably 0.8 to 4.5 mmol / g. Use within this range not only improves the adhesion of the cured film to the substrate, scratch resistance, and hardness, but also tends to reduce wrinkle-like irregularities, thereby achieving reduced RSm, reduced Sa, and, in some cases, increased haze and reduced gloss. The double bond content refers to the (meth)acryloyl group concentration in the (meth)acrylic acid ester copolymer, i.e., the amount of (meth)acryloyl groups introduced.

[0048] (Copolymer (A2)) Examples of the polymer (A2) having an unsaturated double bond other than the (meth)acrylic acid ester copolymer (A1) having an unsaturated double bond (hereinafter referred to as polymer (A2)) include a reactive urethane resin having an unsaturated double bond, a reactive epoxy resin having an unsaturated double bond, an allyl resin having an unsaturated double bond, and a polyester resin having an unsaturated double bond.

[0049] Examples of reactive epoxy resins having a (meth)acryloyl group include those manufactured by Hitachi Chemical Co., Ltd. under the trade names of HITAROID 7851 and HITAROID 7663; those manufactured by Daicel-Allnex Co., Ltd. under the trade names of EBECRYL 645, EBECRYL 648, EBECRYL 860, EBECRYL 1606, EBECRYL 3500, EBECRYL 3603, EBECRYL 3608, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, and EBECRYL 3708; those manufactured by DIC Corporation under the trade names of UNIDICK 5500 and UNIDICK 5502; and those manufactured by Nippon Kayaku Co., Ltd. under the trade name of KAYARAD. Examples include R-115, R-130, R-388, EAM-2160, and RAHN's trade names GENOMER2235, GENOMER2252, GENOMER2263, GENOMER2253, GENOMER2255, and GENOMER2259.

[0050] Examples of commercially available reactive urethane resins having a (meth)acryloyl group include those manufactured by Hitachi Chemical Co., Ltd. under the trade names of HITALOID 4861, HITALOID 4863, HITALOID 7902-1, HITALOID 7909-1, HITALOID 7903-1, HITALOID 7903-3, HITALOID 7903-B, HITALOID 7903-4, HITALOID 7906D-3E, TESLAK 2300, TESLAK 2311, TESLAK 2304, TESLAK 2310, TESLAK 2328, TESLAK 2350, and TA24-195H; and those manufactured by Toagosei Co., Ltd. under the trade name of ARONIX. M-1100, M-1200, Daicel-Allnex Corporation product names: EBECRYL204, EBECRYL205, EBECRYL210, EBECRYL215, EBECRYL220, EBECRYL230, EBECRYL244, EBECRYL245, EBECRYL264, EBECRYL265, EBECRYL270, EBECRYL280 / 15IB, EBECRYL284, EBECRYL285, EBECRYL294 / 25HD, EBECRYL1259, EBECRYL1290, EBECRYL4491, EBECRYL L4820, EBECRYL4858, EBECRYL5129, EBECRYL8210, EBECRYL8254, EBECRYL8301R, EBECRYL8307, EBECRYL8402, EBECRYL8405, EBECRYL8411, EBECRYL8 413, EBECRYL8465, EBECRYL8800, EBECRYL8804, EBECRYL8807, EBECRYL9260, EBECRYL9270, EBECRYL8311, EBECRYL8701, EBECRYL9227EA, KRM8528, KR M8667, KRM8904, KRM8452, KRM8296, KRM7735, KRM8200, Mitsubishi Chemical Corporation product names UV-3610ID80, UV-3640PE80, UV-3630ID80, UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6640B, DIC product names Unidic V-4000BA, Unidic V-4221, Unidic RC29-124,Kyoeisha Chemical Co., Ltd. products: AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G; Nippon Kayaku Co., Ltd. products: KAYARAD UX-3204, UX-4101, UXT-6100, UX-6101, UX-7101, UX-8101, UX-0937, UXF-4002, DPHA-40H, UX-5000, UX-5005, Product name Art Register manufactured by Negami Kogyo Co., Ltd. UN-333, UN-350, UN-1255, UN-2600, UN-2700, UN-5500, UN-5590, UN-5507, UN-6060PTN, UN-6200, UN-6202, UN-6300, UN-6301, U Examples include N-7600, UN-7700, UN-9000PEP, UN-9200A, and RAHN's trade names GENOMER4188 / EHA, GENOMER4215, GENOMER4217, GENOMER4230, GENOMER4267, GENOMER4269 / M22, GENOMER4205, GENOMER4256, GENOMER4297, GENOMER4302, GENOMER4425, GENOMER4622, and GENOMER4690.

[0051] Examples of polyester resins having a (meth)acryloyl group include Aronix M-6100, M-6200, M-6250, M-6500, M-7100, M-8100, and M-9050, both of which are manufactured by Toagosei Co., Ltd.; EBECRYL811, EBECRYL812, EBECRYL851, EBECRYL852, EBECRYL884, and EBECRYL885, both of which are manufactured by Daicel-Allnex; and GENOMER3364, GENOMER3414, GENOMER3485, GENOMER3497, and GENOMER3611, both of which are manufactured by RAHN.

[0052] Examples of polymers having an unsaturated double bond other than a (meth)acryloyl group include diallyl phthalate resins (DAP resins) such as DAP A, DAP S, and DAP K manufactured by Osaka Soda Co., Ltd., and allyl resins such as RADPER AD-32 and AD-044. Examples of unsaturated polyester resins having a vinyl group include U-PICA 7017 and 7015 manufactured by Japan U-PICA Corporation, Rigolac M411 and M543 manufactured by Showa Denko K.K., and Sundoma P101 and P201 manufactured by DH Material Co., Ltd.

[0053] The content of polymer (A) in the curable composition is preferably 5 to 70 mass %, more preferably 7 to 60 mass %, particularly preferably 10 to 55 mass %, and most preferably 20 to 50 mass %, based on the nonvolatile content. When the content of polymer (A) is within this range, excellent scratch resistance and curability are achieved.

[0054] The nonvolatile content of the curable composition is the total mass of components other than the solvent, such as the organic solvent, etc. The nonvolatile content of the curable composition can be measured by a conventionally known method, for example, by measuring the change in weight when 1 g of the composition is spread and heated at 100°C for 1 hour to volatilize the organic solvent.

[0055] (Polyfunctional (meth)acrylate (B)) The polyfunctional (meth)acrylate (B) is a non-polymeric, bifunctional or higher functional compound having a (meth)acryloyl group. By including the polyfunctional (meth)acrylate (B) in the curable composition, it is possible to easily form a textured structure upon irradiation with active energy rays.

[0056] Examples of the polyfunctional (meth)acrylate (B) include compounds obtained by condensation of a polyhydric alcohol with a compound having a (meth)acryloyl group and a carboxyl group, compounds obtained by addition reaction of a polyhydric alcohol with a compound having a (meth)acryloyl group and an isocyanate group, compounds obtained by addition reaction of a polyvalent isocyanate with a compound having a (meth)acryloyl group and a hydroxyl group, and compounds obtained by reacting a polyvalent epoxy group compound with a compound having an acryloyl group and a carboxyl group. These compounds are sometimes simply referred to as polyfunctional (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, etc. However, the polyfunctional (meth)acrylate (B) is not limited to the above-mentioned compound groups.

