JP6838692B1 - Acid group-containing (meth) acrylate resin, acid group-containing (meth) acrylate resin composition, curable resin composition, cured product, insulating material, solder resist resin material and resist member - Google Patents

Abstract

The present invention comprises an aromatic compound (A) having a phenolic hydroxyl group, an aromatic compound having an acid group other than the aromatic compound (A), an acid halide and / or an esterified product (B) thereof, and an epoxy. A reaction product containing a group-containing (meth) acrylate compound (C) and a polybasic acid anhydride (D) as essential reaction raw materials, which is an acid group-containing (meth) acrylate resin containing the acid group. It provides an acid group-containing (meth) acrylate resin characterized in that the (meth) acrylate resin has a structure represented by the structural formula (1). This acid group-containing (meth) acrylate resin has high photosensitivity, excellent heat resistance and dielectric properties, and can be suitably used for a resin material for solder resist, a resist member, and the like.

Description

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

In recent years, as a resin material for solder resist for printed wiring boards, a curable resin composition that can be cured by active energy rays such as ultraviolet rays has been widely used. The required properties of the resin material for solder resist include various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, and dielectric properties of the cured product.

As a conventional resin material for solder resist, an acid group-containing epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and phthalic anhydride. Although a photosensitive resin composition containing (see, for example, Patent Document 1) is known, the heat resistance of the cured product is not sufficient, and the dielectric constant and dielectric loss tangent increase due to the formation of hydroxyl groups. There was a problem such as deterioration of characteristics.

Therefore, a material having excellent dielectric properties in addition to light sensitivity and heat resistance has been required.

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, excellent heat resistance and dielectric properties, and an acid group-containing (meth) acrylate resin composition containing the same. It is an object of the present invention to provide a curable resin composition, a cured product, an insulating material composed of the photosensitive resin composition, 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 conducted diligent studies, and as a result, an aromatic compound having a phenolic hydroxyl group, an aromatic compound having a carboxyl group other than the aromatic compound, an acid halide and / or an acid halide thereof. By using an acid group-containing (meth) acrylate resin, which is a reaction product containing the esterified product, an epoxy group-containing (meth) acrylate compound, and a polybasic acid anhydride as essential reaction raw materials, the above-mentioned problems can be solved. We found that it could be solved and completed the present invention.

That is, the present invention comprises an aromatic compound (A) having a phenolic hydroxyl group, an aromatic compound having a carboxyl group other than the aromatic compound (A), an acid halide and / or an esterified product (B) thereof. , An acid group-containing (meth) acrylate resin which is a reaction product containing an epoxy group-containing (meth) acrylate compound (C) and a polybasic acid anhydride (D) as essential reaction raw materials, and is the above-mentioned acid. The present invention relates to an acid group-containing (meth) acrylate resin, wherein the group-containing (meth) acrylate resin has a structure represented by the following structural formula (1).

〔式（１）中、Ａｒ^１は、置換または非置換の芳香環を表し、Ａｒ^２は、置換または非置換の芳香環を表す。〕

[In formula (1), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring. ]

Since the acid group-containing (meth) acrylate resin of the present invention can form a cured product having high photosensitivity and excellent dielectric properties, it is composed of an insulating material, a resin material for solder resist, and the resin for solder resist. It can be suitably used for a resist member. The "excellent dielectric property" in the present invention means a low dielectric constant and a low dielectric loss tangent.

The acid group-containing (meth) acrylate resin of the present invention includes an aromatic compound (A) having a phenolic hydroxyl group, an aromatic compound having a carboxyl group other than the aromatic compound (A), an acid halide and / or an aromatic compound thereof. The esterified product (B), the epoxy group-containing (meth) acrylate compound (C), and the polybasic acid anhydride (D) are used as essential reaction raw materials, and the structure represented by the following structural formula (1) is formed. It is characterized by having.

〔式（１）中、Ａｒ^１は、置換または非置換の芳香環を表し、Ａｒ^２は、置換または非置換の芳香環を表す。〕

[In formula (1), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring. ]

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.

Examples of the aromatic compound (A) include compounds represented by the following structural formulas (2-1) to (2-10).

In the above structural formulas (2-1) to (2-10), R ¹ independently has an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and an acid group. Alternatively, it is either a halogen atom, and R ² is independently a hydrogen atom or a methyl group. Further, p is an integer of 0 or 1 or more independently, and q is an integer of 1 or more independently. Note that the position of the substituent R ¹ and a hydroxyl group on an aromatic ring in the above formula is optional, for example, may be in the naphthalene ring of the formula (2-2) is substituted on any ring , Structural formulas (2-3) and (2-4) indicate that it may be substituted on any ring of the benzene ring existing in one molecule, and the substituent on the benzene ring in one molecule. It shows that the number of is p + q.

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

Examples of the aromatic compound having an acid group, its acid halide and / or its esterified product (B) (hereinafter, abbreviated as “aromatic compound (B)”) include other than the aromatic compound (A). The compound is not particularly limited as long as it has an acid group in one molecule, and examples thereof include compounds represented by the following structural formulas (3-1) to (3-5).

In the above structural formulas (3-1) to (3-5), R ³ is an acid group, and R ⁴ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl. group, or any one of a halogen atom,, R ⁵ are each independently a hydrogen atom or a methyl group. Further, r is an integer of 1 or more, and s is an integer of 0 or 1 or more. ^{The positions of the substituents R 3} and R ⁴ on the aromatic ring in the above structural formula are arbitrary. For example, in the naphthalene ring of the structural formula (3-2), any ring may be substituted. Often, structural formulas (3-3) to (3-5) indicate that substitution may be made on any ring of the benzene ring present in one molecule, and substitution on the benzene ring in one molecule. It shows that the number of groups is r + s.

