Cured film and laminate, and method for producing the same

Abstract

To provide a cured film and a laminate, excellent in delustering properties and antistatic properties; 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 the cured film has a wrinkle-like uneven structure on the surface thereof, and contains an antistatic agent. Provided is a method for producing the cured film, in which the curable composition containing the antistatic agent is laminated, and irradiated with excimer light to be cured. Provided is a laminate formed by having the cured film laminated on a base material. Provided is a method for producing the laminate, in which the curable composition containing the antistatic agent is laminated on a base material, and is cured by irradiation with the excimer light.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 members, decorative films, and other members, fine irregularities are sometimes imparted to the surface of a substrate. In addition, these members are sometimes required to have antistatic properties. Patent Document 1 discloses a method for forming fine projections and recesses by irradiating the surface of a biaxially oriented thermoplastic resin film used in a magnetic recording medium 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 antireflection 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] JP 2014-224920 A 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. In addition, since the unevenness is formed directly on the biaxially oriented thermoplastic resin film, it is difficult to apply the film 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, so the particles tend to fall off, which may impair visibility when used in displays, etc. In addition, there is a problem 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 having excellent matte properties and antistatic properties, 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, the cured film having a wrinkled uneven structure on the surface and containing an antistatic agent. [2] A cured film obtained by irradiating an active energy ray-curable composition with active energy rays, the cured film having a wrinkled uneven structure on the surface, substantially containing no particles, a 60° gloss of 50 or less, and a surface resistivity of 1.0×10 13 A hardened film with a hardness of Ω or less. [3] The cured film according to [1] or [2] above, wherein the curable composition contains a (meth)acrylate. [4] The cured film according to any one of [1] to [3] above, wherein the uneven structure has a mean length of roughness curve elements (RSm) according to JIS B0601:2013 of 1 μm or more. [5] The cured film according to any one of the above [1] to [4], wherein the uneven structure has an arithmetic mean height (Sa) defined by ISO 25178 of 0.1 μm or more. [6] The cured film according to any one of the above [1] to [5], wherein the average value (θa) of the local tilt angle of the uneven structure is 2° or more. [7] The cured film according to any one of the above [1] to [6], wherein the 60° gloss of the surface is 30 or less. [8] The method for producing a cured film according to any one of the above [1] to [7], comprising laminating a curable composition containing an antistatic agent, and curing the composition by irradiating it with excimer light. [9] A laminate comprising the cured film according to any one of the above [1] to [7] laminated on a substrate.

[10] The laminate according to [9] above, wherein the substrate is a film.

[11] A method for producing a laminate according to [9] or

[10] above, comprising laminating a curable composition containing an antistatic agent on a substrate and curing the composition by irradiating it with excimer light.

[12] A method for producing a laminate according to [9] or

[10] above, comprising laminating a curable composition substantially free of particles on a substrate, and curing the composition by irradiating it with excimer light. Effect of the Invention

[0006] The cured film and laminate of the present invention are excellent in matte property and antistatic property. According to the method for producing the cured film and laminate of the present invention, a cured film and laminate having excellent matte property and antistatic property can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Hereinafter, an embodiment 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. "~" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0008] [Cured film] The cured film of the present invention (hereinafter simply referred to as "cured film") is produced 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 first cured film of the present invention is a cured film having a wrinkled uneven structure on the surface and containing an antistatic agent. The second cured film of the present invention is a cured film having a wrinkled uneven structure on the surface, substantially containing no particles, having a 60° gloss of 50 or less, and a surface resistivity of 1.0×10 13 The cured film of the present invention has an anti-glare film having an excellent matte property and antistatic property.

[0009] (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 better. The smaller the 60° gloss value, the better the matte property. 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 property.

[0010] (Surface resistance value) The surface resistance of the cured film is preferably 1.0×10 13 Ω or less, more preferably 1.0×10 12 Ω or less, more preferably 1.0×10 11 Ω or less, particularly preferably 1.0×10 10 Ω or less, and there is no particular lower limit, but it is preferably 1.0×10 3 Ω or more, preferably 1.0×10 8 The smaller the surface resistance, the better the antistatic properties, and the more easily the adhesion of dust and the like can be prevented.

[0011] (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 also simply referred to as "RSm") according to JIS B0601:2013. The evaluation length for calculating RSm was 236.87 μm. The preferred range of RSm is 1 μm or more, more preferably 2 to 100 μm, even more preferably 3 to 60 μm, particularly preferably 4 to 50 μm, and most preferably 5 to 25 μm. Within the above range, excellent matte properties are obtained, and excellent visibility is obtained when used in displays, etc.

[0012] (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 by ISO25178. The evaluation area for calculating Sa was 177.60 μm × 236.87 μm. Sa is preferably 0.1 μm or more, more preferably 0.15 to 20 μm, even more preferably 0.2 to 10 μm, particularly preferably 0.3 to 5 μm, and most preferably in the range of 0.4 to 3 μm. When within the above range, excellent matte properties are achieved, and excellent visibility is achieved when used in displays, etc.

[0013] (Average value of the inclination 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 described later. 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°. When it is in this range, it has good matte properties.

[0014] (Thickness) From the viewpoint of improving the matte property, 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, further 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.

[0015] (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 further 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.

[0016] [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 surface side of the coating film (the side opposite to the substrate) with active energy rays to form a cured film on the surface of the substrate. By irradiating the surface side of the coating film of the curable composition with active energy rays, the surface side of the coating film is cured first to form a cured coating. When the inside of the coating film subsequently cures, the cured coating on the surface side that has cured first buckles, forming a cured film having a wrinkled uneven structure on the surface.

[0017] (Curable composition) The curable composition used to form the cured film contains an antistatic agent. The curable composition may further contain an active energy ray-curable compound, an organic solvent, a photopolymerization initiator, and other components.

[0018] (Antistatic agent) The curable composition may contain an antistatic agent for the purpose of imparting antistatic properties to the cured film. The imparting of antistatic properties can contribute to preventing adhesion of foreign matter such as dust due to peeling static electricity. The antistatic agent is not particularly limited, and a conventionally known antistatic agent can be used. Examples of the antistatic agent include organic compounds such as polymeric and surfactant types, and inorganic compounds such as metal oxides. Among these, organic compounds are preferred because of the ease of forming a concave-convex structure. Furthermore, polymeric types are more preferred from the viewpoints of heat resistance, moist heat resistance, and durability. Examples of polymeric antistatic agents include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive polymers. The antistatic agent may also be a compound having an active energy ray-curable functional group. An example of the active energy ray-curable functional group is a (meth)acryloyl group. By containing the functional group, it can contribute to the formation of a concave-convex structure and also contribute to the improvement of properties such as scratch resistance.