[0057] The number of functional groups in the polyfunctional (meth)acrylate (B) is preferably 20 or less. From the viewpoint of facilitating the formation of an uneven structure upon irradiation with active energy rays, it is more preferably 15 or less, even more preferably 6 or less, particularly preferably 3 or less, and most preferably 2.

[0058] The viscosity of the polyfunctional (meth)acrylate (B) at 25°C is preferably 1 to 7000 mPa·s, more preferably 2 to 2000 mPa·s, particularly preferably 3 to 1000 mPa·s, and most preferably 4 to 400 mPa·s. When the viscosity of the polyfunctional (meth)acrylate (B) is within this range, it becomes easier to form a concave-convex structure upon irradiation with active energy rays.

[0059] The weight-average molecular weight of the polyfunctional (meth)acrylate (B) is preferably 150 to 5000, more preferably 200 to 4000, particularly preferably 250 to 3000, and most preferably 300 to 2000. When the weight-average molecular weight of the polyfunctional (meth)acrylate (B) is within this range, it becomes easier to form an uneven structure upon irradiation with active energy rays.

[0060] Examples of the polyfunctional (meth)acrylate (B) include bifunctional (meth)acrylates and trifunctional or higher functional (meth)acrylates. The polyfunctional (meth)acrylates may be used alone or in combination of two or more.

[0061] Examples of bifunctional (meth)acrylates include alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; and bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate.

[0062] Among these, in consideration of the ease of forming a wrinkled uneven structure, an unbranched structure is preferred, alkyldiol di(meth)acrylate is more preferred, and alkyldiol di(meth)acrylate having 4 to 18 carbon atoms is even more preferred.

[0063] Examples of trifunctional or higher polyfunctional (meth)acrylates include glycerin tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified pentaerythritol tetra(meth)acrylate. Examples of suitable urethane acrylates include ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified isocyanurate, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, and urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, ethylene oxide-modified types and trifunctional (meth)acrylates are preferred in terms of the ease of forming a wrinkled uneven structure. In particular, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate is more preferred in terms of achieving both the ease of forming a wrinkled uneven structure and scratch resistance and hardness.

[0064] The content of the polyfunctional acrylate (B) in the curable composition is preferably 95 to 30 mass %, more preferably 90 to 40 mass %, particularly preferably 85 to 45 mass %, and most preferably 80 to 50 mass %, based on the nonvolatile content. When the content of the polyfunctional (meth)acrylate (B) is within this range, the antiglare properties are excellent.

[0065] (Monofunctional (meth)acrylate) The curable composition may contain various monofunctional (meth)acrylates for the purposes of improving the coating properties and the adhesion of the cured film to the substrate.

[0066] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, and ethoxypropyl (meth)acrylate; Examples of the methacrylate include alkoxyalkyl (meth)acrylates such as (meth)acrylate, aromatic (meth)acrylates such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate, amino group-containing (meth)acrylates such as diaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, ethylene oxide-modified (meth)acrylates such as methoxyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate and phenylphenol ethylene oxide-modified (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (meth)acrylic acid.

[0067] The content of all active energy ray-curable compounds in the curable composition is preferably 5 to 99.99 mass%, more preferably 30 to 99.9 mass%, even more preferably 40 to 95 mass%, particularly preferably 50 to 90 mass%, and most preferably 60 to 80 mass%, based on the nonvolatile content. Within the above range, a wrinkled uneven structure is easily formed, and a cured film having excellent hardness can be formed.

[0068] (resin) The curable composition may contain a resin that does not have an unsaturated double bond in order to improve adhesion to the substrate, etc. Various resins may be used, including conventionally known resins such as acrylic resins, polyester resins, polyurethane resins, and polyvinyl resins. Among these, acrylic resins are preferred because of their excellent transparency and affinity with (meth)acrylates.

[0069] When a resin is blended into the curable composition, the content thereof is preferably 80% by mass or less, more preferably 3 to 60% by mass, even more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass, based on the nonvolatile content. Within the above range, not only are the adhesion of the cured film to the substrate, scratch resistance, and hardness improved, but the wrinkled uneven structure tends to be finer, and decreases in RSm and Sa, and in some cases, an increase in haze and a decrease in gloss can be achieved.

[0070] (particle) To further improve the matte properties of the cured film due to the wrinkled uneven structure, particles can be incorporated into the curable composition. The type of particles is not particularly limited, and conventionally known particles can be used. Specific examples include inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. The inorganic particles may be surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably crosslinked to maintain their shape, and crosslinked acrylic resin particles and crosslinked styrene resin particles are more preferred. Two or more of these particles may be used in combination.

[0071] The average primary particle size of the particles is preferably in the range of 0.01 to 30 μm, more preferably 0.05 to 10 μm, still more preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm.Within this range, the matte properties are excellently improved.

[0072] When particles are blended into the curable composition, the content thereof is preferably 30% by mass or less, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass, based on the nonvolatile content, from the viewpoint of improving matte properties. The curable composition can form a textured structure on the surface of the cured film without incorporating particles, and therefore has the advantage of being able to use a wide range of materials. Therefore, it is possible to design a curable composition that is substantially free of particles. Here, "substantially" means that particles are not intentionally incorporated.

[0073] (Photopolymerization initiator) A photopolymerization initiator may be blended to promote the curing of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzil dimethyl ketal, 1,1-dichloroacetophenone, and pt-butyl dichloroacetophenone. Examples of the photopolymerization initiator include phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0074] When a photopolymerization initiator is blended in the curable composition, the content thereof is preferably 20% by mass or less, more preferably 0.1 to 10% by mass, even more preferably 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass, based on the nonvolatile content, from the viewpoint of promoting curing.

[0075] (Leveling agent) To improve the appearance of the cured film, a leveling agent may be incorporated into the curable composition. Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, fluorine leveling agents, etc. These leveling agents may be used alone or in combination of two or more.

[0076] When a leveling agent is blended in the curable composition, the content thereof is preferably 10% by mass or less, more preferably 0.01 to 8% by mass, and even more preferably 0.1 to 5% by mass, based on the non-volatile content, from the viewpoint of improving the appearance of the cured film.

[0077] (Various additives) The curable composition may contain various additives, such as a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, an antifouling agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, within the range that does not impair the effects of the present invention.

[0078] (organic solvent) For the purpose of improving workability when applying the composition to a substrate, an organic solvent may be blended into the curable composition as needed. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogenated solvents such as dichloromethane and chloroform. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred in that they can easily improve workability during application.

