(Meth)acrylate resins, curable resin compositions, cured products and articles

Abstract

To provide a (meth)acrylate resin that can form a cured product having excellent heat resistance, resistance to yellowing due to heat and reflectivity, a curable resin composition containing the same, a cured product of the curable resin composition and an article.SOLUTION: A (meth)acrylate resin has, as essential materials: a (meth)acryl copolymer (A) having, as essential materials, a methacrylate compound (a1) having an aromatic ring, and a compound (a2) having a reactive functional group and a polymerizable unsaturated group excluding the compound (a1); and a compound (B) that has a polymerizable unsaturated group excluding the compound (a1) and the compound (a2), having a functional group reactable with a reactive functional group derived from the compound (a2) included in the copolymer (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to (meth)acrylate resins, curable resin compositions, cured products, and articles. [Background technology]

[0002] In recent years, curable compositions, such as active energy ray curable compositions that can be cured by active energy rays like ultraviolet light, and thermosetting compositions that can be cured by heat, have been widely used in fields such as inks, paints, coatings, adhesives, and optical components. In particular, for coating applications, there is a general demand for materials that can impart design properties to the surface of various substrates, have excellent curability, and form coating films that can prevent deterioration of the substrate surface. Furthermore, in recent years, there has been a demand from industry for materials that can form cured coating films with heat resistance and resistance to heat yellowing that can protect the coated object even under various temperature conditions.

[0003] Conventional active energy ray curable compositions include photosensitive resin compositions containing an epoxy acrylate resin obtained by reacting a cresol novolac type epoxy resin with acrylic acid and phthalic anhydride to obtain an intermediate, and then further reacting this intermediate with tetrahydrophthalic anhydride (see, for example, Patent Document 1). However, these compositions have problems such as insufficient heat resistance in the cured product and insufficient resistance to heat yellowing due to high aromatic concentrations.

[0004] Therefore, there was a need for a material that, in addition to heat resistance, also possessed excellent resistance to heat-induced yellowing. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 [Overview of the project] [Problems that the invention aims to solve]

[0006] The problem that the present invention aims to solve is to provide a (meth)acrylate resin capable of forming a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity, a curable resin composition containing the same, a cured product of the curable resin composition, and articles. [Means for solving the problem]

[0007] The present inventors conducted diligent studies to solve the above problems and found that the above problems can be solved by using a (meth)acrylic copolymer (A) which requires a methacrylate compound (a1) having an aromatic ring and a compound (a2) having reactive functional groups and polymerizable unsaturated groups other than compound (a1) as essential raw materials, and a compound (B) which has polymerizable unsaturated groups other than compound (a1) and compound (a2) that has functional groups that can react with the reactive functional groups derived from compound (a2) in copolymer (A), and thus completed the present invention.

[0008] In other words, the present invention relates to a (meth)acrylate polymer (A) which is made from essential raw materials a methacrylate compound (a1) having an aromatic ring and a compound (a2) having a reactive functional group and a polymerizable unsaturated group other than compound (a1), and a compound (B) having a polymerizable unsaturated group other than compound (a1) and compound (a2) which has a functional group that can react with the reactive functional group derived from compound (a2) that copolymer (A) has, a curable resin composition containing the same, a cured product of the curable resin composition and an article. [Effects of the Invention]

[0009] The (meth)acrylate resin of the present invention can form a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. Therefore, a curable resin composition containing the (meth)acrylate resin and a photopolymerization initiator can be used as a coating agent or adhesive, and is particularly suitable for use as a coating agent. [Modes for carrying out the invention]

[0010] The (meth)acrylate resin of the present invention is characterized in that it is made from a (meth)acrylic copolymer (A) which is made from a methacrylate compound (a1) having an aromatic ring (hereinafter sometimes referred to as "compound (a1)") and a compound (a2) having reactive functional groups and polymerizable unsaturated groups other than compound (a1) (hereinafter sometimes referred to as "compound (a2)") as essential raw materials, and a compound (B) having polymerizable unsaturated groups other than compound (a1) and compound (a2) (hereinafter sometimes referred to as "compound (B)") which is made from a compound (a1) having functional groups that can react with the reactive functional groups derived from compound (a2) that copolymer (A) has, as essential raw materials.

[0011] In this invention, "(meth)acrylate" means acrylate and / or methacrylate. Also, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and / or methacrylic.

[0012] The (meth)acrylic copolymer (A) requires the methacrylate compound (a1) and the compound (a2) having the reactive functional group and polymerizable unsaturated group as essential raw materials.

[0013] Examples of the compound (a1) include benzyl methacrylate, phenyl methacrylate, phenylbenzyl methacrylate, phenoxybenzyl methacrylate, biphenylmethyl methacrylate, phenol EO-modified methacrylate, phenol PO-modified methacrylate, nonylphenol EO-modified methacrylate, nonylphenol PO-modified methacrylate, phenylphenol EO-modified methacrylate, phenylphenol PO-modified methacrylate, monohydroxyethyl methacrylate phthalate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, N-phenylmethacrylamide, bisphenol A-type EO-modified dimethacrylate, bisphenol A-type PO-modified dimethacrylate, bisphenol F-type EO-modified dimethacrylate, bisphenol F-type PO-modified dimethacrylate, biphenol dimethacrylate, and the like. These compounds (a1) can be used individually or in combination of two or more. Furthermore, among these, monofunctional methacrylate is preferred, and benzyl methacrylate is more preferred, because it yields a (meth)acrylate resin capable of forming a cured product with excellent heat resistance, heat yellowing resistance, and reflectivity.

[0014] The content of compound (a1) is preferably more than 3% by mass and 18% by mass or less in copolymer (A), and more preferably in the range of 5 to 15% by mass, in order to obtain a (meth)acrylate resin capable of forming a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity.

[0015] The compound (a2) used is one having a reactive functional group and a polymerizable unsaturated group.

[0016] Examples of the reactive functional groups include hydroxyl groups, epoxy groups, isocyanate groups, carboxyl groups, and alkoxy groups. These reactive functional groups may be present individually or in pairs or in combination.

[0017] Examples of the polymerizable unsaturated groups include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, and (meth)acrylamide group.

[0018] Examples of compounds having a hydroxyl group as the reactive functional group and a (meth)acryloyl group as the polymerizable unsaturated group include 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, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Furthermore, (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 the aforementioned compounds, and lactone modified compounds, in which (poly)lactone structures are introduced into the molecular structure of the aforementioned compounds, can also be used. These compounds can be used individually or in combination of two or more.

[0019] Examples of the compound having an epoxy group as the reactive functional group and a (meth)acryloyl group as the polymerizable unsaturated group include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; mono(meth)acrylated products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These compounds can be used alone or in combination of two or more.

[0020] Examples of the compound having an isocyanate group as the reactive functional group and a (meth)acryloyl group as the polymerizable unsaturated group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, and the like. These compounds can be used alone or in combination of two or more.

