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

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

[0004] However, the method described in Patent Document 1 can only obtain a specific uneven structure that does not provide a sufficient matte effect. Moreover, since the unevenness is formed directly on the biaxially oriented thermoplastic resin film, it is difficult to apply it to display applications that require various surface properties such as scratch resistance and antistatic properties. In the method described in Patent Document 2, only the hard coat resin of the hard coat layer is decomposed to expose inorganic fine particles on the surface, which makes the particles more likely to fall off and may impair visibility when used in displays, etc. Another problem is that the surface uneven structure is limited by the shape and distribution of the particles. An object of the present invention is to provide a cured film and a laminate that are excellent in matte properties and 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, which has a wrinkled uneven structure on the surface, is substantially free of particles, has a 60° gloss of 50 or less, and a surface resistivity of 1.0 × 10 13 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 concave-convex 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 arithmetic mean height (Sa) of the concave-convex structure as defined by ISO 25178 is 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 angles of the concave-convex structure is 2° or more. [7] The cured film according to any one of [1] to [6] above, 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 it by irradiating it with excimer light. [9] A laminate obtained by laminating the cured film according to any one of the above [1] to [7] on a substrate.

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

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

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

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

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

[0008] [Cured film] The cured film of the present invention (hereinafter simply referred to as "cured film") is obtained by irradiating an active energy ray-curable composition with active energy rays, and has a wrinkled uneven structure (non-smooth structure) on the surface. The 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 excellent matte properties and antistatic properties, and is therefore suitable as an antiglare film.

[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 value the better. The smaller the 60° gloss value, the better the matte properties. Similarly, the 20° gloss is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, particularly preferably 2 or less, and most preferably 1 or less, with the lower the better. The smaller the 20° gloss value, the better the matte properties.

[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 it can prevent adhesion of dust and the like.

[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 simply referred to as "RSm") according to JIS B0601:2013. The evaluation length used to calculate RSm was 236.87 μm. The RSm range is preferably 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. A value within the above range provides excellent matte properties and excellent visibility 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 in ISO 25178. 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 slope angle of the uneven structure) The average local tilt angle (θa, hereinafter simply referred to as "θa") in the concave-convex structure of the cured film can be measured by the method described in the Examples below. The evaluation length used to calculate 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, with the upper limit being 90°. When θa is in this range, good matte properties are achieved.

[0014] (Thickness) From the viewpoint of improving matte properties, the thickness of the cured film (concave-convex layer) is preferably in the range of 0.1 to 100 μm, more preferably 0.2 to 20 μm, still more preferably 0.3 to 10 μm, and particularly preferably 0.3 to 7 μm. The thickness of the cured film indicates the maximum thickness of the concave-convex layer, and is determined by cross-sectional observation using an electron microscope.

[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 even more preferably 2H or more. When the hardness is in the above range, the film has excellent scratch resistance and is suitable for applications where visibility is important, such as displays.

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

[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) An antistatic agent may be blended into the curable composition to impart antistatic properties to the cured film, which can contribute to preventing adhesion of foreign matter such as dust due to peeling electrification. The antistatic agent is not particularly limited, and conventionally known antistatic agents can be used. Examples of antistatic agents include organic compounds such as polymer types and surfactant types, and inorganic compounds such as metal oxides. Among these, organic compounds are preferred because of the ease with which they can form a concave-convex structure. Furthermore, polymer types are more preferred from the viewpoints of heat resistance, moist heat resistance, and durability. Examples of polymer type 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. The inclusion of such a functional group can contribute to the formation of a concave-convex structure and also 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, such as an aliphatic amine, an alicyclic amine, or an aromatic amine. The compound having an ammonium group is preferably a polymeric compound having an ammonium group. The ammonium group is preferably incorporated into the main chain or side chain of the polymer rather than as a counter ion. Furthermore, among polymers, those capable of increasing the concentration of ammonium groups are preferred to effectively impart antistatic properties, and (meth)acrylic polymers are therefore preferred. 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 single polymer of a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine, or it may be a copolymer of such a monomer with another monomer. Examples of precursor monomers of ammonium groups or amines 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 in 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 product of quaternization of N,N-dimethylaminoethyl methacrylate with methyl chloride [for example, trade 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- Examples of suitable (meth)acrylates include hydroxyalkyl (meth)acrylates such as 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, a polymerizable monomer having a highly hydrophobic long-chain alkyl group is preferred because it can segregate at the air interface of the cured film, thereby enhancing the antistatic properties of the cured film. Such a polymerizable monomer having 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, and examples thereof include lauryl(meth)acrylate, tridecyl(meth)acrylate, and stearyl(meth)acrylate. The proportion of ammonium group-containing monomer units in a (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. A higher proportion tends to improve antistatic properties, while a lower proportion tends to improve the appearance of the cured layer after application; using the compound in the above range achieves a good balance. The proportion 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 the compound in the above range facilitates the development of antistatic properties.

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

[0022] The (meth)acrylic polymer containing an ammonium group can be produced by radical polymerization using the above-mentioned raw material monomers. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator. 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 radical polymerization reactions 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 per 100 parts by mass of the total raw material monomers. In addition, during the radical polymerization reaction, a chain transfer agent can be used to control 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-(ethylenediaminetetraacetic acid)-2-methylpropanol, methyl-3-mercaptopropionate ... Examples of the thiol-based compounds include (oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1.0 to 15 parts by weight, per 100 parts by weight of the total of the raw material monomers. The reaction time for 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, and examples of suitable compounds having a sulfonic acid group include compounds that contain a large amount of sulfonic acid or a sulfonate salt, such as polystyrene sulfonic acid.