[0079] When an organic solvent is blended into the curable composition, the content thereof is preferably 10 parts by mass or more and 1,900 parts by mass or less, and more preferably 40 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the nonvolatile content, from the viewpoint of improving operability in the coating operation.

[0080] (Formation of coating film) Examples of methods for forming a coating film of the curable composition include a method of applying the curable composition to the surface of a substrate or an article to form a coating film, and then drying the coating film as necessary. The coating method is not particularly limited, and examples thereof include known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating. When the curable composition contains an organic solvent, it is preferable to heat-dry the composition before irradiating it with active energy rays. By heating and drying the composition beforehand, the solvent in the coating film can be effectively removed. The drying temperature for the heat-drying is preferably 30°C or higher and 200°C or lower, more preferably 40°C or higher and 150°C or lower. The drying time is preferably 0.01 minutes or higher and 30 minutes or lower, more preferably 0.1 minutes or higher and 10 minutes or lower.

[0081] (Irradiation with active energy rays) A coating film of the curable composition formed on the surface of a substrate or article is irradiated with active energy rays to form a cured film, thereby forming a laminate in which the cured film is laminated on the substrate or article. The active energy rays are preferably those with high energy (short wavelength) that can effectively cure the surface of the coating film, and vacuum ultraviolet rays (ultraviolet rays with a wavelength of 200 nm or less) are more preferred. Among vacuum ultraviolet rays, excimer light with a half-width of 50 nm or less is optimal. Examples of excimer light include argon excimer light (126 nm), krypton excimer light (146 nm), xenon excimer light (172 nm), and argon-fluorine excimer light (193 nm). Among these, xenon excimer light is preferred in terms of ease of use, the ability to form an effective uneven structure in the cured film, and the curability of the curable composition.

[0082] When vacuum ultraviolet light is used, the cumulative amount of light to be irradiated is preferably 1 to 3000 mJ / cm. 2 , more preferably 3 to 1000 mJ / cm 2 , and more preferably 5 to 500 mJ / cm 2 , particularly preferably 10 to 100 mJ / cm 2 The illuminance is preferably in the range of 1 to 500 mW / cm. 2 , more preferably 2 to 300 mW / cm 2 , and more preferably 3 to 100 mW / cm 2 The range is. The vacuum ultraviolet irradiation is preferably performed in an oxygen-poor atmosphere such as a nitrogen atmosphere, etc. The oxygen concentration in the atmosphere is preferably 10% or less, more preferably 5% or less, even more preferably 3% or less, and particularly preferably 1% or less.

[0083] After the vacuum ultraviolet irradiation, it is preferable to irradiate the cured film with an active energy ray other than vacuum ultraviolet ray in order to deep cure the film. Examples of the active energy ray include ultraviolet ray, electron beam, etc. Examples of the ultraviolet ray include ultraviolet ray with a wavelength of 200 nm or more irradiated from a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, etc. Examples of the electron beam include electron beam irradiated from an EB irradiator, etc. Of the active energy ray other than vacuum ultraviolet ray, ultraviolet ray is more preferable in consideration of the curability of the curable composition.

[0084] However, vacuum ultraviolet rays having a wavelength of 200 nm or less are significantly absorbed by oxygen. Therefore, the amount of irradiation that reaches the coating film depends on the oxygen concentration. For this reason, it is preferable that the curable resin composition used in the present invention has good curability even when the intensity of the excimer light is significantly reduced. Specifically, when irradiating only with a high-pressure mercury lamp without irradiating with excimer light, the cumulative light amount until the coating film becomes non-sticky when touched with a finger is 1 to 3,000 mJ / cm. 2 is preferably 5 to 2000 mJ / cm 2 More preferably, it is 10 to 1000 mJ / cm 2 More preferably, it is 15 to 400 mJ / cm 2 It is particularly preferable that the concentration is 20 to 200 mJ / cm 2 By using a curable composition that can be cured within the above-described range, the productivity of the cured film of the present invention can be improved.

[0085] [Laminate] The laminate of the present invention has a layer made of a substrate and a layer (concave-convex layer) made of a cured film of a curable composition. The laminate may further have a primer layer between the substrate and the cured film. It may also have a back functional layer on the surface of the substrate opposite the cured film side. A surface functional layer may also be present on the surface of the cured film opposite the substrate, as long as it does not impair the effects of the present invention.

[0086] (base material) As the substrate, known substrates can be used, for example, resin substrates, metal substrates, and paper substrates. Among these, resin substrates are preferred from the viewpoint of processability. The resin substrate may have a single layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable that the resin substrate has a multi-layer structure of two or more layers, and each layer has its own characteristics to achieve multi-functionality. As the resin substrate, various resin films (sheets) can be used, for example, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, and nylon film. When the laminate is used for a display, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred in terms of transparency, formability, and versatility.

[0087] The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferred. Among these, a uniaxially stretched film stretched in one direction or a biaxially stretched film stretched in two directions is preferred, and a biaxially stretched film is more preferred from the viewpoint of excellent balance of mechanical properties and flatness. The polyester constituting the polyester film that can be used as the substrate may be either a homopolyester or a copolymer polyester. The homopolyester is preferably one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more. Examples of dicarboxylic acid components of the copolymer polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of glycol components include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid components and glycol components may each be used alone or in combination of two or more. Representative examples of polyester include polyethylene terephthalate and polyethylene naphthalate. As the polyester film, from among the above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferred in consideration of mechanical strength and heat resistance, and films formed from polyethylene terephthalate are particularly preferred in consideration of ease of production and handleability for applications such as surface protection films.

[0088] The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the substrate may be any poly(meth)acrylate having a unit based on (meth)acrylate, and various acrylic resins can be used. Examples of the (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, as well as alkyl (meth)acrylates having an alkyl group with a larger number of carbon atoms. In consideration of transparency, processability, and chemical resistance, the poly(meth)acrylate preferably contains, as its main component, units based on alkyl(meth)acrylate having 1 to 4 carbon atoms, more preferably contains, as its main component, at least one selected from the group consisting of units based on methyl(meth)acrylate and units based on ethyl(meth)acrylate, and particularly preferably contains, as its main component, units based on methyl(meth)acrylate. It is also possible to impart properties such as flexibility to the poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl (meth)acrylates or units based on other monomers. The proportion of units based on alkyl(meth)acrylate having 1 to 4 carbon atoms relative to the total mass of the poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

[0089] The substrate may contain particles for the purposes of imparting slipperiness, preventing scratches during each process, and improving blocking resistance. The type of particles can be appropriately selected depending on the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base layer contains a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst during the polyester production process can also be used. Among these, silica particles and calcium carbonate particles are preferred because they are particularly effective even in small amounts. The shape of the particles is not particularly limited, and any of spherical, blocky, rod-like, flat, etc. is acceptable. There are also no particular limitations on the hardness, specific gravity, color, etc. Two or more types of these particles may be used in combination as needed. The average primary particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. If the average primary particle size is 10 μm or less, problems due to a decrease in the transparency of the substrate are unlikely to occur. The average primary particle size of the particles is the cumulative 50% (mass basis) value in the equivalent spherical distribution measured by a centrifugal sedimentation particle size distribution measuring device. When the substrate contains particles, the content of particles is not universally specified because it depends on the average primary particle diameter of the particles, but is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and even more preferably in the range of 0.0005 to 1% by mass, relative to the total mass of the substrate (total mass of the layers containing the particles when the substrate is composed of multiple layers). If the particle content is 5% by mass or less, problems such as particle shedding and a decrease in the transparency of the substrate are unlikely to occur.

