JP2021176954A - (meth)acrylate resin, curable resin composition, cured product and article - Google Patents

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

The present invention relates to (meth) acrylate resins, curable resin compositions, cured products and articles.

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been introduced into inks, paints, coating agents, adhesives, and optics. It is widely used in the field of materials and the like. Among them, as the coating agent application, generally, it is possible to impart designability to the surface of various base materials, have excellent curability, and form a coating film capable of preventing deterioration of the base material surface. Is required. Furthermore, in recent years, there has been a demand from the industrial world for a material capable of forming a cured coating film having a level of heat resistance and heat-resistant yellowing that can protect an object to be coated even under various temperature environments. There is.

As a conventional active energy ray-curable composition, an epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and phthalic anhydride is used. Although a photosensitive resin composition containing the resin is known (see, for example, Patent Document 1), the heat resistance of the cured product is not sufficient, and the heat-resistant yellowing is insufficient due to the high aromatic concentration. There was a problem.

Therefore, there has been a demand for a material having excellent heat-resistant yellowing in addition to heat resistance.

Japanese Unexamined Patent Publication No. 8-259663

The problem to be solved by the present invention is a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity, a curable resin composition containing the same, and the curable resin composition. Is to provide a cured product of the above, and an article.

As a result of diligent studies to solve the above problems, the present inventors have a methacrylate compound (a1) having an aromatic ring, and a reactive functional group and a polymerizable unsaturated group other than the compound (a1). It has a (meth) acrylic copolymer (A) containing the compound (a2) as an essential raw material, and a functional group capable of reacting with the reactive functional group derived from the compound (a2) contained in the copolymer (A). The present invention has been completed by finding that the above problems can be solved by using the compound (a1) and the compound (B) having a polymerizable unsaturated group other than the compound (a2).

That is, the present invention uses a methacrylate compound (a1) having an aromatic ring and a compound (a2) having a reactive functional group and a polymerizable unsaturated group other than the compound (a1) as essential raw materials. Other than the compound (a1) and the compound (a2) having a copolymer (A) and a functional group capable of reacting with the reactive functional group derived from the compound (a2) possessed by the copolymer (A). A (meth) acrylate resin characterized by using a compound (B) having a polymerizable unsaturated group as an essential raw material, a curable resin composition containing the compound (B), a cured product of the curable resin composition, and the like. It is about goods.

Since the (meth) acrylate resin of the present invention can form a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity, the curable resin composition containing the (meth) acrylate resin and a photopolymerization initiator is used. , Can be used as a coating agent or an adhesive, and can be particularly preferably used as a coating agent.

The (meth) acrylate resin of the present invention is a methacrylate compound (a1) having an aromatic ring (hereinafter, may be referred to as “compound (a1)”), and a reactive functional group and polymerization other than the compound (a1). A (meth) acrylic copolymer (A) containing a compound (a2) having a sex unsaturated group (hereinafter, may be referred to as “compound (a2)”) as an essential raw material, and the copolymer (A). ) Has a functional group capable of reacting with the reactive functional group derived from the compound (a2), and has a polymerizable unsaturated group other than the compound (a1) and the compound (a2) (hereinafter, (Sometimes referred to as “compound (B)”)) is an essential raw material.

In the present invention, "(meth) acrylate" means acrylate and / or methacrylate. Further, "(meta) acryloyl" means acryloyl and / or methacryloyl. Further, "(meth) acrylic" means acrylic and / or methacryl.

As the (meth) acrylic copolymer (A), the methacrylate compound (a1) and the compound (a2) having a reactive functional group and a polymerizable unsaturated group are essential raw materials.

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, and phenyl. Phenol EO modified methacrylate, phenylphenol PO modified methacrylate, monohydroxyethyl methacrylate phthalate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, N-phenylmethacrylate, bisphenol A type EO modification Examples thereof include dimethacrylate, bisphenol A-type PO-modified dimethacrylate, bisphenol F-type EO-modified dimethacrylate, bisphenol F-type PO-modified dimethacrylate, and biphenol dimethacrylate. These compounds (a1) can be used alone or in combination of two or more. Among these, monofunctional methacrylate is preferable, and benzyl methacrylate is more preferable, because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing, and reflectivity can be obtained.

The content of the compound (a1) is 3% by mass in the copolymer (A) because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. It is preferably more than% and 18% by mass or less, and more preferably 5 to 15% by mass.

As the compound (a2), a compound having a reactive functional group and a polymerizable unsaturated group is used.

Examples of the reactive functional group include a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, an alkoxy group and the like. These reactive functional groups may have alone or may have two or more kinds.

Examples of the polymerizable unsaturated group include a (meth) acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, a (meth) acrylamide group and the like. Can be mentioned.

Examples of the compound having a hydroxyl group as the reactive functional group and the (meth) acryloyl group as the polymerizable unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and trimethylolpropane (meth). ) Acrylate, trimethylolpropandi (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 (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Ditrimethylol Propane (Meta) Acrylate, Ditrimethylol Propane Di (Meta) Acrylate, Ditrimethylol Propanetri Examples include (meth) acrylate. Further, a (poly) oxyalkylene modified product obtained by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of the various compounds. , A lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various compounds can also be used. These compounds may be used alone or in combination of two or more.

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 (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxy. Glycidyl group-containing (meth) acrylate monomer such as cyclohexylmethyl (meth) acrylate; mono (meth) of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Examples thereof include acrylates. These compounds may be used alone or in combination of two or more.

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, and 1,1-. Examples thereof include bis (acryloyloxymethyl) ethyl isocyanate. These compounds may be used alone or in combination of two or more.

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 may be used alone or in combination of two or more.

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 and N-ethoxymethyl (meth) acrylamide. Examples thereof include N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like. These compounds may be used alone or in combination of two or more.

Further, as the compound (a2), a compound having a reactive functional group and a polymerizable unsaturated group in one molecule can also be used. In the present invention, the "polymerizable unsaturated group" means an unsaturated group capable of radical polymerization.

Examples of the compound having a reactive functional group and a polymerizable unsaturated group in one molecule include an unsaturated acid such as cinnamic acid, a tetrahydrophthalic anhydride, and a maleic anhydride, which have an unsaturated bond in the molecule. Allyl compounds having reactive functional groups such as anhydrides and allyl alcohols, vinyl ether compounds having reactive functional groups such as 2-hydroxyethyl vinyl ether, maleimides having reactive functional groups such as N- (4-aminophenyl) maleimide, etc. Examples thereof include compounds and styryl compounds having a reactive functional group such as 4-vinylbenzoic acid.

