Active energy ray curable resin compositions, cured products, laminates, and articles

Abstract

The present invention provides an active energy ray curable resin composition, cured product, laminate, and article that exhibits excellent adhesion to the substrate and excellent scratch resistance and coating hardness in the cured product. [Solution] An active energy ray curable resin composition comprising (meth)acryloyl group-containing silica particles (A), at least one compound (B) selected from the group consisting of polyfunctional (meth)acrylate, urethane (meth)acrylate, and acrylic (meth)acrylate, and a photopolymerization initiator (C), wherein the particle size of the (meth)acryloyl group-containing silica particles (A) at D10 is 7 to 43 nm, the hydroxyl value of the polyfunctional (meth)acrylate is 300 mg KOH / g or less, and the mass ratio of the (meth)acryloyl group-containing silica particles (A) to the compound (B) is 80 / 20 to 60 / 40.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable resin composition, a cured product using the same, a laminate, and an article.

Background Art

[0002] Cyclic olefin resin films are excellent in transparency, low birefringence, low hygroscopicity, heat resistance, electrical insulation, chemical resistance, etc., and are widely used in optical members, medical applications, packaging films, automobiles, semiconductor applications, etc. In particular, in optical members, in accordance with the diversification of units for liquid crystal displays and touch panel applications, cyclic olefin resin films having high transparency and excellent low hygroscopicity have been widely used instead of the conventionally used triacetyl cellulose (TAC) resin films.

[0003] The surface of a resin film used for an optical member is coated with a transparent photocurable resin composition and cured to form a high-hardness film (hard coat layer), which is protected from scratches and the like. As a material for forming such a hard coat layer, an active energy ray-curable resin composition using polyfunctional (meth)acrylate or the like is known (for example, see Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, because the main structure of cyclic olefin resin films is an alicyclic structure, the polarity of the resin film surface is low and the water contact angle is high at about 90°. Therefore, when an active energy ray curable composition is applied, the coating does not spread easily, and there is a problem of low adhesion between the surface of the cyclic olefin resin film and the hard coat layer.

[0006] As a method to improve the adhesion between the resin film surface and the hard coat layer, a method has been proposed in which a primer layer mainly composed of a modified olefin resin having polar groups is applied to the surface of a cyclic olefin resin film, and then an ionizing radiation-curable resin is applied and cured (see, for example, Patent Document 2). While this method can improve the adhesion between the cyclic olefin resin film surface and the hard coat layer, it has the problem of increasing the number of steps involved in applying and drying the primer layer, further reducing yield and increasing costs.

[0007] Furthermore, methods to improve adhesion between the resin film surface and the hard coat layer include corona discharge treatment, which modifies the surface using discharge in air, and glow discharge treatment, which modifies the surface using discharge in a vacuum, thereby making the resin film surface more easily adhered, and then applying a hard coat layer to the film surface after the above treatments have been completed. However, in the case of cyclic olefin films, because polar groups are not present in their structure, it was sometimes difficult to achieve the desired sufficient adhesion even with corona discharge or glow discharge treatment. In addition, there was the problem of increased costs due to the increased number of surface treatment steps.

[0008] Furthermore, in addition to the problems mentioned above, because cyclic olefin resin films have low hardness, it is difficult to obtain sufficient strength required for optical components even when a hard coat layer is applied to the surface of the cyclic olefin resin film.

[0009] Therefore, in active energy ray curable resin compositions that form a hard coat layer, there was a need for a composition that, even when coated onto an untreated cyclic olefin resin film, would have sufficient adhesion to the substrate, as well as excellent scratch resistance and coating hardness.

[0010] The present invention was made to solve the above-mentioned problems, and aims to provide an active energy ray curable resin composition, cured product, laminate, and article that has excellent adhesion to a substrate and excellent scratch resistance and coating hardness in the cured product.

[0011] The present inventors conducted diligent research to solve the above problems and, as a result, discovered that by primarily incorporating (meth)acryloyl group-containing silica particles of a specific particle size and a specific (meth)acrylate compound in a specific ratio into an active energy ray-curable resin composition, the present invention can be achieved by obtaining a resin composition that has excellent adhesion to the substrate and excellent scratch resistance and coating hardness in the cured product.

[0012] In other words, the present invention encompasses the following embodiments. [1](meth)acryloyl group-containing silica particles (A) and A compound (B) selected from the group consisting of polyfunctional (meth)acrylates, urethane (meth)acrylates, and acrylic (meth)acrylates, Photopolymerization initiator (C) and A curable resin composition containing active energy rays, The particle size of the (meth)acryloyl group-containing silica particles (A) at D10 is 7 to 43 nm, the hydroxyl value of the polyfunctional (meth)acrylate is 300 mg KOH / g or less, and the mass ratio of the (meth)acryloyl group-containing silica particles (A) to the compound (B) is 80 / 20 to 60 / 40. Active energy ray curable resin composition. [2] The active energy ray curable resin composition according to [1], used for coating cyclic olefin substrates. [3] The active energy ray curable resin composition according to [1] or [2], wherein the photopolymerization initiator (C) comprises both a hydrogen abstraction type photopolymerization initiator and an intramolecular cleavage type photopolymerization initiator. A cured product of an active energy ray curable resin composition as described in any of [4][1] to [3]. [5] A laminate having a cured coating film of the active energy ray curable resin composition described in any of [1] to [3] on one or both sides of a substrate. [6] The laminate according to [5], wherein the substrate is a cyclic olefin substrate. [7] The laminate according to [5] or [6], wherein the thickness of the substrate is 90 μm or less. An article having a laminate on its surface as described in any of [8], [5], or [7]. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide active energy ray-curable resin compositions, cured products, laminates, and articles that have excellent adhesion to substrates and excellent scratch resistance and coating hardness in the cured product. [Modes for carrying out the invention]

[0014] The following describes in detail the active energy ray curable resin composition, cured product, laminate, and article of the present invention. However, the description of the constituent elements described below is an example (representative example) of one embodiment of the present invention and is not limited to these contents.