[0019] The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium group is preferably a polymer type compound having an ammonium group. The ammonium group is preferably a structure in which it is incorporated in the main chain or side chain of the polymer, not as a counter ion. In addition, among the polymers, those that can increase the concentration of ammonium groups are preferable in order to effectively impart antistatic properties, and for this purpose, (meth)acrylic polymers are preferable. For example, a polymer having an ammonium group can be obtained by polymerizing a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine. The polymer may be a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine, which is polymerized alone, or may be a copolymer of a monomer containing these and another monomer. Examples of the ammonium group or the precursor monomer of the ammonium group such as amine include (meth)acrylic acid esters of amino alcohols, specifically, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, and N,N-dihydroxyethylaminoethyl (meth)acrylate, with N,N-dimethylaminoethyl (meth)acrylate being particularly preferred. The two alkyl groups of the N,N-dialkylamino group may be different. An example of the ammonium group of the N,N-dialkylamino group-containing monomer is a commercially available N,N-dimethylaminoethyl methacrylate quaternized with methyl chloride [for example, the product name "Light Ester (registered trademark) DQ-100" manufactured by Kyoeisha Chemical Co., Ltd.]. The ammonium group of the N,N-dialkylamino group-containing monomer can also be produced, for example, by a quaternization reaction of a (meth)acrylic acid ester of an amino alcohol.

[0020] In the case of a (meth)acrylic polymer, it may contain a polymerizable monomer unit other than an ammonium group or a precursor monomer of an ammonium group such as an amine. Examples of such a polymerizable monomer include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate; (meth)acrylic acid esters of the above amino alcohols; 2-hydroxyethyl (meth)acrylate, 2-methylethyl (meth)acrylate, and 2-methylethyl (meth)acrylate; and the like. Examples of the hydroxyalkyl (meth)acrylates include hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate; various (meth)acrylates such as benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, butoxyethyl (meth)acrylate, cyanoethyl (meth)acrylate, and glycidyl (meth)acrylate; styrene; and methylstyrene. These may be used alone or in combination of two or more. Among these, when a polymerizable monomer having a highly hydrophobic long-chain alkyl group is contained, it is preferable because it can be segregated at the air interface of the cured film to enhance the antistatic property of the cured film. The polymerizable monomer having such a long-chain alkyl group is preferably an alkyl(meth)acrylate having 8 to 30 carbon atoms, more preferably an alkyl(meth)acrylate having 12 to 22 carbon atoms, such as lauryl(meth)acrylate, tridecyl(meth)acrylate, and stearyl(meth)acrylate. The ratio of ammonium group-containing monomer units in the (meth)acrylic polymer (polymer) of a compound having an ammonium group is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. The higher this ratio, the higher the antistatic property, and the lower this ratio, the better the appearance of the cured layer after application, so using it within the above range will achieve a good balance. The ratio of long-chain alkyl group-containing monomer units in the polymer is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. Using it within the above range makes it easier to develop antistatic properties.

[0021] The weight average molecular weight of the (meth)acrylic polymer containing an ammonium group is preferably 800 to 120,000, and more preferably 2,000 to 60,000.

[0022] The (meth)acrylic polymer having an ammonium group can be produced by radical polymerization reaction 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. Examples of organic solvents used in radical polymerization reactions 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. Examples of radical polymerization initiators used in the radical polymerization reaction 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 mass relative to 100 parts by mass of the total of the raw material monomers. In addition, in the case of radical polymerization reaction, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the polymer. 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-(ethylenediaminetetraacetate), ... Examples of the thiol-based compounds include thiol compounds such as oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decane trithiol, 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. 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, based on 100 parts by weight of the total of the raw material monomers. The reaction time of the radical polymerization reaction 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.

[0023] Examples of polyether compounds that can be blended as antistatic agents include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol in the side chain.

[0024] The compound having a sulfonic acid group that can be blended as an antistatic agent is a compound that contains sulfonic acid or a sulfonate salt in the molecule. For example, a compound having a sulfonic acid group that contains a large amount of sulfonic acid or a sulfonate salt, such as polystyrene sulfonic acid, can be mentioned as a suitable compound having a sulfonic acid group.

[0025] Examples of conductive polymers that can be blended as antistatic agents include polythiophenes, polyanilines, polypyrroles, and polyacetylenes. Among them, polythiophenes, such as poly(3,4-ethylenedioxythiophene) used in combination with polystyrene sulfonic acid, are preferably used. Conductive polymers are more suitable than the other antistatic agents mentioned above in that they have a low resistance. However, conductive polymers are expensive and may cause coloring of the cured film, so it is advisable to appropriately select the type and reduce the amount used.

[0026] Examples of surfactants that can be blended as an antistatic agent include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Among these, from the viewpoint of improving antistatic properties and compatibility with various resins, anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are particularly preferred. Examples of anionic surfactants include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates, and ester sulfonates, phosphoric acid types such as alkyl phosphates or their salts, and polyoxyalkylene alkyl ether phosphates or their salts, sulfate types such as alkyl sulfates and alkyl ether sulfates, and carboxylate types such as alkyl fatty acid salts. Among these, sulfonic acid types are preferred from the viewpoint of excellent antistatic properties. Examples of sulfonic acid type anionic surfactants include alkyl sulfonates such as decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecylsulfonate, and octadecyl sulfonate, alkyl aryl sulfonates such as butyl benzene sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, decyl benzene sulfonate, dodecyl benzene sulfonate, tetradecyl benzene sulfonate, hexadecyl benzene sulfonate, octadecyl benzene sulfonate, dibutyl naphthalene sulfonate, and triisopropyl naphthalene sulfonate, and ester sulfonates such as dibutyl sulfosuccinate, dioctyl sulfosuccinate, dodecyl sulfoacetate, and nonylphenoxy polyethylene glycol sulfoacetate. Among these, from the viewpoint of excellent antistatic properties, the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and more preferably 12 to 18. The salt is preferably a metal salt, more preferably an alkali metal salt such as lithium, sodium or potassium, and even more preferably a sodium salt. As for the type, alkylsulfonate is preferred from the viewpoint of antistatic properties. Examples of the phosphoric acid type anionic surfactants include alkyl phosphoric acid esters or salts thereof such as butyl phosphoric acid ester, butyl phosphoric acid ester salts, hexyl phosphoric acid ester, hexyl phosphoric acid ester salts, octyl phosphoric acid ester, octyl phosphoric acid ester salts, decyl phosphoric acid ester, decyl phosphoric acid ester salts, lauryl phosphoric acid ester, lauryl phosphoric acid ester salts, tetradecyl phosphoric acid ester, tetradecyl phosphoric acid ester salts, hexadecyl phosphoric acid ester, hexadecyl phosphoric acid ester salts, stearyl phosphoric acid ester, and stearyl phosphoric acid ester salts; polyoxyethylene butyl ether phosphate, polyoxyethylene butyl ether phosphate salts, polyoxyethylene hexyl ether phosphate, polyoxyethylene hexyl ether phosphate salts, polyoxyethylene octyl ether phosphate, polyoxyethylene octyl ether phosphate salts, polyoxyethylene decyl ether phosphate, and polyoxyethylene Examples of the polyoxyalkylene alkyl ether phosphate ester include polyoxyalkylene alkyl ether phosphate esters or salts thereof, such as polyoxyethylene decyl ether phosphate salts, polyoxyethylene lauryl ether phosphate ester, polyoxyethylene lauryl ether phosphate salts, polyoxyethylene tetradecyl ether phosphate ester, polyoxyethylene tetradecyl ether phosphate salts, polyoxyethylene hexadecyl ether phosphate ester, polyoxyethylene hexadecyl ether phosphate salts, polyoxyethylene stearyl ether phosphate ester, polyoxyethylene stearyl ether phosphate salts, polyoxypropylene octyl ether phosphate ester, polyoxypropylene octyl ether phosphate ester salts, polyoxypropylene decyl ether phosphate ester, polyoxypropylene decyl ether phosphate ester salts, polyoxypropylene lauryl ether phosphate ester, and polyoxypropylene lauryl ether phosphate salts. Among these, from the viewpoints of surfactant performance and antistatic performance, alkyl phosphate salts and polyoxyalkylene alkyl ether phosphate esters or salts thereof are preferred. As for the alkyl phosphate salts, the number of carbon atoms in the alkyl group is 4 or more, preferably 4 to 22, and more preferably in the range of 6 to 12, and as for the polyoxyalkylene alkyl ether phosphate ester or a salt thereof, the number of carbon atoms in the alkyl group is 4 or more, preferably 6 to 22, and more preferably in the range of 8 to 18. As the salts, metal salts and amine salts are preferred, and in particular, alkali metal salts such as lithium, sodium, and potassium, alkylamine salts, and alcoholamine salts are more preferred, and sodium salts and monoethanolamine salts are even more preferred.

