JP2022006901A - Acid group-containing meth(acrylate) resin, curable resin composition, cured product, insulation material, resin material for solder resist and resist member - Google Patents

Abstract

To provide an acid group-containing meth(acrylate) resin which enables formation of a cured product that has high photosensitivity, and excellent heat resistance, elasticity and adhesion.SOLUTION: An acid group-containing meth(acrylate) resin contains: a (meth)acrylic copolymer (A) containing phenylbenzyl (meth)acrylate (a1) and a compound (a2) having a reactive functional group and a polymerizable unsaturated group other than the phenylbenzyl (meth)acrylate (a1) as essential raw materials; a compound (B) having a functional group capable of reacting with a reactive functional group derived from the compound (a2) that the copolymer (A) has, and a polymerizable unsaturated group other than the phenylbenzyl (meth)acrylate (a1) and the compound (a2); and a polybasic acid anhydride (C), as essential raw materials.SELECTED DRAWING: None

Description

The present invention relates to an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion, a curable resin composition containing the same, and the curable resin. The present invention relates to a cured product of a composition, an insulating material, a resin material for solder resist, and a resist member.

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. In particular, as the coating agent, it is generally 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 surface of the base material. Is required. Further, when used as a curable composition for a solder resist for a printed wiring board, it is also required to be cured with a small exposure amount and to have excellent heat resistance in the cured product.

As a conventional curable composition for solder resist, an acid group-containing epoxy obtained by further reacting a tetrahydroan phthalic acid with an intermediate obtained by reacting a cresol novolac type epoxy resin with an acrylic acid and an anhydrous phthalic acid. Although a photosensitive resin composition containing an acrylate resin is known (see, for example, Patent Document 1), it has problems such as insufficient heat resistance, elasticity, and adhesion in a cured product.

Therefore, there has been a demand for a material having excellent heat resistance, elasticity and adhesion in addition to high light sensitivity.

Japanese Unexamined Patent Publication No. 8-259663

The problem to be solved by the present invention is an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion, and a curable resin composition containing the acid group-containing (meth) acrylate resin. It is an object of the present invention to provide a product, a cured product of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.

As a result of diligent studies to solve the above problems, the present inventors have made reactive functional groups and non-polymerizable groups other than phenylbenzyl (meth) acrylate (a1) and the phenylbenzyl (meth) acrylate (a1). Functionality capable of reacting with the (meth) acrylic copolymer (A) using the compound (a2) having a saturated group as an essential raw material and the reactive functional group derived from the compound (a2) possessed by the copolymer (A). By using the compound (B) having a polymerizable unsaturated group other than the phenylbenzyl (meth) acrylate (a1) and the compound (a2) having a group, and the polybasic acid anhydride (C), the above-mentioned We have found that the problem can be solved and completed the present invention.

That is, the present invention uses a phenylbenzyl (meth) acrylate (a1) and a compound (a2) having a reactive functional group and polymerizable unsaturated group other than the phenylbenzyl (meth) acrylate (a1) as an essential raw material (a2). The phenylbenzyl (meth) acrylate (a1) having a functional group capable of reacting with the (meth) acrylic copolymer (A) and the reactive functional group derived from the compound (a2) of the copolymer (A). An acid group-containing (meth) acrylate resin, which comprises a compound (B) having a polymerizable unsaturated group other than the compound (a2) and a polybasic acid anhydride (C) as essential raw materials. It relates to a curable resin composition containing this, a cured product of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.

Since the acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and can form a cured product having excellent heat resistance, elasticity and adhesion, photopolymerization with the acid group-containing (meth) acrylate resin is started. The curable resin composition containing the agent can be used as a coating agent or an adhesive, and the coating agent can be particularly preferably used for solder resist applications. The "excellent elasticity" in the present invention means that the elastic modulus of the cured product is high.

The acid group-containing (meth) acrylate resin of the present invention is a compound having a reactive functional group and a polymerizable unsaturated group other than phenylbenzyl (meth) acrylate (a1) and the phenylbenzyl (meth) acrylate (a1) (a1). a2) Derived from the (meth) acrylic copolymer (A) containing (hereinafter, may be referred to as "compound (a2)") as an essential raw material and the compound (a2) possessed by the copolymer (A). Compound (B) having a polymerizable unsaturated group other than the phenylbenzyl (meth) acrylate (a1) and the compound (a2) having a functional group capable of reacting with the reactive functional group of (hereinafter, "Compound (B)". ) ”) And the polybasic acid anhydride (C) as essential raw materials.

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

The (meth) acrylic copolymer (A) contains the phenylbenzyl (meth) acrylate (a1) and the compound (a2) having a polymerizable unsaturated group as essential raw materials.

The content of the phenylbenzyl (meth) acrylate (a1) is such that an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained. Therefore, it is preferably 30% by mass or less in the raw material of the copolymer (A), and more preferably 0.1 to 20% 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 acrylamide 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 (meth) acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group and the like.

Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol (meth) acrylate. , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) Examples thereof include acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and ditrimethylolpropanetri (meth) acrylate. In addition, (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain were introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds (). Poly) oxyalkylene modified products, lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, and the like can also be used. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

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

Examples of the isocyanate group-containing (meth) acrylate compound include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. These isocyanate group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

Examples of the carboxyl group-containing compound include (meth) acrylic acid and ω-carboxy-polycaprolactone monoacrylate. These carboxyl group-containing compounds may be used alone or in combination of two or more.

Examples of the acrylamide group-containing compound include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-ethoxyethyl. Examples thereof include (meth) acrylamide and N-butoxyethyl (meth) acrylamide. The acrylamide group-containing compound 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 bond in one molecule can also be used. In the present invention, the "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

Examples of the compound having a reactive functional group and a polymerizable unsaturated bond in one molecule include an unsaturated acid such as cinnamic acid, a tetrahydrophthalic anhydride, and an acid having an unsaturated bond in the molecule such as maleic anhydride. 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, styryl compounds having a reactive functional group such as 4-vinylbenzoic acid, and the like.

The content of the compound (a2) is the same weight because an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained. The range of 40 to 90% by mass is preferable, and the range of 50 to 90% by mass is more preferable in the coalescence (A).

