JP7364098B2 - Acrylic (meth)acrylate resin, active energy ray-curable resin composition, cured product and article - Google Patents

Description

The present invention relates to an acrylic (meth)acrylate resin, an active energy ray-curable resin composition, a cured product, and an article.

Resin materials with (meth)acryloyl groups are widely used in fields such as paints and coatings because they can be easily and instantly cured by ultraviolet irradiation, etc., and the cured products have excellent transparency and hardness. It is being The objects to be coated are wide-ranging, such as optical films, plastic molded products, and wood products, and the required performance varies depending on the type and purpose of the object to be coated. Many resins have been proposed.

As resin materials having (meth)acryloyl groups, active energy ray-curable resin compositions containing acrylic resins having (meth)acryloyl groups, pentaerythritol tetraacrylate, and pentaerythritol triacrylate are known (e.g. , see Patent Document 1). The active energy ray-curable resin composition described in Patent Document 1 has an excellent balance between surface hardness and low curing shrinkage in the cured product, so it is useful as a coating agent for coating relatively thin plastic films. It is. However, there was a problem that the adhesion to the film base material, especially after long-term storage under high temperature and humid conditions, was low and peeling easily occurred.

Therefore, there has been a need for a material with excellent adhesion and scratch resistance that can be used as a coating agent.

JP2011-207947A

The problem to be solved by the present invention is an acrylic (meth)acrylate resin, an active energy ray-curable resin, which has excellent adhesion, and has excellent elongation, scratch resistance, and chemical resistance in the cured product. The purpose of the present invention is to provide compositions, cured products, and articles.

As a result of intensive research to solve the above problems, the present inventors have discovered an acrylic polymer that is a copolymer of a specific polymerizable compound, and an acrylic polymer made from a (meth)acrylic monomer (B) having a carboxyl group. The inventors have discovered that the above problems can be solved by using (meth)acrylate resin, and have completed the present invention.

That is, the present invention is an acrylic (meth)acrylate resin made from an acrylic polymer (A) and a (meth)acrylic monomer (B) having a carboxyl group as raw materials, wherein the acrylic polymer (A) is glycidyl ( Acrylic (a) characterized by being a copolymer of a polymerizable compound containing meth)acrylate (a1) and a (meth)acrylate compound (a2) whose homopolymer glass transition temperature (Tg) is 50°C or higher. The present invention relates to meth)acrylate resins, active energy ray-curable resin compositions, cured products, and articles.

The acrylic (meth)acrylate resin of the present invention has excellent adhesion to substrates and can form a cured product with excellent elongation, scratch resistance, and chemical resistance, so it can be used as a coating agent or adhesive. It can be used as a coating agent, particularly as a coating agent.

The acrylic (meth)acrylate resin of the present invention is characterized in that it is made from an acrylic polymer (A) and a (meth)acrylic monomer (B) having a carboxyl group as raw materials.

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The acrylic polymer (A) is a polymerizable compound containing glycidyl (meth)acrylate (a1) and a (meth)acrylate compound (a2) whose homopolymer glass transition temperature (Tg) is 50°C or higher. Use a copolymer.

The content of the glycidyl (meth)acrylate (a1) is such that the acrylic (meth)acrylate resin has excellent adhesion to the base material and can form a cured product with excellent elongation, scratch resistance, and chemical resistance. Therefore, the amount in the polymerizable compound is preferably in the range of 5 to 50% by weight, more preferably in the range of 5 to 20% by weight.

The (meth)acrylate compound (a2) may be any homopolymer having a glass transition temperature (Tg) of 50° C. or higher, such as methyl (meth)acrylate, tert-butyl (meth)acrylate, Examples include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate. These (meth)acrylate compounds can be used alone or in combination of two or more. Among these, at least two types of acrylic (meth)acrylate resins can be obtained that have excellent adhesion to substrates and can form cured products with excellent elongation, scratch resistance, and chemical resistance. It is preferable to use them in combination, and it is preferable that at least one of them is methyl (meth)acrylate.

When methyl (meth)acrylate is used as the (meth)acrylate compound (a2), the content of methyl (meth)acrylate has excellent adhesion to the base material, elongation, scratch resistance, and chemical resistance. In order to obtain an acrylic (meth)acrylate resin that can form a cured product with excellent properties, the (meth)acrylate compound (a2) preferably contains 25 to 65% by mass, and more preferably 35 to 55% by mass. preferable.