The content of the compound (a2) is 40 to 40 in the copolymer (A) because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. The range of 97% by mass is preferable, and the range of 50 to 97% by mass is more preferable.

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

Examples of the other polymerization component include a (meth) acrylate compound (a3), a compound having a polymerizable unsaturated group other than the (meth) acrylate compound (a4), and the like.

Examples of the compound (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl ( Alicyclic mono (meth) acrylate compounds such as meta) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as tetrahydrofurfuryl acrylate; aromatics such as benzyl acrylate, phenyl acrylate, phenyl benzyl acrylate, phenoxy acrylate, phenoxy ethyl acrylate, phenoxy ethoxyethyl acrylate, phenoxy benzyl acrylate, and phenyl phenoxy ethyl acrylate. Monoacrylate compounds such as monoacrylate compounds: Polyoxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers. (Poly) oxyalkylene-modified mono (meth) acrylate compound; a lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds; ethylene glycol di An aliphatic di (meth) acrylate compound such as (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate; 1, Fats such as 4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, etc. Cyclic di (meth) acrylate compound; aromatic diacrylate compound such as biphenol diacrylate and bisphenol diacrylate; (poly) oxyethylene chain, (poly) oxypropylene in the molecular structure of the various di (meth) acrylate compounds. Polyoxy introduced with (poly) oxyalkylene chains such as chains and (poly) oxytetramethylene chains Alkylene-modified di (meth) acrylate compound; lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds; trimethylolpropane tri (meth) acrylate, glycerin An aliphatic tri (meth) acrylate compound such as tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, or (poly) oxytetramethylene in the molecular structure of the aliphatic tri (meth) acrylate compound. A (poly) oxyalkylene-modified tri (meth) acrylate compound into which a (poly) oxyalkylene chain such as a chain has been introduced; a lactone-modified bird in which a (poly) lactone structure has been introduced into the molecular structure of the aliphatic tri (meth) acrylate compound. (Meta) acrylate compound; tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; A tetrafunctional or higher functional (poly) oxy 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 a (meth) acrylate compound. An alkylene-modified poly (meth) acrylate compound; a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound can be mentioned. These compounds (a3) can be used alone or in combination of two or more. Further, among these, a methacrylate compound is preferable because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.

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

Examples of the polymerizable unsaturated group include an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group and the like.

These compounds (a4) can be used alone or in combination of two or more.

The method for producing the copolymer (A) is not particularly limited, and any method may be used for producing the copolymer (A). For example, a method obtained by polymerizing all of the polymerization components containing the compound (a1) and the compound (a2) at 50 to 200 ° C. can be mentioned.

In the polymerization, a polymerization initiator can be used if necessary.

Examples of the polymerization initiator include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis ( Examples thereof include an azo initiator such as 2-amidinopropane) dihydrochloride. Further, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid, for example. These polymerization initiators can be used alone or in combination of two or more.

Examples of the persulfate include potassium persulfate, sodium persulfate, ammonium persulfate and the like. These persulfates can be used alone or in combination of two or more.

Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, and t-butyl peroxide. Peroxyesters such as -2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, hydroperoxides such as cumenehydroperoxide, paramentanhydroperoxide, t-butylhydroperoxide, etc. And so on. These organic peroxides can be used alone or in combination of two or more. Among these, a peroxy ester is preferable because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained.

The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but with respect to a total of 100 parts by mass of the polymerization component containing the compound (a1) and the compound (a2). The range of 0.1 to 20 parts by mass is preferable, and the range of 0.5 to 10 parts by mass is more preferable.

The compound (B) has a functional group capable of reacting with the reactive functional group derived from the compound (a2) of the copolymer (A).

Examples of the compound (B) include the same compounds as those exemplified as the above-mentioned compound (a2), but when a compound having a hydroxyl group and a (meth) acryloyl group is used as the compound (a2). As compound (B), a compound having an isocyanate group and (meth) acryloyl group and / or a compound having an alkoxy group and (meth) acrylamide group is preferably used, and as compound (a2), an epoxy group and (meth) acryloyl are used. When a compound having a group is used, it is preferable to use a compound having a carboxyl group and a (meth) acryloyl group as the compound (B), and a compound having an isocyanate group and a (meth) acryloyl group as the compound (a2). When used, it is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group as the compound (B), and when using a compound having a carboxyl group and a (meth) acryloyl group as the compound (a2), it is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group. It is preferable to use a compound having an epoxy group and a (meth) acryloyl group as the compound (B), and when a compound having an alkoxy group and a (meth) acrylamide group is used as the compound (a2), the compound (B) is used. It is preferable to use a compound having a hydroxyl group and a (meth) acryloyl group. These compounds (B) can be used alone or in combination of two or more. Further, among these, since a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained, a carboxyl group and a (meth) acryloyl group are used as the compound (a2). It is preferable to use a compound having an epoxy group and a (meth) acryloyl group as the compound (B), and similarly, a compound having an epoxy group and a (meth) acryloyl group is used as the compound (a2). , It is preferable to use a compound having a carboxyl group and a (meth) acryloyl group as the compound (B).

Since the (meth) acrylate resin of the present invention can form a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity, it contains the total amount of the copolymer (A) and the compound (B). The amount is preferably 90% by mass or more, more preferably 95% by mass or more in the (meth) acrylate resin.

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

Examples of the compound (C) include tert-butylcatechol, tert-butylhydroquinone, tert-butylresorcin, 2,5-di-tert-amylhydroquinone, tert-butyl-p-benzoquinone, and 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 (4 ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-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-ethyl) Phenol), N, N'-bis {2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy] ethyl} oxamide, octyl-3,5-di-tert-butyl -4-Hydroxy-hydrocarcinate, 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) propanoart], 3- (3,5-di-tert-butyl-4- Stearyl (hydroxyphenyl) propionate, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)], triethylene glycol-bis- [3- (3) -Tert-Butyl-5-methyl-4hydroxyphenyl) 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-tetra Kiss [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-hydrosin) Namamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 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-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- (3,3) 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 thereof include dioxaphosphocin. These compounds (C) can be used alone or in combination of two or more. Among these, 2,6-di-tert-butyl-p-cresol and pentaerythritol-tetrakis [3- (3) can form a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity. ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] Is preferable.

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

Further, the double bond equivalent of the (meth) acrylate resin of the present invention is preferably 420 or less, more preferably 400 or less, because a cured product having excellent heat resistance, heat-resistant yellowing and reflectability can be formed.