[0015] In the following explanation, "(meth)acryloyl" means acryloyl and / or methacryloyl. Also, "(meth)acrylate" means acrylate and / or methacrylate. Furthermore, "(meth)acrylic" means acrylic and / or methacrylic.

[0016] (Composition of ray-curable resin) The active energy ray-curable resin composition of the present invention (hereinafter, also simply referred to as "composition") contains (meth)acryloyl group-containing silica particles (A), at least one compound (B) selected from the group consisting of polyfunctional (meth)acrylate, urethane (meth)acrylate, and acrylic (meth)acrylate, and a photopolymerization initiator (C). Further, in the composition of the present invention, the particle diameter at D10 of the (meth)acryloyl group-containing silica particles (A) is 7 to 43 nm, the hydroxyl value of the polyfunctional (meth)acrylate is 300 mgKOH / g or less, and the mass ratio of the (meth)acryloyl group-containing silica particles (A) to the compound (B) is 80 / 20 to 60 / 40.

[0017] By containing the (meth)acryloyl group-containing silica particles (A), the composition of the present invention has excellent scratch resistance in the cured product as compared with the conventional composition containing surface-untreated silica. Further, since the particle diameter at D10 of the (meth)acryloyl group-containing silica particles (A) is 7 to 43 nm, it has sufficiently high transparency for use in optical parts and also has excellent substrate adhesion even for coating a cyclic olefin-based substrate. Furthermore, since the mass ratio of the (meth)acryloyl group-containing silica particles (A) to the compound (B) which is an ultraviolet curable resin is 80 / 20 to 60 / 40, a good coating film can be formed and it has excellent coating film hardness.

[0018] Therefore, according to the present invention, it is possible to provide an active energy ray-curable resin composition, a cured product, a laminate, and an article having excellent substrate adhesion, excellent scratch resistance in the cured product, and coating film hardness.

[0019] Hereinafter, after explaining the details of each component constituting the active energy ray-curable resin composition of the present invention, the cured product, the laminate, and the article will be explained.

[0020] <(Meth)acryloyl group-containing silica particles (A)> (Meth)acryloyl group-containing silica particles (A) have (meth)acryloyl groups on the surface of the silica particles. (Meth)acryloyl group-containing silica particles (A) can be used alone or in combination of two or more types.

[0021] (Meth)acryloyl group-containing silica particles (A) can be obtained, for example, by de-alcoholizing a compound having a (meth)acryloyl group and an alkoxysilane partial condensate.

[0022] Compounds having a (meth)acryloyl group are not particularly limited, but examples include hydroxyalkyl (meth)acrylates, ε-caprolactone condensates of said hydroxyalkyl (meth)acrylates, polyethylene glycol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

[0023] Examples of alkoxysilane partial condensates include compounds obtained by partially hydrolyzing and condensing an alkoxysilane compound and water in the presence of an acid or base catalyst. The alkoxysilane compound is not particularly limited, but examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

[0024] The shape of the (meth)acryloyl group-containing silica particles (A) is not particularly limited and may be spherical, hollow, solid, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped. Among these, the spherical shape of the (meth)acryloyl group-containing silica particles (A) is preferred.

[0025] The particle size of the (meth)acryloyl group-containing silica particles (A) at D10 is 7 to 43 nm, preferably 10 to 40 nm, and more preferably 12 to 38 nm. When the particle size is within the above range, a composition is likely to be obtained that can form a cured product with high transparency while having excellent substrate adhesion, scratch resistance, and coating hardness. The above particle size is obtained by measuring with a particle size analyzer, and D10 represents the particle size at which the cumulative value in particle size distribution measurement based on scattered light intensity reaches 10%. The particle size analyzer used for measurement is one that uses the dynamic light scattering method as its measurement principle, such as the ELSZ-2000 (manufactured by Otsuka Electronics Co., Ltd.).

[0026] (Meth)acryloyl group-containing silica particles (A) may be used in the form of a dispersion (sol) of (meth)acryloyl group-containing silica particles (A). Examples of dispersion media for the dispersion include water or an organic solvent, but an organic solvent is preferred from the viewpoint of compatibility and dispersibility with other components.

[0027] The organic solvent used as the dispersion medium is not particularly limited, but examples include: aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halogenated solvents such as methyl chloride, methyl bromide, methyl iodide, methylenedichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and orthodichlorobenzene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1,4- Examples include ether-based solvents such as dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amide-based solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxide-based solvents such as dimethyl sulfoxide; heterocyclic compound-based solvents such as N-methyl-2-pyrrolidone; and mixtures of two or more of these.

[0028] Among the above, preferred organic solvents used as dispersion media are ester-based or ester ether-based solvents, ether-based solvents, ketone-based solvents, alcohol-based solvents, and especially propylene glycol monomethyl ether, methyl ethyl ketone, methanol, isopropanol, ethyl acetate, and the like.

[0029] A dispersion (sol) of (meth)acryloyl group-containing silica particles (A) can be used in a dispersion medium at a silica concentration in the range of, for example, 1 to 50% by mass.

[0030] (meth)acryloyl group-containing silica particles (A) can be commercially available as long as they have a particle size within the range described above. Examples of commercially available (meth)acryloyl group-containing silica particles (A) include "MEK-AC-2140Z", "MEK-AC-4130Y", "MEK-AC-5140Z", "PGM-AC-2140Y", "PGM-AC-3140Y", "PGM-AC-4130Y", "MIBK-AC-2140Z", and "MIBK-SD-L" from Nissan Chemical Corporation, and "V-8802" and "V-8804" from JGC Catalysts & Chemicals Corporation.