[0027] The content of the antistatic agent in the curable composition forming the cured film is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and most preferably 2.0% by mass or more, based on the nonvolatile content (all components excluding the solvent). There is no particular limit to the upper limit, and it may be 100% by mass, but in consideration of the hardness of the cured film, it is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less. When it is equal to or more than the lower limit, the antistatic property is excellent. The non-volatile content of the curable composition is the total mass of components other than the solvent such as the organic solvent. The non-volatile 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.

[0028] (Active energy ray curable compound) In the active energy ray curable composition, it is also preferred that an active energy ray curable compound is blended in order to facilitate the formation of the uneven structure of the cured film, improve scratch resistance, and improve hardness. Examples of the active energy ray curable compound include (meth)acrylate. There is no particular limitation on the (meth)acrylate, and it is possible to use monofunctional (meth)acrylate, bifunctional (meth)acrylate, trifunctional or higher polyfunctional (meth)acrylate, or a commercially available active energy ray curable resin material, or a material further containing other components within a range that does not impair the purpose of this embodiment. As the (meth)acrylate, a monofunctional or bifunctional (meth)acrylate is preferred from the viewpoint of easily forming a wrinkled uneven structure. In order to increase the hardness and scratch resistance of the cured film, a trifunctional or higher polyfunctional (meth)acrylate is generally preferred. However, according to the study by the present inventors, depending on the type of trifunctional or higher polyfunctional (meth)acrylate, it may be difficult to form a wrinkled uneven structure, so it is advisable to appropriately select the type or reduce the amount of the compounded.

[0029] Examples of the bifunctional polyfunctional (meth)acrylate 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, tricyclodecanedimethylol di(meth)acrylate, bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, and epoxy di(meth)acrylate. Among these, in consideration of the ease of forming a wrinkled uneven structure, a structure without a branch is preferable, and alkyl diol di(meth)acrylate is more preferable, and alkyl diol di(meth)acrylate having 4 to 18 carbon atoms is even more preferable.

[0030] Examples of the active energy ray-curable monofunctional (meth)acrylate 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, and methoxypropyl (meth)acrylate. alkoxyalkyl (meth)acrylates such as ethoxypropyl (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, and tetrahydrofurfuryl (meth)acrylate.

[0031] Examples of the trifunctional or higher polyfunctional (meth)acrylate include ethylene oxide-modified (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(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 isocyanuric acid modified tri(meth)acrylates such as ethylene oxide-modified isocyanuric acid tri(meth)acrylate, 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 consideration of the ease of forming a wrinkled uneven structure.

[0032] The curable composition may contain an active energy ray-curable compound other than (meth)acrylate. Examples of such compounds include vinyl compounds such as (meth)acrylic acid, styrene, vinyl halides, and vinyl acetate, and diene compounds such as vinylidene halides, 1,3-butadiene, isoprene, and chloroprene.

[0033] When an active energy ray-curable compound is blended in the curable composition, the content thereof is preferably 5 to 99.99 mass%, more preferably 30 to 99.9 mass%, further preferably 40 to 95 mass%, particularly preferably 50 to 90 mass%, and most preferably 60 to 80 mass% based on the non-volatile content. When in the above range, a wrinkled uneven structure is easily formed, and a cured film having excellent hardness can be formed.

[0034] (resin) The curable composition may further contain various resins for the purpose of improving adhesion to a substrate, and examples of such resins include conventionally known resins such as acrylic resins, polyester resins, polyurethane resins, polyvinyl resins, etc. Among these, acrylic resins are preferred in terms of excellent transparency and adhesion. When the curable composition contains a resin, the content of the resin is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the non-volatile content. The lower the content, the higher the hardness of the cured film tends to be.

[0035] In consideration of improving scratch resistance and hardness, the resin to be blended in the curable composition preferably has an active energy ray-curable functional group such as a carbon-carbon double bond. Examples of the active energy ray-curable functional group include a (meth)acryloyl group and a vinyl ether compound. Among these, in consideration of ease of introduction and reactivity, a (meth)acryloyl group, particularly an acryloyl group, is preferred.

[0036] The inventors of the present application have found that blending a resin having an active energy ray-curable functional group not only improves the properties attributable to the active energy ray-curable functional group, such as improved scratch resistance and hardness, but also makes the wrinkled uneven structure finer. That is, it has been found that RSm and Sa become smaller. In addition, there are cases where the haze becomes higher and the gloss becomes lower. These properties can exert a synergistic effect on the matte property, and are important properties, especially in applications where visibility is important, such as display applications.

[0037] Examples of methods for producing acrylic resins having functional groups of active energy rays such as carbon-carbon double bonds include a method of reacting an acrylic resin having an epoxy group with a compound having a double bond and a carboxyl group (Method 1), a method of reacting an acrylic resin having a carboxyl group with a compound having a double bond and an epoxy group (Method 2), a method of reacting an acrylic resin having a hydroxyl group with a compound having a double bond and a carboxyl group (Method 3), a method of reacting an acrylic resin having a carboxyl group with a compound having a double bond and a hydroxyl group (Method 4), a method of reacting an acrylic resin having an isocyanate group with a compound having a double bond and a hydroxyl group (Method 5), and a method of reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (Method 6). The above methods may be used in combination. In the following, a radically polymerizable monomer having a carbon-carbon double bond may be referred to as a vinyl monomer.

[0038] In the above-mentioned method 1, examples of vinyl monomers having an epoxy group used to obtain an acrylic resin 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 preferable, and glycidyl methacrylate is particularly preferable, in consideration of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

[0039] In addition, examples of the compound having a double bond and a carboxyl group in the 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. The compound having a double bond and a carboxyl group may be used alone or in combination of two or more.

[0040] In the method 2, examples of the vinyl monomer having a carboxyl group used to obtain an acrylic resin 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.

[0041] In the method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Among these, glycidyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.

[0042] In the method 3, examples of the vinyl monomer having a hydroxyl group used to obtain an acrylic resin having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0043] In the method 3, the compound having a double bond and a carboxyl group may be the same as the compound in the method 1.

[0044] In the method 4, the acrylic resin having a carboxyl group may be the same as that in the method 2.