The method for producing the (meth) acrylate resin of the present invention is not particularly limited, and any method may be used for producing the (meth) acrylate resin. For example, a method of reacting all of the raw materials containing the copolymer (A) and the compound (B) at once can be mentioned.

Examples of the method include a method obtained by reacting a reaction raw material containing the copolymer (A) and the compound (B) at 50 to 150 ° C. in the presence of a basic catalyst or an acidic catalyst. Can be mentioned.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 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-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; quaternary such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Ammonium salt; phosphine compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium chloride , Triphenylphosphonium chloride, phosphonium salts such as benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1 , 1,3,3-Tetrabutyl-1,3-Dodecanoyl dystanoxane and other organic tin compounds; Zinc octylate, bismuth octylate and other organic metal compounds; Inorganic tin compounds such as tin octanoate; Inorganic metal compounds and the like Can be mentioned. These basic catalysts can be used alone or in combination of two or more.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more.

The amount of the basic catalyst or the acidic catalyst used in the method ranges from 0.01 to 5 parts by mass with respect to 100 parts by mass of the total mass of the copolymer (A) and the compound (B). preferable.

In the method, when the copolymer (A) has an epoxy group derived from the compound (a2) and the compound (B) has a carboxyl group, or the copolymer (A) When the compound (a2) has a carboxyl group derived from the compound (a2) and the compound (B) has an epoxy group, a phosphorus-based catalyst such as a phosphine compound or a phosphonium salt is preferable as the catalyst used in the reaction. Phosphine compounds are more preferred.

As the phosphine compound, the same compound as those exemplified as the above-mentioned phosphine compound can be used. In addition, these phosphine compounds can be used alone or in combination of two or more.

As the phosphonium salt, the same ones as those exemplified as the above-mentioned phosphonium salt can be used. In addition, these phosphonium salts can be used alone or in combination of two or more.

In the production of the (meth) acrylate resin of the present invention, the ratio of the copolymer (A) to the compound (B) used is based on 1 mol of the reactive functional group of the copolymer (A). , The functional group capable of reacting with the reactive functional group of the compound (B) is preferably in the range of 0.5 to 1.05 mol.

In the production of the (meth) acrylate resin of the present invention, a polymerization inhibitor, an antioxidant or the like can be used in addition to the compound (C), if necessary.

Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3- (N). -Salicyloyl) amino-1,2,4-triazole, N'1, N'12-bis (2-hydroxybenzoyl) dodecandihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Quinone compounds such as 1,4-naphthoquinone, anthraquinone, diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, diphenylamine, 4 , 4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), styrene diphenylamine, styrene diphenylamine and 2,4,4-trimethyl Penten reaction products, amine compounds such as diphenylamine and 2,4,4-trimethylpenten reaction products, phenothiazine, distearylthiodipropionate, 2,2-bis ({[3- (dodecylthio) propionyl] oxy } Methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate], ditridecane-1-yl = 3,3'-thioether compounds such as sulfandyl dipropanoate, N-nitrosodiphenylamine, N- Nitrosophenyl naphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitron -N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitrosodiisopropanolamine, N-nitroso-N- Ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholin, N-nitroso N-phenylhydroxylamine ammonium salt, ditrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide , N-nitroso-N-ethylurethane, N-nitroso-Nn-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfone Nitroso compounds such as sodium acid, 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, phosphoric acid and octadecane- 1-ol ester, triphenylphosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosph Aspiro [5.5] undecane, trisnonylphenylphosphite, phosphite- (1-methylethylidene) -di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl-diphenyl-phosfit, Phosphite compounds such as diphenylisodecylphosphite, triisodecyl-phosfit, tris (2,4-di-tert-butylphenyl) phosphite, bis (dimethyldithiocarbamato-κ (2) S, S') zinc, Zinc compounds such as zinc diethyldithiocarbamate, zinc dibutyl / dithiocarbamate, nickel compounds such as bis (N, N-dibutylcarbamodithioato-S, S') nickel, 1,3-dihydro-2H-benzoimidazole-2 -Thion, 4,6-bis (octylthiomethyl) -o-cresol, 2-methyl-4,6-bis [(octane-1-ylsulfanyl) methyl] phenol, dilaurylthiodipropionic acid ester, 3, Examples thereof include sulfur compounds such as distearyl 3'-thiodipropionate. These polymerization inhibitors may be used alone or in combination of two or more.

As the antioxidant, the same compounds as those exemplified in the polymerization inhibitor can be used, and the antioxidant may be used alone or in combination of two or more.

Examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd. and "Sumilyzer BBM-S" manufactured by Sumitomo Chemical Industries, Ltd. , "Smilizer GA-80" and the like.

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

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.

Examples of commercially available products of the other photopolymerization initiator include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100" Omnirad-754 "," Omnirad-784 "," Omnirad-500 "," Omnirad-81 "(manufactured by IGM)," KayaCure-DETX "," KayaCure-MBP "," KayaCure-DMBI "," KayaCure-EPA " , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "BiCure-10", "BiCure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Akzo) Sands), "Deep" (Apjon), "QuantaCure-PDO", "QuantaCure-ITX", "QuantaCure-EPD" (Wordbrenkinsop), "Runtecure-1104" (Runtec) (Manufactured by the company) and the like.

The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the curable resin composition, for example.

The curable resin composition of the present invention may contain a resin component (hereinafter, may be referred to as “other resin component”) other than the (meth) acrylate resin described above. Examples of the other resin components include resins having a polymerizable unsaturated group, various (meth) acrylate monomers, and the like.

The resin having a polymerizable unsaturated group may be any resin as long as it has a polymerizable unsaturated group in the resin. For example, an epoxy resin having a polymerizable unsaturated group or a urethane having a polymerizable unsaturated group. Examples thereof include a resin, an acrylic resin having a polymerizable unsaturated group, an amidoimide resin having a polymerizable unsaturated group, an acrylamide resin having a polymerizable unsaturated group, and an ester resin having a polymerizable unsaturated group.

Examples of the epoxy resin having a polymerizable unsaturated group include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, a polybasic acid anhydride. Epoxy resin, unsaturated monobasic acid, polyisocyanate compound, hydroxyl group-containing (meth) acrylate compound, and urethane group-containing epoxy (meth) acrylate resin obtained by reacting with polybasic acid anhydride as needed, etc. Can be mentioned.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and oxazolidone type epoxy resin. These epoxy resins can be used alone or in combination of two or more.

Examples of the bisphenol type epoxy resin 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. Examples include resin.