[0090] The substrate may contain additives other than the particles as needed, such as known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments. When the substrate is a film, the thickness is not particularly limited as long as it is within a range that allows film formation, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

[0091] (primer layer) The primer layer is appropriately provided between the substrate and the cured film (concave-convex layer) to impart various functions. The primer layer may be a single layer having a single function or multiple functions, or may be composed of multiple layers. In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the substrate and the uneven layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the substrate and the uneven layer is improved, and the laminate can be used for various applications. From the viewpoint of improving adhesion, it is preferable that the adhesion improving layer contains either one or both of a resin and a compound derived from a crosslinking agent. In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, adhesion of dust and the like due to peeling electrification or frictional electrification can be reduced to the outermost surface of the laminate, particularly to the outermost surface on the side of the substrate on which the uneven layer is present. To make the primer layer an antistatic layer, for example, an antistatic agent may be added to the primer layer.

[0092] The resin contained in the primer layer may be a conventionally known resin. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.), etc. Among these, polyester resin, acrylic resin, and urethane resin are preferred in terms of adhesion performance and coating properties. When the substrate is a resin film, the resin contained in the primer layer is preferably the same type of resin as that of the resin film from the viewpoint of affinity with the substrate. For example, when the substrate is a polyester film, the primer layer preferably contains a polyester resin. When the substrate is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

[0093] The polyester resin may be one whose main constituents are a polycarboxylic acid and a polyhydroxy compound. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof. Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, and potassium dimethylolpropionate. One or more of these compounds may be appropriately selected and subjected to a conventional polycondensation reaction to synthesize a polyester resin.

[0094] The acrylic resin is a polymer of a polymerizable monomer including a (meth)acrylic monomer. Examples of the acrylic resin include a homopolymer or copolymer of a (meth)acrylic monomer, and a copolymer of a (meth)acrylic monomer and a polymerizable monomer other than a (meth)acrylic monomer. The acrylic resin may be a copolymer of such a polymer with another polymer (e.g., polyester, polyurethane, etc.). Such copolymers include, for example, block copolymers and graft copolymers. Also included are polymers (and in some cases, polymer mixtures) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyester. Similarly, also included are polymers (and in some cases, polymer mixtures) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyurethane. Similarly, also included are polymers (and in some cases, polymer mixtures) obtained by polymerizing a polymerizable monomer in a solution or dispersion of another polymer. The polymerizable monomer is not particularly limited, but particularly representative compounds include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and salts thereof; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutylhydroxyfumarate, and monobutylhydroxyitaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate, ... Examples of suitable vinyl monomers include alkyl (meth)acrylates such as dihexyl (meth)acrylate and lauryl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide and (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and vinylidene chloride; and conjugated dienes such as butadiene.

[0095] A urethane resin is a polymeric compound having a urethane bond in the molecule, and is typically synthesized by reacting a polyol with a polyisocyanate compound. A chain extender may be used when synthesizing the urethane resin. Examples of polyols used to obtain the urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination of two or more.

[0096] Polycarbonate polyols are obtained by the reaction (dealcoholization reaction) of polyhydric alcohols with carbonate compounds. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

[0097] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

[0098] Examples of polyester polyols include those obtained by reacting a polycarboxylic acid or an acid anhydride thereof with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, and 2-methyl-2-propyl-1,3-propanediol. , 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamines, and lactonediols.

[0099] As the polyol, polyester polyol and polycarbonate polyol are preferred in view of adhesion performance, and polyester polyol is particularly preferred.

[0100] Examples of polyisocyanate compounds used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidenedicyclohexyl diisocyanate. These may be used alone or in combination of two or more. There are no particular limitations on the chain extender as long as it has two or more active groups that react with isocyanate groups, and generally, chain extenders having two hydroxyl groups or two amino groups can be mainly used. Examples of chain extenders having two hydroxyl groups include glycol compounds such as aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and ester glycols such as neopentyl glycol hydroxypivalate. Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropyltrimoniumcyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

[0101] The urethane resin is typically used in the form of a dispersion or solution. The medium for the dispersion or solution may be a solvent, but is preferably water. Aqueous dispersions or solutions of urethane resins include forced emulsification types using an emulsifier, self-emulsification types in which hydrophilic groups have been introduced into the urethane resin structure, and water-soluble types. In particular, self-emulsification types in which ionic groups have been introduced into the urethane resin structure to form an ionomer are preferred, as they have excellent storage stability as well as excellent water resistance and transparency of the resulting primer layer. Examples of the ionic group to be introduced into the structure of the urethane resin include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a quaternary ammonium base, with the carboxyl group being preferred. The carboxyl groups are preferably neutralized with a neutralizing agent such as ammonia, amines, alkali metals, or inorganic alkalis to form salts. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In a urethane resin having carboxyl groups neutralized with a neutralizing agent, the carboxyl groups from which the neutralizing agent is removed during the drying process after application can be used as crosslinking reaction sites with a crosslinking agent. This not only provides excellent stability in the liquid state before coating, but also makes it possible to improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer. Various methods can be used to introduce carboxyl groups into urethane resins at each stage of the polymerization reaction. Examples include using a resin containing carboxyl groups as a copolymerization component during prepolymer synthesis, or using a component containing carboxyl groups as a component of a polyol, polyisocyanate compound, chain extender, etc. Particularly preferred is a method in which a carboxyl group-containing diol is used and the desired amount of carboxyl groups is introduced by adjusting the amount of this component charged. For example, the carboxyl group-containing diol can be copolymerized with the diol used in synthesizing the urethane resin. Examples of carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts of these acids in which the carboxyl group has been neutralized with a neutralizing agent.

[0102] In order to make the primer layer stronger and improve its performance such as adhesion, the primer layer preferably contains a compound derived from a crosslinking agent. Known crosslinking agents can be used, including, for example, melamine compounds, isocyanate compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among these, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred. From the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, isocyanate compounds, and epoxy compounds are more preferred, and melamine compounds, oxazoline compounds, and isocyanate compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. Using two or more crosslinking agents in combination may further improve adhesion and durability.

[0103] A melamine compound is a compound having a melamine skeleton within the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohols to partially or completely etherify them, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be either a monomer or a dimer or higher polymer, or a mixture thereof. Furthermore, melamine partially co-condensed with urea or the like can also be used, and a catalyst can also be used to increase the reactivity of the melamine compound. Considering the reactivity with various compounds, melamine compounds having a hydroxyl group are preferred.