[0021] Examples of the compound having a carboxyl group as the reactive functional group and a (meth)acryloyl group as the polymerizable unsaturated group include (meth)acrylic acid, ω-carboxy-polycaprolactone monoacrylate, and the like. These compounds can be used alone or in combination of two or more.

[0022] Examples of the compound having an alkoxy group as the reactive functional group and a (meth)acrylamide group as the polymerizable unsaturated group include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide, and the like. These compounds can be used alone or in combination of two or more.

[0023] Furthermore, as the compound (a2), a compound having a reactive functional group and a polymerizable unsaturated group in one molecule can also be used. In this invention, "polymerizable unsaturated group" means an unsaturated group that can be radically polymerized.

[0024] Examples of compounds having a reactive functional group and a polymerizable unsaturated group in a single molecule include unsaturated acids such as cinnamic acid, acid anhydrides having unsaturated bonds in their molecules such as tetrahydrophthalic anhydride and maleic anhydride, allyl compounds having a reactive functional group such as allyl alcohol, vinyl ether compounds having a reactive functional group such as 2-hydroxyethyl vinyl ether, maleimide compounds having a reactive functional group such as N-(4-aminophenyl)maleimide, and styryl compounds having a reactive functional group such as 4-vinylbenzoic acid.

[0025] The content of compound (a2) is preferably in the range of 40 to 97% by mass, and more preferably in the range of 50 to 97% by mass, in copolymer (A), in order to obtain a (meth)acrylate resin capable of forming a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity.

[0026] The copolymer (A) may, if necessary, contain other polymerization components other than compound (a1) and compound (a2).

[0027] Examples of the other polymerization components include (meth)acrylate compounds (a3), compounds having polymerizable unsaturated groups other than the (meth)acrylate compounds (a4), and so on.

[0028] Examples of the compound (a3) ​​include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; and alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate. Monoacrylate compounds such as hydrate compounds; heterocyclic mono(meth)acrylate compounds such as tetrahydrofurfuryl acrylate; aromatic monoacrylate compounds such as benzyl acrylate, phenyl acrylate, phenylbenzyl acrylate, phenoxyacrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenoxybenzyl acrylate, and phenylphenoxyethyl acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the above-mentioned mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate Aliphatic di(meth)acrylate compounds such as phosphates and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic diacrylate compounds such as biphenol diacrylate and bisphenol diacrylate;Polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene-modified tri(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the aliphatic tri(meth)acrylate compounds; the aliphatic Examples include lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of a tri(meth)acrylate compound; tetrafunctional or more aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or more (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and tetrafunctional or more lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound. These compounds (a3) ​​can be used alone or in combination of two or more. Furthermore, among these, methacrylate compounds are preferred because they yield (meth)acrylate resins capable of forming cured products with excellent heat resistance, resistance to heat yellowing, and reflectivity.

[0029] The compound (a4) is not particularly limited as long as it is a compound having one or more polymerizable unsaturated groups in its molecule.

[0030] Examples of the polymerizable unsaturated groups include allyl groups, isopropenyl groups, 1-propenyl groups, styryl groups, styrylmethyl groups, maleimide groups, vinyl ether groups, and the like.

[0031] These compounds (a4) can be used individually or in combination of two or more.

[0032] The method for producing the copolymer (A) is not particularly limited, and it may be produced by any method. For example, one method is to polymerize all of the polymerization components containing compound (a1) and compound (a2) together at 50 to 200°C.

[0033] In the polymerization described above, a polymerization initiator may be used as needed.

[0034] Examples of polymerization initiators include radical polymerization initiators such as persulfates, organic peroxides, and hydrogen peroxide, and azo initiators such as 4,4'-azobis(4-cyanovaleric acid) and 2,2'-azobis(2-amidinopropane) dihydrochloride. Furthermore, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid. These polymerization initiators can be used alone or in combination of two or more.

[0035] Examples of the persulfates include potassium persulfate, sodium persulfate, and ammonium persulfate. These persulfates can be used individually or in combination of two or more.

[0036] Examples of the aforementioned organic peroxides include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide; dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide; peroxyesters such as t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, and t-butyl peroxybenzoate; and hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, and t-butyl hydroperoxide. These organic peroxides can be used individually or in combination of two or more. Among these, peroxyesters are preferred because they yield (meth)acrylate resins capable of forming cured products with excellent heat resistance, resistance to heat yellowing, and reflectivity.

[0037] The amount of polymerization initiator used should be such that polymerization proceeds smoothly, but it is preferably in the range of 0.1 to 20 parts by mass, and more preferably in the range of 0.5 to 10 parts by mass, per 100 parts by mass of the total polymerization component containing compound (a1) and compound (a2).

[0038] The compound (B) has a functional group that can react with the reactive functional group derived from compound (a2) that the copolymer (A) has.

[0039] Examples of compound (B) include those similar to those exemplified as compound (a2) above, but when compound (a2) is a compound having a hydroxyl group and a (meth)acryloyl group, it is preferable to use a compound having an isocyanate group and a (meth)acryloyl group and / or a compound having an alkoxy group and a (meth)acrylamide group as compound (B), and when compound (a2) is a compound having an epoxy group and a (meth)acryloyl group, it is preferable to use a compound having a carboxyl group and a (meth)acryloyl group as compound (B), and compound When a compound having an isocyanate group and a (meth)acryloyl group is used as (a2), it is preferable to use a compound having a hydroxyl group and a (meth)acryloyl group as compound (B). When a compound having a carboxyl group and a (meth)acryloyl group is used as compound (a2), it is preferable to use a compound having an epoxy group and a (meth)acryloyl group as compound (B). When a compound having an alkoxy group and a (meth)acrylamide group is used as compound (a2), it is preferable to use a compound having a hydroxyl group and a (meth)acryloyl group as compound (B). These compounds (B) can be used alone or in combination of two or more. Furthermore, among these, it is preferable to use a compound having a carboxyl group and a (meth)acryloyl group as compound (a2) and a compound having an epoxy group and a (meth)acryloyl group as compound (B) in order to obtain a (meth)acrylate resin capable of forming a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. Similarly, it is preferable to use a compound having an epoxy group and a (meth)acryloyl group as compound (a2) and a compound having a carboxyl group and a (meth)acryloyl group as compound (B).

[0040] As the (meth)acrylate resin of the present invention can form a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity, the total content of the copolymer (A) and the compound (B) in the (meth)acrylate resin is preferably 90% by mass or more, and more preferably 95% by mass or more.

[0041] The (meth)acrylate resin of the present invention may, if necessary, further contain a compound (C) having a phenolic hydroxyl group and a tert-butyl group as a raw material.