Examples of the hydrogenated bisphenol type epoxy resin 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. Examples include resin.

Examples of the biphenol type epoxy resin 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 and the like can be mentioned.

Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy resin. , Hydrophobic tetramethyl-2,2'-biphenol type epoxy resin and the like.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanoceramic acid, β-styrylacrylic acid, β-fulfurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (1) can also be used.

［式（１）中、Ｘは、炭素数１〜１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、又は（ポリ）カーボネート鎖を表し、構造中にハロゲン原子やアルコキシ基等を有していても良い。Ｙは、水素原子又はメチル基である。］

[In the formula (1), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, and a halogen atom in the structure. Or an alkoxy group or the like. Y is a hydrogen atom or a methyl group. ]

Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

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

［式（Ｘ−１）中、Ｒ^１は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。］

[In the formula (X-1), R ¹ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain and the like. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides and the like.

Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid and itacone. Acids, glutaconic acid, acid anhydrides of 1,2,3,4-butanetetracarboxylic acid and the like can be mentioned. Further, as the aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.

As the alicyclic polybasic anhydride, in the present invention, an alicyclic polybasic anhydride having an acid anhydride group bonded to an alicyclic structure is used as an alicyclic polybasic anhydride, and an aromatic ring in other structural parts is used. It does not matter whether it is present or not. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1] heptane-2. 3-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetratetra-3-yl) -1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acids.

Examples of the aromatic polybasic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid and biphenyltetracarboxylic acid. Examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.

These polybasic acid anhydrides can be used alone or in combination of two or more.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedisocyanate, 4,4'-diisocyanato-3 , 3'-Aromatic diisocyanate compounds such as dimethylbiphenyl and o-trizine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (2); these isocyanurate modified products, biuret modified products, Examples thereof include a modified allophanate. Further, these polyisocyanate compounds may be used alone or in combination of two or more.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、又は構造式（２）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１〜３の整数であり、ｍは１〜１５の整数である。］

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

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.

The method for producing the epoxy resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the epoxy resin. In the production of the epoxy resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

Examples of the organic solvent 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; toluene, xylene and solvent. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers. , Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the urethane resin having a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, and if necessary, a polyol compound and a polybasic acid anhydride. Can be mentioned.

As the polyisocyanate compound, the same compound as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.

Examples of the polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol; aromatics such as biphenol and bisphenol. Polyol compounds; (poly) oxyalkylenes in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains have been introduced into the molecular structures of the various polyol compounds. Modified products: lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpropane acid. And so on. The polyol compound may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

The method for producing the urethane resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the urethane resin. In the production of the urethane resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

The acrylic resin having a polymerizable unsaturated group is obtained by polymerizing, for example, a (meth) acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group as an essential component. A reaction product obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups with the acrylic resin intermediate to be obtained. If necessary, a compound obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride and the like can be mentioned.

The acrylic resin intermediate may be a copolymer of the (meth) acrylate compound (α) and other polymerizable unsaturated group-containing compounds, if necessary. The other polymerizable unsaturated group-containing compound is, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Acrylic acid alkyl ester; alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy Aromatic ring-containing (meth) acrylates such as ethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene can be mentioned. These can be used alone or in combination of two or more.

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 the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when water (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate compound (β). When a carboxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use a glycidyl group-containing (meth) acrylate as the (meth) acrylate compound (β). When an 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 a glycidyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use a 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.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more kinds. can.

The method for producing the acrylic resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylic resin. In the production of the acrylic resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the amideimide resin having a polymerizable unsaturated group include an amideimide resin having an acid group and / or an acid anhydride group, a hydroxyl group-containing (meth) acrylate compound and / or an epoxy group-containing (meth) acrylate compound. If necessary, a compound obtained by reacting 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 can be mentioned. The compound having a reactive functional group may or may not have a (meth) acryloyl group.

The amideimide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity with a hydroxyl group-containing (meth) acrylate compound and a (meth) acryloyl group-containing epoxy compound and reaction control, it is preferable that the compound has an acid anhydride group, and both the acid group and the acid anhydride group are used. It is more preferable that the compound has. The solid acid value of the amideimide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not opened. On the other hand, the measured value under the condition that the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.

Examples of the amidoimide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

As the polyisocyanate compound, the same compound as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

In addition to the polyisocyanate compound and the polybasic acid anhydride, the amidimide resin can also use a polybasic acid as a reaction raw material, if necessary.

As the 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, pimelli acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro. Phthalic 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-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like can be mentioned. Be done. Further, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified as the above-mentioned compounds having a hydroxyl group and a (meth) acryloyl group can be used, and the hydroxyl group-containing (meth) acrylate compound is used alone. It is also possible to use two or more kinds together.

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

The method for producing the amidoimide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the amidoimide resin. In the production of the amidoimide resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the acrylamide resin having a polymerizable unsaturated group include a phenolic aqueous compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth) acrylamide compound, and if necessary, a polybasic acid anhydride or a non-acrylamide compound. Examples thereof include those obtained by reacting with a saturated monobasic acid.

The compound having a phenolic hydroxyl group means a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (3-1) to (3-4).

In the above general formulas (3-1) to (3-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. , R ² are independently hydrogen atoms or methyl groups. Further, p is an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 3, and more preferably 0 or 1 of 1. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above general formula is arbitrary. For example, in the naphthalene ring of the general formula (3-2), it may be substituted on any ring, and the general formula (3-2) may be substituted. In 3-3), it may be substituted on any ring of the benzene ring existing in one molecule, and in the general formula (3-4), it may be substituted on any ring of the benzene ring existing in one molecule. It is shown that it may be substituted with, and that the number of substituents in one molecule is p and q.

Examples of the compound having a phenolic hydroxyl group include a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any of the following general formulas (x-1) to (x-5). A reaction product or the like using the above as an essential reaction raw material can also be used. Further, a novolak type phenol resin or the like using one or more compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.

［式（ｘ−１）中、ｈは０または１である。式（ｘ−２）〜（ｘ−５）中、Ｒ^３は、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、アリール基、ハロゲン原子の何れかであり、ｉは、０または１〜４の整数である。式（ｘ−２）、（ｘ−３）及び（ｘ−５）中、Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。式（ｘ−５）中、Ｙは、炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかであり、ｊは１〜４の整数である。］

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

These phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. The alkylene oxide may be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl (meth) acrylamide compound include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxyethyl (meth) acrylamide. , N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like. The N-alkoxyalkyl (meth) acrylamide compound may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. ..