[0031] The content of (meth)acryloyl group-containing silica particles (A) in the solid content of the active energy ray-curable resin composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 20 to 85% by mass, and particularly preferably in the range of 50 to 80% by mass. When the above content is within the above range, a composition capable of forming a cured product with excellent substrate adhesion, scratch resistance, and coating hardness tends to be obtained. The above content of (meth)acryloyl group-containing silica particles (A) is expressed as the percentage (by mass) of the solid content of (meth)acryloyl group-containing silica particles (A) relative to the solid content of the composition (i.e., the components constituting the active energy ray-curable resin composition, excluding components that volatilize at room temperature or by heating as necessary, such as solvents) which is set at 100% by mass.

[0032] <Compound B> Compound (B) is an active energy ray curable compound, and is at least one compound selected from the group consisting of polyfunctional (meth)acrylate (B1), urethane (meth)acrylate (B2), and acrylic (meth)acrylate (B3). Compound (B) can be used alone or in combination of two or more compounds.

[0033] <<Polyfunctional (meth)acrylate (B1)>> A polyfunctional (meth)acrylate is a compound having at least two (meth)acryloyl groups in its molecule. By containing a polyfunctional (meth)acrylate, the composition of the present invention, compared to a composition containing only a monofunctional (meth)acrylate, improves the crosslinking density after curing, resulting in a cured product with excellent scratch resistance and coating hardness. Polyfunctional (meth)acrylates can be used alone or in combination of two or more types.

[0034] Examples of difunctional (meth)acrylates include 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, and hydroxypivalate neopentyl glycol di(meth)acrylate. , propylene oxide modified neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol A propylene oxide modified di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tetraethyl Polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin propylene oxide modified di(meth)acrylate, bisphenoxyethanol fluorene ethylene oxide modified di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated isocyanurate di(meth)acrylate, trifluoroethyl (meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate t, 2,3-[(meth)acryloyloxymethyl]norbornane, 2,5-[(meth)acryloyloxymethyl]norbornane, 2,6-[(meth)acryloyloxymethyl]norbornane, 1,3-adamantyl di(meth)acrylate, 1,3-bis[(meth)acryloyloxymethyl]adamantane, tris(hydroxyethyl)isocyanurate di(meth)acrylate, 3,9-bis[1,1-dimethyl-2-(meth)acryloyloxyethyl]-2,4,8,10-tetraoxospiro[5.5] Examples include undecane, glycerin diacrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and ditrimethylolpropane di(meth)acrylate.

[0035] Examples of trifunctional (meth)acrylates include glycerin triacrylate, EO-modified glycerol tri(meth)acrylate, PO-modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified phosphate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, HPA-modified trimethylolpropane tri(meth)acrylate, (EO) or (PO)-modified pentaerythritol tri(meth)acrylate, (EO) or (PO)-modified trimethylolpropane tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, and tris(methacryloxyethyl) isocyanurate.

[0036] Examples of tetrafunctional (meth)acrylates include ditrimethylolpropanetetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and (EO) or (PO) modified dipentaerythritol tetra(meth)acrylate.

[0037] Examples of pentafunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, and (EO) or (PO)-modified dipentaerythritol penta(meth)acrylate.

[0038] Examples of hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate, (EO) or (PO) modified dipentaerythritol hexa(meth)acrylate, and the like.

[0039] The hydroxyl value of the polyfunctional (meth)acrylate is 300 mgKOH / g or less, preferably 295 mgKOH / g or less, and more preferably 290 mgKOH / g or less. If the upper limit of the hydroxyl value is below the above value, a good coating film can be formed, and a composition with high adhesion to the substrate and excellent scratch resistance and coating film hardness in the cured product tends to be obtained. The above hydroxyl value is a value measured in accordance with JIS K0070-1992, that is, the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of polyfunctional (meth)acrylate.

[0040] For polyfunctional (meth)acrylates, commercially available products can be used as long as the upper limit of the hydroxyl value is below the above value. Examples of commercially available polyfunctional (meth)acrylates include "Aronics® M-920", "Aronics® M-930", "Aronics® M-933", "Aronics® M-934", "Aronics® M-305", "Aronics® M-450", "Aronics® M-403", "Aronics® M-404", "Aronics® M-406", and "Aronics® MT-3545" manufactured by Toagosei Co., Ltd., and "Light Acrylate 9EG-A" manufactured by Kyoeisha Chemical Co., Ltd.

[0041] <<Urethane (meth)acrylate (B2)>> Examples of urethane (meth)acrylates include reaction products of polyisocyanates and compounds having hydroxyl groups and (meth)acryloyl groups. Urethane (meth)acrylates can be used alone or in combination of two or more types.

[0042] Polyisocyanates include, for example, aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; and isocyanurate-modified, biuret-modified, allophanate-modified, etc., of these.

[0043] Compounds having a hydroxyl group and a (meth)acryloyl group include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol tetra(meth)acrylate. )acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, ditrimethylolpropanetri(meth)acrylate; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of these compounds, or lactone modified compounds in which a (poly)lactone structure is introduced into the molecular structure of the above-mentioned compounds having various hydroxyl groups and (meth)acryloyl groups.

[0044] Commercially available urethane (meth)acrylate can be used. Examples of commercially available urethane (meth)acrylate include "EPS-1146" and "UNIDIC® V-4000" from DIC Corporation, "Shiko®" from Nippon Synthetic Chemical Co., Ltd., "Beamset® 500" from Arakawa Chemical Co., Ltd., "EBECRYL®" from Daicel-Scytec Corporation, and "Art Resin®" from Negami Kogyo Co., Ltd.

[0045] <<Acrylic (meth)acrylate (B3)>> Acrylic (meth)acrylates can be obtained, for example, by polymerizing an acrylic resin intermediate obtained by having a reactive functional group (α) having a reactive functional group such as a hydroxyl group, carboxyl group, isocyanate group, or glycidyl group as an essential component, and then further reacting it with an acrylic resin intermediate having a reactive functional group (β) that can react with these functional groups to introduce a (meth)acryloyl group. Acrylic (meth)acrylates can be used alone or in combination of two or more types.