[0042] Examples of the compound (C) include tert-butylcatechol, tert-butylhydroquinone, tert-butylresorcinol, 2,5-di-tert-amylhydroquinone, tert-butyl-p-benzoquinone, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene), 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylenebis(4ethyl-6-tert-butylphenol), 2 ,2'-Methylenebis(4-methyl-6-tert-butylphenol), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-Thiobis(3-methyl-6-tert-butylphenol), 2,5-Di-tert-butylhydroquinone, 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol), N,N'-Bis{2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl}oxamide, Octyl-3,5-Di-tert-butyl-4-H Droxy-hydrocinnamic acid, 3,6-dioxaoctamethylene=bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl=bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate], 3,(3,5-di-tert-butyl-4- Stearyl droxyphenyl propionate, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], triethylene glycol-bis-[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-Triazine, Pentaerythrityl-Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-Thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diet Trimethylester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl)calcium, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanuric acid, N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-tert-butylphenyl)phosphite, 2-(3,5-di-tert-butyl (Tyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-tert-butylphenyl -3,5-di-t-butyl-4-hydroxybenzoate, pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 2,4,6-tri-tert-butylnitronbenzene, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2) Examples include dioxaphosphosine. These compounds (C) can be used alone or in combination of two or more. Among these, 2,6-di-tert-butyl-p-cresol, pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], and 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are preferred because they can form cured products with excellent heat resistance, heat resistance to yellowing, and reflectivity.

[0043] The content of compound (C) is preferably in the range of 0.01 to 10% by mass, and more preferably in the range of 0.01 to 5% by mass, in the (meth)acrylate resin.

[0044] Furthermore, the double bond equivalent of the (meth)acrylate resin of the present invention is preferably 420 or less, and more preferably 400 or less, since it is possible to form a cured product with excellent heat resistance, heat yellowing resistance, and reflectivity.

[0045] The method for producing the (meth)acrylate resin of the present invention is not particularly limited and may be carried out by any method. For example, one method is to react all the raw materials containing the copolymer (A) and the compound (B) together.

[0046] Examples of the aforementioned methods include a method in which a reaction material containing the copolymer (A) and the compound (B) is reacted at 50 to 150°C in the presence of a basic catalyst or an acidic catalyst.

[0047] Examples of the basic catalysts include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, trio Examples include quaternary ammonium salts such as ctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dianeodecanoate, dibutyltin diacetate, tin octyolate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; organometallic compounds such as zinc octyolate and bismuth octyoate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. These basic catalysts can be used individually or in combination of two or more.

[0048] Examples of the acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These acidic catalysts can be used individually or in combination of two or more.

[0049] The amount of the basic catalyst or acidic catalyst used in the above method is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the total mass of the copolymer (A) and the compound (B).

[0050] In the above method, if the copolymer (A) has epoxy groups derived from compound (a2) and compound (B) has carboxyl groups, or if the copolymer (A) has carboxyl groups derived from compound (a2) and compound (B) has epoxy groups, then a phosphorus-based catalyst such as a phosphine compound or a phosphonium salt is preferred as the catalyst used in the reaction, and a phosphine compound is more preferred.

[0051] The phosphine compound can be the same as those exemplified above. Furthermore, these phosphine compounds can be used individually or in combination of two or more.

[0052] The phosphonium salts used can be those similar to those exemplified above. Furthermore, these phosphonium salts can be used individually or in combination of two or more types.

[0053] In the production of the (meth)acrylate resin of the present invention, the ratio of copolymer (A) to compound (B) used is preferably in the range of 0.5 to 1.05 moles of functional groups in compound (B) that can react with the reactive functional groups in copolymer (A) for every 1 mole of reactive functional groups in copolymer (A).

[0054] In the production of the (meth)acrylate resin of the present invention, polymerization inhibitors, antioxidants, and the like may be used in addition to compound (C) as needed.

[0055] Examples of polymerization inhibitors include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyroyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrene-phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenolic compounds such as 1,2-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.

[0056] The antioxidant can be the same as the compound exemplified in the polymerization inhibitor, and the antioxidant can be used alone or in combination of two or more.

[0057] Furthermore, commercially available polymer 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.

[0058] The (meth)acrylate resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

[0059] Examples of the 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.

[0060] Examples of other commercially available photopolymerization initiators include, for example, "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-784", "Omnirad-500", Examples include "Omnirad-81" (manufactured by IGM), "KayaCure-DETX", "KayaCure-MBP", "KayaCure-DMBI", "KayaCure-EPA", "KayaCure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "ByCure-10", "ByCure-55" (manufactured by Stauffa Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoz 1000" (manufactured by Sandoz), "Deep" (manufactured by Apjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0061] The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the curable resin composition.

[0062] The curable resin composition of the present invention may contain resin components other than the (meth)acrylate resin described above (hereinafter sometimes referred to as "other resin components"). Examples of the other resin components include resins having polymerizable unsaturated groups and various (meth)acrylate monomers.

[0063] The resin having polymerizable unsaturated groups can be any resin that has polymerizable unsaturated groups in it, for example, epoxy resins having polymerizable unsaturated groups, urethane resins having polymerizable unsaturated groups, acrylic resins having polymerizable unsaturated groups, amide-imide resins having polymerizable unsaturated groups, acrylamide resins having polymerizable unsaturated groups, ester resins having polymerizable unsaturated groups, and the like.

[0064] Examples of epoxy resins having polymerizable unsaturated groups include epoxy (meth)acrylate resins obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, a polybasic acid anhydride, and urethane group-containing epoxy (meth)acrylate resins obtained by reacting an epoxy resin with an unsaturated monobasic acid, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate compound and, if necessary, a polybasic acid anhydride.

[0065] Examples of the epoxy resins mentioned above include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol copolymer novolac-type epoxy resins, naphthol-cresol copolymer novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used individually or in combination of two or more types.

[0066] Examples of the bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0067] Examples of the hydrogenated bisphenol type epoxy resins include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0068] Examples of the biphenol-type epoxy resins include 4,4'-biphenol-type epoxy resin, 2,2'-biphenol-type epoxy resin, tetramethyl-4,4'-biphenol-type epoxy resin, and tetramethyl-2,2'-biphenol-type epoxy resin.

[0069] Examples of the hydrogenated biphenol-type epoxy resins include hydrogenated 4,4'-biphenol-type epoxy resins, hydrogenated 2,2'-biphenol-type epoxy resins, hydrogenated tetramethyl-4,4'-biphenol-type epoxy resins, and hydrogenated tetramethyl-2,2'-biphenol-type epoxy resins.

[0070] Examples of the aforementioned unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the aforementioned unsaturated monobasic acid can also be used. Furthermore, compounds represented by the following structural formula (1) can also be used.

[0071] [ka] [In formula (1), X represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 to 10 carbon atoms, and may contain halogen atoms, alkoxy groups, etc. in its structure. Y is a hydrogen atom or a methyl group.]

[0072] Examples of the polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains.

[0073] Examples of the (poly)ester chain include the (poly)ester chain represented by the following structural formula (X-1).

[0074] [ka] [In formula (X-1), R 1 This is an alkylene group with 1 to 10 carbon atoms, where n is an integer from 1 to 5.

[0075] Examples of the aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, and binaphthylene chains. Hydrocarbon chains having aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings as partial structures can also be used.

[0076] Examples of the aforementioned polybasic acid anhydrides include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0077] Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. Furthermore, the aliphatic polybasic acid anhydride may have either linear or branched aliphatic hydrocarbon groups and may have unsaturated bonds in its structure.