The copolymer (A) may contain other polymerization components other than the phenylbenzyl (meth) acrylate (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 (. An aliphatic mono (meth) acrylate compound such as meta) acrylate and octyl (meth) acrylate; an alicyclic mono (meth) acrylate compound such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxy. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as ethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: molecules of the various mono (meth) acrylate monomers. A (poly) oxyalkylene-modified mono (meth) acrylate compound in which a polyoxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the structure; A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the (meth) acrylate compound; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butane diol di (meth) acrylate. , Hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate and other aliphatic di (meth) acrylate compounds; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornandi. Alicyclic di (meth) acrylate compounds such as methanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate; biphenol di (meth) acrylate, bisphenol di (meth) acrylate. ) Aromatic di (meth) acrylate compounds such as acrylates; (poly) oxyethylene chains, (po) in the molecular structure of the various di (meth) acrylate compounds. (I) Polyoxyalkylene-modified di (meth) acrylate compounds introduced with (poly) oxyalkylene chains such as (d) oxypropylene chains and (poly) oxytetramethylene chains; A lactone-modified di (meth) acrylate compound introduced with a poly) lactone structure; an aliphatic tri (meth) acrylate compound such as trimetylol propantri (meth) acrylate and glycerin tri (meth) acrylate; A (poly) oxyalkylene-modified tri (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the compound. A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, di A tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as pentaerythritol hexa (meth) acrylate; (poly) oxyethylene chain, (poly) oxypropylene chain, etc. in the molecular structure of the aliphatic poly (meth) acrylate compound. A tetrafunctional or higher functional (poly) oxyalkylene-modified poly (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a (poly) oxytetramethylene chain; Examples thereof include a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound having a poly) lactone structure introduced therein. These compounds (a3) can be used alone or in combination of two or more. Among these, a methacrylate compound is preferable because an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained.

The compound (a4) having a polymerizable unsaturated group 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 phenylbenzyl (meth) acrylate (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 persulfates, organic peroxides, and hydrogen peroxide, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis (. 2-Amidinopropane) An azo initiator such as dihydrochloride can be mentioned. 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 may 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 decanoyle peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, and t-butyl peroxide. Peroxyesters such as -2-ethylhexanoate, t-butylperoxylaurate, and t-butylperoxybenzoate, hydroperoxides such as cumenehydroperoxide, paramentanhydroperoxide, and t-butylhydroperoxide. 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 an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained.

The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but the total mass of the polymerization component containing the phenylbenzyl (meth) acrylate (a1) and the compound (a2) is 100% by mass. 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 hydroxyl group-containing (meth) acrylate compound is used as the compound (a2), the compound is used. It is preferable to use an isocyanate group-containing (meth) acrylate compound and / or an acrylamide group-containing compound as (B), and when an epoxy group-containing (meth) acrylate compound is used as compound (a2), the compound (B) is used. It is preferable to use a carboxyl group-containing compound, and when an isocyanate group-containing (meth) acrylate compound is used as the compound (a2), a hydroxyl group-containing (meth) acrylate is preferably used as the compound (B), and the compound (a2) is preferable. ), It is preferable to use an epoxy group-containing (meth) acrylate as the compound (B), and when a acrylamide group-containing compound is used as the compound (a2), the compound (B) is used. ), It is preferable to use a hydroxyl group-containing (meth) acrylate. These compounds (B) can be used alone or in combination of two or more. Further, among these, since an acid group-containing (meth) acrylate resin having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained, an epoxy is used as the compound (a2). It is preferable to use a group-containing (meth) acrylate compound and a carboxyl group-containing compound as the compound (B).

Examples of the polybasic acid anhydride (C) include saturated polybasic acid anhydride and unsaturated polybasic acid anhydride. In the present invention, the saturated polybasic acid anhydride means a polybasic acid anhydride having no carbon-carbon double bond, and the unsaturated polybasic acid anhydride means a carbon-carbon double bond. It means a polybasic acid anhydride having.

Examples of the saturated polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid. Acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane- Examples thereof include acid anhydrides such as 2,3-dicarboxylic acid.

Examples of the unsaturated polybasic acid anhydride include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, tetrahydrophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid and naphthalenetricarboxylic acid. , Naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, 4- (2,5-dioxotetracarboxylic acid) -1,2,3,4-tetrahydronaphthalene Examples thereof include acid anhydrides such as -1,2-dicarboxylic acid.

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

The acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and can form a cured product having excellent heat resistance, elasticity and adhesion. Therefore, the copolymer (A) and the compound thereof. The total content of (B) and the polybasic acid anhydride (C) is preferably 90% by mass or more, more preferably 95% by mass or more in the acid group-containing (meth) acrylate resin.

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

Examples of the compound (D) include tert-butylcatechol, tert-butylhydroquinone, tert-butylresorcin, 2,5-di-tert-amylhydroquinone, tert-butyl-p-benzoquinone, 2,6-di-. tert-butyl-p-cresol, 2-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene), 2,6-di-tert-butyl-4- Ethylphenol, 2,2'-methylenebis (4ethyl-6-tert-butylphenol), 2,2'-methylenebis (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- (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-tetraki Su [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-hydrocin) 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] Dioxaphosphosin, etc. may be mentioned. These compounds may be used alone or in combination of two or more. Among these, 2,6-di-tert-butyl-p-cresol and pentaerythritol-tetrakis can be formed because they have high photosensitivity and can form a cured product having excellent heat resistance, elasticity and adhesion. [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] is preferable.

The content of the compound (D) 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 acid group-containing (meth) acrylate resin.

Further, the double bond equivalent of the acid group-containing (meth) acrylate resin of the present invention is preferably 500 or less because it has high photosensitivity and can form a cured product having excellent heat resistance, elasticity and adhesion. , 450 or less is more preferable.

The method for producing the acid group-containing (meth) acrylate resin of the present invention is not particularly limited, and any method may be used for producing the acid group-containing (meth) acrylate resin. For example, it may be produced by a method <method 1> in which all of the raw materials containing the copolymer (A), the compound (B), and the polybasic acid anhydride (C) are reacted at once. Then, it may be produced by the method <method 2> in which the raw materials are sequentially reacted.