[0046] Examples of (meth)acrylate compounds (α) having reactive functional groups include hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; carboxyl group-containing (meth)acrylate monomers such as (meth)acrylic acid; isocyanate group-containing (meth)acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; and glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether. These can be used individually or in combination of two or more.

[0047] The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as needed, in addition to the above-mentioned (meth)acrylate compound (α). Examples of other polymerizable unsaturated group-containing compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobolonyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can be used individually or in combination of two or more.

[0048] When the acrylic resin intermediate is obtained by copolymerizing a (meth)acrylate compound (α) with another polymerizable unsaturated group-containing compound, the reaction ratio of the two is such that an acrylic (meth)acrylate with excellent curability is formed. Therefore, the ratio of the (meth)acrylate monomer (α) to the total of the two compounds is preferably in the range of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.

[0049] Acrylic resin intermediates can be manufactured in the same manner as general acrylic resins. For example, they can be manufactured by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60°C to 150°C. Polymerization methods include, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Polymerization modes include, for example, random copolymers, block copolymers, and graft copolymers. When using solution polymerization, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, or glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether can be preferably used.

[0050] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as (meth)acrylate compound (β). (Meth)acrylate compounds (β) can be used alone or in combination of two or more types.

[0051] The reaction between the acrylic resin intermediate and the (meth)acrylate compound (β) can be carried out, for example, in the case of an esterification reaction, at a temperature range of 60 to 150°C, using an appropriate esterification catalyst such as triphenylphosphine. In the case of a urethane reaction, the reaction can be carried out at a temperature range of 50 to 120°C, by adding the compound dropwise to the acrylic resin intermediate. The reaction ratio of the two is preferably in the range of 1.0 to 1.1 moles of (meth)acrylate compound (β) per mole of functional groups in the acrylic resin intermediate.

[0052] Commercially available acrylic (meth)acrylate can be used. Examples of commercially available acrylic (meth)acrylate include "Luxidia® EMS-635" manufactured by DIC Corporation and "8KX" manufactured by Taisei Fine Chemical Co., Ltd.

[0053] The content of compound (B) in the solid content of the active energy ray curable resin composition (by mass of solid content) is preferably in the range of 10 to 50% by mass, more preferably in the range of 15 to 45% by mass, and particularly preferably in the range of 20 to 40% by mass. When the above content is within the above range, a composition capable of forming a cured product with high substrate adhesion, scratch resistance, and coating hardness tends to be obtained.

[0054] The mass ratio of (meth)acryloyl group-containing silica particles (A) to compound (B) ((meth)acryloyl group-containing silica particles (A) / compound (B), solid content ratio) is 80 / 20 to 60 / 40, with 75 / 25 to 65 / 35 being more preferable. From the viewpoint of obtaining high scratch resistance and coating hardness, a higher content of (meth)acryloyl group-containing silica particles (A) is preferable. On the other hand, from the viewpoint of forming a good coating film, a higher content of compound (B) is preferable. Therefore, if the above mass ratio is within the above range, a composition is likely to be obtained that can form a good coating film and a cured product having high substrate adhesion, scratch resistance, and coating hardness.

[0055] <Photopolymerization initiator (C)> The type of photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used. Examples of photopolymerization initiators include hydrogen abstraction type photopolymerization initiators and intramolecular cleavage type photopolymerization initiators. Photopolymerization initiators can be used alone or in combination of two or more types.

[0056] <<Hydrogen abstraction type photopolymerization initiator>> Examples of hydrogen abstraction type photopolymerization initiators include benzophenone, 4-methylbenzophenone, o-benzoyl methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylic benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, and 4-methyl Examples include benzophenone compounds such as benzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; xanthone compounds such as xanthone, 2-isopropylxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone, and 2,4-dichloroxanthone; and polymers having a benzophenone skeleton such as polybutylene glycol bis(4-benzoylphenoxy)acetate. Among these, benzophenone or 4-methylbenzophenone is more preferred from the viewpoint of improving substrate adhesion. These hydrogen abstraction type photopolymerization initiators can be used alone or in combination of two or more.

[0057] <<Intramolecular cleavage type photopolymerization initiator>> Examples of intramolecular cleavage-type photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthones and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone. These intramolecular cleavage-type photopolymerization initiators can be used individually or in combination of two or more.

[0058] The photopolymerization initiator may be a hydrogen abstraction type photopolymerization initiator alone or an intramolecular cleavage type photopolymerization initiator alone, but it is preferable to use a combination of these two types of photopolymerization initiators. Combining the two types of photopolymerization initiators improves substrate adhesion, improves reactivity with compound (B), reduces the amount of unreacted (meth)acrylate compounds in the resulting cured product, improves crosslinking density, and tends to improve the scratch resistance and hardness of the cured product.

[0059] When using a combination of a hydrogen abstraction type photopolymerization initiator and an intramolecular cleavage type photopolymerization initiator, the content ratio of the hydrogen abstraction type photopolymerization initiator to the intramolecular cleavage type photopolymerization initiator (hydrogen abstraction type photopolymerization initiator / intramolecular cleavage type photopolymerization initiator, mass ratio) is preferably in the range of 1 / 1 to 99 / 1, more preferably in the range of 2 / 1 to 99 / 1, and particularly preferably in the range of 3 / 1 to 99 / 1. By using these ranges, substrate adhesion, scratch resistance, and coating film hardness tend to improve.