The method for producing the acrylamide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylamide resin. In the production of the acrylamide resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst and an acidic catalyst may be used if necessary.

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the acidic catalyst, the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst may be used alone or in combination of two or more.

The ester resin having a polymerizable unsaturated group is obtained by reacting, for example, a phenolic aqueous compound, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid with an unsaturated monobasic acid, if necessary, with a polybasic acid anhydride. Can be mentioned.

As the phenolic water compound, the same compounds as those exemplified as the above-mentioned phenolic water compound can be used, and the phenolic water compound may be used alone or in combination of two or more.

As the alkylene oxide, the same ones as those exemplified as the above-mentioned alkylene oxide can be used. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. The alkylene oxide may be used alone or in combination of two or more.

As the alkylene carbonate, the same ones as those exemplified as the above-mentioned alkylene carbonate can be used. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance, heat-resistant yellowing and reflectivity can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. ..

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

The method for producing the ester resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the ester resin. In the production of the ester resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst and an acidic catalyst may be used if necessary.

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the acidic catalyst, the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst may be used alone or in combination of two or more.

The amount of the resin having a polymerizable unsaturated group is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the (meth) acrylate resin of the present invention.

Examples of the various (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate, 2 -Alipid mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate. 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, Aromatic mono (meth) such as phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate. Mono (meth) acrylate compounds such as acrylate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers. A (poly) oxyalkylene-modified mono (meth) acrylate compound having an alkylene chain introduced; a lactone-modified mono (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds; ethylene. An aliphatic di (meth) acrylate compound such as glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; 1,4-Cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, etc. Acrylate-type di (meth) acrylate compound; aromatics such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate Di (meth) acrylate compound; (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound introduced with; a lactone-modified di (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the various di (meth) acrylate compounds; An aliphatic tri (meth) acrylate compound such as a meta) acrylate or a glycerin tri (meth) acrylate; in the molecular structure of the aliphatic tri (meth) acrylate compound, a (poly) oxyethylene chain, a (poly) oxypropylene chain, ( A (poly) oxyalkylene-modified tri (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a poly) oxytetramethylene chain; a (poly) lactone structure in the molecular structure of the aliphatic tri (meth) acrylate compound. Introduced lactone-modified tri (meth) acrylate compound; tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. 4 or more functionals in which (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. (Poly) oxyalkylene-modified poly (meth) acrylate compound; a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound, etc. Can be mentioned.

Further, as the other (meth) acrylate monomer, in addition to the above-mentioned one, a (meth) acrylate monomer containing a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials. Can be used.

Examples of the other phenolic 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, Examples thereof include 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 phenol resin containing cycloring structure. ..

Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more.

Examples of the cyclic ether compound include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more.

As the unsaturated monocarboxylic acid, the same ones as those exemplified as the above-mentioned unsaturated monocarboxylic acid can be used.

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

Further, the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, and leveling. It can also contain various additives such as an agent, a flame retardant, and a storage stabilizer.

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.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and 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-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetra-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, Examples thereof include benzophenone tetracarboxylic acid. Further, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. You can also.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds can be used alone or in combination of two or more.

Examples of the amide compound include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine. These amide compounds may be used alone or in combination of two or more.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkylperoxycarbonates and the like. These organic peroxides can be used alone or in combination of two or more.

Examples of the polyol compound include 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, pentaerythritol di (meth) acrylate and other polyol monomers; , Hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, polyester polyol obtained by cocondensation with dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; A lactone-type polyester polyol obtained by a polycondensation reaction with various lactones such as δ-valerolactone and 3-methyl-δ-valerolactone; the polyol monomer and ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether, propylglycidyl. Examples thereof include a polyether polyol obtained by ring-opening polymerization with a cyclic ether compound such as ether. These polyol compounds can be used alone or in combination of two or more.

As the epoxy resin, the same ones as those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin may be used alone or in combination of two or more.

Examples of the curing accelerator include phosphorus-based compounds, amine-based compounds, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like, which promote the curing reaction. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.

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

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more.

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

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, prussian blue, ultramarine, carbon black, graphite and the like. These inorganic pigments can be used alone or in combination of two or more.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. And so on.

Examples of the organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanslon pigments, flavanthron pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, and the like. Examples thereof include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.

Examples of the flame retardant include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphoric acid amide; phosphoric acid ester compounds and phosphorus compounds. Acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxy) Cyclic organics such as phenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Organophosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers, Silicone-based flame retardants such as silicone resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. These flame retardants may be used alone or in combination of two or more. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

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

As the ultraviolet source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 0.1~50kJ / ^{m 2,} and more preferably 0.5~10kJ / ^{m 2.} When the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

The irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

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, automobile interior / exterior materials, and OA equipment, semiconductor devices, display devices, imaging devices, and the like.

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

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

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

(Example 1: Production of acrylate resin (1))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A1). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (1). The non-volatile content of the 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 the present invention, the double bond equivalent is a calculated value calculated from the amount of raw materials charged.

(Example 2: Production of acrylate resin (2))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A2). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (2). The non-volatile content of the acrylate resin (2) was 52.6% by mass, the weight average molecular weight (Mw) was 11,570, and the double bond equivalent was 269.

(Example 3: Production of acrylate resin (3))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A3). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (3). The non-volatile content of the acrylate resin (3) was 52.6% by mass, the weight average molecular weight (Mw) was 11,780, and the double bond equivalent was 269.

(Example 4: Production of acrylate resin (4))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A4). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (4). The non-volatile content of the acrylate resin (4) was 52.6% by mass, the weight average molecular weight (Mw) was 11,460, and the double bond equivalent was 269.

(Example 5: Production of acrylate resin (5))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A5). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (5). The non-volatile content of the acrylate resin (5) was 52.6% by mass, the weight average molecular weight (Mw) was 11,890, and the double bond equivalent was 269.

(Example 6: Production of acrylate resin (6))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 phenoxyethyl methacrylate, 55.6 parts by mass of butyl acetate, and (2-ethylhexanoyl) (tert-butyl) peroxide (manufactured by Nippon Oil & Fats Co., Ltd. Perbutyl O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A6). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (6). The non-volatile content of the acrylate resin (6) was 52.6% by mass, the weight average molecular weight (Mw) was 12,110, and the double bond equivalent was 269.

(Example 7: Production of acrylate resin (7))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 azobisisobutyronitrile were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A7). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (7). The non-volatile content of the acrylate resin (7) was 52.6% by mass, the weight average molecular weight (Mw) was 12,310, and the double bond equivalent was 269.