Further, the aromatic compound (B) may have at least one acid group in one molecule.

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

Examples of the epoxy group-containing (meth) acrylate compound (C) include glycidyl group-containing (meth) compounds such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate. Examples thereof include an acrylate monomer, a mono (meth) acrylate compound of a diglycidyl ether compound of hydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth) acrylate compounds (C) can be used alone or in combination of two or more.

Examples of the polybasic acid anhydride (D) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

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

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

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

These polybasic acid anhydrides (D) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable because an acid group-containing (meth) acrylate resin having high photosensitivity and excellent heat resistance and dielectric properties can be obtained.

As the acid group-containing (meth) acrylate resin of the present invention, since an acid group-containing (meth) acrylate resin having high photosensitivity, excellent heat resistance and dielectric properties can be obtained, the aromatic compound (A) is obtained. The number of moles of functional groups capable of reacting with the phenolic hydroxyl group of the aromatic compound (B) is preferably in the range of 0.9 to 1.5 with respect to 1 mol of the phenolic hydroxyl group of). , 0.95-1.25.

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, a reaction raw material containing the aromatic compound (A), the aromatic compound (B), the epoxy group-containing (meth) acrylate compound (C), and the polybasic acid anhydride (D). It may be produced by a method of reacting all of them at once, or by a method of sequentially reacting reaction raw materials. As a method for sequentially reacting the reaction raw materials, for example, the aromatic compound (A) and the epoxy group-containing (meth) acrylate compound (C) are first reacted at 60 to 140 ° C. in the presence of a basic catalyst. The reaction product (I) is then reacted with the reaction product (I) and the polybasic acid anhydride (D) at 60 to 140 ° C. under a basic catalyst to obtain the reaction product (II). The reaction product (II) and the aromatic compound (B) are further reacted at 20 to 140 ° C. under basic conditions to produce the reaction product (Method 1).
First, the aromatic compound (A) and the epoxy group-containing (meth) acrylate compound (C) are reacted at 60 to 140 ° C. in the presence of a basic catalyst to obtain a reaction product (I), and then the reaction product (I) is obtained. The reaction product (I) and the polybasic acid anhydride (D) are reacted at 60 to 140 ° C. under a basic catalyst to obtain a reaction product (II), and the reaction product (II) and the above. A method (method 2) of reacting an aromatic compound (A) with an aromatic compound (B) at 20 to 140 ° C. under basic conditions, first, the aromatic compound (A) and the aromatic compound. (B) is reacted with (B) at 60 to 140 ° C. in the presence of a basic catalyst to obtain a reaction product (III), and then the reaction product (III) and an epoxy group-containing (meth) acrylate compound (C). To obtain a reaction product (IV) by reacting with and at 20 to 140 ° C. under basic conditions, and further, the reaction product (IV) and polybasic acid anhydride (D) are combined under a basic catalyst of 60. Examples thereof include a method of producing by reacting at ~ 140 ° C. (method 3). Among these, method 1 or method 2 is preferable, and method 2 is more preferable, because an acid group-containing (meth) acrylate resin having high photosensitivity and excellent heat resistance and dielectric properties can be obtained.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; and four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Class ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanate; inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more.

The reaction between the aromatic compound (A) and the epoxy group-containing (meth) acrylate compound (C) in the method 1 is such that the reaction of the aromatic compound (A) with respect to 1 mol of the phenolic hydroxyl group is described. The number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (C) is preferably 0.4 or more, more preferably 0.5 to 2.5.

In the method 1, the reaction between the reaction product (I) and the polybasic acid anhydride (D) is carried out with respect to 1 mol of the hydroxyl group of the reaction product (I). The number of moles of D) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

The reaction between the reaction product (II) and the aromatic compound (B) in the method 1 is such that the aromatic compound (B) has 1 mol of the phenolic hydroxyl group of the reaction product (II). The number of moles of the functional group capable of reacting with the phenolic hydroxyl group of the above is preferably in the range of 0.8 to 1.3, and more preferably 0.95 to 1.25.

In the method 2, the reaction of the aromatic compound (A) with the epoxy group-containing (meth) acrylate compound (C) is carried out with respect to 1 mol of the phenolic hydroxyl group of the aromatic compound (A). The number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (C) is preferably 0.4 or more, more preferably 0.5 to 2.5.

In the method 2, the reaction between the reaction product (I) and the polybasic acid anhydride (D) is carried out with respect to 1 mol of the hydroxyl group of the reaction product (I). The number of moles of D) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

The reaction between the reaction product (II), the aromatic compound (A), and the aromatic compound (B) in the method 2 is the reaction product (II) and the aromatic compound (A). The number of moles of functional groups capable of reacting with the phenolic hydroxyl group of the aromatic compound (B) is in the range of 0.8 to 1.3 with respect to a total of 1 mol of the phenolic hydroxyl group of the aromatic compound (B). It is preferably in the range of 0.95 to 1.25, more preferably in the range of 0.95 to 1.25. As the aromatic compound (A) in the above reaction, the same aromatic compound (A) as the reaction raw material of the reaction product (I) may be used, or a different one may be used. Although it is good, the aromatic compound (A) that reacts with the reaction product (II) can be obtained because an acid group-containing (meth) acrylate resin having high photosensitivity and excellent heat resistance and dielectric properties can be obtained. An aromatic compound having an aliphatic structure and / or an alicyclic structure is preferable.

In the method 3, the reaction between the aromatic compound (A) and the aromatic compound (B) is such that the aromatic compound (B) has 1 mol of the phenolic hydroxyl group of the aromatic compound (A). The number of moles of the functional group capable of reacting with the phenolic hydroxyl group of) is preferably in the range of 0.5 to 1.5, and more preferably in the range of 0.8 to 1.2.