[0060] Commercially available photopolymerization initiators can be used. Examples of commercially available photopolymerization initiators include IGM's "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", and "Omn irad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81", "Omnirad-MBF", "Omnirad-4MBZ", "Omnirad-OMBB ", "Omnirad-4PBZ", "Omnirad-DETX", "Omnirad-ITX", "Omnirad-TPO", "Omnirad-TPO-L", "Omnirad-1312", "Omnirad-1314", "O "Omnirad-1315", "Omnirad-1316", "Esacure-KIP150", "Esacure-ONE", "Esacure-KIP160", "Esacure-1001M", "Esacure-TZT", "Esacure-A198", "Omnipol-910", "Omnipol-TP", "Omnipol-TX", "Omnipol-BP", "Omnipol-ASA", "Kayacure-DETX", "Kayacure" manufactured by Nippon Kayaku Co., Ltd. Examples include "-MBP", "KayaCure-DMBI", "KayaCure-EPA", "KayaCure-OA", Stoufa Chemical's "ByCure-10", "ByCure-55", Akzo's "Trigonal P1", Sandoz's "Sandray 1000", Apjohn's "Deep", Ward Blenkinsop's "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD", and Runtec's "Runtecure(registered trademark)-1104".

[0061] Photopolymerization initiators can also be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds.

[0062] The content of the photopolymerization initiator (C) in the solid content of the active energy ray curable resin composition is preferably in the range of 0.05 to 20% by mass, more preferably in the range of 0.1 to 10% by mass, and particularly preferably in the range of 1 to 6% by mass. When the above content is within the above range, a composition capable of forming a cured product with high substrate adhesion, scratch resistance, and coating hardness tends to be obtained.

[0063] <Other resin components with active energy ray curing properties> The active energy ray-curable resin composition of the present invention may also be used in combination with other active energy ray-curable resin components other than compound (B), as long as they do not impair the effects of the present invention. Preferably, the total content of (meth)acryloyl group-containing silica particles (A), compound (B), and photopolymerization initiator (C) is 50% by mass or more in the solid content of the active energy ray-curable resin composition.

[0064] <Other optional additives> The active energy ray curable resin composition of the present invention may optionally contain various additives such as ultraviolet absorbers, polymerization inhibitors, antioxidants, organic solvents, inorganic fillers or polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants, and preservation stabilizers.

[0065] Examples of UV absorbers include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthen carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthen carboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These UV absorbers can be used individually or in combination of two or more.

[0066] Examples of polymerization inhibitors include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrene-phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1 Phenolic compounds such as 2-dihydroquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone and other quinone compounds, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrene-diphenylamine, reaction products of styrene-diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecyl Thioether compounds such as ruthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl=3,3'-sulfandiyldipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn Nitroso compounds such as propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfonate sodium, 2-nitroso-1-naphthol-4-sulfonate sodium, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphate compounds such as undecane, trisnonylphenyl phosphite, (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, and diethyldithiocarbamate zinc Examples include zinc compounds such as zinc dibutyldithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thion, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, and 3,3'-distearyl thiodipropionate. These polymerization inhibitors can be used individually or in combination of two or more.

[0067] As antioxidants, compounds similar to those exemplified as polymerization inhibitors can be used, and antioxidants can be used alone or in combination of two or more.

[0068] Furthermore, commercially available polymerization inhibitors and antioxidants include, for example, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumiriser BBM-S" and "Sumiriser GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0069] Any organic solvent that dissolves components (A) to (C) can be used. For example, the organic solvents exemplified in the dispersion (sol) of (meth)acryloyl group-containing silica particles (A) described above can be used. These organic solvents can be used individually or in combination of two or more.

[0070] Examples of inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. These inorganic fillers can be used individually or in combination of two or more types.

[0071] As pigments, commonly known and conventional inorganic pigments and organic pigments can be used.

[0072] Examples of inorganic pigments include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite. These inorganic pigments can be used individually or in combination of two or more.

[0073] Examples of white pigments include titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. These white pigments can be used individually or in combination of two or more.

[0074] Examples of organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ancenthron pigments, indanthron pigments, flavanthron pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used individually or in combination of two or more.

[0075] Examples of defoaming agents include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These defoaming agents can be used individually or in combination of two or more types.

[0076] Examples of viscosity modifiers include acrylic polymers and synthetic rubber latex that can be thickened by adjusting to an alkaline state, urethane resins that can be thickened by molecular association, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, water-added castor oil, amide wax, oxidized polyethylene, metal soap, and dibenzylidene sorbitol. These viscosity modifiers can be used individually or in combination of two or more.

[0077] Examples of leveling agents include silicone compounds, acetylenediol compounds, and fluorine compounds. These leveling agents can be used individually or in combination of two or more.

[0078] Examples of flame retardants include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate, as well as inorganic phosphorus compounds such as phosphate amides; phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Examples include cyclic organophosphorus compounds such as 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used individually or in combination of two or more types.

[0079] The active energy ray curable composition of the present invention is particularly preferred for use in coating cyclic olefin-based substrates, as described later. The cyclic olefin resin film having a cured coating of the active energy ray curable composition of the present invention can be applied to various uses due to its excellent optical properties, dimensional stability, heat resistance, and transparency of the substrate, as well as its excellent scratch resistance on the surface. In particular, it is useful as an optical film for the image display section of image display devices such as liquid crystal displays (LCDs) and organic light-emitting diodes (OLEDs). In particular, because it has excellent scratch resistance even when thin, it can be suitably used as an optical film for the image display section of image display devices in portable electronic terminals where there is a high demand for miniaturization and thinning, such as electronic organizers, mobile phones, smartphones, portable audio players, mobile PCs, and tablet terminals. Furthermore, when used as an optical film, it can be used as a protective film for the outermost surface of the image display section of an image display device, or as a substrate for a touch panel. Moreover, when used as a protective film, for example, in an image display device where a transparent panel is provided on top of an image display module such as an LCD module or an OLED module to protect the image display module, it can be attached to the front or back surface of the transparent panel to prevent scratches and to prevent scattering when the transparent panel is damaged.

[0080] (cured product) The cured product of the present invention can be obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, the irradiation may be carried out under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.