[0045] In the method 4, examples of the compound having a double bond and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0046] In the method 5, examples of the vinyl monomer having an isocyanate group used to obtain an acrylic resin having an isocyanate group include isocyanate ethyl (meth)acrylate.

[0047] In the method 5, the compound having a double bond and a hydroxyl group may be, for example, the same compound as that exemplified in the method 4.

[0048] In the method 6, the acrylic resin having a hydroxyl group may be the same as the compound in the method 3.

[0049] In the method 6, examples of the compound having a double bond and an isocyanate group include isocyanate ethyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0050] Among the above methods, method 1 is preferred because the reaction is easy to control. In method 1, the double bond is introduced by a ring-opening addition reaction between the epoxy group of the acrylic resin having an epoxy group and the carboxyl group of the compound having a double bond and a carboxyl group.

[0051] In the method 1, the monomer having an epoxy group in the acrylic resin having an epoxy group is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more of the total amount of monomers constituting the acrylic resin having an epoxy group. There is no particular upper limit, but it is preferably 99.9% by weight or less, more preferably 80% by weight or less, even more preferably 70% by weight or less, particularly preferably 50% by weight or less, and most preferably 40% by weight or less. By using it in this range, not only the adhesion of the cured film to the substrate, scratch resistance, and hardness are improved, but also the wrinkled uneven structure tends to be finer, and a decrease in RSm, a decrease in Sa, and in some cases an increase in haze and a decrease in gloss can be achieved.

[0052] In the method 1, the compound having a double bond and a carboxyl group is preferably 10 to 150 mol %, more preferably 30 to 130 mol %, and even more preferably 50 to 110 mol %, relative to the epoxy group in the acrylic resin having an epoxy group. By using the compound in the above range, the reaction can be carried out without excess or deficiency, and it is preferable from the viewpoint of reducing the residue of the raw material.

[0053] Furthermore, the acrylic resin, such as the above-mentioned acrylic resin having an epoxy group, may be a copolymer of (meth)acrylates other than those mentioned above or other vinyl monomers. The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

[0054] 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 ... Examples of the monomer include (meth)acrylates such as 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 monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These monomers may be used alone or in combination of two or more.

[0055] The acrylic resin can be produced by a radical polymerization reaction using the above-mentioned raw material vinyl monomers. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0056] 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.

[0057] 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 the range of 0.01 to 5 parts by weight per 100 parts by weight of the total of the vinyl monomers as the raw material.

[0058] In addition, during radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the acrylic resin. 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-(ethylenediaminetetraacetate), ... Examples of the thiol-based compounds include thiol compounds such as oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decane trithiol, 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.

[0059] 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, based on 100 parts by weight in total of the vinyl monomers as the raw material.

[0060] The reaction time of 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.

[0061] In order to react a compound having a double bond and a carboxyl group with an acrylic resin, the compound having a double bond and a carboxyl group is added to the acrylic resin obtained as described above, and the reaction is usually carried out for about 3 to 9 hours at a temperature of usually 90 to 140 ° C., preferably 100 to 120 ° C., in the presence of one or more catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine. Here, the catalyst is preferably used in a ratio of about 0.5 to 3 parts by weight per 100 parts by weight of the total of the raw material (meth)acrylic acid ester polymer and the compound having a double bond and a carboxyl group. This reaction may be carried out continuously after the acrylic resin is produced by polymerization reaction, or may be carried out by adding the compound having a double bond and a carboxyl group after the acrylic resin is once separated from the reaction system.

[0062] The amount of double bonds in the acrylic resin is preferably in the range of 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, further preferably 0.5 to 5.0 mmol / g, particularly preferably 0.8 to 4.0 mmol / g, and most preferably 1.0 to 3.0 mmol / g. By using within this range, not only is it possible to improve the adhesion of the cured film to the substrate, the scratch resistance, and the hardness, but it is also possible to make the wrinkled uneven structure finer, and it is possible to achieve a decrease in RSm, a decrease in Sa, and in some cases an increase in haze and a decrease in gloss. The amount of double bonds means the concentration of (meth)acryloyl groups in the acrylic resin, that is, the amount of (meth)acryloyl groups introduced.

[0063] The weight average molecular weight (Mw) of the resin should be appropriately selected depending on the application of the curable composition, but is usually 5000 or more, preferably 7000 or more, more preferably 9000 or more, and usually 200000 or less, preferably 100000 or less, more preferably 70000 or less, and even more preferably 50000 or less. Within the above range, it is easy to form surface irregularities. The weight average molecular weight (Mw) of the resin can be determined as a converted value based on polystyrene standard using gel permeation chromatography (GPC). Specific measurement conditions are shown in the examples below.

[0064] When a resin is blended in the curable composition, the content is preferably 80% by mass or less, more preferably 3 to 60% by mass, further preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass, based on the non-volatile content. Within the above range, not only is the adhesion of the cured film to the substrate, scratch resistance, and hardness improved, but the wrinkled uneven structure tends to be finer, and a decrease in RSm, a decrease in Sa, and in some cases an increase in haze and a decrease in gloss can be achieved.

[0065] (particle) In order to further improve the matte property due to the wrinkled uneven structure of the cured film, it is also possible to blend particles into the curable composition. The particles are not particularly limited, and any 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, phenol resin, epoxy resin, and benzoguanamine resin. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably of a crosslinked type in order to maintain their shape, and crosslinked acrylic resin particles and crosslinked styrene resin particles are more preferable. Two or more of these particles may be used in combination.

[0066] 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, further preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm. When within this range, the matte properties are excellently improved.

[0067] When particles are blended in the curable composition, the content thereof is preferably 30% by mass or less, more preferably 0.1 to 20% by mass, further preferably 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass, based on the non-volatile content, from the viewpoint of improving matte properties.

[0068] However, particles and antistatic agents are often incompatible, i.e., when they are mixed into a coating solution, or during or after coating, changes such as whitening, aggregation, and sedimentation are likely to occur. This is mainly due to the fact that the particles and / or antistatic agent contain ionic compounds. In particular, care must be taken when using cationic antistatic agents that tend to exhibit antistatic properties, and this is a particular concern when using silica particles as particles. When whitening, aggregation, sedimentation, etc. occur, problems such as uneven coating appearance, insufficient antistatic properties, and poor curing properties of the cured film are likely to occur. Therefore, the selection of each material is important.

[0069] In the present invention, a concave-convex structure can be formed on the surface of a cured film without using particles, and a wide range of materials can be used for this purpose. Therefore, it is possible to design a system that does not substantially contain particles. Here, "substantially" means that particles are not intentionally contained.

[0070] (Photopolymerization initiator) A photopolymerization initiator may be added 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, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl dichloroacetophenone, etc. 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, tribromophenylsulfone, and tribromomethylphenylsulfone. These photopolymerization initiators may be used alone or in combination of two or more. When a photopolymerization initiator is added, the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the non-volatile content, from the viewpoints of promoting curing and hardness of the cured film.

[0071] (Leveling agent) In order to improve the appearance of the cured film, a leveling agent can be added to the curable composition. Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used alone or in combination of two or more. When a leveling agent is added, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on the non-volatile content, from the viewpoint of improving the appearance of the cured film.

[0072] (Various additives) The curable composition may contain various additives, such as a polymerization accelerator such as a compound containing a thiol group, an antifouling agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, as long as the effects of the present invention are not impaired.