[0025] Examples of conductive polymers that can be blended as antistatic agents include polythiophenes, polyanilines, polypyrroles, and polyacetylenes. Among these, polythiophenes, such as poly(3,4-ethylenedioxythiophene) used in combination with polystyrene sulfonic acid, are preferred. Conductive polymers are more suitable than the other antistatic agents mentioned above in that they have a low resistance. However, conductive polymers can be expensive and can cause discoloration of the cured film, so it is advisable to take appropriate measures such as selecting the type and reducing 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, anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are particularly preferred, from the viewpoint of improving antistatic properties and compatibility with various resins. 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 salts thereof, and polyoxyalkylene alkyl ether phosphates or salts thereof, 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, hexadecyl sulfonate, 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 sulfoacetic acid ester, and nonylphenoxy polyethylene glycol sulfoacetic acid ester. Among these, those with an alkyl group having 8 or more carbon atoms, preferably 10 to 22, and more preferably 12 to 18, are preferred from the viewpoint of excellent antistatic properties. 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 phosphoric acid type anionic surfactants include alkyl phosphoric acid esters or salts thereof such as butyl phosphate, butyl phosphate ester salts, hexyl phosphate, hexyl phosphate ester salts, octyl phosphate, octyl phosphate ester salts, decyl phosphate, decyl phosphate ester salts, lauryl phosphate, lauryl phosphate ester salts, tetradecyl phosphate, tetradecyl phosphate ester salts, hexadecyl phosphate, hexadecyl phosphate ester salts, stearyl phosphate, and stearyl phosphate 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 polyoxyalkylene alkyl ether phosphates or salts thereof, such as polyoxyethylene decyl ether phosphate salts, polyoxyethylene lauryl ether phosphate salts, polyoxyethylene lauryl ether phosphate salts, polyoxyethylene tetradecyl ether phosphate salts, polyoxyethylene tetradecyl ether phosphate salts, polyoxyethylene hexadecyl ether phosphate salts, polyoxyethylene hexadecyl ether phosphate salts, polyoxyethylene stearyl ether phosphate salts, polyoxyethylene stearyl ether phosphate salts, polyoxypropylene octyl ether phosphate salts, polyoxypropylene octyl ether phosphate salts, polyoxypropylene decyl ether phosphate salts, polyoxypropylene decyl ether phosphate salts, polyoxypropylene lauryl ether phosphate salts, and polyoxypropylene lauryl ether phosphate salts. Among these, alkyl phosphate ester salts and polyoxyalkylene alkyl ether phosphate esters or salts thereof are preferred from the viewpoint of surfactant performance and antistatic performance. Furthermore, with regard to alkyl phosphate ester 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 with regard to polyoxyalkylene alkyl ether phosphate esters or salts 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. Furthermore, as the salts, metal salts and amine salts are preferred, and in particular, salts of alkali metals 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 that forms 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 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 the content is equal to or greater than the above lower limit, excellent antistatic properties are obtained. The nonvolatile content of the curable composition is the total mass of components other than the solvent, such as the organic solvent, etc. The nonvolatile content of the curable composition can be measured by a conventionally known method, for example, by measuring the change in weight when 1 g of the composition is spread and heated at 100°C for 1 hour to volatilize the organic solvent.

[0028] (Active energy ray curable compound) In a preferred embodiment, the active energy ray-curable composition contains an active energy ray-curable compound to facilitate the formation of an uneven structure in the cured film, improve scratch resistance, and improve hardness. Examples of the active energy ray-curable compound include (meth)acrylates. The (meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, a trifunctional or higher polyfunctional (meth)acrylate, or a commercially available active energy ray-curable resin material, or a material containing other components added thereto, provided that the object of this embodiment is not impaired. As the (meth)acrylate, a monofunctional or bifunctional (meth)acrylate is preferred from the viewpoint of ease of forming a wrinkled uneven structure. Trifunctional or higher polyfunctional (meth)acrylates are generally preferred to increase the hardness and scratch resistance of the cured film. However, according to the inventors' investigations, depending on the type of trifunctional or higher polyfunctional (meth)acrylate, it may be difficult to form a wrinkled uneven structure. Therefore, it is advisable to take appropriate measures such as selecting the type or reducing the amount of the compounded compound.

[0029] Examples of bifunctional polyfunctional (meth)acrylates include alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate, 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 branching is preferred, and alkyldiol di(meth)acrylate is more preferred, with alkyldiol di(meth)acrylates having 4 to 18 carbon atoms being even more preferred.

[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 ethylene oxide-modified isocyanurate tri(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate such as ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, and 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 view of the ease of forming a wrinkled uneven structure.

[0032] The curable composition may contain active energy ray-curable compounds other than (meth)acrylates, such as vinyl compounds (e.g., (meth)acrylic acid, styrene, vinyl halide, vinyl acetate), and diene compounds (e.g., vinylidene halide, 1,3-butadiene, isoprene, 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%, even more preferably 40 to 95 mass%, particularly preferably 50 to 90 mass%, and most preferably 60 to 80 mass%, based on the nonvolatile content. Within the above range, a wrinkled uneven structure is easily formed, and a cured film having excellent hardness can be formed.