[0078] In this invention, the alicyclic polybasic acid anhydride is defined as one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is irrelevant. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and acid anhydrides of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

[0079] Examples of the aforementioned aromatic polybasic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0080] These polybasic acid anhydrides can be used individually or in combination of two or more.

[0081] Examples of the polyisocyanate compounds include 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; and tolylene diisocyanate, Aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (2); and isocyanurate-modified, biuret-modified, allophanate-modified, etc. of these compounds. Furthermore, these polyisocyanate compounds can be used individually or in combination of two or more.

[0082] [ka] [In the formula, R 1 Each of these is independently either a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms. 2 Each of these is either an alkyl group having 1 to 4 carbon atoms, or a bond point linked to the structural site represented by structural formula (2) via a methylene group marked with an asterisk (*). l is 0 or an integer from 1 to 3, and m is an integer from 1 to 15.

[0083] As the hydroxyl group-containing (meth)acrylate compound, the same as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0084] The method for producing the epoxy resin having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the epoxy resin having polymerizable unsaturated groups may be carried out in an organic solvent if necessary, and a basic catalyst may also be used if necessary.

[0085] Examples of the organic solvents include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used individually or in combination of two or more. Furthermore, the amount of the organic solvent used is preferably in the range of 0.1 to 5 times the total mass of the reaction raw materials, as this ensures good reaction efficiency.

[0086] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0087] Examples of urethane resins having polymerizable unsaturated groups include those obtained by reacting polyisocyanate compounds, hydroxyl group-containing (meth)acrylate compounds, and, if necessary, polyol compounds and polybasic acid anhydrides.

[0088] The polyisocyanate compound can be the same as those exemplified above, and the polyisocyanate compound can be used alone or in combination of two or more types.

[0089] As the hydroxyl group-containing (meth)acrylate compound, the same as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0090] Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various polyol compounds; lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various polyol compounds, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds can be used individually or in combination of two or more.

[0091] The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydride can be used alone or in combination of two or more types.

[0092] The method for producing the urethane resin having polymerizable unsaturated groups is not particularly limited and may be carried out by any method. In producing the urethane resin having polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0093] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0094] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0095] Examples of acrylic resins having polymerizable unsaturated groups include reaction products obtained by polymerizing an acrylic resin intermediate obtained by polymerizing an acrylic resin intermediate having reactive functional groups such as hydroxyl groups, carboxyl groups, isocyanate groups, and glycidyl groups, and then further reacting it with an acrylic resin intermediate having reactive functional groups that can react with these functional groups, thereby introducing (meth)acryloyl groups, or, if necessary, products obtained by reacting the hydroxyl groups in the reaction product with a polybasic acid anhydride.

[0096] The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as needed, in addition to the (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.

[0097] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more types.

[0098] The aforementioned polybasic acid anhydride can be the same as those exemplified above, and the aforementioned polybasic acid anhydride can be used alone or in combination of two or more types.

[0099] The method for producing the acrylic resin having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the acrylic resin having polymerizable unsaturated groups may be carried out in an organic solvent if necessary, and a basic catalyst may also be used if necessary.

[0100] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0101] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0102] Examples of the polymerizable unsaturated amide-imide resin include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a hydroxyl group-containing (meth)acrylate compound and / or an epoxy group-containing (meth)acrylate compound, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group.

[0103] The amide-imide resin may have only one of either an acid group or an acid anhydride group, or it may have both. From the viewpoint of reactivity and reaction control with hydroxyl group-containing (meth)acrylate compounds and (meth)acryloyl group-containing epoxy compounds, it is preferable that it has an acid anhydride group, and more preferably that it has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g when measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH / g when measured under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

[0104] Examples of the amide-imide resin include those obtained using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

[0105] The polyisocyanate compound can be the same as those exemplified above, and the polyisocyanate compound can be used alone or in combination of two or more types.

[0106] The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydride can be used alone or in combination of two or more types.

[0107] Furthermore, the amide-imide resin may, if necessary, also use polybasic acids as reaction raw materials in addition to the polyisocyanate compound and polybasic acid anhydride.

[0108] As the aforementioned polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of polybasic acids include dicarboxylic acids, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group in its molecule can also be used. These polybasic acids can be used individually or in combination of two or more.

[0109] As the hydroxyl group-containing (meth)acrylate compound, the same as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0110] As the epoxy group-containing (meth)acrylate compound, the same as those exemplified above as compounds having epoxy groups and (meth)acryloyl groups can be used, and the epoxy group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0111] The method for producing the amide-imide resin having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the amide-imide resin having polymerizable unsaturated groups may be carried out in an organic solvent if necessary, and a basic catalyst may also be used if necessary.

[0112] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0113] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0114] Examples of acrylamide resins having polymerizable unsaturated groups include those obtained by reacting a phenolic aqueous compound with an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

[0115] The aforementioned compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of such compounds include those represented by the following general formulas (3-1) to (3-4).

[0116] [ka]

[0117] In the above general formulas (3-1) to (3-4), R 1 R is one of the following: an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. 2 Each of these is independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer between 1 and 3, and more preferably 0 or 1 or 1. q is an integer of 1 or more, preferably 2 or 3. Note that the positions of the substituents on the aromatic ring in the above general formulas are arbitrary; for example, in the naphthalene ring of general formula (3-2), the substituent may be substituted on any of the benzene rings present in one molecule; and in general formula (3-3), the substituent may be substituted on any of the benzene rings present in one molecule, indicating that the number of substituents in one molecule is p and q.

[0118] Furthermore, as the compound having a phenolic hydroxyl group, for example, a reaction product can be used in which a compound having at least one phenolic hydroxyl group in its molecule and a compound represented by any of the following general formulas (x-1) to (x-5) are essential reaction raw materials. In addition, a novolac-type phenolic resin can be used in which one or more compounds having at least one phenolic hydroxyl group in their molecule are used as reaction raw materials.

[0119] [ka] [In equation (x-1), h is either 0 or 1. In equations (x-2) to (x-5), R 3In formulas (x-2), (x-3), and (x-5), Z is one of the following: an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and i is 0 or an integer from 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is one of the following: a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group. In formula (x-5), Y is one of the following: an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and j is an integer from 1 to 4.

[0120] These phenolic hydroxyl group-containing compounds can be used individually or in combination of two or more.

[0121] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it yields a curable resin composition that can form a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. The alkylene oxide can be used alone or in combination of two or more types.

[0122] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate are preferred because they yield a curable resin composition that can form a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. The alkylene carbonate can be used alone or in combination of two or more types.

[0123] Examples of the N-alkoxyalkyl(meth)acrylamide compounds include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, and N-butoxyethyl(meth)acrylamide. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0124] The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydride can be used alone or in combination of two or more types.

[0125] The unsaturated monobasic acid can be the same as those exemplified above, and the unsaturated monobasic acid can be used alone or in combination of two or more types.