[0073] (Organic solvent) For the purpose of improving the workability when applying the curable composition to a substrate, an organic solvent may be added to the curable composition as necessary. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether-based 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-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide-based solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen-based 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 coating. When an organic solvent is blended in the curable composition, the content thereof is preferably from 10 parts by mass to 1,900 parts by mass, and more preferably from 40 parts by mass to 400 parts by mass, per 100 parts by mass of nonvolatile matter, from the viewpoint of improving operability in a coating operation.

[0074] (Formation of coating film) Examples of the method for forming a coating film of the curable composition include a method in which the curable composition is applied onto a surface of a substrate or an article to form a coating film, and then dried 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.

[0075] (Irradiation with active energy rays) The coating film of the curable composition formed on the surface of the substrate or article is irradiated with active energy rays to form a cured film, and a laminate is formed in which the cured film is laminated on the substrate or article. As the active energy rays, those with high energy (short wavelength) capable of effectively curing the surface of the coating film are preferable, and vacuum ultraviolet rays (ultraviolet rays with a wavelength of 200 nm or less) are more preferable. Among the 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 preferable in consideration of ease of use, the ability to form an effective uneven structure in the cured film, and the curability of the curable composition.

[0076] When using vacuum ultraviolet light, 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. In addition, the vacuum ultraviolet irradiation is preferably performed in an environment with low oxygen content, such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and particularly preferably 1% or less.

[0077] After the vacuum ultraviolet irradiation, it is preferable to irradiate the cured film with an active energy ray other than the vacuum ultraviolet ray in order to cure the film to a deep portion. Examples of the active energy ray include ultraviolet ray and electron beam. 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 an electron beam irradiated from an EB irradiator, etc. As the active energy ray other than the vacuum ultraviolet ray, ultraviolet ray is more preferable in consideration of the curability of the curable composition.

[0078] The cumulative amount of ultraviolet light to be irradiated is preferably 1 to 5000 mJ / cm 2 , more preferably 50 to 3000 mJ / cm 2 , and more preferably 100 to 1000 mJ / cm 2 , particularly preferably 200 to 700 mJ / cm 2 The illuminance is preferably in the range of 1 to 1000 mW / cm 2 , more preferably 50 to 500 mW / cm 2 , and more preferably 80 to 300 mW / cm 2 The range is.

[0079] [Laminate] The laminate of the present invention has a layer made of a substrate and a layer (uneven 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. In addition, the laminate may have a back functional layer on the surface of the substrate opposite to the cured film side. As long as it does not impair the effects of the present invention, the cured film may have a surface functional layer on the surface opposite to the substrate.

[0080] (base material) The substrate may be a known one, for example, a resin substrate, a metal substrate, or a paper substrate. Among these, a resin substrate is preferred from the viewpoint of processability. The resin substrate may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferred that the resin substrate be a multi-layer structure of two or more layers, each layer having its own characteristics, and multi-functional. 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 film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferred. Among these, polyester film, poly(meth)acrylate film, and polyolefin film are preferred for anti-glare applications, and polyester film is more preferred in terms of transparency, moldability, and versatility.

[0081] The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Among them, a uniaxially stretched film stretched in one direction or a biaxially stretched film stretched in two directions is preferable, and a biaxially stretched film is more preferable 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 the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acid and the aliphatic glycol may each be used alone or in combination of two or more. Examples of the dicarboxylic acid component of the copolymer polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid component and the glycol component 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 preferable in consideration of mechanical strength and heat resistance, and from the viewpoint of ease of production and handleability for applications such as surface protection films, films formed from polyethylene terephthalate are particularly preferable.

[0082] The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the substrate may be any one 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, and 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 a main component a unit based on an alkyl(meth)acrylate having 1 to 4 carbon atoms, more preferably contains as a 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 a main component a unit 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, and more preferably 80% by mass or more.

[0083] 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 according to 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, phenol resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base layer includes a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst during the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are preferred because they are particularly effective in small amounts. The shape of the particles is not particularly limited, and any of spherical, block, rod-like, flat, etc. is acceptable. In addition, there is no particular limit to the hardness, specific gravity, color, etc. Two or more kinds of these particles may be used in combination, if necessary. The average primary particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and further preferably in the range of 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 sphericity distribution measured by a centrifugal sedimentation type particle size distribution measuring device. When the substrate contains particles, the content of the particles is not necessarily limited since 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, based on 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, defects such as particle dropout and reduced transparency of the substrate are unlikely to occur.

[0084] The substrate may contain additives other than the above-mentioned particles as necessary. Examples of the additives that can be used include 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.

[0085] (Primer layer) The primer layer is appropriately provided between the substrate and the cured film (concave-convex layer) in order to impart various functions. The primer layer may be a single layer having a single 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. When 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 where the uneven layer is present relative to the substrate. In order to make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

[0086] 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 them, 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.

[0087] The polyester resin may be one whose main components are a polyvalent carboxylic acid and a polyvalent hydroxy compound. Examples of polyvalent carboxylic 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.

[0088] 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 a copolymer is, for example, a block copolymer or a graft copolymer. Alternatively, it also includes a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyester. Similarly, it also includes a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyurethane. Similarly, it also includes a polymer (or a mixture of polymers, as the case may be) 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, monobutyl hydroxyl fumarate, and monobutyl hydroxy itaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl Examples of suitable monomers include alkyl (meth)acrylates such as dihexyl (meth)acrylate and lauryl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylol acrylamide and (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene and vinyl toluene, 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.

[0089] The urethane resin is a polymeric compound having a urethane bond in the molecule, and is typically synthesized by the reaction of 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.

[0090] Polycarbonate polyol is obtained by the reaction (dealcoholization reaction) of polyhydric alcohol with carbonate compound. Examples of polyhydric alcohol 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.

[0091] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

[0092] Examples of polyester polyols include those obtained by reacting a polyvalent carboxylic 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 polyvalent carboxylic 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, alkyl dialkanolamines, and lactone diols.

[0093] As the polyol, in consideration of adhesion performance, polyester polyol and polycarbonate polyol are preferred, and polyester polyol is particularly preferred.

[0094] 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'-tetramethyl xylylene 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 an isocyanate group, and generally, a chain extender 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, isopropylidincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

[0095] 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. The aqueous dispersion or solution of the urethane resin may be a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, or a water-soluble type, etc. In particular, a self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferred, since it has excellent storage stability of the liquid and 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 variety of groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a quaternary ammonium salt group, with the carboxyl group being preferred. The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amines, alkali metals, inorganic alkalis, etc. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent is removed in the drying process after application can be used as a crosslinking reaction point with a crosslinking agent. This makes it possible to provide excellent stability in the liquid state before coating, and to improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the obtained primer layer. As a method for introducing carboxyl groups into urethane resin, various methods can be used in each stage of polymerization reaction. For example, a method using a resin having carboxyl groups as a copolymerization component during prepolymer synthesis, or a method using a component having carboxyl groups as one component of polyol, polyisocyanate compound, chain extender, etc. is mentioned. In particular, a method using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups by the amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with the diol used in synthesizing the urethane resin. Examples of the carboxyl group-containing diol 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.