The mass ratio [(a1)/(a2)] of the glycidyl (meth)acrylate (a1) and the (meth)acrylate compound (a2) has excellent base material adhesion, elongation, and scratch resistance. The range is preferably from 0.05 to 20, and more preferably from 0.1 to 8, since an acrylic (meth)acrylate resin can be obtained that can form a cured product with excellent chemical resistance.

The polymerizable compound may include (meth)acrylate compounds other than the glycidyl (meth)acrylate (a1) and the (meth)acrylate compound (a2) (hereinafter referred to as "other (meth)acrylate compounds"), if necessary. (abbreviated)) may be included.

Examples of the other (meth)acrylate compounds include (meth)acrylic acid alkyl esters such as ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; cyclohexyl ( (meth)acrylates containing alicyclic structures such as meth)acrylates; (meth)acrylates containing aromatic rings such as phenyl (meth)acrylate and phenoxyethyl acrylate; (meth)acrylates containing silyl groups such as 3-methacryloxypropyltrimethoxysilane ) Acrylate; Examples include styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can be used alone or in combination of two or more.

Examples of the (meth)acrylic monomer (B) having a carboxyl group include acrylic acid, methacrylic acid, acrylic anhydride, and methacrylic anhydride. These (meth)acrylic monomers having a carboxyl group can be used alone or in combination of two or more. In addition, among these, acrylic acid is preferred because it provides an acrylic (meth)acrylate resin that has excellent substrate adhesion and can form a cured product with excellent elongation, scratch resistance, and chemical resistance. preferable.

The amount of the (meth)acrylic monomer (B) having a carboxyl group used is determined by the amount of the acrylic (meth)acrylic monomer (B) that can form a cured product that has excellent substrate adhesion and has excellent elongation, scratch resistance, and chemical resistance. ) Since an acrylate resin can be obtained, the amount is preferably in the range of 0.98 to 1.02 mol % based on 1 mol of glycidyl (meth)acrylate (a1).

The method for producing the acrylic (meth)acrylate resin of the present invention is not particularly limited, and can be produced by any known method as appropriate. For example, a method may be mentioned in which the acrylic polymer (A) and the (meth)acrylic monomer (B) having a carboxyl group are added dropwise in a nitrogen atmosphere for 4 to 10 hours by a dropping method.

The (meth)acryloyl group equivalent of the acrylic (meth)acrylate resin of the present invention is such that the acrylic (meth)acrylate resin can form a cured product with excellent substrate adhesion and excellent elongation, scratch resistance, and chemical resistance. ) Since an acrylate resin can be obtained, the range is preferably from 400 to 3000 g/equivalent, and more preferably from 500 to 2000 g/equivalent.

Since the acrylic (meth)acrylate resin of the present invention has a (meth)acryloyl group in its molecular structure, it can be used as an active energy ray-curable resin composition, for example, by adding a photopolymerization initiator. .

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-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-morpholinopropane-1- Examples include photoradical polymerization initiators such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.

Examples of commercially available photopolymerization initiators include "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”, “Omnirad 2100”, “Omnirad 754”, “Omnirad ad 784”, “Omnirad 500”, "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", " "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quan tacure PDO”, “Quantacure ITX” , "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15% by mass, and 0.1 to 10% by mass in the total of components other than the solvent of the active energy ray-curable resin composition. % range is more preferable.

Further, the photopolymerization initiator may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound, if necessary.

The active energy ray-curable resin composition of the present invention may contain resin components other than the above-mentioned acrylic (meth)acrylate resin. Examples of the other resin components include dendrimer type (meth)acrylate resin, urethane (meth)acrylate resin, acrylic (meth)acrylate resin, and epoxy (meth)acrylate resin. These other (meth)acrylate resins can be used alone or in combination of two or more.

The above-mentioned dendrimer type (meth)acrylate resin refers to a resin having a regular multi-branched structure and a (meth)acryloyl group at the end of each branched chain, and includes dendrimer type, hyperbranched type or It is also called star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (1-1) to (1-8). Any resin can be used as long as it has a (meth)acryloyl group at the end of each branched chain.