[0126] The method for producing the acrylamide resin having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the acrylamide resin having polymerizable unsaturated groups may be carried out in an organic solvent as needed, and basic catalysts and acidic catalysts may also be used as needed.

[0127] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0128] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0129] The acidic catalyst can be the same as those exemplified above, and the acidic catalyst can be used alone or in combination of two or more types.

[0130] Examples of ester resins having polymerizable unsaturated groups include those obtained by reacting a phenolic aqueous compound with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

[0131] The phenolic aqueous compound can be the same as those exemplified above, and the phenolic aqueous compound can be used alone or in combination of two or more types.

[0132] The alkylene oxide can be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it yields a curable resin composition that can form a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. The alkylene oxide can be used alone or in combination of two or more types.

[0133] As the alkylene carbonate, the same type as those exemplified above can be used. Among these, ethylene carbonate or propylene carbonate is preferred because it yields a curable resin composition capable of forming a cured product with excellent heat resistance, heat resistance to yellowing, and reflectivity. The alkylene carbonate can be used alone or in combination of two or more types.

[0134] The unsaturated monobasic acid can be the same as those exemplified above, and the unsaturated monobasic acid can be used alone or in combination of two or more types.

[0135] The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydride can be used alone or in combination of two or more types.

[0136] The method for producing the ester resin having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the ester resin having polymerizable unsaturated groups may be carried out in an organic solvent as needed, and basic catalysts and acidic catalysts may also be used as needed.

[0137] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0138] The basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more types.

[0139] The acidic catalyst can be the same as those exemplified above, and the acidic catalyst can be used alone or in combination of two or more types.

[0140] The amount of resin having polymerizable unsaturated groups used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the (meth)acrylate resin of the present invention.

[0141] Examples of the various (meth)acrylate monomers mentioned above include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl(meth)acrylate. Compounds; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, phenyl(meth)acrylate, phenylbenzyl(meth)acrylate, phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, phenylphenoxyethyl(meth)acrylate, etc. Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (Poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the above di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structure of the above di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the above aliphatic tri(meth)acrylate compounds Examples include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; tetrafunctional or more aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or more (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and tetrafunctional or more lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound.

[0142] In addition to those mentioned above, other (meth)acrylate monomers can be used that require a phenol compound, a cyclic carbonate compound or cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

[0143] Examples of the aforementioned other phenol compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and cyclocyclic structure-containing phenol resins.

[0144] Examples of the aforementioned cyclic carbonate compounds include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds can be used individually or in combination of two or more.

[0145] Examples of the aforementioned cyclic ether compounds include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used individually or in combination of two or more.

[0146] As the aforementioned unsaturated monocarboxylic acid, the same as those exemplified above as unsaturated monobasic acids can be used.

[0147] The content of the aforementioned other (meth)acrylate monomers is preferably 90% by mass or less in the curable resin composition of the present invention.

[0148] Furthermore, the curable resin composition of the present invention may optionally contain various additives such as curing agents, curing accelerators, ultraviolet absorbers, organic solvents, inorganic fillers or polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants, and preservation stabilizers.

[0149] Examples of the curing agent include polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, epoxy resins, and the like.

[0150] Examples of the aforementioned polybasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo[2.2.1]heptate Examples of polybasic acids include n-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group in its molecule can also be used. These polybasic acids can be used individually or in combination of two or more.

[0151] The unsaturated monobasic acid can be the same as those exemplified above, and the unsaturated monobasic acid can be used alone or in combination of two or more types.

[0152] Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives. These amine compounds can be used individually or in combination of two or more.

[0153] Examples of the aforementioned amide compounds include dicyandiamide and polyamide resins synthesized from a linolenic acid dimer and ethylenediamine. These amide compounds can be used individually or in combination of two or more.

[0154] Examples of the azo compound include azobisisobutyronitrile.

[0155] Examples of the aforementioned organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and alkyl peroxycarbonates. These organic peroxides can be used individually or in combination of two or more types.

[0156] Examples of the polyol compounds include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and the polyol monomers and succinic acid, adipic acid, azelaic acid, and sebacin. Examples include polyester polyols obtained by co-condensation with acids, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation reactions of the polyol monomer with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used individually or in combination of two or more.

[0157] The epoxy resin can be the same as those exemplified above, and the epoxy resin can be used alone or in combination of two or more types.

[0158] The curing accelerator is an agent that promotes the curing reaction, and examples include phosphorus compounds, amine compounds, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. Furthermore, the amount of curing accelerator added is preferably in the range of 0.01 to 10% by mass of the solid content of the curable resin composition.

[0159] Examples of the aforementioned 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'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These UV absorbers can be used alone or in combination of two or more.

[0160] The organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more types.

[0161] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0162] As the aforementioned pigment, known and conventional inorganic pigments and organic pigments can be used.

[0163] Examples of the inorganic pigments mentioned above include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite. These inorganic pigments can be used individually or in combination of two or more types.

[0164] Examples of the aforementioned 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, zinc sulfide, and the like.

[0165] Examples of the aforementioned organic pigments include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ancenthron pigment, indanthron pigment, flavanthron pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, quinophthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, and azo pigment. These organic pigments can be used individually or in combination of two or more.

[0166] Examples of the aforementioned flame retardants include inorganic phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, polyammonium phosphate, and other ammonium phosphates; 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-oxy Examples of flame retardants 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. When these flame retardants are used, it is preferable that their concentration be in the range of 0.1 to 20% by mass of the total resin composition.

[0167] The cured product of the present invention can be obtained by irradiating the curable resin composition 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.

[0168] 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.

[0169] The integrated light quantity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 and more preferably 0.5 to 10 kJ / m 2 . When the integrated light quantity is within the above range, it is preferable because the generation of uncured portions can be prevented or suppressed.

[0170] Note that the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

[0171] The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, interior and exterior automotive materials, and OA equipment, as well as semiconductor devices, display devices, imaging devices, and the like.

Examples

[0172] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

[0173] In this example, the weight average molecular weight (Mw) is a value measured under the following conditions using gel permeation chromatography (GPC).

[0174] Measuring device: HLC - 8220 manufactured by Tosoh Corporation Column: Guard column H manufactured by Tosoh Corporation XL -H +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°C Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: Polystyrene Sample: 100 μl of a tetrahydrofuran solution containing 0.4% by mass (based on resin solids content) filtered through a microfilter.

[0175] (Example 1: Production of acrylate resin (1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 23 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A1). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (1). The non-volatile content of this acrylate resin (1) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,530, and the double bond equivalent was 269. In this invention, the double bond equivalent is a calculated value obtained from the amount of raw materials used.

[0176] (Example 2: Production of acrylate resin (2)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A2). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (2). The non-volatile content of this acrylate resin (2) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,570, and the double bond equivalent was 269.

[0177] (Example 3: Production of acrylate resin (3)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 13 parts by mass of methyl methacrylate, 15 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A3). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (3). The non-volatile content of this acrylate resin (3) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,780, and the double bond equivalent was 269.