The reaction of the reaction product (III) with the epoxy group-containing (meth) acrylate compound (C) in the method 3 is carried out on 1 mol of a functional group capable of reacting with the epoxy group of the reaction product (III). On the other hand, the number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (a3) is preferably in the range of 0.9 to 1.1, preferably in the range of 0.95 to 1.05. Is more preferable.

In the method 3, the reaction between the reaction product (IV) and the polybasic acid anhydride (D) is carried out with respect to 1 mol of the hydroxyl group of the reaction product (IV). The number of moles of D) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

Further, the reaction of the aromatic compound (A), the aromatic compound (B), the epoxy group-containing (meth) acrylate compound (C), and the polybasic acid anhydride (D) is necessary. Alternatively, it can be carried out in an organic solvent.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers. , Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more.

Further, 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, if necessary.

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

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

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

The (meth) acryloyl group equivalent of the acid group-containing (meth) acrylate resin of the present invention is preferably 900 g / equivalent or less because it has high sensitivity and excellent heat resistance and dielectric properties. , 450 to 750 g / equivalent, more preferably 500 to 750 g / equivalent.

The acid group-containing (meth) acrylate resin of the present invention may be used in combination with an acid group other than the acid group-containing (meth) acrylate resin described above and a resin (E) having a polymerizable unsaturated bond, if necessary. , The acid group-containing (meth) acrylate resin composition of the present invention can also be used as an acid group-containing (meth) acrylate resin composition containing the acid group and the resin (E) having a polymerizable unsaturated bond.

The resin (E) having an acid group and a polymerizable unsaturated bond may be any resin (E) having an acid group and a polymerizable unsaturated bond in the resin, and other specific structures, molecular weights, etc. are not particularly limited. , A wide variety of resins can be used.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable because it exhibits excellent alkali developability.

In the present invention, the "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

Examples of the resin (E) having an acid group and a polymerizable unsaturated bond include an epoxy resin having an acid group and a polymerizable unsaturated bond, a urethane resin having an acid group and a polymerizable unsaturated bond, an acid group and polymerization. Examples thereof include acrylic resins having sex unsaturated bonds, amidimide resins having acid groups and polymerizable unsaturated bonds, and acrylamide resins having acid groups and polymerizable unsaturated bonds.

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 reaction raw materials. , Epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and acid group- and urethane group-containing epoxy (meth) acrylate resins using hydroxyl group-containing (meth) acrylate compounds as reaction raw materials.

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

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy. Examples include resin.

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

Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'. -Biphenol type epoxy resin and the like can be mentioned.

Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy resin. , Hydrophobic tetramethyl-2,2'-biphenol type epoxy resin and the like.
The same epoxy resin as those exemplified above can be used, and the epoxy resin may be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-fulfurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (4) can also be used.

［式（４）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、または（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、水素原子またはメチル基である。］

[In formula (4), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, and a halogen atom in the structure. Or an alkoxy group or the like. Y is a hydrogen atom or a methyl group. ]

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

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

［式（Ｘ−１）中、Ｒ_１は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。］

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

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

Examples of the (poly) carbonate chain include a (poly) carbonate chain represented by the following structural formula (X-2).

［式（Ｘ−２）中、Ｒ_２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-2), R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

The molecular weight of the compound represented by the structural formula (1) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

These unsaturated monobasic acids can be used alone or in combination of two or more.

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

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

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

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

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

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-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 (5); these isocyanurate modified products, biuret modified products, Examples thereof include a modified allophanate. Further, these polyisocyanate compounds may be used alone or in combination of two or more.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、または構造式（５）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または１〜３の整数であり、ｍは１〜１５の整数である。］

[In the formula, R ¹ is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is either an alkyl group having 1 to 4 carbon atoms independently, or a bond point connected to a structural site represented by the structural formula (5) via a methylene group marked with *. l is an integer of 0 or 1-3 and m is an integer of 1-15. ]

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 chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains were introduced into the molecular structures 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.

The method for producing the epoxy resin having the acid group and the 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.

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

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

Examples of the 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. Reacting 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 can be mentioned.

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

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified as the above-mentioned 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-dimethylolvaleric 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 can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

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 biphenol and bisphenol; (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure 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 compounds 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 the acid group and the 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 catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the 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. A reaction obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups with the acrylic resin intermediate thus obtained. Examples thereof include a product and a product 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, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Acrylic acid alkyl ester; alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy Aromatic ring-containing (meth) acrylates such as ethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene can be mentioned. These can be used alone or in combination of two or more.

The (meth) acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate compound (α), but the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when 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 can be used, and the polybasic acid anhydride may be used alone or in combination of two or more kinds. it can.

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

Examples of the amideimide resin having 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 that the compound has. The solid acid value of the amideimide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not opened. On the other hand, the measured value under the condition that the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.

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

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

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

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

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 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-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like can be mentioned. Be done. Further, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, the same compounds as those exemplified as the above-mentioned 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 epoxy group-containing (meth) acrylate compound is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. .. For example, glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenedi glycidyl ether, etc. Examples thereof include mono (meth) acrylate compounds of diglycidyl ether compounds such as 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. Among these, a (meth) acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and a cured product having high photosensitivity and excellent heat resistance and dielectric properties can be formed. A glycidyl group-containing (meth) acrylate monomer is preferable because an acid group-containing (meth) acrylate resin composition can be obtained. The molecular weight of the glycidyl group-containing (meth) acrylate monomer is preferably 500 or less. Further, the ratio of the glycidyl group-containing (meth) acrylate monomer to the total mass of the epoxy group-containing (meth) acrylate compound is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the amidoimide resin having an acid group and a 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 catalyst as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the acrylamide resin having 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, a polybasic acid anhydride, and the like. Examples thereof include those obtained by reacting with an unsaturated monobasic acid as needed.