［式（１－１）～（１－８）中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素原子数１～４の炭化水素基である。］

[In formulas (1-1) to (1-8), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 1 to 4 carbon atoms. ]

As a commercial product of the dendrimer type (meth)acrylate resin, for example, "Viscoat #1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average per molecule (meth) Acryloyl group number 14], “Viscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], MIWON “SP- 1106" [weight average molecular weight (Mw) 1,630, average number of (meth)acryloyl groups per molecule 18], manufactured by SARTOMER "CN2301", "CN2302" [average number of (meth)acryloyl groups per molecule 16], "CN2303" [average number of (meth)acryloyl groups per molecule: 6], "CN2304" [average number of (meth)acryloyl groups per molecule: 18], "Esdrimer HU-22" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Shin Nakamura Chemical Examples include "A-HBR-5" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "New Frontier R-1150" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "Hypertech UR-101" manufactured by Nissan Chemical Co., Ltd.

The weight average molecular weight (Mw) of the dendrimer type (meth)acrylate resin is preferably in the range of 1,000 to 30,000. Further, the average number of (meth)acryloyl groups per molecule is preferably in the range of 5 to 30.

Examples of the urethane (meth)acrylate resin (B2) include those obtained by reacting various polyisocyanate compounds, (meth)acrylate compounds having a hydroxyl group, and, if necessary, various polyol compounds. The polyisocyanate compounds include, for example, aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, and water. Alicyclic diisocyanate compounds such as doped xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; Aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate; The following structural formula Polymethylene polyphenyl polyisocyanate having a repeating structure represented by (2); examples thereof include isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like. Each of these may be used alone, or two or more types may be used in combination.

［式（２）中、Ｒ^３はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^４はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（２）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１～３の整数であり、ｍは１以上の整数である。］

[In formula (2), R ³ is each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁴ each independently represents either an alkyl group having 1 to 4 carbon atoms or a bonding point connected to the structural moiety represented by Structural Formula (2) via a methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]

The (meth)acrylate compound having a hydroxyl group is, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. ) acrylate, dipentaerythritol (meth)acrylate compounds having a hydroxyl group such as penta(meth)acrylate; (meth)acrylate compounds having various hydroxyl groups have (poly)oxyethylene chains and (poly)oxypropylene in their molecular structures; (poly)oxyalkylene modified product into which a (poly)oxyalkylene chain such as a (poly)oxytetramethylene chain or the like is introduced; Examples include introduced lactone modified products.

The polyol compounds include, for example, aliphatic polyol compounds such as ethylene glycol, propene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol. Polyol compound; (poly)oxyalkylene in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of the various polyol compounds mentioned above. Modified products: Examples include lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds described above.

The acrylic (meth)acrylate resin is, for example, an acrylic resin obtained by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component. Examples include those obtained by introducing a (meth)acryloyl group into the intermediate by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups.

The (meth)acrylate compound (α) having a reactive functional group is, for example, a (meth)acrylate monomer having a hydroxyl group such as hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate; (Meth)acrylate monomers having carboxyl groups; (meth)acrylate monomers having isocyanate groups such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate; glycidyl ( Examples include (meth)acrylate monomers having a glycidyl group such as meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether. These can be used alone or in combination of two or more.

In addition to the (meth)acrylate compound (α), the acrylic resin intermediate may be one obtained by copolymerizing other compounds having polymerizable unsaturated groups as necessary. Examples of the other compounds having polymerizable unsaturated groups include (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ) Acrylic acid alkyl ester; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, Examples include aromatic ring-containing (meth)acrylates such as phenoxyethyl acrylate; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can be used alone or in combination of two or more.

The acrylic resin intermediate can be produced in the same manner as general acrylic resins. As an example of production conditions, it can be produced, for example, by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60°C to 150°C. Examples of polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Moreover, examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like. When carrying out the solution polymerization method, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferably used. I can do it.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but from the viewpoint of reactivity it should be the following combination: is preferred. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more.

For example, when the reaction is an esterification reaction, the reaction between the acrylic resin intermediate and the (meth)acrylate compound (β) is carried out at a temperature range of 60 to 150°C using an esterification catalyst such as triphenylphosphine. Examples of such methods include appropriately using . In addition, when the reaction is a urethanization reaction, a method such as allowing the reaction to occur while dropping the compound (β) onto the acrylic resin intermediate at a temperature range of 50 to 120°C can be mentioned. The reaction ratio between the two is preferably 1.0 to 1.1 mol of the (meth)acrylate compound (β) per 1 mol of functional groups in the acrylic resin intermediate.