[0034] (resin) The curable composition may further contain various resins for the purpose of improving adhesion to the substrate, etc. 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 because of their 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, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the nonvolatile 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 incorporated into 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 present inventors have discovered 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 results in a finer wrinkled texture. This results in a smaller RSm and a smaller Sa. In addition, the haze sometimes increases and the gloss sometimes decreases. These properties can exert a synergistic effect on the matte finish, which is particularly important for applications where visibility is important, such as display applications.

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

[0038] In the above-mentioned method 1, examples of the vinyl monomer 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 preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

[0039] Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride, and an adduct of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid and an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. 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 the 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 and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These compounds may be used alone or in combination of two or more.

[0042] In the method 3, examples of the vinyl monomer having a hydroxyl group used to obtain the 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 same acrylic resin having a carboxyl group as in the method 2 can be used.

[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 above-mentioned method 5, examples of the vinyl monomer having an isocyanate group used to obtain the 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 compounds as those listed in the method 4.

[0048] In the method 6, the same compounds as those in the method 3 can be used as the acrylic resin having a hydroxyl group.

[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 epoxy group-containing monomer in the epoxy group-containing acrylic resin preferably accounts for 5 wt% or more, more preferably 10 wt% or more, and even more preferably 15 wt% or more of the total amount of monomers constituting the epoxy group-containing acrylic resin. There is no particular upper limit, but the upper limit is preferably 99.9 wt% or less, more preferably 80 wt% or less, even more preferably 70 wt% or less, particularly preferably 50 wt% or less, and most preferably 40 wt% or less. By using within this range, not only are the adhesion of the cured film to the substrate, scratch resistance, and hardness improved, but also wrinkle-like unevenness tends to be reduced, resulting in reduced RSm, reduced Sa, and in some cases, increased haze and reduced gloss.

[0052] In the method 1, the ratio of the compound having a double bond and a carboxyl group to the epoxy groups in the acrylic resin having an epoxy group is preferably 10 to 150 mol %, more preferably 30 to 130 mol %, and even more preferably 50 to 110 mol %. Using the compound in this range is preferable from the viewpoints of allowing the reaction to proceed just right and reducing the amount of raw material residue.

[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 glycol ( Examples of the monomer include (meth)acrylates such as (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, and stearoxy(poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl(meth)acrylamide, n-butyl(meth)acrylamide, i-butyl(meth)acrylamide, t-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, and N,N-dihydroxyethyl(meth)acrylamide; and styrene-based monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These monomers may be used alone or in combination of two or more.

[0055] The acrylic resin can be produced by radical polymerization using the above-mentioned vinyl monomers as raw materials. 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 an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total of the vinyl monomers used as raw materials.

[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, etc. Examples of the chain transfer agent include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenediaminetetraacetic acid)-2-methylpropanol, methyl-3-mercaptopropionate ... Examples of the thiol-based compounds include (oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

[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, per 100 parts by weight of the total of the vinyl monomers as raw materials.

[0060] The reaction time for the radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours, and the reaction temperature is preferably 40 to 120°C, more preferably 50 to 100°C.

[0061] To react an acrylic resin with a compound having a double bond and a carboxyl group, the compound having a double bond and a carboxyl group is added to the acrylic resin obtained as described above, and the reaction is carried out in the presence of one or more catalysts, such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, or triethylamine, typically at a temperature of 90 to 140°C, preferably 100 to 120°C, for typically 3 to 9 hours. The catalyst is preferably used in an amount of approximately 0.5 to 3 parts by weight per 100 parts by weight of the combined raw materials (meth)acrylic acid ester polymer and the compound having a double bond and a carboxyl group. This reaction may be carried out immediately after the acrylic resin is produced by polymerization, or the acrylic resin may be separated from the reaction system and then the compound having a double bond and a carboxyl group is added.

[0062] The double bond content in the acrylic resin is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, even more preferably 0.5 to 5.0 mmol / g, particularly preferably 0.8 to 4.0 mmol / g, and most preferably 1.0 to 3.0 mmol / g. Using a compound within this range not only improves the adhesion of the cured film to the substrate, scratch resistance, and hardness, but also tends to reduce the wrinkle-like unevenness, thereby achieving reduced RSm, reduced Sa, and, in some cases, increased haze and reduced gloss. The double bond content refers to the (meth)acryloyl group concentration in the acrylic resin, i.e., the amount of (meth)acryloyl groups introduced.

[0063] The weight-average molecular weight (Mw) of the resin should be selected appropriately depending on the application of the curable composition, but is usually 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, and usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. Within the above range, surface irregularities are easily formed. The weight-average molecular weight (Mw) of the resin can be determined as a polystyrene-standardized value using gel permeation chromatography (GPC). Specific measurement conditions are shown in the Examples below.

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

[0065] (particle) To further improve the matte properties of the cured film due to the wrinkled uneven structure, particles can be incorporated into the curable composition. The type of particles is not particularly limited, and conventionally known particles can be used. Specific examples include inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. The inorganic particles may be surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably crosslinked to maintain their shape, and crosslinked acrylic resin particles and crosslinked styrene resin particles are more preferred. Two or more of these particles may be used in combination.

[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, still more preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm.Within this range, the matte properties are excellently improved.

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

[0068] However, particles and antistatic agents are often incompatible. This means that when formulated as a coating solution, or during or after application, changes such as whitening, aggregation, and sedimentation are likely to occur. This is primarily due to the presence of ionic compounds in the particles and / or antistatic agent. Care must be taken when using cationic antistatic agents, which tend to exhibit antistatic properties, and this is a particular concern when using particles such as silica particles. When whitening, aggregation, and sedimentation occur, problems such as uneven coating appearance, insufficient antistatic properties, and poor curing of the cured film are likely to occur. Therefore, the selection of each material is important.