[0096] 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. As the crosslinking agent, a known material can be used, for example, a melamine compound, an isocyanate compound, an oxazoline compound, an epoxy compound, a carbodiimide compound, a silane coupling compound, a hydrazide compound, and an aziridine compound. Among them, a melamine compound, an isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a silane coupling compound are preferred, and from the viewpoint of further improving adhesion and durability, a melamine compound, an oxazoline compound, an isocyanate compound, and an epoxy compound are more preferred, and a melamine compound, an oxazoline compound, and an isocyanate compound are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more types in combination, adhesion and durability may be further improved.

[0097] The melamine compound is a compound having a melamine skeleton in the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting an alkylolated melamine derivative with an alcohol to partially or completely etherify the same, 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, a melamine compound obtained by co-condensing a part of the melamine with urea or the like may be used, and a catalyst may be used to increase the reactivity of the melamine compound. In consideration of reactivity with various compounds, a melamine compound having a hydroxyl group is preferable.

[0098] The isocyanate compound refers to a compound having an isocyanate derivative structure, such as an isocyanate compound or 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, methylene bis(4-cyclohexyl isocyanate), and isopropylidenedicyclohexyl diisocyanate. Also included are polymers and derivatives such as biuretized products, isocyanurate products, uretdione products, and carbodiimide modified products of these isocyanate compounds. 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 compounds in which the isocyanate group of the 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 terms of improving the dispersibility and crosslinking property of the isocyanate compound, it is preferable to use a mixture or bond with a polyester resin or a urethane resin.

[0099] 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 is obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of the addition-polymerizable oxazoline group-containing monomer 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 suitable because it is easily available industrially. The other monomer is not particularly limited as long as it is a monomer that can be copolymerized with the addition-polymerizable oxazoline group-containing monomer, and examples thereof include (meth)acrylates such as alkyl (meth)acrylates (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid, and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, and the like); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylonitrile; Examples of such unsaturated amides include acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); vinyl esters include vinyl acetate and vinyl propionate; vinyl ethers include methyl vinyl ether and ethyl vinyl ether; α-olefins include 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 the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, further 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.

[0100] An epoxy compound is a compound having an epoxy group in the molecule. Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), and include 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.

[0101] 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, condensation reaction of diisocyanate compounds is used. The diisocyanate compounds are not particularly limited, and both aromatic and aliphatic compounds 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 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 hydroxyalkylsulfonate may be added, within a range that does not impair the effects of the present invention.

[0102] 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 the silane coupling compound 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, N-2 -(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, N-phenyl-3-aminopropyltriethoxysilane and other amino group-containing compounds; tris(trimethoxysilylpropyl)isocyanurate, tris(triethoxysilylpropyl)isocyanurate and other isocyanurate group-containing compounds; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and other mercapto group-containing compounds. Among the above-mentioned compounds, from the viewpoint of the strength of the primer layer, preferred silane coupling compounds are epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds.

[0103] These crosslinking agents react during the drying process and film-forming process to improve the performance of the primer layer. It is assumed that the crosslinking agent-derived compounds present in the formed primer layer include unreacted crosslinking agents, reacted compounds, or mixtures thereof.

[0104] The antistatic agent contained in the primer layer is not particularly limited, and any known antistatic agent can be used. Examples of the antistatic agent include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive organic polymers. 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 necessary, within the scope of the present invention.

[0105] 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 are more excellent. 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 further 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 are more excellent. The thickness of the primer layer depends on the material used in the primer layer and the performance to be achieved, so cannot be generalized, 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.

[0106] (Surface functional layer) The surface functional layer is a layer provided on the surface of the cured film (uneven layer) opposite to the substrate layer to impart various functions. Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjustment 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 or multiple functions, or may be composed of multiple layers.

[0107] The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. As the material used for the antifouling layer, conventionally known materials such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used. Among these, silicone compounds and fluorine compounds are preferred for exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of not contaminating the other party with which the antifouling layer comes into contact.

[0108] The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, and phenyl silicone and methylphenyl silicone having a phenyl group. Silicones having various functional groups can also be used, and examples thereof include ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various aromatic groups and other hydrocarbon groups. As other functional groups, silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and it is also possible to use both in combination as addition type silicones (types obtained by the addition reaction of vinyl groups and hydrogen silane). In addition, a method of introducing a double bond such as an acryloyl group and reacting at the double bond is also preferred. In addition, as the silicone compound, modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino modified silicone, perfluoroalkyl modified silicone, etc. are also usable. In consideration of heat resistance and contamination, it is preferable to use a curable silicone resin, and as the type of curable type, any curing reaction type such as condensation type, addition type, active energy ray curable type, etc. can be used.

[0109] The fluorine compound is a compound containing fluorine atoms. 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, the fluorine compound can also be a compound containing a long chain alkyl compound as described later. Examples of the compound having a perfluoroalkyl group include perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl (meth)acrylate, perfluoroalkyl methyl (meth)acrylate, 2-perfluoroalkyl ethyl (meth)acrylate, 3-perfluoroalkyl propyl (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 perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, and 3-perfluoroalkyl-2-propenyl vinyl ether, and polymers thereof. In consideration of heat resistance and staining resistance, a polymer is preferable. The polymer may be a single compound or a polymer of multiple compounds. In addition, from the viewpoint of stain resistance, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, it may be a polymer with a compound containing a long-chain alkyl compound as described below.

[0110] The long-chain alkyl compound is a compound having a straight-chain or branched alkyl group having usually 6 or more, preferably 8 or more, more preferably 12 or more carbon atoms. Examples of the alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, and a behenyl group. Examples of the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. Considering heat resistance and stain resistance, a polymer compound is preferable. In addition, from the viewpoint of effectively obtaining antifouling properties, a polymer compound having a long-chain alkyl group in the side chain is more preferable. A polymer compound having a long-chain alkyl group in the 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 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 a long-chain alkyl group in the side chain can also be obtained by polymerization of a long-chain alkyl (meth)acrylate or copolymerization of a long-chain alkyl (meth)acrylate with another vinyl group-containing monomer. 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.

[0111] The content of the above-mentioned antifouling material for expressing the antifouling performance in the surface functional layer depends on the material used, so it cannot be generally stated, but in the case of silicone compounds and fluorine compounds, it is usually 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, and the upper limit may be 100 mass%. In addition, in the case of using a long-chain alkyl group-containing compound, it is usually 0.1 mass% or more, preferably 1 mass% or more, and even more preferably 3 mass% or more, and the upper limit may be 100 mass%. By using it in the above range, it is possible to obtain effective antifouling performance.

[0112] As the antistatic agent used when forming the antistatic layer as the surface functional layer, various conventionally known antistatic agents can be used. In addition, for example, a method of introducing a double bond such as an acryloyl group into a compound having an ammonium group and reacting at the double bond is also preferred.