[0104] The isocyanate compound is an isocyanate compound or a compound having an isocyanate derivative structure, such as a blocked isocyanate compound. Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanate compounds having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanate compounds such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isopropylidenedicyclohexyl diisocyanate. Further examples include polymers and derivatives of these isocyanate compounds, such as biuretized products, isocyanurated products, urethodionated products, and carbodiimide-modified products. These may be used alone or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are preferred over aromatic isocyanate compounds, from the viewpoint of avoiding yellowing due to ultraviolet rays. Examples of the blocked isocyanate compound include those in which the isocyanate group of the above-mentioned isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include bisulfites, phenol-based compounds such as phenol, cresol, and ethylphenol, alcohol-based compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, active methylene-based compounds such as dimethyl malonate, diethyl malonate, isobutanoyl methyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan-based compounds such as butyl mercaptan and dodecyl mercaptan, lactam-based compounds such as ε-caprolactam and δ-valerolactam, amine-based compounds such as diphenylaniline, aniline, and ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime-based compounds such as formaldehyde, acetaldoxime, acetoneoxime, methyl ethyl ketoneoxime, and cyclohexanoneoxime. These may be used alone or in combination of two or more. As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferred from the viewpoint that the primer layer is less likely to be destroyed. The isocyanate compound may be used alone or as a mixture or bond with various polymers. In order to improve the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or bond with a polyester resin or a urethane resin.

[0105] The oxazoline compound is a compound having an oxazoline group in the molecule. The oxazoline compound is preferably a polymer containing an oxazoline group. The polymer containing an oxazoline group can be obtained by polymerizing an addition-polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and examples thereof include (meth)acrylates such as alkyl(meth)acrylates (the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid, and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylates Examples of suitable monomers include unsaturated amides such as acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide (the alkyl group can be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, or a cyclohexyl group); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These may be used alone or in combination of two or more. The amount of oxazoline groups per 1 g of oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, even more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. If the amount of oxazoline groups is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

[0106] An epoxy compound is a compound having an epoxy group in the molecule. Examples of epoxy compounds include condensates of epichlorohydrin with compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), such as polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl)isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

[0107] The carbodiimide compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule. From the viewpoint of the strength of the primer layer, the carbodiimide compound is preferably a polycarbodiimide compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule. Carbodiimide compounds can be synthesized by known methods, and generally involve the condensation reaction of a diisocyanate compound. The diisocyanate compound is not particularly limited, and either an aromatic or aliphatic diisocyanate can be used, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate. In order to improve the water solubility or water dispersibility of the polycarbodiimide-based compound, a surfactant may be added, or a hydrophilic monomer such as a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, or a hydroxyalkyl sulfonate may be added, within a range that does not impair the effects of the present invention.

[0108] A silane coupling compound is an organosilicon compound that has an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. Examples of silane coupling compounds include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; (meth)acryloyl group-containing compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; Examples of such compounds include amino group-containing compounds such as N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate and tris(triethoxysilylpropyl)isocyanurate; and mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among the above-mentioned compounds, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl group and (meth)acrylic group, and amino group-containing silane coupling compounds are preferred as the silane coupling compound from the viewpoint of the strength of the primer layer.

[0109] These crosslinking agents react during the drying process and film-forming process to improve the performance of the primer layer. It is presumed that the formed primer layer contains compounds derived from the crosslinking agent, such as unreacted crosslinking agents, reacted compounds, or a mixture thereof.

[0110] The antistatic agent to be contained in the primer layer is not particularly limited, and any known antistatic agent can be used, such as a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, or a conductive organic polymer. The primer layer may contain particles to improve blocking and slip properties. The primer layer may contain additives such as antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments, as needed, within the scope of the present invention.

[0111] The proportion of the resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer will be better. The proportion of the compound derived from the crosslinking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and strength of the primer layer will be better. The thickness of the primer layer cannot be generalized as it depends on the material used in the primer layer and the performance to be achieved, but is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and even more preferably 0.02 to 1 μm. The primer layer can be formed by a known method.

[0112] (Surface functional layer) The surface functional layer is a layer provided on the surface of the cured film (concave-convex layer) opposite the substrate layer to impart various functions. Examples of surface functional layers include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low-reflection layer, etc.), an infrared absorbing layer, an ultraviolet absorbing layer, and a color correction layer. The surface functional layer may be a single layer having a single function or multiple functions, or may be composed of multiple layers.

[0113] The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. Materials used for the antifouling layer include conventionally known materials such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds. Among these, silicone compounds and fluorine compounds are preferred for achieving stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of preventing the antifouling layer from contaminating objects that come into contact with it.

[0114] Silicone compounds refer to compounds having a silicone structure in the molecule, such as alkyl silicones such as dimethyl silicone and diethyl silicone, as well as phenyl silicones and methylphenyl silicones having a phenyl group. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and hydrocarbon groups such as various aromatic groups. Other common functional groups include silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms. It is also possible to use both in combination to form an addition-type silicone (a type resulting from the addition reaction of a vinyl group with a hydrogen silane). Another preferred method involves introducing a double bond such as an acryloyl group and reacting at the double bond. Furthermore, as the silicone compound, modified silicones such as acrylic-grafted silicone, silicone-grafted acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, etc. In consideration of heat resistance and contamination resistance, it is preferable to use a curable silicone resin, and any curing reaction type such as a condensation type, an addition type, or an active energy ray curable type can be used.

[0115] The fluorine compound is a compound containing a fluorine atom. As the fluorine compound, an organic fluorine compound is preferably used, for example, a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, an aromatic fluorine compound such as fluorobenzene, etc. From the viewpoint of mold releasability, a compound having a perfluoroalkyl group is preferable. Furthermore, as the fluorine compound, a compound containing a long-chain alkyl compound as described below can also be used. Examples of compounds having a perfluoroalkyl group include perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl(meth)acrylate, perfluoroalkylmethyl(meth)acrylate, 2-perfluoroalkylethyl(meth)acrylate, 3-perfluoroalkylpropyl(meth)acrylate, 3-perfluoroalkyl-1-methylpropyl(meth)acrylate, and 3-perfluoroalkyl-2-propenyl(meth)acrylate, and polymers thereof; and perfluoroalkyl group-containing vinyl ethers such as perfluoroalkylmethylvinylether, 2-perfluoroalkylethylvinylether, 3-perfluoropropylvinylether, 3-perfluoroalkyl-1-methylpropylvinylether, and 3-perfluoroalkyl-2-propenylvinylether, and polymers thereof. Considering heat resistance and stain resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Furthermore, from the viewpoint of stain resistance, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, the polymer may be a polymer with a compound containing a long-chain alkyl compound, as described below.