As the method 1, for example, a reaction raw material containing the copolymer (A), the compound (B), and the polybasic acid anhydride (C) is used in the presence of a basic catalyst or an acidic catalyst. Examples thereof include a method obtained by reacting at 50 to 150 ° C.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 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; phosphinic compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium chloride , Triphenylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, phosphonium salts such as benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, Organic tin compounds such as dibutyltin diacetate, tin octylate, 1,1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organic metal compounds such as zinc octylate and bismuth octylate; tin octanate Inorganic tin compounds such as; Inorganic metal compounds and the like. 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 1 is 100 parts by mass in total of the polymer (A), the compound (B), and the polybasic acid anhydride (C). The range of 0.01 to 5 parts by mass is preferable.

As the method 2, for example, the copolymer (A) and the compound (B) are reacted in advance at 70 to 140 ° C. in the presence of a basic catalyst or an acidic catalyst to obtain a reaction product (I). Next, a method obtained by reacting the reaction product (I) with the polybasic acid anhydride (C) at 70 to 140 ° C. in the presence of a basic catalyst or an acidic catalyst can be mentioned.

As the basic catalyst, the same catalysts as those exemplified as the above-mentioned basic catalyst can be used. These basic catalysts can 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. 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 reaction of the copolymer (A) and the compound (B) of the method 2 is 100 mass by mass of the total mass of the copolymer (A) and the compound (B). The range of 0.01 to 5 parts by mass is preferable with respect to the part. The amount of the basic catalyst or the acidic catalyst used in the reaction of the reaction product (I) and the polybasic acid anhydride (C) is the reaction product (I) and the polybasic acid anhydride (C). ) Is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass.

In the above methods 1 and 2, when the copolymer (A) has an epoxy group derived from the compound (a2) and the compound (B) has a carboxyl group, or the copolymer. When (A) has a carboxyl group derived from the compound (a2) and the compound (B) has an epoxy group, the catalyst used for the reaction is a phosphorus-based catalyst such as a phosphine compound or a phosphonium salt. Is preferable, and a phosphine compound is more preferable.

As the phosphine compound, the same compounds as those exemplified as the above-mentioned phosphine compound can be used. Further, these phosphine compounds may 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 acid group-containing (meth) acrylate resin of the present invention, the ratio of the copolymer (A) to the compound (B) to be used is 1 mol of the reactive functional group of the copolymer (A). On the other hand, the compound (B) is preferably in the range of 0.9 to 1.1 mol, more preferably in the range of 0.95 to 1.05.

Further, in the production of the acid group-containing (meth) acrylate resin of the present invention, the ratio of the copolymer (A) to the heavy polybasic acid anhydride (C) is determined by the copolymer (A). The polybasic acid anhydride (C) is preferably in the range of 0.25 to 0.95 mol, more preferably in the range of 0.3 to 0.9 with respect to 1 mol of the reactive functional group having.

In the production of the acid group-containing (meth) acrylate resin of the present invention, a polymerization inhibitor, an antioxidant or the like can be used in addition to the compound (D), 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) dodecanedihydrazide, 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 and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.I. 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), sylated diphenylamine, sylated 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- Nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N, N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitron -N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N- Ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-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 sodium, 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 thiodipropionate. These polymerization inhibitors may be used alone or in combination of two or more.

As the antioxidant, the same compounds as those exemplified for 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 "Smilizer BBM-S" manufactured by Sumitomo Chemical Industries, Ltd. , "Smilizer GA-80 is" and the like.

The acid group-containing (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-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-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- Examples thereof include photoradical polymerization initiators such as on, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.

Examples of commercially available products of the other photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 90". "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 2100", "Omnirad 754", "Omnirad" "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10" "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemistry), "QuantuQua", "Quantacure PDO" , "Chemistry EPD" (manufactured by Ward Brenkinsop); "Runtecure 1104" (manufactured by Runtec) and the like. These photopolymerization initiators may be used alone or in combination of two or more.

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 acid group-containing (meth) acrylate resin described above. Examples of the other resin components include resins having an acid group and a polymerizable unsaturated bond, various (meth) acrylate monomers, and the like.

The resin having an acid group and a polymerizable unsaturated bond may be any resin as long as it has an acid group and a polymerizable unsaturated bond in the resin. For example, an epoxy resin having an acid group and a polymerizable unsaturated bond. , Urethane resin with acid groups and polymerizable unsaturated bonds, acrylic resin with acid groups and polymerizable unsaturated bonds, amidoimide resin with acid groups and polymerizable unsaturated bonds, acid groups and polymerizable unsaturated bonds Examples thereof include an acrylamide resin, an acid group and an ester resin having a polymerizable unsaturated bond.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include an acid group-containing epoxy (meth) acrylate resin containing an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential raw materials, and an epoxy. Examples thereof include resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and acid group-containing and urethane group-containing epoxy (meth) acrylate resins using a hydroxyl group-containing (meth) acrylate compound as a reaction raw material.

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 novolak type epoxy resin, naphthol novolak 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 reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin and the like. 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. 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-cyanocinnamic acid, β-styrylacrylic acid, β-flufurylacrylic acid and the like. Further, the esterified product of the unsaturated monobasic acid, the acid halide, the 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 is 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.

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

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

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified for the above-mentioned hydroxyl group-containing (meth) acrylate compound can be used, and the hydroxyl group-containing (meth) acrylate compound may be used alone. It is also possible to use more than seeds together.

The method for producing the epoxy resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the epoxy resin. In the production of the epoxy resin having an acid group and a polymerizable unsaturated bond, 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 dioxolan; 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 may 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 catalysts 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 an acid group and a polymerizable unsaturated bond include a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride and the carboxyl group. It is reacted with a polyol compound other than the contained polyol compound, a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound. The ones obtained from the above are 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 for the above-mentioned hydroxyl group-containing (meth) acrylate compound can be used, and the hydroxyl group-containing (meth) acrylate compound may be used alone. It is also possible to use more than seeds together.

Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolpropane valeric acid. The carboxyl group-containing 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 (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.

Examples of the polyol compound other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are contained in the molecular structures of the various polyol compounds. Introduced (poly) oxyalkylene modified product; a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds can be mentioned. The polyol compound other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more.

The method for producing the urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the urethane resin. In the production of the urethane resin having an acid group and a polymerizable unsaturated bond, 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 catalysts 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 acrylic resin having an acid group and a polymerizable unsaturated bond, 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 is polymerized as an essential component. The reaction obtained by introducing a (meth) acryloyl group by further reacting the (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups with the acrylic resin intermediate obtained by the above treatment. Examples thereof include products obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

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 (meth) such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. Acrylic acid alkyl ester; alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isoboronyl (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 a hydroxyl group-containing (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 a hydroxyl group-containing (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 (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the acrylic resin. In the production of the acrylic resin having an acid group and a polymerizable unsaturated bond, 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 catalysts 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 an acid group and a polymerizable unsaturated bond 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. Examples thereof include those obtained by reacting a compound with 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, if necessary. Be done. The compound having a reactive functional group may or may not have a (meth) acryloyl group.