Examples of the epoxy (meth)acrylate resin include those obtained by reacting an epoxy resin with (meth)acrylic acid or its anhydride. The epoxy resin is, for example, diglycidyl ether of dihydric phenol such as hydroquinone or catechol; diglycidyl ether of biphenol compound such as 3,3'-biphenyldiol or 4,4'-biphenyldiol; bisphenol A type epoxy resin; Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; 1,4-naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 2,6-naphthalene Polyglycidyl ethers of naphthol compounds such as diols, 2,7-naphthalenediol, binaphthol, and bis(2,7-dihydroxynaphthyl)methane; triglycidyl ethers such as 4,4',4''-methylidine trisphenol; phenol Novolak type epoxy resins such as novolac type epoxy resins and cresol novolac resins; ) A (poly)oxyalkylene modified product in which an oxyalkylene chain is introduced; a lactone modified product in which a (poly)lactone structure is introduced into the molecular structure of the various epoxy resins mentioned above.

Moreover, the active energy ray-curable resin composition of the present invention may further contain other components. Examples of the other components include inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, ultraviolet absorbers, antioxidants, silicon additives, fluorine additives, antistatic agents, organic beads, quantum Examples include dots (QD), rheology control agents, defoaming agents, antifogging agents, coloring agents, and the like.

The inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, etc. of the cured coating film of the active energy ray-curable resin composition, and various known and commonly used inorganic fine particles can be used. Examples include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These may be used alone or in combination of two or more.

Among these inorganic fine particles, silica particles are preferred because they are easily available and easy to handle. Examples of the silica particles include various silica particles such as fumed silica, wet silica called precipitated silica, gel silica, and sol-gel silica, and any of them may be used.

The inorganic fine particles may have functional groups introduced onto their surfaces using various silane coupling agents. By introducing a functional group onto the surface of the inorganic fine particles, the miscibility with organic components such as the acrylic (meth)acrylate resin (A) is increased, and storage stability is improved.

Examples of the silane coupling agent that modifies the inorganic fine particles include [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, and [(meth)acryloyloxyalkyl]alkyldialkoxysilane. , [(meth)acryloyloxyalkyl]trialkoxysilane, the (meth)acryloyloxy-based silane coupling agent; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylarylsilane, dialkylalkoxyallylsilane , alkyldialkoxyallylsilane, trialkoxyallylsilane; styrenic silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, styryltrialkoxysilane; (glycidyloxyalkyl) ) trialkylsilane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)trialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]trimethoxysilane, [( 3,4-epoxycyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3,4-epoxycyclohexyl)alkyl]alkyldialkoxysilane, [(3,4- Epoxy-based silane coupling agents such as epoxycyclohexyl)alkyl]trialkoxysilane; (isocyanatealkyl)trialkylsilane, (isocyanatealkyl)dialkylalkoxysilane, (isocyanatealkyl)alkyldialkoxysilane, (isocyanatealkyl)trialkoxysilane, etc. Examples include isocyanate-based silane coupling agents. Each of these may be used alone, or two or more types may be used in combination.

Among the silane coupling agents, (meth)acryloyloxy-based silane coupling agents are preferred because they form inorganic fine particles with excellent miscibility with organic components such as the acrylic (meth)acrylate resin. Particularly preferred are [(meth)acryloyloxyalkyl]trialkoxysilanes such as acryloyloxypropyltrimethoxysilane.

The average particle diameter of the inorganic fine particles is not particularly limited, and may be adjusted as appropriate depending on the desired performance of the cured product. In particular, the average particle diameter of the inorganic fine particles is preferably in the range of 80 to 250 nm, since a cured coating film having excellent anti-blocking properties and transparency in addition to scratch resistance and crack prevention properties can be obtained. The range is more preferably from 90 to 180 nm, and particularly preferably from 100 to 150 nm.

The average particle diameter of the inorganic fine particles is a value obtained by measuring the particle diameter in the active energy ray-curable resin composition under the following conditions.
Particle size measuring device: “ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: A solution of an active energy ray-curable resin composition in methyl isobutyl ketone with a nonvolatile content of 1% by mass.

In the active energy ray-curable resin composition of the present invention, the content of the inorganic fine particles is not particularly limited, and may be adjusted as appropriate depending on the desired performance of the cured product. In particular, since a cured coating film with excellent scratch resistance can be obtained, the content of the inorganic fine particles is preferably in the range of 10 to 100 parts by mass based on 100 parts by mass of the acrylic (meth)acrylate resin.