[0116] A long-chain alkyl compound is a compound having a linear or branched alkyl group typically having 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably 12 or more carbon atoms. Examples of alkyl groups include hexyl, octyl, decyl, lauryl, octadecyl, and behenyl groups. Examples of compounds having an alkyl group include various long-chain alkyl group-containing polymeric compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. In consideration of heat resistance and stain resistance, polymeric compounds are preferred. Furthermore, from the viewpoint of effectively achieving stain resistance, polymeric compounds having a long-chain alkyl group in the side chain are more preferred. A polymer compound having a long-chain alkyl group in its side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Examples of compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a polyester resin containing a reactive group, and a poly(meth)acrylic resin containing a reactive group. Among these, polyvinyl alcohol is preferred in terms of its antifouling properties and ease of handling. Examples of compounds having an alkyl group capable of reacting with the reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, in consideration of releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred. Furthermore, polymeric compounds having long-chain alkyl groups in their side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0117] The content of the antifouling material described above for achieving antifouling performance in the surface functional layer depends on the material used and cannot be generalized. However, in the case of silicone compounds or fluorine compounds, it is usually 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. Furthermore, when a long-chain alkyl group-containing compound is used, it is usually 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, and the upper limit may be 100% by mass. Using the above range can provide effective antifouling performance.

[0118] As the antistatic agent used in forming the antistatic layer as the surface functional layer, various conventionally known antistatic agents can be used. In addition, a method in which a double bond such as an acryloyl group is introduced into a compound having an ammonium group and the double bond is reacted is also preferred.

[0119] Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof. When the objective is to increase the refractive index, conventionally known materials can be used as the material for the refractive index adjusting layer. Examples of such materials include aromatic-containing compounds such as those with a benzene structure, bisphenol A structure, melamine structure, and fluorene structure; condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structure, which are considered to have high refractive indexes among aromatic compounds; metal-containing compounds such as metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), and ITO (indium tin oxide); and metal chelate compounds such as titanium chelate and zirconium chelate; sulfur-containing compounds; and halogen-containing compounds. Metal oxides are preferably used in the form of particles, since there is a concern that their adhesion may decrease depending on the form of use. From the viewpoint of coating appearance and the like, the average primary particle diameter is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less. When the refractive index is to be reduced, the material of the refractive index adjusting layer can be a conventionally known material, such as a low refractive index acrylic resin or urethane resin. In particular, compounds in which fluorine atoms are incorporated into the resin, such as fluororesins, compounds containing fluororesins in the main skeleton, and compounds containing perfluoroalkyl groups in the side chain, can be used. Inorganic materials can also be hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles or nanoporous particles thereof.

[0120] The thickness of the surface functional layer is preferably 5 times or less, more preferably 2 times or less, the height from the recesses to the protrusions of the uneven structure of the cured film. The smaller this ratio, the less likely the matte performance of the cured film to be reduced. The thickness of the surface functional layer cannot be generalized because it depends on the height from the recesses to the protrusions of the uneven structure of the cured film, but it is usually in the range of 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, even more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. Using a thickness within the above range makes it possible to achieve both the functionality of the surface functional layer and the matte properties of the cured film. The surface functional layer can be formed by a known method.

[0121] (Back functional layer) The back surface functional layer is a layer provided on the surface opposite to the cured film (concave-convex layer) of the base layer to impart various functions. Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjustment layer, and an antiblocking layer. The back surface functional layer may be a single layer having a single function or multiple functions, or may be composed of multiple layers.

[0122] The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to prevent adhesion of dust and the like due to peeling electrification or frictional electrification on the outermost surface of the laminate, particularly on the outermost surface opposite the uneven layer side of the base layer, and to prevent defects caused thereby. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate. The antiblocking layer is provided to reduce blocking of the laminate. Examples of adhesives that can be used to form the adhesive layer include known acrylic, polyester, urethane, and rubber adhesives. Among these, acrylic adhesives are preferred in terms of versatility. The components forming the antistatic layer and the refractive index adjusting layer are the same as those explained for the surface functional layer.

[0123] The thickness of the back functional layer cannot be generalized because it depends on the material used in the back functional layer and the performance to be achieved, but it is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm. The back surface functional layer can be formed by a known method.

[0124] (Formation of surface functional layer and back functional layer) The surface functional layer and the back surface functional layer can be formed, for example, by coating a liquid containing the above-mentioned components as a solution or dispersion in a solvent, adjusted to a solids concentration of approximately 0.1 to 80% by mass, onto a specified surface, and then drying and curing the liquid. Examples of the coating method include conventionally known coating methods such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating, and extrusion coating. The drying and curing conditions for forming the front functional layer and the back functional layer are not particularly limited. However, for the drying of solvents such as water used in the coating liquid, the drying temperature is typically in the range of 50 to 150°C, preferably 80 to 130°C, and more preferably 90 to 120°C. The drying time is typically in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Furthermore, to improve the strength of the front functional layer and the back functional layer, it is preferable to perform a heat treatment after drying, typically in the range of 150 to 270°C, preferably 170 to 230°C, and more preferably 180 to 210°C. The heat treatment time is typically in the range of 3 to 200 seconds, preferably 5 to 120 seconds. This type of heat treatment is suitable when the laminate is a film.

[0125] (Total light transmittance) The laminate preferably has a total light transmittance measured by the method described in the Examples below of preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more, with the higher the better (the upper limit is 100%).

[0126] (Hayes) The haze of the laminate measured by the method described in the Examples below is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, particularly preferably 10% or more, and most preferably 20% or more, with the upper limit being, for example, 99%. The higher the haze, the better the matte properties tend to be. Furthermore, particularly when used for anti-glare applications in various displays, the range is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more, with the upper limit being, for example, 99%. Depending on the application, the higher the range, the more preferable it is. [Example]

[0127] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The measurement and evaluation methods used in the present invention are as follows.

[0128] (1) Intrinsic viscosity of polyester 1 g of polyester from which components incompatible with the polyester had been removed was precisely weighed, dissolved in 100 ml of a mixed solvent of phenol / tetrachloroethane = 50 / 50 (weight ratio), and measured at 30°C.

[0129] (2) Average primary particle diameter (d50:μm) The cumulative 50% (by weight) value in the equivalent sphericity distribution measured using a centrifugal sedimentation particle size distribution analyzer, Model SA-CP3, manufactured by Shimadzu Corporation, was taken as the average primary particle size.

[0130] (3) Weight average molecular weight (Mw) of acrylic polymer The weight-average molecular weight (Mw) of the acrylic polymer was measured using a gel permeation chromatography (GPC) "HLC-8120" (manufactured by Tosoh Corporation). The column used was a TSKgel G5000HXL*GMHXL-L (manufactured by Tosoh Corporation). A calibration curve was created using standard polystyrenes F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (manufactured by Tosoh Corporation) and styrene. Measurements were performed at a column oven temperature of 40°C using 100 μl of a solution prepared by dissolving the polymer in tetrahydrofuran to a concentration of 0.4%. The weight-average molecular weight (Mw) was calculated in terms of standard polystyrene.