The phenolic hydroxyl group-containing compound refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (6-1) to (6-4).

In the structural formulas (6-1) to (6-4), 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 0 or an integer of 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 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of the structural formula (6-2), it may be substituted on any ring, and the structural formula (6-2) may be substituted. In 6-3), it may be substituted on any ring of the benzene ring existing in one molecule, and in the structural formula (6-4), it may be substituted on any ring of the benzene ring existing in one molecule. It is shown that it may be substituted with, and 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.

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

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

Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (7-1) to (7-4).

In the above structural formulas (7-1) to (7-4), 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. , R ⁵ are independently hydrogen atoms or methyl groups. Further, p is 0 or an integer of 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. For example, in the naphthalene ring of the structural formula (7-2), it may be substituted on any ring, and the structural formula (7-2) may be substituted. In 7-3), it may be substituted on any ring of the benzene ring existing in one molecule, and in the structural formula (7-4), it may be substituted on any ring of the benzene ring existing in one molecule. Indicates that it may be replaced with.

As the compound having at least two phenolic hydroxyl groups in the molecule, compounds in which q is represented by an integer of 2 or more in the above structural formulas (6-1) to (6-4) can be used.

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

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The alkylene oxide may be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

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

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

As the unsaturated monobasic acid, the same as those exemplified as the unsaturated monobasic acid described above 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, and a basic catalyst and an acidic catalyst may be used if necessary.

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

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

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

The content of the resin (E) having an acid group and a polymerizable unsaturated bond is an acid group-containing (meth) acrylate resin capable of forming a cured product having high photosensitivity and excellent heat resistance and dielectric properties. Since the composition can be obtained, the range of 10 to 1000 parts by mass is preferable with respect to 100 parts by mass of the acid group-containing (meth) acrylate resin of the present invention.

Since the acid group-containing (meth) acrylate resin of the present invention has a polymerizable (meth) acryloyl group in its molecular structure, it can be used as a curable resin composition by adding, for example, a photopolymerization initiator. Can be done.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Examples 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 initiator include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 379", and "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 Upjon Chemical), "QuantaQUA", "Quantacure PDO" , "Chemistry EPD" (manufactured by Ward Brenkinsop); "Runtecure 1104" (manufactured by Runtec) and the like. These photopolymerization initiators can be used alone or in combination of two or more.

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

The curable resin composition of the present invention may contain other resin components. Examples of the other resin components include epoxy resins and various (meth) acrylate monomers.

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.

The various (meth) acrylate monomers are not particularly limited as long as they have a (meth) acryloyl group, and are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth). ) Acrylate mono (meth) acrylate compounds such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate. , Alicyclic mono (meth) acrylate compounds such as adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) ) Acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as benzylbenzyl (meth) acrylate and phenylphenoxyethyl (meth) acrylate: (poly) in the molecular structure of the various mono (meth) acrylate monomers. ) A (poly) oxyalkylene modified mono (meth) acrylate compound introduced with a polyoxyalkylene chain such as an oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain; the various mono (meth) acrylate compounds described above. A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the above; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( Aliphalic di (meth) acrylate compounds such as meta) acrylate and neopentyl glycol di (meth) acrylate; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth). Alicyclic di (meth) acrylics such as acrylates, dicyclopentanyldi (meth) acrylates, and tricyclodecanedimethanol di (meth) acrylates. Rate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; (poly) oxyethylene chains, (poly) in the molecular structure of the various di (meth) acrylate compounds. ) Polyoxyalkylene-modified di (meth) acrylate compounds introduced with (poly) oxyalkylene chains such as oxypropylene chains and (poly) oxytetramethylene chains; (poly) in the molecular structure of the various di (meth) acrylate compounds. ) A lactone-modified di (meth) acrylate compound having a lactone structure introduced; an aliphatic tri (meth) acrylate compound such as trimethylpropantri (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 has been 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, dipenta. A tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as erythritol hexa (meth) acrylate; in the molecular structure of the aliphatic poly (meth) acrylate compound, a (poly) oxyethylene chain, a (poly) oxypropylene chain, ( A tetrafunctional or higher functional (poly) oxyalkylene-modified poly (meth) acrylate compound into which a (poly) oxyalkylene chain such as a poly) oxytetramethylene chain has been introduced; ) A tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound having a lactone structure introduced; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylpropandi (meth) acrylate, Pentaerythritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, Hydroxyl-containing (meth) such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and ditrimethylolpropanetri (meth) acrylate. Acrylate compound: 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 hydroxyl group-containing (meth) acrylate compound (poly). ) Oxyalkylene modified product; A lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound; 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis. Isocyanate group-containing (meth) acrylate compounds such as (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) groups such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate. ) Acrylate monomer, epoxy group-containing (meth) acrylate compound such as mono (meth) acrylate of diglycidyl ether compound of droxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. Can be mentioned. These various (meth) acrylate monomers can be used alone or in combination of two or more.

Further, the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles and polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, etc. It can also contain various additives such as a storage stabilizer.

Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds and the like.

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 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-dioxotetra-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, Examples thereof include benzophenone tetracarboxylic acid. Further, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

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

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds 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 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.

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.