Examples of the silane coupling agent added to the active energy ray-curable resin composition include [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, and [(meth)acryloyloxy]. (meth)acryloyloxy-based silane coupling agents such as [alkyl]alkyldialkoxysilane, [(meth)acryloyloxyalkyl]trialkoxysilane; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkyl Vinyl silane coupling agents such as allylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, and trialkoxyallylsilane; Styrenic silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane ; (glycidyloxyalkyl)trialkylsilane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)trialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]tri Methoxysilane, [(3,4-epoxycyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3,4-epoxycyclohexyl)alkyl]alkyldialkoxysilane, [ Epoxy-based silane coupling agents such as (3,4-epoxycyclohexyl)alkyl]trialkoxysilane; (isocyanatealkyl)trialkylsilane, (isocyanatealkyl)dialkylalkoxysilane, (isocyanatealkyl)alkyldialkoxysilane, (isocyanatealkyl) ) Isocyanate-based silane coupling agents such as trialkoxysilane and the like. Each of these may be used alone, or two or more types may be used in combination.

Examples of commercially available phosphate ester compounds include "Kayamar PM-2" and "Kayamar PM-21" manufactured by Nippon Kayaku Co., Ltd., which are phosphoric ester compounds having a (meth)acryloyl group in their molecular structure. "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A (N)" manufactured by Kyoeisha Chemical Co., Ltd. "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300" manufactured by SOLVAY ”, “SIPOMER PAM 4000”, “Viscoat #3PA”, “Viscoat #3PMA”, manufactured by Osaka Organic Chemical Industry Co., Ltd., “New Frontier S-23A”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; Examples include "SIPOMER PAM 5000" manufactured by SOLVAY, which is an acid ester compound.

The solvent is added for the purpose of controlling the coating viscosity of the active energy ray-curable resin composition, and the type and amount thereof are adjusted as appropriate depending on the desired performance. Generally, the active energy ray-curable resin composition is used so that the nonvolatile content is in the range of 10 to 90% by mass. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; and aromatic solvents such as toluene and xylene. Solvents: Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Examples include glycol ether solvents such as glycol monopropyl ether. These solvents can be used alone or in combination of two or more.

Examples of the ultraviolet absorber include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, Triazine derivatives such as 3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2 -xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.

Examples of the silicone additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified copolymer. Polyorganosiloxanes having alkyl groups or phenyl groups such as dimethylpolysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, polydimethylsiloxanes having polyester-modified acrylic groups, etc. Can be mentioned. These silicon-based additives can be used alone or in combination of two or more.

Examples of commercially available fluorine additives include the "Megaface" series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.

Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. These antistatic agents can be used alone or in combination of two or more.

Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, and polyolefin resin beads. , polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluoroethylene resin beads, polyethylene resin beads, and the like. These organic beads can be used alone or in combination of two or more. Further, the average particle size of these organic beads is preferably in the range of 1 to 10 μm.

The quantum dots (QDs) include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, III-VI group semiconductor compounds, and IV-VI group semiconductor compounds. , I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, group IV elements or compounds containing them, etc. It will be done. The II-VI group semiconductor compound is, for example, a binary compound such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZ. nTe, CdSeS, Ternary compounds such as CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe; CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSe Quaternary elements such as S, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, HgZnSTe, etc. Examples include compounds. Examples of the III-IV group semiconductor compounds include B ₄ C ₃ , Al ₄ C ₃ , and Ga ₄ C ₃ . The III-V semiconductor compound is, for example, a binary compound such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; GaNP, GaNAs, GaNSb, Ternary compounds such as GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP , GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP , InAlNAs, InAlNSb, InAlPAs, InAlPSb, and other quaternary compounds. The III-VI group semiconductor compounds include, for example, Al ₂ S ₃ , Al ₂ Se ₃ , Al ₂ Te ₃ , Ga 2 S 3 , Ga ₂ Se ₃ , _{Ga 2 Te 3 ,} GaTe, In ₂ S ₃ , In _{2 Se3} , _In2Te3 , _InTe , etc. are mentioned. The IV-VI group semiconductor compound is, for example, a binary compound such as SnS, SnSe, SnTe, PbS, PbSe, PbTe; or a ternary compound such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, etc. ; Examples include quaternary compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe. The I-III-VI group semiconductor compounds include, for example, _{CuInS 2} , CuInSe ₂ , CuInTe 2 , CuGaS ₂ , CuGaSe ₂ , CuGaSe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaSe 2 , AgGaS ₂ , AgGaTe _{2 etc.} Can be mentioned. Examples of the group IV element or a compound containing the same include C, Si, Ge, SiC, and SiGe. A quantum dot may be made of a single semiconductor compound, or may have a core-shell structure made of a plurality of semiconductor compounds. Moreover, the surface may be modified with an organic compound.