[0069] In the present invention, a roughness 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 blended to promote the curing of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzil dimethyl ketal, 1,1-dichloroacetophenone, and pt-butyl dichloroacetophenone. Examples of the photopolymerization initiator include phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, and tribromomethylphenyl sulfone. 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, even more preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the nonvolatile components, from the viewpoints of promoting curing and improving the hardness of the cured film.

[0071] (Leveling agent) To improve the appearance of the cured film, a leveling agent can be blended into 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 nonvolatile 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, within the range that does not impair the effects of the present invention.

[0073] (organic solvent) For the purpose of improving workability when applying the curable composition to a substrate, an organic solvent may be blended into the curable composition as needed. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogenated solvents such as dichloromethane and chloroform. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred in that they can easily improve workability during application. When an organic solvent is blended into the curable composition, the content thereof is preferably 10 parts by mass or more and 1,900 parts by mass or less, and more preferably 40 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the nonvolatile content, from the viewpoint of improving operability in the coating operation.

[0074] (Formation of coating film) Examples of methods for forming a coating film of the curable composition include a method of applying the curable composition to the surface of a substrate or an article to form a coating film, and then drying the coating film as necessary. The coating method is not particularly limited, and examples thereof include known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating. When the curable composition contains an organic solvent, it is preferable to heat-dry the composition before irradiating it with active energy rays. By heating and drying the composition beforehand, the solvent in the coating film can be effectively removed. The drying temperature for the heat-drying is preferably 30°C or higher and 200°C or lower, more preferably 40°C or higher and 150°C or lower. The drying time is preferably 0.01 minutes or higher and 30 minutes or lower, more preferably 0.1 minutes or higher and 10 minutes or lower.

[0075] (Irradiation with active energy rays) A coating film of the curable composition formed on the surface of a substrate or article is irradiated with active energy rays to form a cured film, thereby forming a laminate in which the cured film is laminated on the substrate or article. The active energy rays are preferably those with high energy (short wavelength) that can effectively cure the surface of the coating film, and vacuum ultraviolet rays (ultraviolet rays with a wavelength of 200 nm or less) are more preferred. Among vacuum ultraviolet rays, excimer light with a half-width of 50 nm or less is optimal. Examples of excimer light include argon excimer light (126 nm), krypton excimer light (146 nm), xenon excimer light (172 nm), and argon-fluorine excimer light (193 nm). Among these, xenon excimer light is preferred in terms of ease of use, the ability to form an effective uneven structure in the cured film, and the curability of the curable composition.

[0076] When vacuum ultraviolet light is used, the cumulative amount of light to be irradiated is preferably 1 to 3000 mJ / cm. 2 , more preferably 3 to 1000 mJ / cm 2 , and more preferably 5 to 500 mJ / cm 2 , particularly preferably 10 to 100 mJ / cm 2 The illuminance is preferably in the range of 1 to 500 mW / cm. 2 , more preferably 2 to 300 mW / cm 2 , and more preferably 3 to 100 mW / cm 2 The range is. The vacuum ultraviolet irradiation is preferably performed in an oxygen-poor atmosphere such as a nitrogen atmosphere, etc. The oxygen concentration in the atmosphere is preferably 10% or less, more preferably 5% or less, even more preferably 3% or less, and particularly preferably 1% or less.

[0077] After the vacuum ultraviolet irradiation, it is preferable to irradiate the cured film with an active energy ray other than vacuum ultraviolet ray in order to deep cure the film. Examples of the active energy ray include ultraviolet ray, electron beam, etc. Examples of the ultraviolet ray include ultraviolet ray with a wavelength of 200 nm or more irradiated from a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, etc. Examples of the electron beam include electron beam irradiated from an EB irradiator, etc. Of the active energy ray other than vacuum ultraviolet ray, ultraviolet ray is more preferable in consideration of the curability of the curable composition.

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

[0080] (base material) As the substrate, known substrates can be used, for example, resin substrates, metal substrates, and paper substrates. Among these, resin substrates are preferred from the viewpoint of processability. The resin substrate may have a single layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable that the resin substrate has a multi-layer structure of two or more layers, and each layer has its own characteristics to achieve multi-functionality. As the resin substrate, various resin films (sheets) can be used, for example, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, and nylon film. When the laminate is used for a display, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred in terms of transparency, formability, and versatility.

[0081] The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferred. Among these, a uniaxially stretched film stretched in one direction or a biaxially stretched film stretched in two directions is preferred, and a biaxially stretched film is more preferred from the viewpoint of excellent balance of mechanical properties and flatness. The polyester constituting the polyester film that can be used as the substrate may be either a homopolyester or a copolymer polyester. The homopolyester is preferably one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more. Examples of dicarboxylic acid components of the copolymer polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of glycol components include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid components and glycol components may each be used alone or in combination of two or more. Representative examples of polyester include polyethylene terephthalate and polyethylene naphthalate. As the polyester film, from among the above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferred in consideration of mechanical strength and heat resistance, and films formed from polyethylene terephthalate are particularly preferred in consideration of ease of production and handleability for applications such as surface protection films.