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

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

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 10~5,000mJ / cm ^2, more preferably 50~1,000mJ / 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, excellent heat resistance and dielectric properties, for example, solder resists, interlayer insulating materials, packaging materials, underfill materials and circuits in semiconductor device applications. It can be suitably used as a package adhesive layer for an element or the like, or 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 LCD and OELD. 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 volatile-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 active energy ray, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing 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 the examples of the present application, the weight average molecular weight of the acid group-containing (meth) acrylate resin was measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0% by mass of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

(Synthesis Example 1: Production of Reaction Product (I-1))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 108 parts by mass of methylisobutylketone, 138 parts by mass of salicylic acid, 145 parts by mass of glycidyl methacrylate, 0.1 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methquinone, 0.8 parts by mass of triphenylphosphine was added, and the mixture was reacted at 70 ° C. for 25 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-1). In addition, glycidyl methacrylate corresponding to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention is added to 1 mol of the phenolic hydroxyl group contained in salicylic acid corresponding to the aromatic compound (A) specified in the present invention. The number of moles of the epoxy group contained was 1.

(Synthesis Example 2: Production of Reaction Product (I-2))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 108 parts by mass of methylisobutylketone, 138 parts by mass of 4-hydroxybenzoic acid, 145 parts by mass of glycidyl methacrylate, 0.1 parts by mass of dibutylhydroxytoluene, and 0. 1 part by mass and 0.8 part by mass of triphenylphosphine were added, and the mixture was reacted at 70 ° C. for 25 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-2). It should be noted that 1 mol of the phenolic hydroxyl group of 4-hydroxybenzoic acid corresponding to the aromatic compound (A) specified in the present invention corresponds to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention. The number of moles of the epoxy group contained in the glycidyl methacrylate was 1.

(Synthesis Example 3: Production of Reaction Product (I-3))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 95 parts by mass of methylisobutylketone, 138 parts by mass of salicylic acid, 145 parts by mass of glycidyl methacrylate, 0.1 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methquinone, 0.8 parts by mass of triphenylphosphine was added, and the mixture was reacted at 70 ° C. for 25 hours while blowing air and stirring. Then, 97 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-3). In addition, glycidyl methacrylate corresponding to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention is added to 1 mol of the phenolic hydroxyl group contained in salicylic acid corresponding to the aromatic compound (A) specified in the present invention. The number of moles of the epoxy group contained was 1.

(Synthesis Example 4: Production of Reaction Product (I-4))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 111 parts by mass of methylisobutylketone, 152 parts by mass of 3-hydroxyphenylacetic acid, 145 parts by mass of glycidyl methacrylate, 0.1 parts by mass of dibutylhydroxytoluene, and 0. 1 part by mass and 0.9 part by mass of triphenylphosphine were added, and the mixture was reacted at 90 ° C. for 20 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-4). It should be noted that 1 mol of the phenolic hydroxyl group of 3-hydroxyphenylacetic acid corresponding to the aromatic compound (A) specified in the present invention corresponds to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention. The number of moles of the epoxy group contained in the glycidyl methacrylate was 1.

(Synthesis Example 5: Production of Reaction Product (I-5))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 101 parts by mass of methylisobutylketone, 110 parts by mass of resorcinol, 145 parts by mass of glycidyl methacrylate, 0.1 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methquinone, 1.3 parts by mass of triphenylphosphine was added, and the mixture was reacted at 120 ° C. for 10 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-5). In addition, glycidyl methacrylate corresponding to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention is added to 1 mol of the phenolic hydroxyl group contained in resorcinol corresponding to the aromatic compound (A) specified in the present invention. The number of moles of the epoxy group contained was 0.5.

(Synthesis Example 6: Production of Reaction Product (I-6))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 112 parts by mass of methylisobutylketone, 154 parts by mass of 3,4-dihydroxybenzoic acid, 145 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, and methquinone. 0.2 parts by mass and 0.9 parts by mass of triphenylphosphine were added, and the mixture was reacted at 70 ° C. for 25 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-6). The epoxy group-containing (meth) acrylate compound (C) specified in the present invention has an epoxy group-containing (meth) acrylate compound (C) with respect to 1 mol of the phenolic hydroxyl group contained in 3,4-dihydroxybenzoic acid corresponding to the aromatic compound (A) specified in the present invention. The number of moles of the epoxy group contained in glycidyl methacrylate corresponding to was 0.5.

(Synthesis Example 7: Production of Reaction Product (I-7))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 116 parts by mass of methylisobutylketone, 170 parts by mass of 3,4,5-trihydroxybenzoic acid, 145 parts by mass of glycidyl methacrylate, and 0.2 parts by mass of dibutylhydroxytoluene. , 0.2 part by mass of methquinone and 0.9 part by mass of triphenylphosphine were added, and the mixture was reacted at 70 ° C. for 25 hours while blowing air and stirring. Then, 147 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-7). The epoxy group-containing (meth) acrylate compound specified in the present invention is based on 1 mol of the phenolic hydroxyl group of 3,4,5-trihydroxybenzoic acid corresponding to the aromatic compound (A) specified in the present invention. The number of moles of the epoxy group contained in glycidyl methacrylate corresponding to (C) was 0.3.

(Synthesis Example 8: Production of Reaction Product (I-8))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 188 parts by mass of methylisobutylketone, 182 parts by mass of 5-hydroxyisophthalic acid, 284 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, and 0. 2 parts by mass and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 80 ° C. for 20 hours while blowing air and stirring. Then, 289 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-8). The number of moles of the epoxy group of glycidyl methacrylate was 2 with respect to 1 mole of the phenolic hydroxyl group of 5-hydroxyisophthalic acid corresponding to the aromatic compound (A) defined in the present invention.

(Synthesis Example 9: Production of Reaction Product (I-9))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 210 parts by mass of methylisobutylketone, 182 parts by mass of 5-hydroxyisophthalic acid, 327 parts by mass of glycidyl methacrylate, 0.3 parts by mass of dibutylhydroxytoluene, and 0. 3 parts by mass and 1.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120 ° C. for 15 hours while blowing air and stirring. Then, 332 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain the desired reaction product (I-9). It should be noted that 1 mol of the phenolic hydroxyl group of 5-hydroxyisophthalic acid corresponding to the aromatic compound (A) specified in the present invention corresponds to the epoxy group-containing (meth) acrylate compound (C) specified in the present invention. The number of moles of the epoxy group contained in the glycidyl methacrylate was 2.3.