[0178] (Example 4: Production of acrylate resin (4)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 25 parts by mass of methyl methacrylate, 3 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A4). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (4). The non-volatile content of this acrylate resin (4) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,460, and the double bond equivalent was 269.

[0179] (Example 5: Production of acrylate resin (5)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 9 parts by mass of methyl methacrylate, 19 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A5). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (5). The non-volatile content of this acrylate resin (5) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,890, and the double bond equivalent was 269.

[0180] (Example 6: Production of acrylate resin (6)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of phenoxyethyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A6). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (6). The non-volatile content of this acrylate resin (6) was 52.6% by mass, the weight-average molecular weight (Mw) was 12,110, and the double bond equivalent was 269.

[0181] (Example 7: Production of acrylate resin (7)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of azobisisobutyronitrile were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A7). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (7). The non-volatile content of this acrylate resin (7) was 52.6% by mass, the weight-average molecular weight (Mw) was 12,310, and the double bond equivalent was 269.

[0182] (Example 8: Production of acrylate resin (8)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A8). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of tetrabutylphosphonium chloride were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Then, 14.3 parts by mass of butyl acetate was charged and stirred to obtain the target acrylate resin (8). The non-volatile content of this acrylate resin (8) was 49.8% by mass, the weight-average molecular weight (Mw) was 16,320, and the double bond equivalent was 269.

[0183] (Example 9: Production of acrylate resin (9)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A9). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triethylamine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Then, 14.3 parts by mass of butyl acetate was charged and stirred to obtain the target acrylate resin (9). The non-volatile content of this acrylate resin (9) was 49.8% by mass, the weight-average molecular weight (Mw) was 12,550, and the double bond equivalent was 269.

[0184] (Example 10: Production of acrylate resin (10)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A10). Next, 0.5 parts by mass of pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (10). The non-volatile content of this acrylate resin (10) was 52.6% by mass, the weight-average molecular weight (Mw) was 12,550, and the double bond equivalent was 269.

[0185] (Example 11: Production of acrylate resin (11)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A11). Next, 0.5 parts by mass of stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (11). The non-volatile content of this acrylate resin (11) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,910, and the double bond equivalent was 269.

[0186] (Example 12: Production of acrylate resin (12)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A12). Next, 0.5 parts by mass of bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (12). The non-volatile content of this acrylate resin (12) was 52.6% by mass, the weight-average molecular weight (Mw) was 11,880, and the double bond equivalent was 269.

[0187] (Example 13: Production of acrylate resin (13)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 90 parts by mass of glycidyl methacrylate, 5 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A13). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 45.6 parts by mass of acrylic acid, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 13 hours while blowing in air and stirring. Then, 23.4 parts by mass of butyl acetate was charged and stirred to obtain the target acrylate resin (13). The non-volatile content of this acrylate resin (13) was 49.8% by mass, the weight-average molecular weight (Mw) was 14,770, and the double bond equivalent was 269.

[0188] (Example 14: Production of acrylate resin (14)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 90 parts by mass of glycidyl methacrylate, 5 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 28.3 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A14). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 25.4 parts by mass of acrylic acid, and 0.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 8 hours while blowing in air and stirring to obtain the target acrylate resin (14). The non-volatile content of this acrylate resin (14) was 55.4% by mass, the weight-average molecular weight (Mw) was 10,150, and the double bond equivalent was 356.

[0189] (Example 15: Production of acrylate resin (15)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 40 parts by mass of glycidyl methacrylate, 55 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 20.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A15). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 20.3 parts by mass of acrylic acid, and 0.4 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 7 hours while blowing in air and stirring to obtain the target acrylate resin (15). The non-volatile content of this acrylate resin (15) was 56.4% by mass, the weight-average molecular weight (Mw) was 9,820, and the double bond equivalent was 427.

[0190] (Example 16: Production of acrylate resin (16)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A16). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 25.6 parts by mass of acrylic acid, 48.2 parts by mass of ω-carboxy-polycaprolactone monoacrylate ("Aronics M-5300" manufactured by Toagosei Co., Ltd.), and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 12 hours while blowing in air and stirring to obtain the target acrylate resin (16). The non-volatile content of this acrylate resin (16) was 58.5% by mass, the weight-average molecular weight (Mw) was 12,230, and the double bond equivalent was 343.

[0191] (Example 17: Production of acrylate resin (17)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 85 parts by mass of glycidyl methacrylate, 15 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A17). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 43.1 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 12 hours while blowing in air and stirring to obtain the target acrylate resin (17). The non-volatile content of this acrylate resin (17) was 53.7% by mass, the weight-average molecular weight (Mw) was 14,270, and the double bond equivalent was 239.

[0192] (Example 18: Production of acrylate resin (18)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A18). Next, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (18). The non-volatile content of this acrylate resin (18) was 52.6% by mass, the weight-average molecular weight (Mw) was 12,730, and the double bond equivalent was 269.

[0193] (Example 19: Production of acrylate resin (19)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A19). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 87.9 parts by mass of 4-hydroxybutyl acrylate glycidyl ether, and 0.7 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 14 hours while blowing in air and stirring to obtain the target acrylate resin (19). The non-volatile content of this acrylate resin (19) was 55.4% by mass, the solid content acid value was 80 mgKOH / g, the weight-average molecular weight (Mw) was 47,910, and the double bond equivalent was 428. Furthermore, the number of moles of 4-hydroxybutyl acrylate glycidyl ether corresponding to compound (B) having polymerizable unsaturated groups as defined in this invention was 0.63 per mole of carboxyl groups in the acrylic copolymer (A19) corresponding to copolymer (A) as defined in this invention.

[0194] (Example 20: Production of acrylate resin (20)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 67 parts by mass of butyl acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Then, 80 parts by mass of glycidyl methacrylate, 15 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 51 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A20). Next, 0.7 parts by mass of pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 0.7 parts by mass of 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.1 parts by mass of methylhydroquinone, 41 parts by mass of acrylic acid, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (20). The solid content acid value of the obtained acrylate resin (20) was 2 mg KOH / g. Furthermore, the number of moles of acrylic acid corresponding to the polymerizable unsaturated group compound (B) as defined in the present invention was 1 for every 1 mole of epoxy group in the acrylic copolymer (A20) corresponding to copolymer (A) as defined in the present invention.

[0195] (Example 21: Production of acrylate resin (21)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 67 parts by mass of butyl acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Then, 80 parts by mass of glycidyl methacrylate, 15 parts by mass of methyl methacrylate, 5 parts by mass of benzyl methacrylate, 51 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A21). Next, 0.9 parts by mass of pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 0.9 parts by mass of 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.1 parts by mass of methylhydroquinone, 28 parts by mass of acrylic acid, 53 parts by mass of ω-carboxy-polycaprolactone monoacrylate (Toagosei Co., Ltd. "Aronics M-5300"), and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 15 hours while blowing in air and stirring to obtain the target acrylate resin (21). The solid content acid value of the obtained acrylate resin (21) was 3 mg KOH / g. Furthermore, the number of moles of acrylic acid corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 0.7 per mole of epoxy group in the acrylic copolymer (A21) corresponding to copolymer (A) as defined in this invention.