[0131] (4) RSm, Sa and tilt angle (θa) Using a surface profile measurement system (Hitachi High-Tech Science Corporation's scanning white light interference microscope "VS1330"), the surface profile of a 177.60 μm x 236.87 μm area on the surface of the cured film was measured by optical interferometry, and the data was analyzed. The evaluation length used to calculate RSm and θa was 236.87 μm. The magnification of the objective lens during measurement was set to 20x. The presence or absence of a wrinkled uneven structure was also confirmed during this evaluation. The processing conditions used for data analysis are as follows. Surface correction: 4th order Interpolation: Full Interpolation Filter: Median 3x3 pixels Boundary processing: Symmetrical expansion and edge interpolation Trimming: None

[0132] (5) Total light transmittance / haze The measurement object was a laminate consisting of a cured film formed on a substrate. Total light transmittance and haze were measured using a Nippon Denshoku Industries haze meter "SH7000" in accordance with JIS Z8722:2009 (geometric conditions for irradiating and receiving light on a transparent object), JIS K7361-1:1997 (test method for total light transmittance of plastic transparent materials), and JIS K7136:2000 (determination of haze for plastic transparent materials).

[0133] (6) 20° and 60° gloss and matte The measurement object was a laminate having a cured film formed on a substrate. The 20° and 60° gloss (20° and 60° specular gloss) was measured in accordance with JIS Z 8741-1997 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. The lower the gloss value, the better the matte properties.

[0134] (7) Curability The curable composition was applied and dried by the method described in Examples and Comparative Examples, and then exposed to an illuminance of 100 mW / cm 2 using only a high-pressure mercury lamp in an air atmosphere. 2 When irradiated with ultraviolet light from a UV conveyor of a high-output UV device (model US5-X1802-X1202) manufactured by Eye Graphics, the cumulative light dose (mJ / cm) until the coating surface becomes non-sticky when touched with a finger is measured. 2 ) was evaluated. The smaller the cumulative amount of light required to remove stickiness, the better the curability and the higher the productivity of the cured film. In addition, even if problems such as attenuation of the vacuum ultraviolet light irradiation due to oxygen occur, the coating equipment is less likely to be contaminated. The evaluation criteria for curability are as follows: A: 200mJ / cm 2 Stickiness disappears with the following cumulative light intensity B: 200 mJ / cm 2Over 400mJ / cm 2 Stickiness disappears with the following cumulative light intensity C: 400mJ / cm 2 Over 1000mJ / cm 2 Stickiness disappears with the following cumulative light intensity D: 1000mJ / cm 2 Over 3000mJ / cm 2 Stickiness disappears with the following cumulative light intensity E: 3000mJ / cm 2 With more accumulated light, stickiness disappears

[0135] (8)Pencil hardness The pencil hardness of the cured film was measured in accordance with JIS K5600-5-4:1999 General testing methods for paints - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method).

[0136] (9) Matte finish The laminate was placed in a room lit by a white linear fluorescent lamp, and the distance between the fluorescent lamp and the laminate was set at 2.5 m. The matte appearance of the uneven layer side (reflection of the fluorescent lamp) was visually evaluated according to the following evaluation criteria A to D. Evaluations A to C indicate that the matte appearance could be confirmed. A: The reflected image of the fluorescent light is very blurred and the outline of the fluorescent light cannot be seen. B: The reflected image from the fluorescent light is blurred, but you can still see a faint outline. C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be seen, it appears wavy and dark white. D: The reflected image of the fluorescent light is clear and the outline can be clearly seen, and it appears linear and white.

[0137] The materials used in the examples and comparative examples are as follows. (base material) Polyester (S1): Polyethylene terephthalate homopolymer with an intrinsic viscosity of 0.63 dl / g obtained using magnesium acetate tetrahydrate and tetrabutyl titanate as polymerization catalysts. Polyester (S2): Polyethylene terephthalate homopolymer with an intrinsic viscosity of 0.64 dl / g obtained using magnesium acetate tetrahydrate, orthophosphoric acid and germanium dioxide as polymerization catalysts. · Polyester (S3): Polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles with an average primary particle diameter of 2 μm.

[0138] (Production of Polymer (A1-1) Having Unsaturated Double Bonds) A polymer (A1-1) having an unsaturated double bond was prepared by the following method. Propylene glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (98.0 parts by mass), methyl methacrylate (1.0 part by mass), ethyl acrylate (1.0 part by mass), 3-mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (1.0 part by mass) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was reacted at 65°C for 3 hours. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was added and the mixture was reacted for 3 hours, after which propylene glycol monomethyl ether (98 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (50.0 parts by mass) and triphenylphosphine (1.6 parts by mass) were added, and the mixture was reacted at 110°C for 6 hours to obtain a polymer (A1-1) having an unsaturated double bond with a radically polymerizable double bond in the side chain, with a double bond amount (acryloyl group concentration (amount of acryloyl group introduced)) of 4.50 mmol / g and a weight-average molecular weight of 19,700.

[0139] (Production of Polymer (A1-2) Having Unsaturated Double Bonds) A polymer (A1-2) having an unsaturated double bond was prepared by the following method. Propylene glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (66 parts by mass), methyl methacrylate (33 parts by mass), ethyl acrylate (1.0 part by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (0.8 parts by mass) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was reacted for 3 hours at 65°C. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.4 parts by mass) was added and the mixture was reacted for 3 hours, after which propylene glycol monomethyl ether (58 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (30.4 parts by mass) and triphenylphosphine (1.6 parts by mass) were added, and the mixture was reacted at 110°C for 6 hours to obtain a polymer (A1-2) having an unsaturated double bond with a radically polymerizable double bond in the side chain, with a double bond amount (acryloyl group concentration (amount of acryloyl group introduced)) of 3.45 mmol / g and a weight-average molecular weight of 37,600.

[0140] (Production of Polymer (A1-3) Having Unsaturated Double Bonds) A polymer (A1-3) having an unsaturated double bond was prepared by the following method. Propylene glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate (79 parts by mass), ethyl acrylate (1.0 part by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (0.6 parts by mass) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was allowed to react for 3 hours at 65°C. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was added and the mixture was allowed to react for 3 hours, after which propylene glycol monomethyl ether (20 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added, and the mixture was reacted at 110°C for 6 hours to obtain a polymer (A1-3) having an unsaturated double bond with a radically polymerizable double bond in the side chain, with a double bond amount (acryloyl group concentration (amount of acryloyl group introduced)) of 1.27 mmol / g and a weight-average molecular weight of 42,700.