(Example 8: Production of acrylate resin (8))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A8). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of tetrabutylphosphonium chloride were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. The reaction was carried out for 10 hours, 14.3 parts by mass of butyl acetate was charged, and the mixture was stirred to obtain the desired acrylate resin (8). The non-volatile content of the acrylate resin (8) was 49.8% by mass, the weight average molecular weight (Mw) was 16,320, and the double bond equivalent was 269.

(Example 9: Production of acrylate resin (9))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A9). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triethylamine were charged, and the reaction was carried out at 120 ° C. for 10 hours while blowing air and stirring. Then, 14.3 parts by mass of butyl acetate was charged and stirred to obtain the desired acrylate resin (9). The non-volatile content of the acrylate resin (9) was 49.8% by mass, the weight average molecular weight (Mw) was 12,550, and the double bond equivalent was 269.

(Example 10: Production of acrylate resin (10))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A10). Then, pentaerythritol = tetrakis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] 0.5 parts by mass, methylhydroquinone 0.1 parts by mass, acrylic acid 36.5 parts by mass. A part, 0.6 parts by mass of triphenylphosphine was charged, and the reaction was carried out at 120 ° C. for 10 hours while blowing air and stirring to obtain the desired acrylate resin (10). The non-volatile content of the acrylate resin (10) was 52.6% by mass, the weight average molecular weight (Mw) was 12,550, and the double bond equivalent was 269.

(Example 11: Production of acrylate resin (11))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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 methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0. 6 parts by mass was charged, air was blown into the mixture, and the mixture was reacted at 120 ° C. for 10 hours with stirring to obtain the desired acrylate resin (11). The non-volatile content of the acrylate resin (11) was 52.6% by mass, the weight average molecular weight (Mw) was 11,910, and the double bond equivalent was 269.

(Example 12: Production of acrylate resin (12))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A12). Next, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] 0.5 parts by mass, methylhydroquinone 0.1 parts by mass, acrylic acid 36. 5.5 parts by mass and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120 ° C. for 10 hours while blowing air and stirring to obtain the desired acrylate resin (12). The non-volatile content of the acrylate resin (12) was 52.6% by mass, the weight average molecular weight (Mw) was 11,880, and the double bond equivalent was 269.

(Example 13: Production of acrylate resin (13))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A13). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 45.6 parts by mass of acrylic acid, and 0.5 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 13 parts. After reacting for a time, 23.4 parts by mass of butyl acetate was charged and stirred to obtain the desired acrylate resin (13). The non-volatile content of the acrylate resin (13) was 49.8% by mass, the weight average molecular weight (Mw) was 14,770, and the double bond equivalent was 269.

(Example 14: Production of acrylate resin (14))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A14). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 25.4 parts by mass of acrylic acid, and 0.4 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. at 8%. The reaction was carried out for a time to obtain the desired acrylate resin (14). The non-volatile content of the acrylate resin (14) was 55.4% by mass, the weight average molecular weight (Mw) was 10,150, and the double bond equivalent was 356.

(Example 15: Production of acrylate resin (15))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A15). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 20.3 parts by mass of acrylic acid, and 0.4 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 7 parts. The reaction was carried out for a time to obtain the desired acrylate resin (15). The non-volatile content of the acrylate resin (15) was 56.4% by mass, the weight average molecular weight (Mw) was 9,820, and the double bond equivalent was 427.

(Example 16: Production of acrylate resin (16))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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, ω-carboxy-polycaprolactone monoacrylate (“Aronix M-5300” manufactured by Toa Synthetic Co., Ltd.) 48. 2 parts by mass and 0.6 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 120 ° C. for 12 hours while blowing air and stirring to obtain the desired acrylate resin (16). The non-volatile content of the acrylate resin (16) was 58.5% by mass, the weight average molecular weight (Mw) was 12,230, and the double bond equivalent was 343.

(Example 17: Production of acrylate resin (17))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 added. It was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. to 12 parts. The reaction was carried out for a time to obtain the desired acrylate resin (17). The non-volatile content of the acrylate resin (17) was 53.7% by mass, the weight average molecular weight (Mw) was 14,270, and the double bond equivalent was 239.

(Example 18: Production of acrylate resin (18))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A18). Next, 0.1 part by mass of methyl hydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 part by mass of triphenylphosphine were charged, and the mixture was reacted at 120 ° C. for 10 hours while blowing air and stirring to obtain the desired acrylate resin ( 18) was obtained. The non-volatile content of the acrylate resin (18) was 52.6% by mass, the weight average molecular weight (Mw) was 12,730, and the double bond equivalent was 269.

(Example 19: Production of acrylate resin (19))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A19). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 87.9 parts by mass of 4-hydroxybutylacrylate glycidyl ether, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 110 ° C. for 14 hours to obtain the desired acrylate resin (19). The non-volatile content of this acrylate resin (19) is 55.4% by mass, the solid acid value is 80 mgKOH / g, the weight average molecular weight (Mw) is 47,910, and the double bond equivalent is It was 428. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A19) corresponding to the copolymer (A) specified in the present invention. The number of moles of 4-hydroxybutyl acrylate glycidyl ether corresponding to) was 0.63.

(Example 20: Production of acrylate resin (20))
67 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd. ) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A20). Then, pentaerythritol = tetrakis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] 0.7 parts by mass, 2,2'-thiodiethylbis [3- (3, 3,) 5-Di-tert-butyl-4-hydroxyphenyl) propionate] 0.7 parts by mass, 0.1 parts by mass of methylhydroquinone, 41 parts by mass of acrylic acid, 0.5 parts by mass of triphenylphosphine were charged, and air was blown into it. The reaction was carried out at 120 ° C. for 10 hours with stirring to obtain the desired acrylate resin (20). The solid acid value of the obtained acrylate resin (20) was 2 mgKOH / g. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of an epoxy group contained in the acrylic copolymer (A20) corresponding to the copolymer (A) specified in the present invention. The number of moles of acrylic acid corresponding to) was 1.

(Example 21: Production of acrylate resin (21))
67 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd. ) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A21). Then, pentaerythritol = tetrakis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] 0.9 parts by mass, 2,2'-thiodiethylbis [3- (3, 3,) 5-Di-tert-butyl-4-hydroxyphenyl) propionate] 0.9 parts by mass, 0.1 parts by mass of methylhydroquinone, 28 parts by mass of acrylic acid, ω-carboxy-polycaprolactone monoacrylate (manufactured by Toa Synthetic Co., Ltd. Aronix M-5300 ") 53 parts by mass and 0.6 parts by mass of triphenylphosphine were charged and reacted at 120 ° C. for 15 hours while blowing air and stirring to obtain the desired acrylate resin (21). The solid acid value of the obtained acrylate resin (21) was 3 mgKOH / g. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of an epoxy group contained in the acrylic copolymer (A21) corresponding to the copolymer (A) specified in the present invention. The number of moles of acrylic acid corresponding to) was 0.7.