(Synthesis Example 10: Production of Reaction Product (III-1))
138 parts by mass of salicylic acid, 165 parts by mass of dicyclopentadiene and phenol heavy adduct (hydroxyl equivalent 165 g / eq), 1008 parts by mass of methyl isobutyl ketone in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. Part was added. Next, 202 parts by mass of isophthalic acid chloride and 0.6 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.4 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methquinone, and 185 parts by mass of diethylene glycol monomethyl ether acetate were added, and methyl isobutyl ketone was desolvated at 80 ° C. while blowing air to obtain the desired reaction product. (III-1) was obtained. It should be noted that 1 mol of the phenolic hydroxyl group contained in the salicylic acid corresponding to the aromatic compound (A) specified in the present invention and the polyaddition of dicyclopentadiene and phenol is added to the aromatic compound (B) specified in the present invention. The number of moles of the acid halide group of the corresponding isophthalic acid chloride was 1.

(Synthesis Example 11: Synthesis of Aromatic Ester Compound (R))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer was charged with 244 parts by mass of 2,5-xylenol and 1120 parts by mass of toluene, and the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 parts by mass of isophthalic acid chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure. Next, 0.6 parts by mass of tetrabutylammonium bromide was added, and while performing nitrogen gas purging treatment, the inside of the system was controlled to 60 ° C. or lower, and 410 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was heated and dried under reduced pressure to obtain an aromatic ester compound (R) represented by the following structural formula.

(Synthesis Example 12: Synthesis of resin (E-1) having an acid group and a polymerizable unsaturated bond)
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 dibutylhydroxytoluene 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 produce a resin having an acid group having a solid content of 64.0% by mass and a polymerizable unsaturated bond. (E-1) was obtained. The solid acid value of the resin (E-1) having an acid group and a polymerizable unsaturated bond was 85 mgKOH / g, and the weight average molecular weight was 8850.

(Example 1: Production of acid group-containing methacrylate resin (1))
540 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1586 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.8 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 324 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (1) was obtained. The solid acid value of the target acid group-containing methacrylate resin (1) was 62 mgKOH / g, the weight average molecular weight was 1860, and the methacryloyl group equivalent was 710 g / equivalent. In the present invention, the methacryloyl group equivalent is a value calculated from the amount of raw materials charged. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-1) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 2: Production of acid group-containing methacrylate resin (2))
1080 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1 and 2101 parts by mass of methyl isobutyl ketone were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. Next, 202 parts by mass of isophthalic acid chloride and 1.6 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 824 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 1.1 parts by mass of dibutylhydroxytoluene, 0.5 parts by mass of methquinone, and 426 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (2) was obtained. The solid acid value of the target acid group-containing methacrylate resin (2) was 100 mgKOH / g, the weight average molecular weight was 1040, and the methacryloyl group equivalent was 486 g / g. The number of moles of acid halides of the isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention is 1 with respect to 1 mole of the phenolic hydroxyl group of the reaction product (I-1). there were.

(Example 3: Production of acid group-containing methacrylate resin (3))
540 parts by mass of the reaction product (I-2) obtained in Synthesis Example 2 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1586 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.8 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 324 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (3) was obtained. The solid acid value of the target acid group-containing methacrylate resin (3) was 66 mgKOH / g, the weight average molecular weight was 1690, and the methacryloyl group equivalent was 710 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-2) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 4: Production of acid group-containing methacrylate resin (4))
475 parts by mass of the reaction product (I-3) obtained in Synthesis Example 3 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1478 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 289 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (4) was obtained. The target acid group-containing methacrylate resin (4) had a solid acid value of 92 mgKOH / g, a weight average molecular weight of 1720, and a methacryloyl group equivalent of 662 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-3) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 5: Production of acid group-containing methacrylate resin (5))
558 parts by mass of the reaction product (I-4) obtained in Synthesis Example 4 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1616 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 317 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (5) was obtained. The target acid group-containing methacrylate resin (5) had a solid acid value of 66 mgKOH / g, a weight average molecular weight of 1910, and a methacryloyl group equivalent of 724 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-4) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 6: Production of acid group-containing methacrylate resin (6))
505 parts by mass of the reaction product (I-5) obtained in Synthesis Example 5 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1528 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 299 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (6) was obtained. The solid acid value of the target acid group-containing methacrylate resin (6) was 66 mgKOH / g, the weight average molecular weight was 2030, and the methacryloyl group equivalent was 682 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-5) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 7: Production of acid group-containing methacrylate resin (7))
560 parts by mass of the reaction product (I-6) obtained in Synthesis Example 6 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1868 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride, 144 parts by mass of benzyl chloride, and 1.3 parts by mass of tetrabutylammonium bromide were added to control the inside of the system to 60 ° C. or lower, and 3 parts by mass of 828 parts by mass of a 20% sodium hydroxide aqueous solution. The mixture was added dropwise over time, and after completion of the addition, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.9 parts by mass of dibutylhydroxytoluene, 0.5 parts by mass of methquinone, and 364 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (7) was obtained. The target acid group-containing methacrylate resin (7) had a solid acid value of 60 mgKOH / g, a weight average molecular weight of 2410, and a methacryloyl group equivalent of 830 g / g. It should be noted that, with respect to 1 mol of the phenolic hydroxyl group contained in the reaction product (I-6) and the polyadduct of dicyclopentadiene and phenol, isophthalic acid chloride and benzyl corresponding to the aromatic compound (B) specified in the present invention. The number of moles of the acid halide group contained in the chloride was 1.