[0141] (Curable composition) The materials shown below were mixed in the amounts (parts by mass, calculated as nonvolatile content) shown in Table 1. Next, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM:MEK (mass ratio) 7:3) was added so that the solid content concentration was 30 mass %, and the mixture was stirred until homogenous to obtain a curable composition (coating liquid) used in each of the Examples and Comparative Examples. Polymer (A1-1): Polymer (A1-1) having an unsaturated double bond produced by the above method Polymer (A1-2): Polymer (A1-2) having an unsaturated double bond produced by the above method Polymer (A1-3): Polymer (A1-3) having an unsaturated double bond produced by the above method Polymer with unsaturated double bonds (A2-1): Modified epoxy acrylate (EBECRYL 3708, manufactured by Daicel-Allnex Co., Ltd.) (Meth)acrylate (B-1): 6-hexanediol diacrylate (bifunctional) (Meth)acrylate (B-2): Urethane acrylate (Mitsubishi Chemical Corporation, Shiko UV-1700B) Particles (C): Cross-linked acrylic particles with an average particle size of 1.8 μm (MX-180TA manufactured by Soken Chemical & Engineering Co., Ltd.) Photopolymerization initiator (E): Omnirad 184 manufactured by IGM Resins BV

[0142] [Table 1]

[0143] (Composition for forming primer layer) The polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) shown below were mixed in a solid content mass ratio of polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) = 60 / 25 / 10 / 5 to obtain a composition for forming a primer layer. Polyester resin (P1): Aqueous dispersion of polyester resin having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid / / (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56 / 40 / 4 / / 70 / 20 / 10 (mol%) Urethane resin (P2): Aqueous dispersion of polyester-based urethane resin with the following composition Isophorone diisocyanate: terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12:19:18:21:25:5 (mol%) Melamine compound (P3): Hexamethoxymethylolmelamine Particles: (P4): Silica particles with an average primary particle diameter of 0.07 μm

[0144] (Polyester film base) The raw material for the outermost layer (surface layer) was a mixture of polyesters (S1), (S2), and (S3) in proportions of 91%, 3%, and 6% by mass, respectively, and the raw material for the middle layer was a mixture of polyesters (S1) and (S2) in proportions of 97% and 3% by mass, respectively. Each of these materials was fed into two extruders, melted at 285°C, and then co-extruded onto a cooling roll set at 40°C in a layer structure of two types and three layers (surface layer / middle layer / surface layer = discharge rate 1:8:1), cooled, and solidified to obtain an unstretched sheet. Next, the film was stretched 3.1 times in the longitudinal direction at a film temperature of 85°C using the difference in roll peripheral speed, and then a composition for forming a primer layer was applied to one side of this longitudinally stretched film, which was then introduced into a tenter and dried at 95°C for 10 seconds.Then, the film was stretched 4.2 times in the transverse direction at 120°C, heat-treated at 230°C for 10 seconds, and then relaxed 2% in the transverse direction to obtain a polyester film substrate 50 μm thick (after drying) with a 0.1 μm thick primer layer on one side.

[0145] [Examples 1 to 7] The coating solution shown in Table 1 was applied onto the primer layer of the polyester film using a bar coater and dried for 1 minute at 70°C. The resulting coating film was then irradiated with excimer light (half width 14 nm) from xenon (wavelength 172 nm) at an irradiation dose of 15 mJ / cm. 2 , illuminance 5mW / cm 2 (Ushio Inc. xenon excimer 172 nm light irradiation device, lamp unit model: SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less)) and then irradiated with a high-pressure mercury lamp in an air atmosphere with an integrated light dose of 400 mJ / cm 2 , illuminance 200mW / cm 2 The laminate was irradiated with ultraviolet light from a UV conveyor of a high-power UV device (model US5-X1802-X1202) manufactured by Eye Graphics Co., Ltd., to form a cured film having a wrinkled uneven structure with a thickness (after drying) of 5 μm, thereby obtaining a laminate. Separately, the coating liquid shown in Table 1 was applied to the laminate, and the curability was evaluated for a sample that was dried at 70°C for 1 minute. The laminate obtained had good scratch resistance (pencil hardness) and matte finish. All evaluation results are shown in Table 2.

[0146] [Comparative Examples 1 to 4] A laminate having a cured film was obtained in the same manner as in the examples, except that the coating agent composition was changed to the coating agent composition shown in Table 1. All evaluation results of the obtained laminate are shown in Table 2.

[0147] Comparative Example 5 In Example 6, instead of excimer light, a high-pressure mercury lamp was used in an air atmosphere with an integrated light dose of 250 mJ / cm 2 , illuminance 100mW / cm 2 A laminate having a cured film was obtained in the same manner as in Example 6, except that ultraviolet light was irradiated using a UV conveyor of a high-output UV device (model: US5-X1802-X1202) manufactured by Eye Graphics. When the obtained laminate was evaluated, as shown in Table 2, no uneven structure was formed and it was not matte.

[0148] [Table 2]

Claims

1. A cured film having a wrinkled uneven structure on its surface, formed by irradiating a coating film of an active energy ray-curable composition with excimer light to cure the surface side of the coating film and then irradiating the coating film with ultraviolet light other than vacuum ultraviolet light to cure the interior of the coating film, thereby buckling the cured coating film, wherein the cured film has a wrinkled uneven structure on its surface, wherein the active energy ray-curable composition contains a polymer (A) having an unsaturated double bond in its main chain or side chain and a polyfunctional (meth)acrylate (B), and the polymer (A) is a (meth)acrylic acid ester copolymer (A1) having an unsaturated double bond.

2. The cured film according to claim 1 , wherein the content of particles in the active energy ray-curable composition is 30 mass % or less based on the nonvolatile content.

3. 3. The cured film according to claim 2, wherein the particles are at least one type of particles selected from silica particles, hollow silica particles, calcium carbonate particles, magnesium carbonate particles, barium carbonate particles, calcium sulfate particles, calcium phosphate particles, magnesium phosphate particles, kaolin particles, aluminum oxide particles, zirconium oxide particles, titanium oxide particles, acrylic resin particles, styrene resin particles, urea resin particles, phenolic resin particles, epoxy resin particles, and benzoguanamine resin particles.

4. The cured film according to claim 2 or 3, wherein the particles have an average primary particle size of 0.01 to 30 μm.

5. The cured film according to any one of claims 1 to 4, wherein the uneven structure has a mean length (RSm) of roughness curve elements according to JIS B0601:2013 of 1 to 50 µm and an arithmetic mean height (Sa) defined in ISO 25178 of 0.1 to 5 µm.

6. The cured film according to any one of claims 1 to 5, wherein the average value (θa) of the local tilt angles in the concave-convex structure is 2° or more.

7. The cured film according to any one of claims 1 to 6, which has a 60° gloss of 50 or less.

8. The method for producing a cured film according to any one of claims 1 to 7, wherein an active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth)acrylate (B) is irradiated with excimer light and then irradiated with ultraviolet light other than vacuum ultraviolet light.

9. A laminate having the cured film according to any one of claims 1 to 7 on a substrate.

10. The laminate according to claim 9 , wherein the substrate is a film.

11. 11. The method for producing a laminate according to claim 9 or 10, comprising: laminating an active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth)acrylate (B) on a substrate; irradiating the active energy ray-curable composition with excimer light; and then irradiating the composition with ultraviolet light other than vacuum ultraviolet light to cure the composition.

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