The amideimide resin may have only one of an acid group and 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 to have. 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 (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.

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, pimelic 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-dioxotetratetra-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. Will be. 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 for the above-mentioned hydroxyl group-containing (meth) acrylate compound can be used, and the hydroxyl group-containing (meth) acrylate compound may be used alone. It is also possible to use more than seeds together.

As the epoxy group-containing (meth) acrylate compound, the same ones as those exemplified as the above-mentioned epoxy group-containing (meth) acrylate compound can be used, and the epoxy group-containing (meth) acrylate compound is used alone. It is also possible to use two or more types together.

The method for producing the amidoimide resin having the acid group and the polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the amidimide resin. In the production of the amidoimide resin having an acid group and a polymerizable unsaturated bond, 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 catalysts 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 an acid group and a polymerizable unsaturated bond include a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth) acrylamide compound, and a polybasic acid anhydride. Examples thereof include those obtained by reacting with an unsaturated monobasic acid, if necessary.

The phenolic hydroxyl group-containing compound refers to a compound having at least two phenolic hydroxyl groups in the molecule. Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).

In the structural 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, more preferably 0 or 1, and further preferably 0. q is an integer of 2 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and the structural formula ( In 3-3), it may be substituted on any ring of the benzene ring present in one molecule, and in the structural formula (3-4), it may be substituted on any ring of the benzene ring present in one molecule. It is shown that it may be substituted with, and it is shown that the number of substituents in one molecule is p and q.

Further, as the phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) are indispensable. An essential reaction between the reaction product used as the reaction raw material of the above, a compound having at least two phenolic hydroxyl groups in the molecule, and a compound represented by any of the following structural formulas (x-1) to (x-5). Reaction products used as raw materials can also be used. Further, a novolak-type phenol resin using one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl compounds in the molecule. A novolak type phenol resin used as a reaction raw material can also be used.

[In equation (x-1), h is 0 or 1. In the formulas (x-2) to (x-5), R ³ 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, and i. Is 0 or an integer from 1 to 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. ]

Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (4-1) to (4-4).

In the structural formulas (4-1) to (4-4), R ⁴ 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. , ^R5 are independent hydrogen atoms or methyl groups, respectively. Further, p is an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (4-2), it may be substituted on any ring, and the structural formula ( In 4-3), it may be substituted on any ring of the benzene ring present in one molecule, and in the structural formula (4-4), it may be substituted on any ring of the benzene ring present in one molecule. Indicates that it may be replaced with.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above-mentioned structural formulas (3-1) to (3-4) can be used.

These phenolic hydroxyl group-containing compounds may 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 having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained. The alkylene oxide can be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion 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 (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.

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 the acid group and the polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the acrylamide resin. In the production of the acrylamide resin having an acid group and a polymerizable unsaturated bond, 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 catalysts 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 an acid group and a polymerizable unsaturated bond is obtained by reacting, for example, a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride. The ones that have been given are mentioned.

As the phenolic hydroxyl group-containing compound, the same compounds as those exemplified for the above-mentioned phenolic hydroxyl group-containing compound can be used, and the phenolic hydroxyl group-containing compound may be used alone or in combination of two or more. You can also.

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 having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion can be obtained. The alkylene oxide can 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 having high photosensitivity and capable of forming a cured product having excellent heat resistance, elasticity and adhesion 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 (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.

The method for producing the ester resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the ester resin. In the production of the ester resin having an acid group and a polymerizable unsaturated bond, 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 catalysts 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 an acid group and a polymerizable unsaturated bond is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the acid group-containing (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 compounds; (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains 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 and a glycerin tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, (poly) oxypropylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound. 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, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. 4 functional or higher 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 having a (poly) lactone structure introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. 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 phenol compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-. Trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether Examples thereof include type diols, polynaphthylene ether type diols, phenol novolac resins, cresol novolak resins, bisphenol novolak type resins, naphthol novolak type resins, phenol aralkyl type resins, naphthol aralkyl type resins, cycloring structure-containing phenol resins and the like.

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 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, pimelic 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-dioxotetraxoxy-3-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, and guanidine derivative. These amine compounds may 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, neopentylglycol, 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; , Δ-Valerolactone, 3-methyl-δ-Valerolactone and other lactone-type polyester polyols obtained by polycondensation reaction with various lactones; Examples thereof include a polyether polyol obtained by ring-opening polymerization with a cyclic ether compound such as ether. These polyol compounds may 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 -Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like can be mentioned. 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, a known and commonly used inorganic pigment or organic pigment 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 pigment include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanslon pigments, flavanthron pigments, perylene pigments, diketopyrrolopyrrole pigments, and perinone pigments. 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 phosphate amide; phosphoric acid ester compounds and phosphoruses. Acid compounds, phosphinic acid compounds, phosphin oxide compounds, phosphoran compounds, organonitrous 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 the ultraviolet rays.

As an ultraviolet ray generation 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.

The integrated light amount of the active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ / cm ² , and more preferably 50 to 1,000 mJ / cm 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.

Further, since the cured product of the present invention has high photosensitivity and excellent heat resistance, elasticity and adhesion, for example, a solder resist, an interlayer insulating material, a package material and an underfill material in semiconductor device applications. , It can be suitably used as a package adhesive layer for circuit elements and the like, and as an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer and the like in thin display applications typified by LCDs and OELDs. Among these, it can be particularly preferably used for solder resist applications.

The resin material for solder resist of the present invention comprises the curable resin composition.

The resist member of the present invention is, for example, a photomask in which the resin material for solder resist is applied onto a substrate, an organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C., and then a desired pattern is formed. It can be obtained by exposing the unexposed portion with an alkaline aqueous solution, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing the unexposed portion in a temperature range of about 140 to 200 ° C.

Examples of the base material include metal foils such as copper foil and aluminum foil.