(Example 22: Production of methacrylate resin (1))
66.7 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide ("Perbutyl" manufactured by Nippon Oil & Fats Co., Ltd. O ”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A22). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 43.6 parts by mass of methacrylic acid, and 0.5 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. to 12 parts. The reaction was carried out for a time to obtain the desired methacrylic acid resin (1). The non-volatile content of the methacrylate resin (1) was 53.8% by mass, the weight average molecular weight (Mw) was 11,290, and the double bond equivalent was 283. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of an epoxy group contained in the acrylic copolymer (A22) corresponding to the copolymer (A) specified in the present invention. The number of moles of methacrylic acid corresponding to) was 0.45.

(Example 23: Production of methacrylate resin (2))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A23). Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 44.6 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 110 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired methacrylate resin (2). The non-volatile content of the methacrylate resin (2) is 48.9% by mass, the solid acid value is 150 mgKOH / g, the weight average molecular weight (Mw) is 45,420, and the double bond equivalent is , 461. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A23) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 0.45.

(Example 24: Production of methacrylate resin (3))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A24). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 51.5 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 110 ° C. for 12 parts. The reaction was carried out for a time to obtain the desired methacrylate resin (3). The non-volatile content of the methacrylate resin (3) is 50.1% by mass, the solid acid value is 125 mgKOH / g, the weight average molecular weight (Mw) is 46,010, and the double bond equivalent is It was 418. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A24) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 0.52.

(Example 25: Production of methacrylate resin (4))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (A25). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 65.4 parts by mass of glycidyl methacrylate, and 0.6 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 110 ° C. The reaction was carried out for a time to obtain the desired methacrylate resin (4). The non-volatile content of the methacrylate resin (4) is 52.2% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 48,540, and the double bond equivalent is It was 359. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A25) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 0.66.

(Example 26: Production of methacrylate resin (5))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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 air was blown into the mixture, and the mixture was stirred at 110 ° C. for 20 parts. After reacting for a time, 49.1 parts by mass of dipropylene glycol monomethyl ether was added, and the mixture was stirred to obtain the desired methacrylate resin (5). The non-volatile content of the methacrylate resin (5) was 49.8% by mass, the weight average molecular weight (Mw) was 50,960, and the double bond equivalent was 285. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A26) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 1.0.

(Example 27: Production of methacrylate resin (6))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (Nippon Yushi Co., Ltd.) 5 parts by mass of "Perbutyl O" manufactured by Japan, Ltd. was mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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 charged, and the reaction was carried out at 110 ° C. for 19 hours while blowing air and stirring. Then, 56 parts by mass of dipropylene glycol monomethyl ether was added, and the mixture was stirred to obtain the desired methacrylate resin (6). The non-volatile content of the methacrylate resin (6) was 49.8% by mass, the weight average molecular weight (Mw) was 49,860, and the double bond equivalent was 276. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A27) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 1.07.

(Example 28: Production of (meth) acrylate resin (1))
66.7 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 50 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 10 parts by mass of ω-carboxy-polycaprolactone monoacrylate (“Aronix M-5300” manufactured by Toa Synthetic Co., Ltd.), 10 parts by mass of benzyl methacrylate, and dipropylene glycol monomethyl. 83.3 parts by mass of ether and 5 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.) were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an 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 air was blown into the mixture, and the mixture was stirred at 110 ° C. for 20 parts. After reacting for a time, 5.7 parts by mass of dipropylene glycol monomethyl ether was added, and after stirring, the desired (meth) acrylate resin (1) was obtained. The non-volatile content of this (meth) acrylate resin (1) is 49.8% by mass, the solid acid value is 80 mgKOH / g, the weight average molecular weight (Mw) is 49,140, and the double. The binding equivalent was 397. Further, a compound (B) having a polymerizable unsaturated group specified in the present invention with respect to 1 mol of the carboxyl group of the acrylic copolymer (A28) corresponding to the copolymer (A) specified in the present invention. The number of moles of glycidyl methacrylate corresponding to) was 0.64.

(Synthesis Example 1: Production of Epoxy Acrylate Resin (1))
Put 101 parts by mass of diethylene glycol monomethyl ether acetate in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd., epoxy equivalent: 214) 428. After dissolving 4 parts by mass of dibutyl hydroxytoluene and 0.4 parts by mass of methquinone, 144 parts by mass of epoxy acid and 1.6 parts by mass of triphenylphosphine were added, and air was blown at 120 ° C. for 10 hours. The esterification reaction was carried out. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain the desired epoxy acrylate resin (1). The solid acid value of the epoxy acrylate resin (1) was 85 mgKOH / g.

(Comparative Example 1: Production of Acrylate Resin (R1))
66.7 parts by mass of diethylene glycol monomethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised 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 (2-ethylhexanoyl) (tert-butyl) peroxide (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.) 5 The parts by mass were mixed in advance and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain an acrylic copolymer (AR1). Next, 0.5 parts by mass of dibutylhydroxytoluene, 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 air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (R1). The weight average molecular weight (Mw) of this acrylate resin (R1) was 11,160, and the double bond equivalent was 269.

(Comparative Example 2: Production of Acrylate Resin (R2))
66.7 parts by mass of diethylene glycol monomethyl ether acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 (2-ethylhexanoyl) (tert-butyl) peroxide (manufactured by Nippon Oil & Fats Co., Ltd.). “Perbutyl O”) 5 parts by mass were mixed in advance and added dropwise over 3 hours. Hold 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 methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. The reaction was carried out for a time to obtain the desired acrylate resin (R2). The solid acid value of the acrylate resin (R2) had a weight average molecular weight (Mw) of 12,070 and a double bond equivalent of 269.

(Example 29: Preparation of curable resin composition (1))
100 parts by mass of the acrylate resin (1) having a non-volatile content of 58.6% by mass obtained in Example 1 and 2.6 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM) are mixed to form a curable resin. The composition (1) was obtained.

(Examples 30 to 58: Preparation of curable resin compositions (2) to (30))
The same as in Example 29 except that the (meth) acrylate resin obtained in Examples 2 to 28 was used in the blending amounts shown in Tables 1 and 2 instead of the acrylate resin (1) used in Example 29. The curable resin compositions (2) to (30) were obtained.