[0081] For practical and economic reasons, ultraviolet lamps are commonly used as sources of ultraviolet light. Specifically, these include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0082] The integrated light intensity of active energy rays is not particularly limited, but is between 0.1 and 50 kJ / m 2 Preferably, it is 0.3 to 20 kJ / m³. 2 It is more preferable that the cumulative light intensity is within the above range, as this can prevent or suppress the occurrence of uncured areas.

[0083] The irradiation with active energy rays may be performed in one stage or in two or more stages.

[0084] (Laminated structure) The laminate of the present invention has a cured coating film of the active energy ray curable resin composition of the present invention on one or both sides of a substrate, and can be obtained by coating the substrate with the active energy ray curable resin composition and curing it by irradiation with active energy rays.

[0085] Examples of substrates include cyclic olefin-based substrates and linear olefin-based substrates. Since the active energy ray-curable resin composition of the present invention yields a cured coating film with excellent adhesion to cyclic olefin resins, a cyclic olefin-based substrate is preferred as the substrate. The substrate may also be in the form of a film.

[0086] As for the cyclic olefin resin, there are no particular restrictions on its use, whether it is a homopolymer or a copolymer, as long as it is obtained by polymerizing cyclic olefins.

[0087] A cyclic olefin resin film is a substrate formed by molding a cyclic olefin resin onto a film. Since the active energy ray curable resin composition of the present invention exhibits excellent adhesion to cyclic olefin resins, an untreated cyclic olefin resin film may be used as the substrate. However, in order to further improve the adhesion to the substrate, a cyclic olefin resin film that has been treated by sandblasting, solvent treatment, electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet / electron beam irradiation treatment, oxidation treatment, etc., may also be used.

[0088] The thickness of the substrate is preferably 90 μm or less, more preferably 85 μm or less, and particularly preferably 80 μm or less. On the other hand, the thickness of the substrate is preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more. By keeping the thickness of the substrate within the above range, curling is more easily suppressed even when a hard coat layer is provided on one side of the cyclic olefin resin film.

[0089] Methods for forming the cured coating film that constitutes the laminate include, for example, painting methods, transfer methods, and sheet bonding methods.

[0090] Painting methods involve either spray-coating the product with paint, or applying a topcoat to the molded product using printing equipment such as curtain coaters, roll coaters, or gravure coaters, and then curing it by irradiating it with active energy rays.

[0091] The transfer method involves applying the above-mentioned active energy ray curable resin composition onto a release-type substrate sheet to obtain a transfer material, adhering the transfer material to the surface of a molded product, peeling off the substrate sheet to transfer the top coat to the surface of the molded product, and then irradiating it with active energy rays to cure it; or, after adhering the transfer material to the surface of a molded product, irradiating it with active energy rays to cure it, and then peeling off the substrate sheet to transfer the top coat to the surface of the molded product.

[0092] The sheet bonding method is a method of forming a protective layer on the surface of a molded product by bonding a protective sheet having a coating made of a curable composition on a base sheet, or a protective sheet having a coating made of a curable composition and a decorative layer on a base sheet, to a molded product.

[0093] Sheet bonding methods include, specifically, a method in which a base sheet of a protective layer-forming sheet, which has been prepared in advance, is bonded to the molded product, and then the resin layer is cross-linked and cured by heat curing to form a B-stage (post-bonding method), and a method in which a protective layer-forming sheet is sandwiched in a molding die, resin is injected and filled into the cavity to obtain a resin molded product, and at the same time the surface of the product is bonded to the protective layer-forming sheet, and then the resin layer is cross-linked and cured by heat curing (simultaneous molding bonding method).

[0094] If the active energy ray-curable composition contains an organic solvent, it is preferable to heat it at 40 to 120°C for several tens of seconds to several minutes after application to volatilize the organic solvent, and then cure the active energy ray-curable composition by irradiating it with active energy rays.

[0095] The laminate of the present invention may have other layer configurations besides the cured coating film made of an active energy ray curable resin composition. The method for forming these various layer configurations is not particularly limited; for example, they may be formed by directly applying resin raw materials, or by bonding pre-formed sheets together with an adhesive.

[0096] (Goods) The articles of the present invention have the laminate of the present invention on their surface. Examples of articles include various products such as mobile phones, home appliances, automotive interior and exterior materials, and plastic molded products for office automation equipment. [Examples]

[0097] 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. Unless otherwise specified, "parts," "%," etc., in the examples refer to mass-based measurements.

[0098] [Raw materials] The raw materials used in the examples and comparative examples are as follows:

[0099] <(meth)acryloyl group-containing silica particles (A)> <a1>Silica particles having methacryloyl groups on their surface (product name: PGM-AC-3140Y, manufactured by Nissan Chemical Corporation, particle size calculated by the BET method described in the catalog: 22 nm, dispersion medium: propylene glycol monomethyl ether (PGM)) <a2>Silica particles having methacryloyl groups on their surface (Product name: PGM-AC-2140Y, manufactured by Nissan Chemical Corporation, particle size calculated by the BET method described in the catalog: 12 nm, dispersion medium: PGM) <a3>Silica particles having methacryloyl groups on their surface (product name: PGM-AC-4130Y, manufactured by Nissan Chemical Corporation, particle size calculated by the BET method described in the catalog: 45 nm, dispersion medium: PGM)

[0100] <Silica particles> <ra1>Silica particles (product name: MA-ST-M, manufactured by Nissan Chemical Corporation, particle size calculated by the BET method described in the catalog: 22 nm, dispersion medium: methanol)

[0101] Table 1 below shows a list of the above raw materials. [Table 1]