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% by mass in terms of resin solid content Tetrahydrofuran solution filtered through a microfilter (100 μl)

(Synthesis Example 1: Production of Phenylbenzyl Acrylate Composition (1))
A flask equipped with a stirrer, a cooling tube, a thermometer, and a hydrogen chloride gas introduction device was charged with 709 parts by mass of diphenyl, 276 parts by mass of paraformaldehyde, 1381 parts by mass of acetic acid, and 958 parts by mass of concentrated hydrochloric acid, and the temperature was raised to 80 ° C. After confirming that the charged solution was at 80 ° C., hydrogen chloride gas was introduced into the charged solution at a rate of 20 g / hr using a Kinoshita type glass ball filter. After confirming that the dissolution of hydrogen chloride gas in the charging solution was saturated, 1061 parts by mass of phosphoric acid was added dropwise over 1 hour, and the reaction was further carried out for 30 hours. Immediately after the reaction was completed, the lower layer was removed from the reaction solution, 2300 parts by mass of toluene was added to the organic layer, and the organic layer was washed with 400 parts by mass of 12.5% sodium hydroxide aqueous solution, saturated sodium hydrogen carbonate aqueous solution, and distilled water. .. After distilling off the organic layer, a chloro intermediate (1) was obtained. Then, it was dissolved in 1603 parts by mass of dimethylformamide as a reaction solvent, and 372 parts by mass of potassium carbonate and methquinone were added so as to be 300 ppm with respect to the total amount. After raising the temperature of the intermediate solution to 40 ° C., 323 parts by mass of acrylic acid was added dropwise to the intermediate solution in 1.5 hours. After completion of the dropping, the temperature was raised to 80 ° C. over 2 hours, and the mixture was heated and stirred at 80 ° C. for 3 hours. 3400 parts by mass of water and 1800 parts by mass of toluene were added to the obtained solution for extraction, and then the organic layer was washed until the aqueous layer became neutral. The organic layer was concentrated to obtain a liquid phenylbenzyl acrylate composition (1).

(Synthesis Example 2: Production of Phenylbenzylmethacrylate Composition (1))
In a flask equipped with a stirrer, a cooling tube, a thermometer, and a hydrogen chloride gas introduction device, 908 parts by mass of the chloro intermediate (1) obtained in Synthesis Example 1 was dissolved in 1603 parts by mass of dimethylformamide as a reaction solvent, and carbon dioxide was added. 372 parts by mass of potassium and methquinone were added so as to be 300 ppm with respect to the total amount. After raising the temperature of the intermediate solution to 40 ° C., 386 parts by mass of methacrylic acid was added dropwise to the intermediate solution in 1.5 hours. After completion of the dropping, the temperature was raised to 80 ° C. over 2 hours, and the mixture was heated and stirred at 80 ° C. for 3 hours. 3400 parts by mass of water and 1800 parts by mass of toluene were added to the obtained solution for extraction, and then the organic layer was washed until the aqueous layer became neutral. The organic layer was concentrated to obtain a liquid phenylbenzyl methacrylate composition (1).

(Synthesis Example 3: Production of Acid Group-Containing 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 as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added. The esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. 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 acid group-containing epoxy acrylate resin (1). The solid acid value of the acid group-containing epoxy acrylate resin (1) was 85 mgKOH / g.

(Example 1: Production of acid group-containing acrylate resin (1))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (1). The non-volatile content of the acid group-containing acrylate resin (1) is 58.5% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 23,800, and the double. The binding equivalent was 344. In the present invention, the double bond equivalent is a calculated value calculated from the charged amount of the raw material. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A1) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A1) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 2: Production of acid group-containing acrylate resin (2))
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, 8 parts by mass of methyl methacrylate, 20 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (2). The non-volatile content of the acid group-containing acrylate resin (2) is 58.5% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 23,950, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A2) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A2) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 3: Production of acid group-containing acrylate resin (3))
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, 69 parts by mass of glycidyl methacrylate, 31 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2-ethylhexanoate (Japan). 5 parts by mass of "Perbutyl O" manufactured by Yushi Co., Ltd.) was mixed in advance and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A3). Next, 0.5 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methylhydroquinone, 35 parts by mass of acrylic acid, and 0.6 part by mass of triphenylphosphine were charged, and the reaction was carried out at 120 ° C. for 10 hours while blowing air and stirring. I let you. Then, 36.2 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (3). The non-volatile content of the acid group-containing acrylate resin (3) is 58.1% by mass, the solid acid value is 80 mgKOH / g, the weight average molecular weight (Mw) is 24,130, and the double. The binding equivalent was 352. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A3) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A3) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 4: Production of acid group-containing acrylate resin (4))
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, 2 parts by mass of methyl methacrylate, 26 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (4). The non-volatile content of the acid group-containing acrylate resin (4) is 58.5% by mass, the solid acid value is 81 mgKOH / g, the weight average molecular weight (Mw) is 24,050, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A4) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A4) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 5: Production of acid group-containing acrylate resin (5))
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, 25 parts by mass of methyl methacrylate, 3 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (5). The non-volatile content of the acid group-containing acrylate resin (5) is 58.5% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 23,510, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A5) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A5) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 6: Production of acid group-containing acrylate resin (6))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and 5 parts of azobisisobutyronitrile. The parts by mass were mixed in advance and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (6). The non-volatile content of the acid group-containing acrylate resin (6) is 58.5% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 24,080, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A6) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A6) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 7: Production of acid group-containing acrylate resin (7))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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 tetrabutylphosphonium chloride were charged, and air was blown into the mixture at 120 ° C. with stirring. The reaction was carried out for 16 hours. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (7). The non-volatile content of the acid group-containing acrylate resin (7) is 58.5% by mass, the solid acid value is 84 mgKOH / g, the weight average molecular weight (Mw) is 76,060, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A7) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A7) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 8: Production of acid group-containing acrylate resin (8))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A8). Next, 0.5 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.6 part by mass of triethylamine were charged, and the reaction was carried out at 120 ° C. for 12 hours while blowing air and stirring. I let you. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (8). The non-volatile content of the acid group-containing acrylate resin (8) is 58.5% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 22,580, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A8) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A8) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 9: Production of acid group-containing acrylate resin (9))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic 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 triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 10 parts. Reacted for time. Next, 38.3 parts by mass of hexahydroisobenzofuran-1,3-dione was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (9). The non-volatile content of the acid group-containing acrylate resin (9) is 58.6% by mass, the solid acid value is 81 mgKOH / g, the weight average molecular weight (Mw) is 22,940, and the double. The binding equivalent was 345. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A9) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A9) corresponding to the copolymer (A) specified in the present invention. The number of moles of hexahydroisobenzofuran-1,3-dione was 0.49 mol.