(Comparative Example 3: Preparation of Curable Resin Composition (R1))
A curable resin is obtained by mixing 100 parts by mass of the acrylate resin (R1) having a non-volatile content of 52.6% by mass obtained in Comparative Example 1 and 2.6 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM). The composition (R3) was obtained.

(Comparative Example 4: Preparation of curable resin composition (R2))
Curability in the same manner as in Comparative Example 3 except that the acrylate resin (R2) obtained in Comparative Example 2 was used in the blending amount shown in Table 2 instead of the acrylate resin (R1) used in Comparative Example 3. A resin composition (R4) was obtained.

The following evaluations were carried out using the curable resin compositions obtained in the above Examples and Comparative Examples.

[Evaluation method of heat resistance]
The curable resin composition obtained in each Example and Comparative Example was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) so as to have a film thickness of 50 μm using an applicator. Then, it was dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with ultraviolet rays of 10 kJ / m 2} using a metal halide lamp, the mixture was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A 6 mm × 35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Leometric Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C./min) was used. The temperature at which the change in viscoelasticity was maximized was evaluated as the glass transition temperature according to the following criteria. The higher the glass transition temperature, the better the heat resistance.

A: The glass transition temperature (Tg) was 140 ° C. or higher.
B: Tg was 135 ° C. or higher and lower than 140 ° C.
C: Tg was 130 ° C. or higher and lower than 135 ° C.
D: Tg was 125 ° C. or higher and lower than 130 ° C.
E: Tg was less than 125 ° C.

[Evaluation method for heat-resistant yellowing]
The curable resin compositions obtained in each Example and Comparative Example were applied onto glass using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with ultraviolet rays of 10 kJ / m 2} using a metal halide lamp, the mixture was heated at 160 ° C. for 1 hour to obtain a cured coating film. The obtained cured coating film is heated to 260 ° C. in a hot air circulation type drying furnace, accelerated and deteriorated, taken out after 30 minutes, and the color difference from the unheated one is measured by the color difference meter "ZE6000" manufactured by Nippon Denshoku Industries Co., Ltd. ], And evaluated according to the following criteria.

A: The color difference (ΔE) was less than 5.
B: ΔE was 5 or more and less than 6.
C: ΔE was 6 or more and less than 7.
D: ΔE was 7 or more and less than 8.
E: ΔE was 8 or more.

[Evaluation method of reflectivity]
The curable resin compositions obtained in each Example and Comparative Example were applied onto glass using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with ultraviolet rays of 10 kJ / m 2} using a metal halide lamp, the mixture was heated at 160 ° C. for 1 hour to obtain a cured coating film. The obtained cured coating film is heated to 260 ° C. in a hot air circulation type drying furnace to be accelerated and deteriorated, and the reflectance (Y) of the obtained cured coating film taken out after 60 minutes is measured by a color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. <After heat resistance test> measured by "ZE6000" and evaluated according to the following criteria.

A: The reflectance (Y) was 89 or more.
B: Y was 88 or more and less than 89.
C: Y was 87 or more and less than 88.
D: Y was 86 or more and less than 87.
E: Y was less than 86.

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 are shown. It is shown in Tables 1 and 2.

In addition, the description of the mass part of the acrylate resin, the methacrylate resin, the (meth) acrylate resin and the epoxy acrylate resin in Tables 1 and 2 is a solid content value.

“Photopolymerization initiator” in Tables 1 and 2 indicates “Omnirad-907” manufactured by IGM.

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 product of the curable resin composition containing the (meth) acrylate resin of the present invention has a good balance of heat resistance, heat-resistant yellowing and reflectivity.

On the other hand, Comparative Example 3 is an example in which the methacrylate compound (a1) having an aromatic ring specified in the present invention is not used. It was confirmed that the cured product of this curable resin composition did not have heat resistance, heat-resistant yellowing, and reflectivity.

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

Claims (16)

A (meth) acrylic copolymer (A) containing a methacrylate compound (a1) having an aromatic ring and a compound (a2) having a reactive functional group and a polymerizable unsaturated group other than the compound (a1) as essential raw materials. When,
A compound having a polymerizable unsaturated group other than the compound (a1) and the compound (a2) having a functional group capable of reacting with a reactive functional group derived from the compound (a2) of the copolymer (A). (B) and
(Meta) acrylate resin, which is characterized by using the above as an essential raw material. The (meth) acrylate resin according to claim 1, wherein the content of the compound (a1) is more than 3% by mass and 18% by mass or less in the raw material of the (meth) acrylic copolymer (A). The (meta) acrylate resin according to claim 1 or 2, wherein the compound (a1) contains benzyl methacrylate. The one according to any one of claims 1 to 3, wherein the reactive functional group of the compound (a2) is at least one selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group and an acrylamide group. Meta) Acrylate resin. Claims 1 to 4, wherein the copolymer (A) further contains the compound (a1) and other (meth) acrylate compound (a3) other than the compound (a2) as a raw material thereof. The (meth) acrylate resin according to any one of the above. The (meth) acrylate resin according to claim 5, wherein the compound (a3) is a methacrylate compound. The (meta) acrylate according to any one of claims 1 to 6, wherein the (meth) acrylate resin further contains a compound (C) having a phenolic hydroxyl group and a tert-butyl group as a raw material thereof. resin. The (meta) acrylate resin according to any one of claims 1 to 7, wherein the (meth) acrylate resin further contains a phosphorus-based catalyst as a raw material thereof. The (meta) acrylate resin according to any one of claims 1 to 8, wherein the double bond equivalent of the (meth) acrylate resin is 420 or less. The ratio of the copolymer (A) to the compound (B) used is such that the reactive functional group of the compound (B) is relative to 1 mol of the reactive functional group of the copolymer (A). The (meth) acrylate resin according to any one of claims 1 to 9, wherein the functional group capable of reacting with is in the range of 0.5 to 1.05 mol. A curable resin composition containing the (meth) acrylate resin according to any one of claims 1 to 10 and a photopolymerization initiator. The curable resin composition according to claim 11, wherein the curable resin composition further contains a resin having a polymerizable unsaturated group other than the (meth) acrylate resin. The curable resin composition according to claim 11 or 12, wherein the curable resin composition further contains an organic solvent. The curable resin composition according to any one of claims 11 to 13, wherein the curable resin composition further contains a curing agent. A cured product of the curable resin composition according to any one of claims 11 to 14. An article characterized by having a coating film made of the cured product according to claim 15.