[0082] The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the substrate may be any poly(meth)acrylate having a unit based on (meth)acrylate, and various acrylic resins can be used. Examples of the (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, as well as alkyl (meth)acrylates having an alkyl group with a larger number of carbon atoms. In consideration of transparency, processability, and chemical resistance, the poly(meth)acrylate preferably contains, as its main component, units based on alkyl(meth)acrylate having 1 to 4 carbon atoms, more preferably contains, as its main component, at least one selected from the group consisting of units based on methyl(meth)acrylate and units based on ethyl(meth)acrylate, and particularly preferably contains, as its main component, units based on methyl(meth)acrylate. It is also possible to impart properties such as flexibility to the poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl (meth)acrylates or units based on other monomers. The proportion of units based on alkyl(meth)acrylate having 1 to 4 carbon atoms relative to the total mass of the poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

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

[0084] The substrate may contain additives other than the particles as needed, such as known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments. When the substrate is a film, the thickness is not particularly limited as long as it is within a range that allows film formation, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

[0085] (Primer layer) The primer layer is appropriately provided between the substrate and the cured film (concave-convex layer) to impart various functions. The primer layer may be a single layer having a single function or multiple functions, or may be composed of multiple layers. In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the substrate and the uneven layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the substrate and the uneven layer is improved, and the laminate can be used for various applications. From the viewpoint of improving adhesion, it is preferable that the adhesion improving layer contains either one or both of a resin and a compound derived from a crosslinking agent. In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, adhesion of dust and the like due to peeling electrification or frictional electrification can be reduced to the outermost surface of the laminate, particularly to the outermost surface on the side of the substrate on which the uneven layer is present. To make the primer layer an antistatic layer, for example, an antistatic agent may be added to the primer layer.

[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 these, polyester resin, acrylic resin, and urethane resin are preferred in terms of adhesion performance and coating properties. When the substrate is a resin film, the resin contained in the primer layer is preferably the same type of resin as that of the resin film from the viewpoint of affinity with the substrate. For example, when the substrate is a polyester film, the primer layer preferably contains a polyester resin. When the substrate is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

[0087] The polyester resin may be one whose main constituents are a polycarboxylic acid and a polyhydroxy compound. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof. Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, and potassium dimethylolpropionate. One or more of these compounds may be appropriately selected and subjected to a conventional polycondensation reaction to synthesize a polyester resin.

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

[0089] A urethane resin is a polymeric compound having a urethane bond in the molecule, and is typically synthesized by reacting a polyol with a polyisocyanate compound. A chain extender may be used when synthesizing the urethane resin. Examples of polyols used to obtain the urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination of two or more.

[0090] Polycarbonate polyols are obtained by the reaction (dealcoholization reaction) of polyhydric alcohols with carbonate compounds. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

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

[0093] As the polyol, polyester polyol and polycarbonate polyol are preferred in view of adhesion performance, 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'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidenedicyclohexyl diisocyanate. These may be used alone or in combination of two or more. There are no particular limitations on the chain extender as long as it has two or more active groups that react with isocyanate groups, and generally, chain extenders having two hydroxyl groups or two amino groups can be mainly used. Examples of chain extenders having two hydroxyl groups include glycol compounds such as aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and ester glycols such as neopentyl glycol hydroxypivalate. Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropyltrimoniumcyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

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

[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. Known crosslinking agents can be used, including, for example, melamine compounds, isocyanate compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among these, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred. From the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, isocyanate compounds, and epoxy compounds are more preferred, and melamine compounds, oxazoline compounds, and isocyanate compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. Using two or more crosslinking agents in combination may further improve adhesion and durability.

[0097] A melamine compound is a compound having a melamine skeleton within the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohols to partially or completely etherify them, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be either a monomer or a dimer or higher polymer, or a mixture thereof. Furthermore, melamine partially co-condensed with urea or the like can also be used, and a catalyst can also be used to increase the reactivity of the melamine compound. Considering the reactivity with various compounds, melamine compounds having a hydroxyl group are preferred.

[0098] The isocyanate compound is an isocyanate compound or a compound having an isocyanate derivative structure, such as a blocked isocyanate compound. Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanate compounds having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanate compounds such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isopropylidenedicyclohexyl diisocyanate. Further examples include polymers and derivatives of these isocyanate compounds, such as biuretized products, isocyanurated products, urethodionated products, and carbodiimide-modified products. These may be used alone or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are preferred over aromatic isocyanate compounds, from the viewpoint of avoiding yellowing due to ultraviolet rays. Examples of the blocked isocyanate compound include those in which the isocyanate group of the above-mentioned isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include bisulfites, phenol-based compounds such as phenol, cresol, and ethylphenol, alcohol-based compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, active methylene-based compounds such as dimethyl malonate, diethyl malonate, isobutanoyl methyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan-based compounds such as butyl mercaptan and dodecyl mercaptan, lactam-based compounds such as ε-caprolactam and δ-valerolactam, amine-based compounds such as diphenylaniline, aniline, and ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime-based compounds such as formaldehyde, acetaldoxime, acetoneoxime, methyl ethyl ketoneoxime, and cyclohexanoneoxime. These may be used alone or in combination of two or more. As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferred from the viewpoint that the primer layer is less likely to be destroyed. The isocyanate compound may be used alone or as a mixture or bond with various polymers. In order to improve the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or bond with a polyester resin or a urethane resin.