(Example 10: Production of acid group-containing acrylate resin (10))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A10). 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. Reacted for time. Next, 22.8 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (10). The non-volatile content of the acid group-containing acrylate resin (10) is 56.4% by mass, the solid acid value is 85 mgKOH / g, the weight average molecular weight (Mw) is 22,150, and the double. The binding equivalent was 345. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A10) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A10) corresponding to the copolymer (A) specified in the present invention. The number of moles of succinic anhydride was 0.45 mol.

(Example 11: Production of acid group-containing acrylate resin (11))
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, 80 parts by mass of glycidyl methacrylate, 10 parts by mass of methyl methacrylate, 10 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A11). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 40.6 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 11 parts. Reacted for time. Next, 38.5 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours, 18.5 parts by mass of diethylene glycol monomethyl ether acetate was charged, and after stirring, the desired acid group-containing acrylate resin (11) was added. Obtained. The non-volatile content of the acid group-containing acrylate resin (11) is 55.8% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 23,820, and the double. The binding equivalent was 318. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A11) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A11) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.45 mol.

(Example 12: Production of acid group-containing acrylate resin (12))
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, 90 parts by mass of glycidyl methacrylate, 5 parts by mass of methyl methacrylate, 5 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A12). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 45.6 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. Reacted for time. Next, 39.5 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours, 29.7 parts by mass of diethylene glycol monomethyl ether acetate was charged, and after stirring, the desired acid group-containing acrylate resin (12) was added. Obtained. The non-volatile content of the acid group-containing acrylate resin (12) is 54.8% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 24,220, and the double. The binding equivalent was 292. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A12) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A12) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.41 mol.

(Example 13: Production of acid group-containing acrylate resin (13))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A13). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 32.1 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. for 7 parts. Reacted for time. Next, 37.8 parts by mass of tetrahydrophthalic anhydride was added, reacted at 110 ° C. for 5 hours, 16.8 parts by mass of diethylene glycol monomethyl ether acetate was charged, and the mixture was stirred, and then the desired acid group-containing acrylate resin (13) was added. Obtained. The non-volatile content of the acid group-containing acrylate resin (13) is 54.8% by mass, the solid acid value is 73 mgKOH / g, the weight average molecular weight (Mw) is 33,590, and the double. The binding equivalent was 381. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A13) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 0.88. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A13) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 14: Production of acid group-containing acrylate resin (14))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A14). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 40.5 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. at 8%. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (14). The non-volatile content of this acid group-containing acrylate resin (14) is 59.1% by mass, the solid content acid value is 90 mgKOH / g, the weight average molecular weight (Mw) is 20,930, and the double. The binding equivalent was 317. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A14) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.11. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A14) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 15: Production of acid group-containing acrylate resin (15))
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, 46 parts by mass of glycidyl methacrylate, 44 parts by mass of methyl methacrylate, 10 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A15). Next, 0.5 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methylhydroquinone, 23.3 parts by mass of acrylic acid, and 0.6 part by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. at 8%. Reacted for time. Then, 34.5 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (15). The non-volatile content of this acid group-containing acrylate resin (15) is 56.1% by mass, the solid content acid value is 84 mgKOH / g, the weight average molecular weight (Mw) is 19,390, and the double. The binding equivalent was 487. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A15) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A15) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.70 mol.

(Example 16: Production of acid group-containing acrylate resin (16))
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, 44 parts by mass of glycidyl methacrylate, 46 parts by mass of methyl methacrylate, 10 parts by mass of the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A16). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 22.3 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. at 8%. Reacted for time. Then, 34.4 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (16). The non-volatile content of the acid group-containing acrylate resin (16) is 56% by mass, the solid acid value is 85 mgKOH / g, the weight average molecular weight (Mw) is 17,630, and the double bond equivalent. Was 506. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A16) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A16) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.73 mol.

(Example 17: Production of acid group-containing acrylate resin (17))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A17). 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. Reacted for time. Then, 23.9 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours to obtain the desired acid group-containing acrylate resin (17). The non-volatile content of the acid group-containing acrylate resin (17) is 56.5% by mass, the solid acid value is 57 mgKOH / g, the weight average molecular weight (Mw) is 20,390, and the double. The binding equivalent was 316. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A17) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A17) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.31 mol.

(Example 18: Production of acid group-containing acrylate resin (18))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A18). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 9 parts. Reacted for time. Next, 69.4 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 6 hours, 46.2 parts by mass of diethylene glycol monomethyl ether acetate was charged, and after stirring, the desired acid group-containing acrylate resin (18) was added. Obtained. The non-volatile content of the acid group-containing acrylate resin (18) is 54.8% by mass, the solid acid value is 128 mgKOH / g, the weight average molecular weight (Mw) is 23,820, and the double. The binding equivalent was 406. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A18) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A18) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.90 mol.

(Example 19: Production of acid group-containing acrylate resin (19))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. Hold at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A19). Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.5 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. Reacted for time. Then, 18.5 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours to obtain the desired acid group-containing acrylate resin (19). The non-volatile content of this acid group-containing acrylate resin (19) is 55.7% by mass, the solid acid value is 47 mgKOH / g, the weight average molecular weight (Mw) is 19,160, and the double. The binding equivalent was 306. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A19) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A19) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.24 mol.

(Example 20: Production of acid group-containing acrylate resin (20))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A20). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 36.5 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. for 9 parts. Reacted for time. Next, 74 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 6 hours to charge 50 parts by mass of diethylene glycol monomethyl ether acetate, and after stirring, the desired acid group-containing acrylate resin (20) was obtained. The non-volatile content of the acid group-containing acrylate resin (20) is 54.8% by mass, the solid acid value is 134 mgKOH / g, the weight average molecular weight (Mw) is 23,510, and the double. The binding equivalent was 415. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A20) corresponding to the copolymer (A) specified in the present invention, acrylic acid corresponding to the compound (B) specified in the present invention can be used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A20) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.96 mol.