These various additives can be added in any amount depending on the desired performance, etc., but usually 0.0% to 100% by mass of the total components excluding the solvent in the active energy ray-curable resin composition. It is preferable to use it in a range of 0.01 to 40% by mass.

The active energy ray-curable resin composition used in the present invention is produced by mixing the above ingredients. The mixing method is not particularly limited, and a paint shaker, disperser, roll mill, bead mill, ball mill, attritor, sand mill, bead mill, etc. may be used.

The cured product of the present invention can be obtained by irradiating the active energy ray-curable resin composition with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Further, when ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, the irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere.

As a source of ultraviolet light, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. can be mentioned.

The cumulative amount of active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , more preferably 0.5 to 10 kJ/m ² . It is preferable that the cumulative light amount is within the above range because it is possible to prevent or suppress the occurrence of uncured portions.

Note that the irradiation with the active energy rays may be performed in one step, or may be performed in two or more steps.

In addition, the tan δ measured by the dynamic viscoelasticity spectrum of the cured product in the temperature range of 120 to 200°C has excellent adhesion to the base material and excellent elongation, scratch resistance, and chemical resistance. , preferably in the range of 0.1 to 1.

The article of the present invention has the above-mentioned laminate on its surface. Examples of the articles include plastic molded articles such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that the present invention is not limited to the examples listed below.

In this example, the weight average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) under the following conditions.

Measuring device: “HLC-8220” manufactured by Tosoh Corporation
Column: “Guard Column H _XL -H” manufactured by Tosoh Corporation
+ “TSKgel G5000HXL” manufactured by Tosoh Corporation
+ “TSKgel G4000HXL” manufactured by Tosoh Corporation
+ “TSKgel G3000HXL” manufactured by Tosoh Corporation
+ “TSKgel G2000HXL” manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: “SC-8010” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40℃
Solvent Tetrahydrofuran
Flow rate 1.0ml/min Standard: Polystyrene Sample: 0.4% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100μl)

(Example 1: Preparation of acrylic acrylate resin (1))
67.9 parts by mass of methyl isobutyl ketone was charged into a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised while stirring until the internal temperature of the system reached 110°C. Next, 8.4 parts by mass of glycidyl methacrylate, 37.8 parts by mass of methyl methacrylate, 53.8 parts by mass of tert-butyl methacrylate, 0.2 parts by mass of ethyl acrylate, t-butylperoxy-2-ethylhexanoate (Japan) A mixed solution consisting of 1.8 parts by mass of "Perbutyl O" (manufactured by Emulsifier Co., Ltd.) was added dropwise from the dropping funnel over 4 hours, and maintained at 110° C. for 15 hours. Next, after lowering the temperature to 90 ° C., 0.05 parts by mass of methoquinone and 4.3 parts by mass of acrylic acid were added, and 0.5 parts by mass of triphenylphosphine was added, and after reacting at 100 ° C. for 8 hours or more, The mixture was diluted with methyl isobutyl ketone to obtain 238 parts by mass (nonvolatile content: 45.0 mass %) of a solution of acrylic acrylate resin in methyl isobutyl ketone. The weight average molecular weight (Mw) of this acrylic acrylate resin (1) was 26,000, and the theoretical acryloyl group equivalent in terms of solid content was 1790 g/equivalent.

(Examples 2 to 5: Production of acrylic acrylate resins (2) to (6))
Acrylic acrylates (2) to (6) were obtained in the same manner as in Example 1 using the blending ratios shown in Table 1.

(Comparative Examples 1 and 2: Production of acrylic acrylate resins (R1) and (R2))
Acrylic acrylates (2) to (5) were obtained in the same manner as in Example 1 using the blending ratios shown in Table 1.

Table 1 shows the compositions of the acrylic acrylate resins (1) to (6), (R1) and (R2) prepared in Examples 1 to 6 and Comparative Examples 1 and 2.

"GMA" in Table 1 indicates glycidyl methacrylate (Tg of homopolymer: 46°C).

"MMA" in Table 1 indicates methyl methacrylate (Tg of homopolymer: 105°C).

"tBMA" in Table 1 indicates tertiary butyl methacrylate (Tg of homopolymer: 107°C).

"CHMA" in Table 1 indicates cyclohexyl methacrylate (Tg of homopolymer: 66°C).

"IBXMA" in Table 1 indicates isobornyl methacrylate (Tg of homopolymer: 180°C).