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

[0100] An epoxy compound is a compound having an epoxy group in the molecule. Examples of epoxy compounds include condensates of epichlorohydrin with compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), such as polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl)isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

[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 involve the condensation reaction of a diisocyanate compound. The diisocyanate compound is not particularly limited, and either an aromatic or aliphatic diisocyanate can be used, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate. In order to improve the water solubility or water dispersibility of the polycarbodiimide-based compound, a surfactant may be added, or a hydrophilic monomer such as a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, or a hydroxyalkyl sulfonate may be added, within a range that does not impair the effects of the present invention.

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

[0103] These crosslinking agents react during the drying process and film-forming process to improve the performance of the primer layer. It is presumed that the formed primer layer contains compounds derived from the crosslinking agent, such as unreacted crosslinking agents, reacted compounds, or a mixture thereof.

[0104] The antistatic agent to be contained in the primer layer is not particularly limited, and any known antistatic agent can be used, such as a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, or a conductive organic polymer. The primer layer may contain particles to improve blocking and slip properties. The primer layer may contain additives such as antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments, as needed, within the scope of the present invention.

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

[0106] (Surface functional layer) The surface functional layer is a layer provided on the surface of the cured film (concave-convex layer) opposite the substrate layer to impart various functions. Examples of surface functional layers include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low-reflection layer, etc.), an infrared absorbing layer, an ultraviolet absorbing layer, and a color correction layer. The surface functional layer may be a single layer having a single function or multiple functions, or may be composed of multiple layers.

[0107] The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. Materials used for the antifouling layer include conventionally known materials such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds. Among these, silicone compounds and fluorine compounds are preferred for achieving stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of preventing the antifouling layer from contaminating objects that come into contact with it.

[0108] Silicone compounds refer to compounds having a silicone structure in the molecule, such as alkyl silicones such as dimethyl silicone and diethyl silicone, as well as phenyl silicones and methylphenyl silicones having a phenyl group. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and hydrocarbon groups such as various aromatic groups. Other common functional groups include silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms. It is also possible to use both in combination to form an addition-type silicone (a type resulting from the addition reaction of a vinyl group with a hydrogen silane). Another preferred method involves introducing a double bond such as an acryloyl group and reacting at the double bond. Furthermore, as the silicone compound, modified silicones such as acrylic-grafted silicone, silicone-grafted acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, etc. In consideration of heat resistance and contamination resistance, it is preferable to use a curable silicone resin, and any curing reaction type such as a condensation type, an addition type, or an active energy ray curable type can be used.

[0109] The fluorine compound is a compound containing a fluorine atom. As the fluorine compound, an organic fluorine compound is preferably used, for example, a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, an aromatic fluorine compound such as fluorobenzene, etc. From the viewpoint of mold releasability, a compound having a perfluoroalkyl group is preferable. Furthermore, as the fluorine compound, a compound containing a long-chain alkyl compound as described below can also be used. Examples of compounds having a perfluoroalkyl group include perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl(meth)acrylate, perfluoroalkylmethyl(meth)acrylate, 2-perfluoroalkylethyl(meth)acrylate, 3-perfluoroalkylpropyl(meth)acrylate, 3-perfluoroalkyl-1-methylpropyl(meth)acrylate, and 3-perfluoroalkyl-2-propenyl(meth)acrylate, and polymers thereof; and perfluoroalkyl group-containing vinyl ethers such as perfluoroalkylmethylvinylether, 2-perfluoroalkylethylvinylether, 3-perfluoropropylvinylether, 3-perfluoroalkyl-1-methylpropylvinylether, and 3-perfluoroalkyl-2-propenylvinylether, and polymers thereof. Considering heat resistance and stain resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Furthermore, from the viewpoint of stain resistance, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, the polymer may be a polymer with a compound containing a long-chain alkyl compound, as described below.

[0110] A long-chain alkyl compound is a compound having a linear or branched alkyl group typically having 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably 12 or more carbon atoms. Examples of alkyl groups include hexyl, octyl, decyl, lauryl, octadecyl, and behenyl groups. Examples of compounds having an alkyl group include various long-chain alkyl group-containing polymeric compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. In consideration of heat resistance and stain resistance, polymeric compounds are preferred. Furthermore, from the viewpoint of effectively achieving stain resistance, polymeric compounds having a long-chain alkyl group in the side chain are more preferred. A polymer compound having a long-chain alkyl group in its side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Examples of compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a polyester resin containing a reactive group, and a poly(meth)acrylic resin containing a reactive group. Among these, polyvinyl alcohol is preferred in terms of its antifouling properties and ease of handling. Examples of compounds having an alkyl group capable of reacting with the reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, in consideration of releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred. Furthermore, polymeric compounds having long-chain alkyl groups in their side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0111] The content of the antifouling material described above for achieving antifouling performance in the surface functional layer depends on the material used and cannot be generalized. However, in the case of silicone compounds or fluorine compounds, it is usually 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. Furthermore, when a long-chain alkyl group-containing compound is used, it is usually 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, and the upper limit may be 100% by mass. Using the above range can provide effective antifouling performance.

[0112] As the antistatic agent used in forming the antistatic layer as the surface functional layer, various conventionally known antistatic agents can be used. In addition, a method in which a double bond such as an acryloyl group is introduced into a compound having an ammonium group and the double bond is reacted is also preferred.