(Example 8: Production of acid group-containing methacrylate resin (8))
580 parts by mass of the reaction product (I-7) obtained in Synthesis Example 7 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 2151 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride, 288 parts by mass of benzyl chloride, and 1.5 parts by mass of tetrabutylammonium bromide were added to control the inside of the system to 60 ° C. or lower, and 3 parts by mass of 1039 parts by mass of a 20% sodium hydroxide aqueous solution. The mixture was added dropwise over time, and after completion of the addition, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 1 part by mass of dibutylhydroxytoluene, 0.5 part by mass of methquinone, and 416 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to obtain the desired acid group-containing methacrylate resin. (8) was obtained. The target acid group-containing methacrylate resin (8) had a solid acid value of 53 mgKOH / g, a weight average molecular weight of 2630, and a methacryloyl group equivalent of 951 g / equivalent. It should be noted that, with respect to 1 mol of the phenolic hydroxyl group contained in the reaction product (I-7) and the polyadduct of dicyclopentadiene and phenol, isophthalic acid chloride and benzyl corresponding to the aromatic compound (B) specified in the present invention. The number of moles of the acid halide group contained in the chloride was 1.

(Example 9: Production of acid group-containing methacrylate resin (9))
943.5 parts by mass of the reaction product (I-8) obtained in Synthesis Example 8 and a heavy adduct of dicyclopentadiene and phenol in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 parts by mass of hydroxyl group equivalent (165 g / eq) and 2259 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.6 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 824 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 1.1 parts by mass of dibutylhydroxytoluene, 0.6 parts by mass of methquinone, and 450 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (9) was obtained. The target acid group-containing methacrylate resin (9) had a solid acid value of 104 mgKOH / g, a weight average molecular weight of 2240, and a methacryloyl group equivalent of 525 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-8) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 10: Production of acid group-containing methacrylate resin (10))
1051 parts by mass of the reaction product (I-9) obtained in Synthesis Example 9 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 2438 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.7 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 824 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 1.1 parts by mass of dibutylhydroxytoluene, 0.6 parts by mass of methquinone, and 486 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (10) was obtained. The target acid group-containing methacrylate resin (10) had a solid acid value of 110 mgKOH / g, a weight average molecular weight of 2080, and a methacryloyl group equivalent of 494 g / g. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-9) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.

(Example 11: Production of acid group-containing methacrylate resin (11))
540 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1, 55 parts by mass of catechol, and 1329 parts by mass of methyl isobutyl ketone were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. Added. Next, 202 parts by mass of isophthalic acid chloride and 0.9 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 618 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methquinone, and 264 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (11) was obtained. The target acid group-containing methacrylate resin (11) had a solid acid value of 80 mgKOH / g, a weight average molecular weight of 1690, and a methacryloyl group equivalent of 603 g / equivalent. The number of moles of acid halides contained in the isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention is, with respect to 1 mol of the phenolic hydroxyl group contained in the reaction product (I-1) and catechol. It was 1.

(Example 12: Production of acid group-containing methacrylate resin (12))
599 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1685 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 1.2 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 641 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.8 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 332 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (12) was obtained. The target acid group-containing methacrylate resin (12) had a solid acid value of 70 mgKOH / g, a weight average molecular weight of 1690, and a methacryloyl group equivalent of 682 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-1) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 0.9.

(Example 13: Production of acid group-containing methacrylate resin (13))
416 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1 and a heavy adduct of dicyclopentadiene and phenol (hydroxyl equivalent) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 165 g / eq) 165 parts by mass and 1379 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthalic acid chloride and 0.9 parts by mass of tetrabutylammonium bromide were added, the temperature inside the system was controlled to 60 ° C. or lower, and 641 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by static separation. Water was further added to the obtained methyl isobutyl ketone layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methquinone, and 269 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed from the solvent at 80 ° C. to contain the desired acid group. A methacrylate resin (13) was obtained. The solid acid value of the target acid group-containing methacrylate resin (13) was 59 mgKOH / g, the weight average molecular weight was 2040, and the methacryloyl group equivalent was 796 g / equivalent. The isophthalic acid chloride corresponding to the aromatic compound (B) specified in the present invention has 1 mol of the phenolic hydroxyl group contained in the reaction product (I-1) and the polyadduct of dicyclopentadiene and phenol. The number of moles of the acid halide group was 1.3.

(Example 14: Production of acid group-containing methacrylate resin (14))
1224 parts by mass of reaction product (III-1) obtained in Synthesis Example 10, 248 parts by mass of diethylene glycol monomethyl ether acetate, 287 parts by mass of glycidyl methacrylate in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a distillate tube, and a stirrer. Parts, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methquinone, and 3.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 90 ° C. for 18 hours while blowing air and stirring. Next, 292 parts by mass of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 6 hours to obtain the desired acid group-containing methacrylate resin (14). The target acid group-containing methacrylate resin (14) had a solid acid value of 64 mgKOH / g, a weight average molecular weight of 2090, and a methacryloyl group equivalent of 711 g / equivalent.

(Example 15: Preparation of curable resin composition (1))
The acid group-containing methacrylate resin (1) obtained in Example 1, orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, diethylene glycol monoethyl ether acetate, and a photopolymerization initiator. (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, dipentaerythritol hexaacrylate, and phthalocyanine green are mixed in the amounts shown in Table 1 to obtain a curable resin composition (1). Obtained.

(Examples 16 to 29: Preparation of curable resin compositions (2) to (15))
Curable resin compositions (2) to (15) were obtained in the same manner as in Example 15 with the compositions and formulations shown in Tables 1 and 2.

(Comparative Examples 1 and 2: Preparation of curable resin compositions (C1) and (C2))
Curable resin compositions (C1) and (C2) were obtained in the same manner as in Example 15 with the compositions and formulations shown in Table 2.