"BZMA" in Table 1 indicates benzyl methacrylate (Tg of homopolymer: 54°C).

"EA" in Table 1 indicates ethyl acrylate (Tg of homopolymer: -20°C).

"AA" in Table 1 indicates acrylic acid.

"MIBK" in Table 1 indicates methyl isobutyl ketone.

"p-O" in Table 1 indicates t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Nyukazai Co., Ltd.).

"TPP" in Table 1 indicates triphenylphosphine.

(Example 7: Preparation of active energy ray-curable resin composition (1))
15.5 parts by mass of the acrylic acrylate resin with a non-volatile content of 45% by mass (7 parts by mass as solid content) obtained in Example 1, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“Aronix” manufactured by Toagosei Co., Ltd.) 3 parts by mass of "M-403") and 0.3 parts by mass of a photopolymerization initiator ("Omnirad-184" manufactured by IGM Resins) were mixed to obtain an active energy ray-curable resin composition (1).

(Examples 8 to 12: Preparation of active energy ray-curable resin compositions (2) to (6))
Active energy ray-curable resin compositions (2) to (6) were obtained in the same manner as in Example 6 using the blending ratios shown in Table 1.

The following evaluations were performed using the active energy ray-curable resin compositions (1) to (6), (R1), and (R2) obtained in the above Examples and Comparative Examples.

[Method for measuring tanδ]
The active energy ray-curable resin composition is applied to a mirror-finished aluminum plate using an applicator, and after preheating at 100°C for 30 minutes, it is cured by irradiating ultraviolet rays (150 mJ/cm ² ) with a high-pressure mercury lamp in a nitrogen atmosphere. A membrane was created. The obtained cured film was isolated from the mirror-finished aluminum plate, and a test piece with a thickness of 50 μm, a width of 6 mm, and a length of 54 mm was prepared. DMA (dynamic viscoelasticity) was measured using TA Instruments'"Solid Rheological Elasticity Measurement Device RSA-G2" at a heating rate of 5°C/min, a frequency of 1Hz, and a load strain of 0.1%. The elastic modulus of the test piece was measured. For tan δ, the value at 130° C., which is the same temperature as the elongation measurement temperature, was adopted.

[Evaluation method of base material adhesion]
The active energy ray-curable resin composition was applied onto a 250 μm thick polycarbonate-acrylic laminate film (“ShineTech AW-10U” manufactured by Shine Techno Co., Ltd.) using a bar coater, and dried at 80° C. for 1 minute. Next, 400 mJ/cm ² of ultraviolet rays were irradiated with an 80 W high-pressure mercury lamp in an air atmosphere to obtain a laminate (2) having a cured coating film with a thickness of 5 μm on the acrylic film. Cut the surface of the cured coating film of this laminate (2) with a cutter knife to create 100 grids of 1 mm x 1 mm, apply cellophane adhesive tape on top of the grid, and then rapidly peel it off. The number of grids remaining without peeling was counted and evaluated according to the following criteria.

A: The number of remaining pieces on the grid was 80 or more.
B: The number of remaining pieces of the grid was less than 80.

[Evaluation method of elongation]
The elongation was measured based on a tensile test.
<Production of laminated film 1>
The active energy ray-curable resin compositions obtained in Examples and Comparative Examples were applied to a 188 μm thick polyethylene terephthalate (PET) film (Toray Mirror SF-20) using a bar coater, and dried at 80° C. for 1 minute. Next, by irradiating ultraviolet rays (150 mJ/cm ² ) with a high-pressure mercury lamp in a nitrogen atmosphere, a laminated film 1 in which a cured product having a thickness of 5 μm was laminated on a PET film was obtained.

<Tensile test>
The obtained laminated film was cut into test pieces with a width of 10 mm and a length of 100 mm, and the obtained test pieces were subjected to a tensile test under the following conditions. The tensile elongation until breakage was measured and evaluated using a universal testing machine (manufacturer: Shimadzu Corporation, Autograph AG-IS) according to the following criteria.

Measurement conditions: tensile speed: 100 mm/min, distance between chucks: 40 mm, temperature: 130°C
Load cell: 1kN

[Evaluation method of scratch resistance]
A disc-shaped indenter with a diameter of 2.4 cm is wrapped with 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a load of 500 g is applied to the indenter. Then, an abrasion test was conducted by making the coated surface of the laminated film obtained in <Preparation of Laminated Film 1> reciprocate 10 times. The haze value of the laminated film before and after the abrasion test was measured using "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd., and the difference value (dH) was used to determine the haze value according to the following standards. evaluated. Note that the smaller the difference value (dH), the higher the resistance to scratches.