[0196] (Example 22: Production of methacrylate resin (1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of butyl acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 55.6 parts by mass of butyl acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A22). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 43.6 parts by mass of methacrylic acid, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 12 hours while blowing in air and stirring to obtain the target methacrylate resin (1). The non-volatile content of this methacrylate resin (1) was 53.8% by mass, the weight-average molecular weight (Mw) was 11,290, and the double bond equivalent was 283. Furthermore, the number of moles of methacrylic acid corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 0.45 per mole of epoxy group in the acrylic copolymer (A22) corresponding to copolymer (A) as defined in this invention.

[0197] (Example 23: Production of methacrylate resin (2)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A23). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 44.6 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 10 hours while blowing in air and stirring to obtain the target methacrylate resin (2). The non-volatile content of this methacrylate resin (2) was 48.9% by mass, the solid content acid value was 150 mgKOH / g, the weight-average molecular weight (Mw) was 45,420, and the double bond equivalent was 461. Furthermore, the number of moles of glycidyl methacrylate corresponding to compound (B) having polymerizable unsaturated groups as defined in this invention was 0.45 per mole of carboxyl groups in the acrylic copolymer (A23) corresponding to copolymer (A) as defined in this invention.

[0198] (Example 24: Production of methacrylate resin (3)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A24). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 51.5 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 12 hours while blowing in air and stirring to obtain the target methacrylate resin (3). The non-volatile content of this methacrylate resin (3) was 50.1% by mass, the solid content acid value was 125 mgKOH / g, the weight-average molecular weight (Mw) was 46,010, and the double bond equivalent was 418. Furthermore, the number of moles of glycidyl methacrylate corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 0.52 per mole of carboxyl group in the acrylic copolymer (A24) corresponding to copolymer (A) as defined in this invention.

[0199] (Example 25: Production of methacrylate resin (4)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A25). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 65.4 parts by mass of glycidyl methacrylate, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 14 hours while blowing in air and stirring to obtain the target methacrylate resin (4). The non-volatile content of this methacrylate resin (4) was 52.2% by mass, the solid content acid value was 82 mgKOH / g, the weight-average molecular weight (Mw) was 48,540, and the double bond equivalent was 359. Furthermore, the number of moles of glycidyl methacrylate corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 0.66 per mole of carboxyl group in the acrylic copolymer (A25) corresponding to copolymer (A) as defined in this invention.

[0200] (Example 26: Production of methacrylate resin (5)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A26). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 99.1 parts by mass of glycidyl methacrylate, and 0.7 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 20 hours while blowing in air and stirring. Then, 49.1 parts by mass of dipropylene glycol monomethyl ether was added, and after stirring, the target methacrylate resin (5) was obtained. The non-volatile content of this methacrylate resin (5) was 49.8% by mass, the weight-average molecular weight (Mw) was 50,960, and the double bond equivalent was 285. Furthermore, the number of moles of glycidyl methacrylate corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 1.0 for every 1 mole of carboxyl group in the acrylic copolymer (A26) corresponding to copolymer (A) as defined in this invention.

[0201] (Example 27: Production of methacrylate resin (6)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A27). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 106 parts by mass of glycidyl methacrylate, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 19 hours while blowing in air and stirring. Then, 56 parts by mass of dipropylene glycol monomethyl ether was added, and after stirring, the target methacrylate resin (6) was obtained. The non-volatile content of this methacrylate resin (6) was 49.8% by mass, the weight-average molecular weight (Mw) was 49,860, and the double bond equivalent was 276. Furthermore, the number of moles of glycidyl methacrylate corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 1.07 for every 1 mole of carboxyl group in the acrylic copolymer (A27) corresponding to copolymer (A) as defined in this invention.

[0202] (Example 28: Production of (meth)acrylate resin (1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of dipropylene glycol monomethyl ether was added and the mixture was heated to 120°C under a nitrogen atmosphere. Then, 50 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of ω-carboxy-polycaprolactone monoacrylate (Toagosei Co., Ltd. "Aronics M-5300"), 10 parts by mass of benzyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide (Nippon Oil & Fats Co., Ltd. "Perbutyl O") were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (A28). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 55.7 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 110°C for 20 hours while blowing in air and stirring. Then, 5.7 parts by mass of dipropylene glycol monomethyl ether was added, and after stirring, the target (meth)acrylate resin (1) was obtained. The non-volatile content of this (meth)acrylate resin (1) was 49.8% by mass, the solid content acid value was 80 mgKOH / g, the weight-average molecular weight (Mw) was 49,140, ​​and the double bond equivalent was 397. Furthermore, the number of moles of glycidyl methacrylate corresponding to the polymerizable unsaturated group compound (B) as defined in this invention was 0.64 for every 1 mole of carboxyl group in the acrylic copolymer (A28) corresponding to copolymer (A) as defined in this invention.

[0203] (Synthesis Example 1: Production of epoxy acrylate resin (1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was added, and 428 parts by mass of orthocresol novolac type epoxy resin (DIC Corporation's "EPICLON N-680", epoxy equivalent: 214) was dissolved. After adding 4 parts by mass of dibutylhydroxytoluene and 0.4 parts by mass of methoquinone, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120°C for 10 hours while blowing in air. Subsequently, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110°C for 2.5 hours to obtain the target epoxy acrylate resin (1). The solid content acid value of this epoxy acrylate resin (1) was 85 mg KOH / g.

[0204] (Comparative Example 1: Manufacturing of acrylate resin (R1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of diethylene glycol monomethyl ether acetate was added and the mixture was heated to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 28 parts by mass of methyl methacrylate, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain acrylic copolymer (AR1). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (R1). The weight-average molecular weight (Mw) of this acrylate resin (R1) was 11,160, and the double bond equivalent was 269.

[0205] (Comparative Example 2: Production of acrylate resin (R2)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 66.7 parts by mass of diethylene glycol monomethyl ether acetate was added and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of benzyl acrylate, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl) peroxide ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.) were pre-mixed and added dropwise over 3 hours. The mixture was held at 120°C for 4 hours to obtain an acrylic copolymer (AR2). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring to obtain the target acrylate resin (R2). The solid content acid value of this acrylate resin (R2) was 12,070 for its weight-average molecular weight (Mw), and 269 for its double bond equivalent.

[0206] (Example 29: Preparation of curable resin composition (1)) A curable resin composition (1) was obtained by mixing 100 parts by mass of the acrylate resin (1) with a non-volatile content of 58.6% by mass obtained in Example 1 with 2.6 parts by mass of a photopolymerization initiator ("Omnirad907" manufactured by IGM).

[0207] (Examples 30-58: Preparation of curable resin compositions (2)-(30)) Curable resin compositions (2) to (30) were obtained in the same manner as in Example 29, except that the (meth)acrylate resins obtained in Examples 2 to 28 were used in the amounts shown in Tables 1 and 2, instead of the acrylate resin (1) used in Example 29.