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

[0114] The thickness of the surface functional layer is preferably 5 times or less, more preferably 2 times or less, the height from the recesses to the protrusions of the uneven structure of the cured film. The smaller this ratio, the less likely the matte performance of the cured film to be reduced. The thickness of the surface functional layer cannot be generalized because it depends on the height from the recesses to the protrusions of the uneven structure of the cured film, but it is usually in the range of 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, even more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. Using a thickness within the above range makes it possible to achieve both the functionality of the surface functional layer and the matte properties of the cured film. The surface functional layer can be formed by a known method.

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

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

[0117] The thickness of the back functional layer cannot be generalized because it depends on the material used in the back functional layer and the performance to be achieved, but it is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm. The back surface functional layer can be formed by a known method.

[0118] (Formation of surface functional layer and back functional layer) The surface functional layer and the back surface functional layer can be formed, for example, by coating a liquid containing the above-mentioned components as a solution or dispersion in a solvent, adjusted to a solids concentration of approximately 0.1 to 80% by mass, onto a specified surface, and then drying and curing the liquid. Examples of the coating method include conventionally known coating methods such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating, and extrusion coating. The drying and curing conditions for forming the front functional layer and the back functional layer are not particularly limited. However, for the drying of solvents such as water used in the coating liquid, the drying temperature is typically in the range of 50 to 150°C, preferably 80 to 130°C, and more preferably 90 to 120°C. The drying time is typically in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Furthermore, to improve the strength of the front functional layer and the back functional layer, it is preferable to perform a heat treatment after drying, typically in the range of 150 to 270°C, preferably 170 to 230°C, and more preferably 180 to 210°C. The heat treatment time is typically in the range of 3 to 200 seconds, preferably 5 to 120 seconds. This type of heat treatment is suitable when the laminate is a film.

[0119] (Total light transmittance) The laminate preferably has a total light transmittance measured by the method described in the Examples below of preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more, with the higher the better (the upper limit is 100%).

[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 properties tend to be. Furthermore, particularly when used for anti-glare applications in various displays, the range is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more, with the upper limit being, for example, 99%. Depending on the application, the higher the range, the more preferable it is. [Example]

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

[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% (by weight) value in the equivalent sphericity distribution measured using a centrifugal sedimentation particle size distribution analyzer, Model SA-CP3, manufactured by Shimadzu Corporation, was taken as the average primary particle size.

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

[0125] (4) RSm, Sa and tilt angle (θa) Using a surface profile measurement system (Hitachi High-Tech Science Corporation's scanning white light interference microscope "VS1330"), the surface profile of a 177.60 μm x 236.87 μm area on the surface of the cured film was measured by optical interferometry, and the data was analyzed. The evaluation length used to calculate RSm and θa was 236.87 μm. The objective lens magnification during measurement was set to 20x. The presence or absence of wrinkle-like unevenness was also confirmed during this evaluation. The processing conditions used for data analysis are as follows. Surface correction: 4th order Interpolation: Full Interpolation Filter: Median 3x3 pixels Boundary processing: Symmetrical expansion and edge interpolation Trimming: None

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

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

[0128] (7) Surface resistance measurement method Using a high resistivity meter, Hiresta MCP-HP450, manufactured by Mitsubishi Chemical Analytech Co., Ltd., the surface resistivity of the sample was measured after 30 minutes of humidity conditioning in a measurement atmosphere 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 in accordance with JIS K5600-5-4:1999 General testing methods for paints - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method).

[0130] (9) Matte finish The laminate was placed in a room lit by a white linear fluorescent lamp, and the distance between the fluorescent lamp and the laminate was set at 2.5 m. The matte appearance of the uneven layer side (reflection of the fluorescent lamp) was visually evaluated according to the following evaluation criteria A to D. Evaluations A to C indicate that the matte appearance could be confirmed. A: The reflected image of the fluorescent light is very blurred and the outline of the fluorescent light cannot be seen. B: The reflected image from the fluorescent light is blurred, but you can still see a faint outline. C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be seen, it appears wavy and dark white. D: The reflected image of the fluorescent light is clear and the outline can be clearly seen, and it appears linear and white.

[0131] (10) Blocking resistance A laminate having a cured film formed on a substrate was placed with a polyester film on top of the cured film, and the polyester film 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% by mass of 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 weight of DQ100, 7.5 parts by weight of SL, 4.5 parts by weight of DM, 20 parts by weight of methyl ethyl ketone (MEK), and 50 parts by weight of isopropyl alcohol (IPA). After stirring began, the system was purged with nitrogen and heated to 55°C. 0.6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., V-65) was added, and the system was heated to 65°C. After stirring for 3 hours, 0.6 parts by weight 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 for the above raw materials mean the following: DQ-100: Light Ester (registered trademark) DQ-100 manufactured by Kyoeisha Chemical Co., Ltd. SL: Acryester (registered trademark) SL manufactured by Mitsubishi Chemical Corporation A 45:55 (weight ratio) mixture of lauryl methacrylate and tridecyl methacrylate DM: Acryester (registered trademark) DM manufactured by Mitsubishi Chemical Corporation N,N-dimethylaminoethyl methacrylate Mixture of quaternized N,N-dimethylaminoethyl methacrylate with methyl chloride