(Example 21: Production of acid group-containing acrylate resin (21))
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 the phenylbenzyl acrylate composition (1) obtained in Synthesis Example 1, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. The acrylic copolymer (A21) was obtained by holding at 120 ° C. for 4 hours. 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (21). The non-volatile content of this acid group-containing acrylate resin (21) is 58.5% by mass, the solid content acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 22,970, and the double. The binding equivalent was 344. Further, for 1 mol of the epoxy group contained in the acrylic copolymer (A21) corresponding to the copolymer (A) specified in the present invention, the acrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the acrylic copolymer (A21) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Example 22: Production of acid group-containing methacrylate resin (1))
66.7 parts by mass of cyclohexanone 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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of cyclohexanone, and t-butylperoxy-2-ethylhexa. 5 parts by mass of Noate (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.) was mixed in advance and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A22). Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 69.3 parts by mass of glycidylmethacrylate, 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. Reacted for time. Next, 18.6 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110 ° C. for 5 hours to charge 31.5 parts by mass of cyclohexanone, and after stirring, the desired acid group-containing methacrylate resin (1) was obtained. The non-volatile content of the acid group-containing methacrylate resin (1) is 54.8% by mass, the solid acid value is 102 mgKOH / g, the weight average molecular weight (Mw) is 47,930, and the double. The binding equivalent was 385. Further, for 1 mol of the epoxy group of the methacrylic copolymer (A22) corresponding to the copolymer (A) specified in the present invention, the glycidyl methacrylate corresponding to the compound (B) specified in the present invention is used. The number of moles was 0.7. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A22) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.25 mol.

(Example 23: Production of acid group-containing methacrylate resin (2))
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 the phenylbenzyl methacrylate composition (1) obtained in Synthesis Example 2, 55.6 parts by mass of diethylene glycol monomethyl ether acetate, and t-butylperoxy-2. -Ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fat Co., Ltd.) was mixed in advance by 5 parts by mass and added dropwise over 3 hours. It was held at 120 ° C. for 4 hours to obtain a methacrylic copolymer (A23). Next, 0.6 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methylhydroquinone, 43.6 parts by mass of methacrylic acid, and 0.6 part by mass of triphenylphosphine were charged, and air was blown into the mixture, and the mixture was stirred at 120 ° C. to 12 parts. Reacted for time. Then, 39.3 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing methacrylate resin (2). The non-volatile content of the acid group-containing methacrylate resin (2) is 59.8% by mass, the solid acid value is 83 mgKOH / g, the weight average molecular weight (Mw) is 21,970, and the double. The binding equivalent was 361. Further, for 1 mol of the epoxy group contained in the methacrylic copolymer (A23) corresponding to the copolymer (A) specified in the present invention, methacrylic acid corresponding to the compound (B) specified in the present invention is used. The number of moles was 1.0. Further, it corresponds to the polybasic acid anhydride (C) specified in the present invention with respect to 1 mol of the epoxy group contained in the methacrylic copolymer (A23) corresponding to the copolymer (A) specified in the present invention. The number of moles of tetrahydrophthalic anhydride was 0.49 mol.

(Comparative Example 1: Production of Acid Group-Containing 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 5 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF CORPORATION). The portions were mixed in advance and added dropwise over 3 hours. The acrylic copolymer (AR1) was obtained by holding at 120 ° C. for 4 hours. 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. Reacted for time. Then, 37.8 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin (R1). The non-volatile content of this acid group-containing acrylate resin (R1) is 58.6% by mass, the solid acid value is 82 mgKOH / g, the weight average molecular weight (Mw) is 21,210, and the double. The binding equivalent was 345.

(Example 24: Preparation of curable resin composition (1))
100 parts by mass of the acid group-containing acrylate resin (1) having a non-volatile content of 58.5% by mass obtained in Example 1 and an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd., epoxy equivalent) as a curing agent. : 214) 22 parts by mass, 11.8 parts by mass of diethylene glycol monoethyl ether acetate, 2.9 parts by mass of photopolymerizable initiator (“Omnirad 907” manufactured by IGM Resins), and 5.9 parts by mass of dipentaerythritol hexaacrylate. A curable resin composition (curable resin composition) was prepared by mixing 0.4 parts by mass of 2-ethyl-4-methyl-imidazole and 0.6 parts by mass of titanium oxide (“R-820” manufactured by Ishihara Sangyo Co., Ltd.) by mass. 1) was obtained.

(Examples 25 to 47: Preparation of curable resin compositions (2) to (24))
Instead of the acid group-containing acrylate resin (1) used in Example 30, the acid group-containing acrylate resins (2) to (21) obtained in Examples 2 to 23, the acid group-containing methacrylate resin (1) and (2). ) And the acid group-containing epoxy acrylate (1) were used in the blending amounts shown in Tables 1 and 2, and curable resin compositions (2) to (24) were obtained in the same manner as in Example 24. ..

(Comparative Example 2: Preparation of Curable Resin Composition (R1))
100 parts by mass of an acid group-containing acrylate resin (R1) having a non-volatile content of 58.6% by mass obtained in Comparative Example 1, and an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd., epoxy equivalent) as a curing agent. : 214) 22 parts by mass, 11.8 parts by mass of diethylene glycol monoethyl ether acetate, 2.9 parts by mass of photopolymerizable initiator (“Omnirad 907” manufactured by IGM Resins), and 5.9 parts by mass of dipentaerythritol hexaacrylate. By mass, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole and 0.6 parts by mass of "R-820" were mixed to obtain a curable resin composition (R1).

The following evaluations were carried out using the curable resin compositions (1) to (24) and (R1) obtained in the above Examples and Comparative Examples.

[Evaluation method of light sensitivity]
The curable resin compositions obtained in each Example and Comparative Example were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and then dried at 80 ° C. for 30 minutes each. Next, Kodak's step tablet No. Ultraviolet rays of 1000 mJ / cm ² were irradiated through 2 using a metal halide lamp. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining stages. The larger the number of remaining stages, the higher the light sensitivity.

Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (24) prepared in Examples 24 to 47 and the curable resin composition (R1) prepared in Comparative Example 2.

(Example 48: Preparation of curable resin composition (25))
100 parts by mass of the acid group-containing acrylate resin (1) having a non-volatile content of 58.5% by mass obtained in Example 1 and a bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Co., Ltd., epoxy equivalent: 188 g / equivalent) 22 A curable resin composition (25) was obtained by mixing 0.0 part by mass, 11.8 parts by mass of an organic solvent, and 2.9 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM Resins). rice field.