[0208] (Comparative Example 3: Preparation of Curable Resin Composition (R1)) A curable resin composition (R3) was obtained by mixing 100 parts by mass of the acrylate resin (R1) with a non-volatile content of 52.6% by mass obtained in Comparative Example 1 with 2.6 parts by mass of a photopolymerization initiator ("Omnirad907" manufactured by IGM).

[0209] (Comparative Example 4: Preparation of Curable Resin Composition (R2)) A curable resin composition (R4) was obtained in the same manner as in Comparative Example 3, except that the acrylate resin (R2) obtained in Comparative Example 2 was used in the amount shown in Table 2, instead of the acrylate resin (R1) used in Comparative Example 3.

[0210] The curable resin compositions obtained in the above examples and comparative examples were used for the following evaluations.

[0211] [Method for evaluating heat resistance] The curable resin compositions obtained in each example and comparative example were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS", 18 μm) using an applicator to a thickness of 50 μm, and dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the copper foil to obtain a cured material. A 6 mm x 35 mm test piece was cut from the cured material and evaluated using a viscoelasticity measuring device (DMA: Rheometric RSAII solid viscoelasticity measuring device, tensile method: frequency 1 Hz, heating rate 3°C / min) to determine the temperature at which the change in elastic modulus was maximum, which was defined as the glass transition temperature, according to the following criteria. Note that a higher glass transition temperature indicates better heat resistance.

[0212] A: The glass transition temperature (Tg) was 140°C or higher. B:Tg was between 135°C and 140°C. The C:Tg was between 130°C and 135°C. The D:Tg was between 125°C and 130°C. E:Tg was below 125°C.

[0213] [Evaluation method for heat resistance to yellowing] The curable resin compositions obtained in each example and comparative example were applied to glass using an applicator to a film thickness of 50 μm and dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. The obtained cured coating was heated to 260°C in a hot air circulating drying oven to accelerate degradation, and after 30 minutes it was removed. The color difference between the cured coating and the unheated coating was measured using a colorimeter "ZE6000" manufactured by Nippon Denshoku Industries Ltd. and evaluated according to the following criteria.

[0214] A: The color difference (ΔE) was less than 5. B: ΔE was between 5 and 6. C:ΔE was between 6 and 7 (inclusive). D:ΔE was between 7 and 8 (inclusive). E:ΔE was 8 or greater.

[0215] [Method for evaluating reflectivity] The curable resin compositions obtained in each example and comparative example were applied to glass using an applicator to a film thickness of 50 μm and dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. The obtained cured coating was heated to 260°C in a hot air circulating drying oven to accelerate degradation, and the reflectance (Y) of the material removed after 60 minutes was measured using a colorimeter "ZE6000" manufactured by Nippon Denshoku Industries Ltd. and evaluated according to the following criteria <after heat resistance test>.

[0216] A: The reflectance (Y) was 89 or higher. B:Y was between 88 and 89. C:Y was between 87 and 88. D:Y was between 86 and 87. E:Y was less than 86.

[0217] Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (30) obtained in Examples 29 to 58, and the curable resin compositions (R1) and (R2) obtained in Comparative Examples 3 and 4.

[0218] [Table 1]

[0219] [Table 2]

[0220] Note that the values ​​listed in parts by mass for acrylate resin, methacrylate resin, (meth)acrylate resin, and epoxy acrylate resin in Tables 1 and 2 represent the solid content.

[0221] In Tables 1 and 2, "photopolymerization initiator" refers to "Omnirad-907" manufactured by IGM.

[0222] Examples 29 to 58 shown in Tables 1 and 2 are examples using the (meth)acrylate resin of the present invention. It was confirmed that the cured products of the curable resin composition containing the (meth)acrylate resin of the present invention possess a good balance of heat resistance, heat resistance to yellowing, and reflectivity.

[0223] On the other hand, Comparative Example 3 is an example in which the methacrylate compound (a1) having an aromatic ring as defined in the present invention is not used. It was confirmed that the cured product of this curable resin composition does not possess heat resistance, heat resistance to yellowing, and reflectivity.

[0224] Comparative Example 4 is an example in which an acrylate compound having an aromatic ring was used instead of the methacrylate compound (a1) having an aromatic ring as defined in the present invention. It was confirmed that the cured product of this curable resin composition did not possess heat resistance, heat yellowing resistance, and reflectivity, similar to Comparative Example 3.

Claims

1. A (meth)acrylic copolymer (A) is made from essential raw materials a methacrylate compound (a1) having an aromatic ring, and a compound (a2) having reactive functional groups and polymerizable unsaturated groups other than compound (a1), A (meth)acrylate resin characterized in that it uses as an essential raw material a compound (B) having polymerizable unsaturated groups other than compound (a1) and compound (a2), which has functional groups that can react with the reactive functional groups derived from compound (a2) that the copolymer (A) has, The (meth)acrylate resin is a polymer obtained in the presence of a compound (C) having a phenolic hydroxyl group and a tert-butyl group. The content of the compound (a1) in the raw materials of the (meth)acrylic copolymer (A) is more than 3% by mass and 18% by mass or less. The polymerizable unsaturated group in the compound (a2) is a (meth)acryloyl group. A (meth)acrylate resin in which the reactive functional group of compound (a2) is one or more selected from the group consisting of epoxy groups and carboxyl groups.

2. The (meth)acrylate resin according to claim 1, wherein the compound (a1) contains benzyl methacrylate.

3. The (meth)acrylate resin according to claim 1 or 2, wherein the copolymer (A) further contains, as a raw material, other (meth)acrylate compounds (a3) ​​other than the compound (a1) and the compound (a2).

4. The (meth)acrylate resin according to claim 3, wherein the compound (a3) ​​is a methacrylate compound.

5. The (meth)acrylate resin according to any one of claims 1 to 4, wherein the (meth)acrylate resin further contains a phosphorus-based catalyst as a raw material.

6. The (meth)acrylate resin according to any one of claims 1 to 5, wherein the double bond equivalent of the (meth)acrylate resin is 420 or less.

7. The (meth)acrylate resin according to any one of claims 1 to 6, wherein the ratio of the copolymer (A) and the compound (B) used is in the range of 0.5 to 1.05 moles of functional groups in the compound (B) that can react with the reactive functional groups in the copolymer (A) per mole of reactive functional groups in the copolymer (A).

8. A curable resin composition characterized by containing a (meth)acrylate resin according to any one of claims 1 to 7 and a photopolymerization initiator.

9. The curable resin composition according to claim 8, wherein the curable resin composition further contains a resin having other polymerizable unsaturated groups other than the (meth)acrylate resin.

10. The curable resin composition according to claim 8 or 9, wherein the curable resin composition further contains an organic solvent.

11. The curable resin composition according to any one of claims 8 to 10, wherein the curable resin composition further contains a curing agent.

12. A cured product of a curable resin composition according to any one of claims 8 to 11.

13. An article characterized by having a coating film made of the cured product described in claim 12.

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