[0134] (Production of Acrylic Resin (C) Having Active Energy Ray-Curable Functional Groups) An acrylic resin (C) having an active energy ray-curable functional group was prepared by the following method. 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 to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was allowed to react for 3 hours at 65°C. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was added and the mixture was allowed to react for 3 hours, after which propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110°C for 6 hours to obtain acrylic resin (C) with a double bond content (acryloyl group concentration (amount of acryloyl group introduced)) of 1.2 mmol / g and radically polymerizable double bonds in the side chains. 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 nonvolatile content) shown in Table 1. Next, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM:MEK (mass ratio) 7:3) was added so that the solid content concentration was 30 mass %, and the mixture was stirred until homogenous to obtain a curable composition (coating liquid) used in each of the Examples and Comparative Examples. Antistatic agent (A1): Antistatic agent (A1) prepared by the above method Antistatic agent (A2): Quaternary ammonium base-containing (meth)acrylic polymer (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 Co., Ltd.) (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 Engineering Co., Ltd.) Photopolymerization initiator (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 solid content mass ratio of polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) = 60 / 25 / 10 / 5 to obtain a composition for forming a primer layer. Polyester resin (P1): Aqueous dispersion of polyester resin having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid / / (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56 / 40 / 4 / / 70 / 20 / 10 (mol%) Urethane resin (P2): Aqueous dispersion of polyester-based urethane resin with the following composition Isophorone diisocyanate: terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12:19:18:21:25:5 (mol%) Melamine compound (P3): Hexamethoxymethylolmelamine Particles: (P4): Silica particles with an average primary particle 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 middle layer was a mixture of polyesters (S1) and (S2) in proportions of 97% and 3% by mass, respectively. Each of these materials was fed into two extruders, melted at 285°C, and then co-extruded onto a cooling roll set at 40°C in a layer structure of two types and three layers (surface layer / middle layer / surface layer = discharge rate 1:8:1), cooled, and solidified to obtain an unstretched sheet. Next, the film was stretched 3.1 times in the longitudinal direction at a film temperature of 85°C using the difference in roll peripheral speed, and then a composition for forming a primer layer was applied to one side of this longitudinally stretched film, which was then introduced into a tenter and dried at 95°C for 10 seconds.Then, the film was stretched 4.2 times in the transverse direction at 120°C, heat-treated at 230°C for 10 seconds, and then relaxed 2% in the transverse direction to obtain a polyester film substrate 50 μm thick (after drying) with a 0.1 μm thick primer layer on one side.

[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 then irradiated with excimer light (half width 14 nm) from xenon (wavelength 172 nm) at an irradiation dose of 15 mJ / cm 2 , illuminance 5mW / cm 2 The coating film made from the coating solution in Table 1 was irradiated with a xenon excimer 172 nm light irradiator (Ushio Inc., lamp unit model: SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less)), and then irradiated with a high-pressure mercury lamp in an air atmosphere with an integrated light dose of 400 mJ / cm. 2 , illuminance 200mW / cm 2The film 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 of 5 μm (after drying), thereby obtaining a laminate. The resulting laminate had low surface resistance and 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 in the same manner as in Example 1, except that the composition of the coating liquid in Example 1 was changed to the composition shown in Table 1 and curing was carried out only by ultraviolet irradiation 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 was not matte. Furthermore, when excimer light was not used, poor curing was observed 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 raise the pencil hardness to 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, including a high surface resistance value.

[0142] [Table 2]

Claims

1. A cured film having a wrinkled uneven structure on its surface, formed by irradiating a coating film of an active energy ray-curable composition containing (meth)acrylate and particles (excluding SiOx nanoparticles) with excimer light to form a cured coating on the surface side of the coating film, and then irradiating the coating film with active energy rays other than vacuum ultraviolet rays to cure the interior of the coating film and buckle the cured coating, the cured film containing an antistatic agent, wherein the antistatic agent is an organic compound.

2. The amount of the particles is 30% by mass or less relative to the nonvolatile content in the active energy ray-curable composition, the 60° gloss is 50 or less, and the surface resistance is 1.0 × 10 １３ The cured film according to claim 1 , having a hardness of Ω or less.

3. 3. The cured film according to claim 1, wherein the particles are at least one type of particles selected from the group consisting of calcium carbonate particles, magnesium carbonate particles, barium carbonate particles, calcium sulfate particles, calcium phosphate particles, magnesium phosphate particles, kaolin particles, aluminum oxide particles, zirconium oxide particles, titanium oxide particles, acrylic resin particles, styrene resin particles, urea resin particles, phenolic resin particles, epoxy resin particles, and benzoguanamine resin particles.

4. The cured film according to any one of claims 1 to 3, wherein the particles have an average primary particle size of 0.01 to 30 µm.

5. The cured film according to any one of claims 1 to 4, wherein the concave-convex structure has a mean length (RSm) of roughness curve elements according to JIS B0601:2013 of 1 µm or more.

6. The cured film according to any one of claims 1 to 5, wherein the uneven structure has an arithmetic mean height (Sa) defined by ISO 25178 of 0.1 µm or more.

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

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

9. A method for producing a cured film described in any one of claims 1 to 8, which comprises forming a coating film of the active energy ray-curable composition and curing it by irradiating it with excimer light and active energy rays other than vacuum ultraviolet rays in that order.

10. A laminate comprising the cured film according to any one of claims 1 to 8 laminated on a substrate.

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

12. The method for producing a laminate according to claim 10 or 11, comprising laminating the active energy ray-curable composition on a substrate and curing the composition by irradiating it with excimer light and an active energy ray other than vacuum ultraviolet light in that order.

13. 12. The method for producing a laminate according to claim 10 or 11, comprising: laminating the active energy ray-curable composition, in which the amount of particles is 30 mass% or less based on the nonvolatile content, on a substrate; and curing the composition by irradiating the composition with excimer light and an active energy ray other than vacuum ultraviolet light in that order.

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