[0102] <Compound (B)> <Polyfunctional (meth)acrylate (B1)> <b1-1>Glycerin and triacrylate (product name: Aronics® M-920, manufactured by Toagosei Co., Ltd., hydroxyl value: 235 mg KOH / g) <b1-2>Glycerin triacrylate (Product name: Aronics® M-930, manufactured by Toagosei Co., Ltd., hydroxyl value: 30 mg KOH / g) <b1-3>High hydroxyl value pentaerythritol acrylate (product name: Aronics® M-933, manufactured by Toagosei Co., Ltd., hydroxyl value: 271 mg KOH / g) <b1-4>High hydroxyl value pentaerythritol acrylate (product name: Aronics® M-934, manufactured by Toagosei Co., Ltd., hydroxyl value: 209 mgKOH / g) <b1-5>Pentaerythritol tritetraacrylate (Trade name: Aronics® M-305, manufactured by Toagosei Co., Ltd., Hydroxyl value: 117 mg KOH / g) <b1-6>Pentaerythritol tritetraacrylate (Trade name: Aronics® M-450, manufactured by Toagosei Co., Ltd., Hydroxyl value: 8 mg KOH / g) <b1-7>High hydroxyl value dipentaerythritol acrylate (product name: Aronics® MT-3545, manufactured by Toagosei Co., Ltd., hydroxyl value: 123 mg KOH / g) <b1-8>Dipentaerythritol penta-hexaacrylate (product name: Aronics® M-403, manufactured by Toagosei Co., Ltd., hydroxyl value: 93 mg KOH / g) <b1-9>Dipentaerythritol penta-hexaacrylate (product name: Aronics® M-404, manufactured by Toagosei Co., Ltd., hydroxyl value: 45 mg KOH / g)

[0103] Table 2 below shows a list of the above raw materials. [Table 2]

[0104] <Urethane (meth)acrylate (B2)> <b2-1>Urethane acrylate (product name: EPS-1146, manufactured by DIC Corporation)

[0105] <Acrylic (meth)acrylate (B3)> <b3-1>Acrylic acrylate (product name: Luxidia EMS-635, manufactured by DIC Corporation)

[0106] (Photopolymerization initiator (C)) <c1>1-Hydroxycyclohexylphenyl ketone (Trade name: Runtecure® 1104, manufactured by Runtec) <c2>4-Methylbenzophenone (Trade name: Omnirad-4MBZ, manufactured by IGM Resins)

[0107] (base material) <s1>Cycloolefin film substrate (Product name: ZeonorFilm® ZF-16, manufactured by Zeon Corporation, film thickness: 50 μm) <s2>Cycloolefin film substrate (Product name: ZeonorFilm® ZF-14, manufactured by Zeon Corporation, film thickness: 23 μm)

[0108] Table 3 below shows a list of the above raw materials. [Table 3]

[0109] The active energy ray-curable resin composition was prepared as follows. (Example 1: Preparation of Active Energy Ray Curable Resin Composition (1)) A ray-curable resin composition (1) was obtained by mixing 70 parts by mass (solid content) of silica particles having methacryloyl groups on the particle surface (Nissan Chemical Corporation's "PGM-AC-3140Y", particle size at D10: 18-20 nm), 30 parts by mass of glycerin and triacrylate (product name: Aronics M-920, manufactured by Toagosei Co., Ltd., hydroxyl value: 235 mg KOH / g), 0.3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Runtecure-1104, manufactured by Runtec), and 3 parts by mass of 4-methylbenzophenone (product name: Omnirad-4MBZ, manufactured by IGM Resins), and adjusting the non-volatile content to 38% with methyl ethyl ketone. In the active energy ray curable resin composition (1), the particle size of the (meth)acryloyl-containing silica particles (A) at D10 was 19 nm, the mass ratio of (meth)acryloyl-containing silica particles (A) to compound (B) was 70 / 30, and the solid content was 40%.

[0110] The particle size at D10 of the (meth)acryloyl-containing silica particles (A) in the active energy ray-curable resin composition was measured by dynamic light scattering using a zeta potential / particle size measurement system (ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.), and is the particle size at 10% of the cumulative value obtained from the particle size distribution. The measurement procedure is as follows. First, the measurement sample was diluted with an organic solvent so that the solid content concentration was 0.01 to 1.0 wt%, and a portion of the resulting solution was placed in a quartz cell and set in the sample holder. After setting, the light intensity monitor was checked and the sample concentration was adjusted as appropriate to achieve the optimal light intensity. Then, measurements were performed under the conditions of a temperature of 25°C, 10 dust cuts (cut method: Intensity, cut level Upper 15%, cut level Lower 100%), and 100 cumulative counts.

[0111] (Examples 2-18: Preparation of active energy ray curable resin compositions (2)-(18)) Active energy ray curable resin compositions (2) to (18) were obtained using the same method as in Example 1 with the compositions and formulations shown in Table 4.

[0112] [Table 4]

[0113] (Comparative Examples 1-9: Preparation of Active Energy Ray Curable Resin Compositions (R1)-(R9)) Active energy ray curable resin compositions (R1) to (R9) were obtained using the same method as in Example 1 with the compositions and formulations shown in Table 5.

[0114] [Table 5]

[0115] Note that all values ​​for parts by mass in Tables 4 and 5 represent solid content.

[0116] The laminate was prepared as follows: (Examples 19-29: Fabrication of laminates (L1)-(L11)) The active energy ray-curable resin compositions (1) to (11) obtained in Examples 1 to 11 were each applied to a cycloolefin film substrate (ZeonorFilm ZF-16, manufactured by Zeon Corporation) with a thickness of 50 μm using a bar coater, and then solvent-dried at 70°C for 30 seconds. Subsequently, under a nitrogen atmosphere, ultraviolet light at 200 mJ / cm² was applied using a high-pressure mercury lamp. 2 Irradiation was performed to obtain laminates (L1) to (11) having a cured coating film with a thickness of 4 μm on a cycloolefin film.

[0117] (Example 30: Fabrication of laminate (L12)) Using the active energy ray curable resin composition (12) obtained in Example 12, a laminate (L12) was obtained in the same manner as the laminations (L1) to (L11) of Examples 1 to 11, except that a cycloolefin film substrate (ZeonorFilm ZF-14, manufactured by Zeon Corporation) with a thickness of 23 μm was used instead of a cycloolefin film substrate (ZeonorFilm ZF-16, manufactured by Zeon Corporation) with a thickness of 50 μm.