A: dH was 1.0% or less B: dH was more than 1.0% to 3.0% or less.
C: dH was over 3.0%.

[Method for evaluating chemical resistance]
<Production of laminated film 2>
The active energy ray-curable resin compositions obtained in Examples and Comparative Examples were coated on a 250 μm thick polycarbonate (PC) film (“ShineTech PC-10U” manufactured by Shine Techno Co., Ltd.) using a bar coater, and coated at 90°C for 2 hours. Dry for a minute. Next, by irradiating ultraviolet rays (500 mJ/cm ² ) with a high-pressure mercury lamp in an air atmosphere, a laminated film 2 in which a cured product having a thickness of 5 μm was laminated on the PC film was obtained.
<Chemical resistance test>
A sunscreen cream ("Neutrogena Ultra Sheer Sunscreen" manufactured by Johnson & Johnson Consumer Inc.) was applied to the cured coating surface of the laminated film 2 at a concentration of 0.1 g/cm ² and then heated in an oven at 80° C. for 4 hours. Let it stand for a while. After taking it out of the oven and returning it to room temperature, the sunscreen cream was wiped off with a cloth, and the condition of the coating film surface after wiping was evaluated according to the following criteria.

A: There is no change compared to the laminate before the test.
B: A thin transparent mark remains on the coating film.
C: Whitening and cracks occur in a part of the coated area.
D: Whitening and cracks occur on the entire surface of the coated area.

Table 1 shows the compositions and evaluation results of active energy ray-curable resin compositions (1) to (6) prepared in Examples 7 to 12, and (R1) and (R2) prepared in Comparative Examples 3 and 4. .

"Aronix M-403" in Table 2 refers to "Aronix M-403" manufactured by Toagosei Co., Ltd.; a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

"Omnirad 184" in Table 2 indicates a photopolymerization initiator manufactured by IGM Resins.

Examples 7 to 12 shown in Table 2 are examples of active energy ray-curable resin compositions containing the acrylic acrylate resin of the present invention. It was confirmed that the cured products of these active energy ray-curable resin compositions had excellent substrate adhesion, elongation, scratch resistance, and chemical resistance.

On the other hand, Comparative Example 3 shown in Table 2 is an example of an active energy ray-curable resin composition using a (meth)acrylate compound having a homopolymer glass transition temperature (Tg) of less than 50° C. as a raw material. Although the cured product of this active energy ray-curable resin composition had excellent adhesion to substrates, it was confirmed that it was significantly insufficient in elongation, scratch resistance, and chemical resistance.

Comparative Example 4 is an example of an active energy ray-curable resin composition in which a (meth)acrylate compound (a2) whose homopolymer has a glass transition temperature (Tg) of 50° C. or higher is not used as a raw material. It was confirmed that the cured product of this active energy ray-curable resin composition was extremely insufficient in terms of elongation, scratch resistance, and chemical resistance.

Claims (7)

An acrylic (meth)acrylate resin made from an acrylic polymer (A) and a (meth)acrylic monomer (B) having a carboxyl group,
Polymerization in which the acrylic polymer (A) contains glycidyl (meth)acrylate (a1) and two or more (meth)acrylate compounds (a2) whose homopolymer glass transition temperature (Tg) is 66 ° C. or higher. It is a copolymer of chemical compounds,
The (meth)acrylate compound (a2) contains methyl methacrylate,
The content of the methyl methacrylate is in the range of 25 to 65% by mass in the (meth)acrylate compound (a2),
The content of the glycidyl (meth)acrylate (a1) in the polymerizable compound is 5% by mass or more and 20% by mass or less of the acrylic (meth)acrylate resin. The (meth)acrylate compound (a2) is selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate. The acrylic (meth)acrylate resin according to claim 1, comprising at least one type of acrylic (meth)acrylate resin. The acrylic (meth)acrylate resin according to claim 1 or 2, wherein the (meth)acryloyl group equivalent is 400 to 3000 g/equivalent. An active energy ray-curable resin composition comprising the acrylic (meth)acrylate resin according to claim 1 or 2 and a photopolymerization initiator . A cured product of the active energy ray-curable resin composition according to claim 4. The cured product according to claim 5, which has a tan δ of 0.1 to 1 as measured by dynamic viscoelasticity spectrum in a temperature range of 120 to 200°C. An article comprising a coating film made of the cured product according to claim 5 or 6.