The following evaluations were carried out using the curable resin compositions (1) to (15), (C1) and (C2) 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 to 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. 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.

Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (15) prepared in Examples 15 to 29, and the curable resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2. And 2.

(Example 30: Preparation of curable resin composition (16))
The acid group-containing methacrylate resin (1) obtained in Example 1, orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, diethylene glycol monoethyl ether acetate, and a photopolymerization initiator. (“Omnirad 907” manufactured by IGM) and 4-dimethylaminopyridine were mixed in the blending amounts shown in Table 2 to obtain a curable resin composition (15).

(Examples 31 to 41: Preparation of curable resin compositions (17) to (30))
Curable resin compositions (17) to (30) were obtained in the same manner as in Example 28 with the compositions and formulations shown in Tables 3 and 4.

(Comparative Examples 3 and 4: Preparation of curable resin compositions (C3) and (C4))
Curable resin compositions (C3) and (C4) were obtained in the same manner as in Example 30 with the compositions and formulations shown in Table 4.

The following evaluations were carried out using the curable resin compositions (16) to (30), (C3) and (C4) obtained in the above Examples and Comparative Examples.

[Evaluation method of heat resistance]
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 dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate 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.

[Measurement method of permittivity]
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 dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours was used as a test piece, and the dielectric constant of the test piece at 1 GHz was determined by a cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies. It was measured.

[Measurement method of dielectric loss tangent]
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 dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours was used as a test piece, and a dielectric loss tangent of the test piece at 1 GHz was performed by a cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies. It was measured.

The evaluation results of the curable resin compositions (16) to (30) prepared in Examples 30 to 44 and the curable resin compositions (C3) and (C4) prepared in Comparative Examples 3 and 4 are shown in Tables 3 and 4. Shown in.

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

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

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

The description of the mass part of the resin having an acid group and a polymerizable unsaturated bond in Tables 2 and 4 is a solid content value.

Examples 15 to 44 shown in Tables 1 to 4 are examples of curable resin compositions using the acid group-containing (meth) acrylate resin of the present invention. It was confirmed that this curable resin composition has high photosensitivity and also has excellent heat resistance and dielectric properties in the cured product.

On the other hand, Comparative Examples 1 and 3 are examples of a curable resin composition that does not use the acid group-containing (meth) acrylate resin of the present invention. It was confirmed that this curable resin composition has a high dielectric constant and dielectric loss tangent and is insufficient in dielectric properties.

Comparative Examples 2 and 4 are examples of a curable resin composition containing an aromatic ester compound having no acryloyl group and a resin having an acid group and a polymerizable unsaturated bond. It was confirmed that this curable resin composition has low photosensitivity and is insufficient in heat resistance.

Claims (12)

Aromatic compound (A) having a phenolic hydroxyl group and
An aromatic compound having an acid group other than the aromatic compound (A), an acid halide thereof and / or an esterified product (B) thereof,
Epoxy group-containing (meth) acrylate compound (C) and
Polybasic acid anhydride (D) and
An acid group-containing (meth) acrylate resin, which is a reaction product containing the above as an essential reaction raw material.
The aromatic compound (A) having a phenolic hydroxyl group contains a compound having at least one hydroxyl group on the aromatic ring and at least one acid group in one molecule.
An acid group-containing (meth) acrylate resin, wherein the acid group-containing (meth) acrylate resin has a structure represented by the following structural formula (1).

[In formula (1), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring. ] With respect to 1 mol of the phenolic hydroxyl group contained in the aromatic compound (A), an aromatic compound having an acid group other than the aromatic compound (A), an acid halide thereof and / or an esterified product (B) thereof. The acid group-containing (meth) acrylate resin according to claim 1, wherein the number of moles of functional groups capable of reacting with the phenolic hydroxyl group is in the range of 0.9 to 1.5. The acid group-containing (meth) acrylate resin
The reaction product (I) of the aromatic compound (A) having a phenolic hydroxyl group and the epoxy group-containing (meth) acrylate compound (C),
The aromatic compound (A) having a phenolic hydroxyl group and
A claim which is a reaction product of an aromatic compound having an acid group other than the aromatic compound (A), an acid halide thereof and / or an esterified product (B) thereof, and the polybasic acid anhydride (D). The acid group-containing (meth) acrylate resin according to 1. The number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (C) with respect to 1 mol of the phenolic hydroxyl group contained in the aromatic compound (A), which is the reaction raw material of the reaction product (I). The acid group-containing (meth) acrylate resin according to claim 3, wherein the epoxy is 0.4 or more. An aromatic compound having an acid group other than the aromatic compound (A), an acid halide thereof, and an acid halide thereof with respect to a total of 1 mol of the phenolic hydroxyl groups of the reaction product (I) and the aromatic compound (A). / Or the acid group-containing (meth) acrylate resin according to claim 3 , wherein the number of moles of the functional group capable of reacting with the phenolic hydroxyl group of the esterified product (B) thereof is in the range of 0.95 to 1.25. The acid group-containing (meth) acrylate resin according to any one of claims 1 to 5 and the resin (E) having an acid group other than the acid group-containing (meth) acrylate resin and a polymerizable unsaturated bond are contained. An acid group-containing (meth) acrylate resin composition. A curable resin composition comprising the acid group-containing (meth) acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator. The curable resin composition according to claim 7 , further comprising an organic solvent and a curing agent. A cured product, which is a cured reaction product of the curable resin composition according to claim 7 or 8. An insulating material comprising the curable resin composition according to claim 7 or 8. A resin material for a solder resist, which comprises the curable resin composition according to claim 7 or 8. A resist member comprising the resin material for solder resist according to claim 11.