[0118] (Examples 31-35: Fabrication of laminates (L13)-(L17)) Using the active energy ray curable resin compositions (14) to (18) obtained in Examples 14 to 18, laminates (L13) to (L17) were obtained in the same manner as the preparation of laminates (L1) to (L11) in Examples 19 to 29.

[0119] (Comparative Examples 10-18: Fabrication of laminates (L18)-(L26)) Using the active energy ray curable resin compositions (R1) to (R9) obtained in Comparative Examples 1 to 9, laminates (L18) to (L26) were obtained in the same manner as the preparation of laminates (L1) to (L11) in Examples 19 to 29.

[0120] The laminates (L1) to (L26) obtained in the above examples and comparative examples were used for the following evaluations.

[0121] [Method for evaluating coating film formation] The cured coating film of the laminate was visually inspected and evaluated according to the following criteria. A (Good): Almost no unevenness in the coating is observed. B (Practical): Some unevenness in the coating is observed. C (Not practical): Unevenness in the coating is observed throughout, or no coating is formed.

[0122] [Method for evaluating substrate adhesion (initial stage)] Cuts were made on the surface of the cured coating of the laminate using a utility knife to create 100 grid patterns of 1 mm x 1 mm. Cellophane adhesive tape was then applied over these grid patterns and rapidly peeled off five times. The number of grid patterns that remained without peeling was counted and evaluated according to the following criteria. A (Good): The number of remaining grid squares was 95 or more. B (Practical): The number of remaining grid squares was 90 or more but less than 95. C (Not practical): The number of remaining grid squares was less than 90.

[0123] [Methods for evaluating transparency] The haze value of the laminate was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number HZ-V3), and the transparency was evaluated as follows. A (Good): Three measurements were taken, and the average haze value was 2.0% or less. B (Not practical): After three measurements, the average haze value was over 2.0%.

[0124] [Method for evaluating coating hardness] The pencil hardness of the surface of the cured coating film of the laminate was measured under a 500g load condition in accordance with JIS K5600-5-4 (1999). Six measurements were taken for each hardness value, and the hardness value for which no scratches occurred in five or more measurements was defined as the coating film hardness of the laminate. The hardness of pencils, from hardest to hardest, is 2H, H, F, HB, and B.

[0125] [Method for evaluating scratch resistance] A 1.0 cm diameter disc-shaped indenter was wrapped in 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a 500 g load was applied to the indenter. The indenter was then subjected to an abrasion test by moving it back and forth 10 times across the surface of the laminate coating. The haze value of the laminate before and after the abrasion test was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number HZ-V3), and the difference between these values ​​(dH) was used for evaluation according to the following criteria. A smaller difference value (dH) indicates higher resistance to abrasion. A (Good): dH was 0.5 or less. B (Practical): dH was greater than 0.5 and less than or equal to 1.0. C (Not practical): dH was greater than 1.0.

[0126] Tables 6-8 show the evaluation results.

[0127] [Table 6]

[0128] [Table 7]

[0129] [Table 8]

[0130] Examples 19-35 shown in Tables 6 and 7 are examples of laminates using the active energy ray curable composition of the present invention. These laminates were found to have high transparency, excellent adhesion to cyclic olefin substrates, and excellent scratch resistance and coating hardness.

[0131] On the other hand, Comparative Examples 10 to 18 shown in Table 8 were not laminates that satisfied all of the requirements for transparency, substrate adhesion, scratch resistance, and coating hardness. For example, Comparative Example 10, which did not contain compound (B), and Comparative Example 11, in which the mass ratio of (meth)acryloyl group-containing silica particles (A) / compound (B) was 90 / 10, failed to form a good coating film. Furthermore, Comparative Example 12, in which the mass ratio of (meth)acryloyl group-containing silica particles (A) / compound (B) was 50 / 50, and Comparative Examples 14 and 16, in which the particle size of (meth)acryloyl group-containing silica particles (A) at D10 was 6 nm or less, were insufficient in terms of coating hardness. In addition, Comparative Examples 15 and 17, in which the particle size of (meth)acryloyl group-containing silica particles (A) at D10 was 44 nm or more, were insufficient in terms of substrate adhesion. Furthermore, Comparative Example 13, which did not contain (meth)acryloyl group-containing silica particles (A), was insufficient in terms of substrate adhesion and coating hardness. Furthermore, Comparative Example 18, which contained untreated silica particles instead of (meth)acryloyl group-containing silica particles (A), was insufficient in terms of scratch resistance.

Claims

1. (Meth)acryloyl group-containing silica particles (A), A compound (B) selected from the group consisting of polyfunctional (meth)acrylates, urethane (meth)acrylates, and acrylic (meth)acrylates, Photopolymerization initiator (C), A curable resin composition containing active energy rays, The particle size of the (meth)acryloyl group-containing silica particles (A) at D10 is 7 to 43 nm. The hydroxyl value of the polyfunctional (meth)acrylate is 300 mg KOH / g or less. The mass ratio of the (meth)acryloyl group-containing silica particles (A) to the compound (B) is 80 / 20 to 60 / 40. Active energy ray curable resin composition.

2. The active energy ray curable resin composition according to claim 1, used for coating cyclic olefin substrates.

3. The active energy ray curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) comprises both a hydrogen abstraction type photopolymerization initiator and an intramolecular cleavage type photopolymerization initiator.

4. A cured product of the active energy ray curable resin composition according to claim 1 or 2.

5. A laminate having a cured coating film of the active energy ray curable resin composition described in claim 1 or 2 on one or both sides of a substrate.

6. The laminate according to claim 5, wherein the substrate is a cyclic olefin-based substrate.

7. The laminate according to claim 5, wherein the thickness of the substrate is 90 μm or less.

8. An article having the laminate described in claim 5 on its surface.

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