JP7066989B2 - Acid group-containing (meth) acrylate resin and resin material for solder resist - Google Patents

Description

The present invention relates to an acid group-containing (meth) acrylate resin having high developability and excellent heat resistance and strength in a cured product, a curable resin composition containing the resin, an insulating material composed of the curable resin composition, and a solder. The present invention relates to a resin material for resist and a resist member.

As a resin material for solder resist for a printed wiring substrate, an acid group-containing epoxy acrylate resin obtained by reacting an epoxy resin with acrylic acid and then reacting with an acid anhydride is widely used. The required performance of the resin material for solder resist includes various things such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, dielectric property, etc. in the cured product.

As a conventionally known resin material for solder resist, an acid group-containing epoxy obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and anhydrous methacrylic acid. Although acrylate resins are known (see Patent Document 1 below), they do not have sufficient heat resistance and strength, especially in cured products, and do not satisfy the ever-increasing demands for performance.

Japanese Unexamined Patent Publication No. 8-259663

Therefore, the problem to be solved by the present invention is an acid group-containing (meth) acrylate resin having high developability and excellent heat resistance and strength in a cured product, a curable resin composition containing the resin, and the curable resin. It is an object of the present invention to provide an insulating material composed of a 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 used an acid group-containing epoxy (meth) acrylate resin having an oxazolidone ring structure as the epoxy resin, and also as a (meth) acrylate agent. We have found that by using an unsaturated monocarboxylic acid and an unsaturated monocarboxylic acid anhydride in combination, it becomes a resin material having excellent heat resistance and strength in a cured product as well as photosensitivity and alkali developability. It came to be completed.

That is, the present invention requires an epoxy resin (A) having an oxazolidone ring structure in the molecule, an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid anhydride (D). The present invention relates to an acid group-containing (meth) acrylate resin as a reaction raw material.

The present invention further relates to a curable resin composition containing the acid group-containing (meth) acrylate resin and a photopolymerization initiator.

The present invention further relates to a cured product of the curable resin composition.

The present invention further relates to an insulating material comprising the curable resin composition.

The present invention further relates to a resin material for a solder resist comprising the curable resin composition.

The present invention further relates to a resist member made of the resin material for solder resist.

According to the present invention, an insulating material comprising an acid group-containing (meth) acrylate resin having high developability and excellent heat resistance and strength in a cured product, a curable resin composition containing the resin composition, and the curable resin composition. , A resin material for solder resist and a resist member can be provided.

FIG. 1 is a GPC chart of the acid group-containing (meth) acrylate resin (1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The acid group-containing (meth) acrylate resin of the present invention includes an epoxy resin (A) having an oxazolidone ring structure in the molecule, an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid. An anhydride (D) is used as an essential reaction raw material.

The epoxy resin (A) having an oxazolidone ring structure in the molecule is not particularly limited as long as it has an oxazolidone ring structure in the molecule, and various materials may be used. can. As an example of the epoxy resin (A) having an oxazolidone ring structure in the molecule, for example, an epoxy resin (a1) which is a polyglycidyl etherified product of various phenolic hydroxyl group-containing compounds and a polyisocyanate compound (a2) are indispensable. Examples thereof include reaction products used as the reaction raw materials of the above.

Regarding the epoxy resin (a1) which is a polyglycidyl etherified product of the phenolic hydroxyl group-containing compound, examples of the phenolic hydroxyl group-containing compound include bisphenol, hydrogenated bisphenol, biphenol, hydrogenated biphenol, polyphenylene ether type diol, and poly. Examples thereof include naphthylene ether type diol, phenol novolak fat, cresol novolak resin, bisphenol novolak type resin, naphthol novolak type resin, phenol aralkyl type resin, naphthol aralkyl type resin, cycloring structure-containing phenol resin and the like. Among them, a cyclocyclic structure-containing phenol resin is preferable in that it is an acid group-containing (meth) acrylate resin having excellent photosensitivity and heat resistance. Further, in terms of being an acid group-containing (meth) acrylate resin having an excellent balance between developability and physical properties of the cured product, one or more of them are selected from the group consisting of bisphenol, hydrogenated bisphenol, biphenol and hydrogenated biphenol. Is preferable.

Specific examples of the cycloring structure-containing phenol resin include a resin obtained by an addition reaction between dicyclopentadiene and a phenolic hydroxyl group-containing compound. Examples of the phenolic hydroxyl group-containing compound include phenol, naphthol, and compounds having one or more substituents on their aromatic nuclei. The substituent may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a cycloalkyl group such as a cyclohexyl group; a vinyl group, an allyl group, a propagyl group or the like. Unsaturated bond-containing group; methoxy group, ethoxy group, propyloxy group, butoxy group alkoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nuclei thereof. Examples thereof include an aryl group having a structure in which the aliphatic hydrocarbon group, an alkoxy group, a halogen atom and the like are substituted.

Examples of the cycloring structure-containing phenolic resin include those represented by the following structural formula (1).