(Examples 49 to 71: Preparation of curable resin compositions (26) to (48))
Instead of the acid group-containing acrylate resin (1) used in Example 48, the acid group-containing acrylate resins (2) to (23) obtained in Examples 2 to 23 are used in the blending amounts shown in Tables 3 and 4. Curable resin compositions (26) to (48) were obtained in the same manner as in Example 48.

(Comparative Example 3: Preparation of Curable Resin Composition (R2))
100 parts by mass of an acid group-containing acrylate resin (R1) having a non-volatile content of 58.6% by mass obtained in Comparative Example 1 and a bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Co., Ltd., epoxy equivalent: 188 g / equivalent) 22 .0 parts by mass, 11.8 parts by mass of organic solvent, and 2.9 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM Resins) are mixed to obtain a curable resin composition (R2). rice field.

The following evaluation was performed 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 an ultraviolet ray of 1,000 mJ / cm ² using a metal halide lamp, the mixture was heated at 160 ° C. for 1 hour to obtain a cured coating film. Then, 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. The higher the glass transition temperature, the better the heat resistance.

[Evaluation method of elasticity]
The elasticity was measured based on the tensile test.

<Preparation of test piece>
The curable resin compositions obtained in Examples and Comparative Examples were applied onto the electrolytic copper foil "F2-WS" with a 50 μm applicator and dried at 80 ° C. for 30 minutes. After irradiating with an ultraviolet ray of 1000 mJ / cm ² using a metal halide lamp, the mixture was heated at 160 ° C. for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece (cured product).

<Tensile test>
The test piece was cut into a size of 10 mm × 80 mm, and a tensile test was performed on the test piece under the following measurement conditions using a precision universal testing machine Autograph “AG-IS” manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured.

Measurement conditions: temperature 23 ° C, humidity 50%, distance between marked lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm / min

[Adhesion evaluation method]
The adhesion was evaluated by measuring the peel strength.
<Preparation of test piece 2>
The curable resin composition obtained in Examples and Comparative Examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm applicator, and 1000 mJ / using a metal halide lamp. After irradiating with ultraviolet rays of cm2, it was heated at 160 ° C. for 1 hour to obtain a test piece 2.

<Measuring method of peel strength>
The test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and the 90 ° peel strength was measured using a peeling tester (“A & D Tencilon” manufactured by A & D Co., Ltd., peeling speed 50 mm / min).

Tables 3 and 4 show the compositions and evaluation results of the curable resin compositions (25) to (48) obtained in Examples 48 to 71 and the curable resin compositions (R2) obtained in Comparative Example 3. ..

In addition, the description of the mass part of the acid group-containing (meth) acrylate resin and the acid group-containing epoxy acrylate resin in Tables 1 to 4 is a solid content value.

“Curing agent” in Tables 1 to 4 indicates an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation).

“Organic solvent” in Tables 1 to 4 indicates diethylene glycol monomethyl ether acetate.

“Photopolymerization initiator” in Tables 1 to 4 indicates “Omnirad 907” manufactured by IGM Resins.

Examples 24 to 71 shown in Tables 1 to 4 are examples using the acid group-containing (meth) acrylate resin of the present invention. It was confirmed that the cured product of the curable resin composition containing the acid group-containing (meth) acrylate resin of the present invention has high photosensitivity and has a good balance of heat resistance, elasticity and adhesion. ..

On the other hand, Comparative Examples 2 and 3 are examples in which the phenylbenzyl (meth) acrylate (a1) 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, elasticity and adhesion.

Claims (17)

A (meth) acrylic co-weight using phenylbenzyl (meth) acrylate (a1) and a compound (a2) having a reactive functional group and a polymerizable unsaturated group other than the phenylbenzyl (meth) acrylate (a1) as essential raw materials. Combined (A) and
Non-polymerizable other than the phenylbenzyl (meth) acrylate (a1) and the compound (a2) having a functional group capable of reacting with the reactive functional group derived from the compound (a2) of the copolymer (A). Compound (B) having a saturated group and
Polybasic acid anhydride (C) and
An acid group-containing (meth) acrylate resin, which is characterized by using the above as an essential raw material. The acid group-containing (meth) acrylate resin according to claim 1, wherein the content of the phenylbenzyl (meth) acrylate (a1) is 30% by mass or less in the raw material of the copolymer (A). The acid according to any one of claims 1 or 2, 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. Group-containing (meth) acrylate resin. Any of claims 1 to 3, wherein the copolymer (A) further contains the phenylbenzyl (meth) acrylate (a1) and a (meth) acrylate compound (a3) other than the compound (a2). The acid group-containing (meth) acrylate resin according to item 1. The acid group-containing (meth) acrylate resin according to claim 4, wherein the compound (a3) is a methacrylate compound. The acid group-containing (meth) acrylate resin according to any one of claims 1 to 5, wherein the acid group-containing (meth) acrylate resin has a double bond equivalent of 500 or less. The ratio of the copolymer (A) to the compound (B) used is 0.9 to 1 for the compound (B) with respect to 1 mol of the reactive functional group of the copolymer (A). The acid group-containing (meth) acrylate resin according to any one of claims 1 to 6, which is in the range of 1 mol. The ratio of the copolymer (A) to the polybasic acid anhydride (C) used is the polybasic acid anhydride (C) with respect to 1 mol of the reactive functional group of the copolymer (A). The acid group-containing (meth) acrylate resin according to any one of claims 1 to 6, wherein) is in the range of 0.25 to 0.95 mol. A curable resin composition comprising the acid group-containing (meth) acrylate resin according to any one of claims 1 to 8 and a photopolymerization initiator. The curable resin composition according to claim 9, wherein the curable resin composition further contains a resin having an acid group other than the acid group-containing (meth) acrylate resin and a polymerizable unsaturated group. The curable resin composition according to claim 9 or 10, wherein the curable resin composition further contains an organic solvent. The curable resin composition according to any one of claims 9 to 11, wherein the curable resin composition further contains a curing agent. The curable resin composition according to any one of claims 9 to 12, wherein the curable resin composition further contains a white pigment. A resin material for a solder resist, which comprises the curable resin composition according to any one of claims 9 to 13. The cured product of the curable resin composition according to any one of claims 9 to 13. An insulating material comprising the cured product according to claim 15. A resist member comprising the cured product according to claim 15.