[0113] 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, materials that have been conventionally known can be used as the material for the refractive index adjusting layer. Examples of such materials include aromatic-containing compounds such as a benzene structure, a bisphenol A structure, a melamine structure, and a fluorene structure, condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered to have high refractive indexes among aromatic compounds, 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), metal-containing compounds such as metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing a sulfur element, and compounds containing a halogen element. 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, and 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, from the viewpoint of coating appearance, etc. When the refractive index adjustment layer is intended to have a low refractive index, the material of the refractive index adjustment layer can be a conventionally known material, for example, low refractive index acrylic resin or urethane resin.In addition, in particular, compounds in which fluorine atoms are incorporated in the resin, for example, fluorine resin, compounds containing fluorine resin in the main skeleton, and compounds containing perfluoroalkyl groups in the side chain, can be mentioned.In addition, inorganic materials can be, for example, hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles or nanoporous particles thereof.

[0114] The thickness of the surface functional layer is preferably 5 times or less, more preferably 2 times or less, the height from the concave to the convex of the uneven structure of the cured film. The smaller this ratio is, the less likely the matte performance of the cured film is to decrease. The thickness of the surface functional layer depends on the height from the concave to the convex of the uneven structure of the cured film, so it cannot be generalized, 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. By using within the above range, it is possible to achieve both the expression of the function of the surface functional layer and the matte property of the cured film. The surface functional layer can be formed by a known method.

[0115] (Back functional layer) The back functional layer is a layer provided on the surface opposite to the cured film (uneven layer) of the base layer to impart various functions. Examples of the back functional layer include an adhesive layer, an antistatic layer, a refractive index adjustment layer, and an antiblocking layer. The back functional layer may be a single layer having a single or multiple functions, or may be composed of multiple layers.

[0116] 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 charge or frictional charge on the outermost surface of the laminate, particularly on the outermost surface opposite to the uneven layer side of the base layer, and to prevent defects and the like 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 the adhesive that forms the adhesive layer include known adhesives such as acrylic, polyester, urethane and rubber adhesives. Among these, acrylic adhesives are preferred in view 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.

[0117] The thickness of the back functional layer depends on the material used in the back functional layer and the performance to be achieved, so it cannot be generally stated, but is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, the thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, the thickness 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.

[0118] (Formation of surface functional layer and back functional layer) The front surface functional layer and the back surface functional layer can be formed, for example, by coating a liquid prepared by dispersing the above-mentioned components in a solution or solvent so that the solid content is approximately 0.1 to 80% by mass onto a specified surface, followed by drying and curing. 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 when forming the front functional layer and the back functional layer are not particularly limited, but the drying temperature of the solvent such as water used in the coating liquid is usually in the range of 50 to 150 ° C, preferably 80 to 130 ° C, and more preferably 90 to 120 ° C. The drying time is generally in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In addition, in order to improve the strength of the front functional layer and the back functional layer, it is preferable to perform a heat treatment after drying at a temperature of usually 150 to 270 ° C, preferably 170 to 230 ° C, and more preferably 180 to 210 ° C. The heat treatment time is generally in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Such a heat treatment is suitable when the laminate is a film.

[0119] (Total light transmittance) The laminate preferably has transparency. The total light transmittance measured by the method described in the Examples below is 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, and the higher the transmittance the better (the upper limit is 100%).

[0120] (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 property tends to be. In particular, 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 may be. EXAMPLES

[0121] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. The measurement and evaluation methods used in the present invention are as follows.

[0122] (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.

[0123] (2) Average primary particle diameter (d50:μm) The cumulative 50% value (by weight) in the equivalent sphericity distribution measured using a centrifugal sedimentation type particle size distribution measuring device SA-CP3 manufactured by Shimadzu Corporation was taken as the average primary particle size.

[0124] (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). As the column, TSKgel G5000HXL*GMHXL-L (manufactured by Tosoh Corporation) was used. In addition, a calibration curve was created using F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (manufactured by Tosoh Corporation) and styrene as standard polystyrene. The measurement was performed at a column oven temperature of 40°C using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran to a concentration of 0.4%. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

[0125] (4) RSm, Sa and inclination angle (θa) Using a surface profile measurement system (Hitachi High-Tech Science Corporation's scanning white light interference microscope "VS1330"), the surface profile was measured by optical interference over an area of ​​177.60 μm × 236.87 μm on the surface of the cured film, and the data was analyzed. The evaluation length used to calculate RSm and θa was 236.87 μm. The objective lens magnification during measurement was set to 20 times. The presence or absence of a wrinkled uneven structure was also confirmed in 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

[0126] (5) Total light transmittance / haze The laminate in which the cured film was formed on the substrate was used as the measurement subject. The total light transmittance and haze were measured using a Nippon Denshoku Industries haze meter "SH7000" in accordance with JIS Z8722:2009 (geometric conditions of irradiation and reception of a transmitting object), JIS K7361-1:1997 (test method for total light transmittance of plastic transparent materials), and JIS K7136:2000 (method of determining haze of plastic transparent materials).

[0127] (6) 20° and 60° gloss and matte The laminate having a cured film formed on a substrate was used as the measurement subject. The 20° and 60° gloss (20° and 60° specular gloss) was measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8741-1997. The lower the gloss value, the better the matte property.

[0128] (7) Method for measuring surface resistance Using a high resistivity meter, Hiresta MCP-HP450, manufactured by Mitsubishi Chemical Analytech Co., Ltd., the surface resistivity was measured after the sample was conditioned for 30 minutes at an applied voltage of 100V, 23°C, and 50% RH. If the surface resistance value shows OVER, it means that the surface resistance value is too high to measure.

[0129] (8)Pencil hardness The pencil hardness of the cured film was measured according to JIS K5600-5-4:1999 General testing methods for paints - Part 5: Mechanical properties of coatings - Section 4: Scratch hardness (pencil method).

[0130] (9) Matte finish The laminate was placed in a room illuminated by a linear white fluorescent lamp, and the distance between the fluorescent lamp and the laminate was set at 2.5 m. The matte finish on the uneven layer side (reflection of the fluorescent lamp) was evaluated by visual inspection according to the following evaluation criteria A to D. Evaluations A to C are judgments that confirm the matte finish. A: The reflected image of the fluorescent light is very blurry and the outline of the fluorescent light cannot be seen. B: The reflected image of the fluorescent light is blurred, but you can faintly see its outline. C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be seen, it appears wavy and appears dark white. D: The reflected image of the fluorescent light is clear, the contours can be clearly seen, and it appears linear and white.

[0131] (10) Blocking resistance A polyester film without a cured film was placed on the cured film of the laminate having the substrate and the cured film formed thereon, and the laminate was pressed with a pressure of 5 g / cm. 2 After that, the polyester film placed on the cured film was peeled off, and the peeled polyester film was observed and evaluated. Evaluation A was judged to be better than Evaluation B, which indicates that there was no problem with blocking. A: No traces of the cured film can be seen. B: Traces of the cured film can be seen.

[0132] 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 mass% silica particles with an average primary particle diameter of 2 μm.

[0133] (Production of Antistatic Agent (A1)) An antistatic agent (A1), which is a (meth)acrylic polymer containing ammonium groups, was prepared by the following method. A reactor equipped with a stirrer, reflux condenser, and thermometer was charged with 18 parts by mass of DQ100, 7.5 parts by mass of SL, 4.5 parts by mass of DM, 20 parts by mass of methyl ethyl ketone (MEK), and 50 parts by mass of isopropyl alcohol (IPA). After stirring was started, the system was replaced with nitrogen and heated to 55°C. 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd. V-65) was added thereto, and the system was heated to 65°C and stirred for 3 hours, after which 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and stirred at 65°C for 3 hours. The system was heated to 80°C, stirred for 2 hours, and then cooled to room temperature to obtain a polymer solution. The composition of this solution was polymer / MEK / IPA=30 / 20 / 50 (weight ratio). The weight average molecular weight (Mw) of the polymer was 45200. The abbreviations of the above raw materials mean the following: DQ-100: Light Ester (registered trademark) DQ-100 manufactured by Kyoeisha Chemical Co., Ltd. SL: Acrylates (registered trademark) SL manufactured by Mitsubishi Chemical Corporation A mixture of lauryl methacrylate and tridecyl methacrylate in a ratio of 45:55 (by weight). DM: Acrylates (registered trademark) DM manufactured by Mitsubishi Chemical Corporation N,N-Dimethylaminoethyl methacrylate Mixture of N,N-dimethylaminoethyl methacrylate quaternized with methyl chloride

[0134] (Production of acrylic resin (C) having active energy ray-curable functional group) An acrylic resin (C) having an active energy ray-curable functional group was prepared by the following method. In a flask equipped with a thermometer, a stirrer, and a reflux condenser, propylene glycol monomethyl ether (178 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 and reacted for 3 hours at 65°C. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was further added and reacted for 3 hours, after which propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110°C for 6 hours to obtain an acrylic resin (C) having a double bond capable of radical polymerization in the side chain with a double bond amount (acryloyl group concentration (amount of acryloyl group introduced)) of 1.2 mmol / g. The weight average molecular weight (Mw) was 48,800.

[0135] (Curable composition) The materials shown below were mixed in the amounts (parts by mass, calculated as non-volatile 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 uniform, to obtain a curable composition (coating liquid) used in each of the Examples and Comparative Examples. Antistatic agent (A1): Antistatic agent (A1) produced by the above method Antistatic agent (A2): (meth)acrylic polymer containing quaternary ammonium base (Nikka Taibo, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 28,000) Antistatic agent (A3): Anionic surfactant (Kao Electrostripper ME-2) (Meth)acrylate (B1): 1,6-hexanediol diacrylate (bifunctional) (Meth)acrylate (B2): Modified epoxy acrylate (EBECRYL 3708, manufactured by Daicel-Allnex) (Meth)acrylate (B3): Urethane acrylate (Mitsubishi Chemical Corporation, Shiko UV-1700B) (Meth)acrylate (B4): Dipentaerythritol hexaacrylate (Meth)acrylate (B5): Pentaerythritol tetraacrylate (Meth)acrylate (B6): Methoxyethyl acrylate Acrylic resin (C): Acrylic resin (C) having an active energy ray-curable functional group produced by the above method. Particles (D): Cross-linked acrylic particles with an average particle size of 1.8 μm (MX-180TA manufactured by Soken Chemical Industries, Ltd.) Photoinitiator (E): Omnirad 184 manufactured by IGM Resins BV

[0136] [Table 1]

[0137] (Composition for forming primer layer) The polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) shown below were mixed in a ratio of polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) (solid content mass ratio) = 60 / 25 / 10 / 5 to obtain a composition for forming a primer layer. Polyester resin (P1): Water 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): Water 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 size of 0.07 μm

[0138] (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 intermediate layer was a mixture of polyesters (S1) and (S2) in proportions of 97% and 3% by mass, respectively. Each of these raw materials was supplied to two extruders and melted at 285°C. After that, they were co-extruded onto a cooling roll set at 40°C in a layer structure of two types and three layers (surface layer / intermediate layer / surface layer = extrusion amount 1:8:1), and then 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 by 2% in the transverse direction to obtain a polyester film substrate 50 μm thick (after drying) and having a 0.1 μm thick primer layer on one side.

[0139] [Examples 1 to 12] The coating solution shown in Table 1 was applied onto the primer layer of the polyester film, dried at 70°C for 1 minute, and irradiated with excimer light (half width 14 nm) from xenon (wavelength 172 nm) at a dose of 15 mJ / cm 2 , illuminance 5mW / cm 2 The coating film made of the coating solution in Table 1 was irradiated with a 172 nm xenon excimer light irradiator (Ushio Inc., lamp unit type: SUS05 (lamp house type: H0011, lighting power supply type: B0005), nitrogen flow (oxygen concentration 1% or less)) and then irradiated with a high-pressure mercury lamp in an air atmosphere with an accumulated light dose of 400 mJ / cm. 2 , illuminance 200mW / cm 2The mixture was irradiated with ultraviolet light using a UV conveyor of a high-output 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. The obtained laminate had a low surface resistance and a good matte finish. The properties of this laminate are shown in Table 2.

[0140] [Comparative Examples 1 to 3] A laminate having a cured film was obtained by manufacturing in the same manner as in Example 1, except that the composition of the coating solution in Example 1 was changed to the composition shown in Table 1, and curing was performed only by irradiation with ultraviolet light from a high-pressure mercury lamp without using excimer light. When the obtained laminate was evaluated, as shown in Table 2, no uneven structure was formed and it did not have a matte finish. When excimer light was not used, it was found that the curing was poor in some cases. For those with poor curing (low pencil hardness), even when the amount of ultraviolet light irradiated from a high-pressure mercury lamp was increased to make the pencil hardness F or higher, wrinkle-like irregularities were not formed, and no changes were observed in other physical properties such as matte finish, and no improvement was observed.

[0141] [Comparative Examples 4 and 5] A laminate having a cured film was obtained in the same manner as in Example 1, except that the coating agent composition in Example 1 was changed to the coating agent composition shown in Table 1. As shown in Table 2, the properties of the obtained laminate were high, such as surface resistance.

[0142] [Table 2]

Claims

1. A cured film obtained by irradiating an active energy ray-curable composition with active energy rays, the cured film having a wrinkled, uneven surface structure and containing an antistatic agent.

2. A cured film obtained by irradiating an active energy ray-curable composition with active energy rays, having a wrinkled, uneven surface structure, substantially free of particles, with a 60° gloss of 50 or less, and a surface resistance of 1.0 × 10⁻⁶. １３ A cured film with an Omega value of less than Ω.

3. The cured film according to claim 1 or 2, wherein the curable composition contains (meth)acrylate.

4. The cured film according to any one of claims 1 to 3, wherein the average length (RSm) of the roughness curve elements of the uneven structure according to JIS B0601:2013 is 1 μm or more.

5. The cured film according to any one of claims 1 to 4, wherein the arithmetic mean height (Sa) of the uneven structure, as defined in ISO 25178, is 0.1 μm or more.

6. The cured film according to any one of claims 1 to 5, wherein the average value (θa) of the local inclination angle of the uneven structure is 2° or more.

7. A cured film according to any one of claims 1 to 6, wherein the surface 60° gloss is 30 or less.

8. A method for producing a cured film according to any one of claims 1 to 7, comprising laminating a curable composition containing an antistatic agent and curing it by irradiation with excimer light.

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

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

11. A method for producing a laminate according to claim 9 or 10, comprising laminating a curable composition containing an antistatic agent onto a substrate and curing it by irradiation with excimer light.

12. A method for producing a laminate according to claim 9 or 10, comprising laminating a substantially particle-free curable composition onto a substrate and curing it by irradiation with excimer light.