（式中Ｒ^１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかである。ｍは０又は１～４の整数であり、ｎは０又は１であり、ｔは０又は１以上の整数である。）

(In the formula, R ¹ is independently any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. M is 0 or an integer of 1 to 4, and n is 0 or 1. And t is an integer greater than or equal to 0 or 1.)

The bisphenol, hydrogenated bisphenol, biphenol, hydrogenated biphenol more specifically, bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol S and the like; hydrogenated bisphenol A, water. Hydrogenated bisphenols such as supplemented bisphenol B, hydrogenated bisphenol E, hydrogenated bisphenol F, hydrogenated bisphenol S; 4,4'-biphenol, 2,2'-biphenol, tetramethyl-4,4'-biphenol, tetramethyl -2,2'-biphenols such as biphenols; hydrogenated 4,4'-biphenols, hydrogenated 2,2'-biphenols, hydrogenated tetramethyl-4,4'-biphenols, hydrogenated tetramethyl-2,2' -Hydrogenized biphenols such as biphenols can be mentioned.

The polyglycidyl etherification of the phenolic hydroxyl group-containing compound can be carried out in the same manner as in the production of a general epoxy resin. Specifically, for example, 2 to 10 mol of epihalohydrin is used for 1 mol of the hydroxyl group of the phenolic hydroxyl group-containing compound, and 0.9 to 2.0 mol of a basic catalyst is used for 1 mol of the phenolic hydroxyl group. Examples thereof include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding all at once or in portions.

In the present invention, one type of the epoxy resin (a1) may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the phenolic hydroxyl group-containing compound may be mixed individually with polyglycidyl etherification, or the phenolic hydroxyl group-containing compound mixed with two or more kinds may be made into polyglycidyl ether. May be used.

The epoxy group equivalent of the epoxy resin (a1) is preferably in the range of 150 to 400 g / equivalent because it is an acid group-containing (meth) acrylate resin having an excellent balance between developability and physical properties of the cured product.

The polyisocyanate compound (a2) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule, and its specific structure and the presence or absence of other functional groups are not particularly limited, and various compounds can be used. Specific examples of the polyisocyanate compound (a2) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; Alicyclic diisocyanate compounds such as norbornan diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatics such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalenedi isocyanate. Group diisocyanate compounds; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (2); examples thereof include isocyanurate-modified products, biuret-modified products, and allophanate-modified products. These polyisocyanate compounds (a2) may be used alone or in combination of two or more.

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

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

Among the polyisocyanate compounds (a2) exemplified above, various diisocyanate compounds are preferable in that they are acid group-containing (meth) acrylate resins having excellent strength in the cured product. Further, a polyisocyanate compound having an aromatic ring in its molecular structure is preferable in terms of excellent heat resistance in the cured product.

As the epoxy resin (A) having an oxazolidone ring structure in the molecule, in addition to the epoxy resin (a1) and the polyisocyanate compound (a2), other compounds may be used as a part of the reaction raw material. .. Examples of the other compounds include various phenolic hydroxyl group-containing compounds (a3).

Examples of the phenolic hydroxyl group-containing compound (a3) include the same phenolic hydroxyl group-containing compounds exemplified as the raw material of the epoxy resin (a1). Among them, one or more selected from the group consisting of bisphenol, hydrogenated bisphenol, biphenol and hydrogenated biphenol because it is an acid group-containing (meth) acrylate resin having an excellent balance between developability and physical properties of the cured product. Is preferable.

When the phenolic hydroxyl group-containing compound (a3) is used as a reaction raw material for the epoxy resin (A) having an oxazolidone ring structure in the molecule, it contains an acid group (meth) having an excellent balance between developability and physical properties of the cured product. ) Since it is an acrylate resin, it is preferable to use the phenolic hydroxyl group-containing compound (a3) in a ratio of 0.01 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (a1), preferably 0.5 to 20 parts by mass. It is more preferable to use it in a ratio of 10 parts by mass.

In the production of the epoxy resin (A) having an oxazolidone ring structure in the molecule, the ratio of each reaction raw material is appropriately adjusted according to the desired performance, but in particular, it contains an acid group having sufficiently high developability ( Since it is a meta) acrylate resin, it is preferable that the epoxy group equivalent of the obtained epoxy resin (A) is adjusted to be in the range of 180 to 500 g / equivalent.

The method for producing the epoxy resin (A) having an oxazolidone ring structure in the molecule is not particularly limited, but as an example, the polyisocyanate compound (a2) is dividedly added to the epoxy resin (a1) and 60 to 180. Examples thereof include a method of reacting under a temperature condition of about ° C. When the phenolic hydroxyl group-containing compound (a3) is used as a reaction raw material for the epoxy resin (A) having an oxazolidone ring structure in the molecule, the epoxy resin (a1) and the phenolic hydroxyl group-containing compound (a3) are used. Is preferably reacted in advance under a temperature condition of about 60 to 180 ° C., the polyisocyanate compound (a2) is added in portions to the reaction mixture, and the reaction is carried out in the range of 60 to 180 ° C.

The reaction is preferably carried out under catalytic conditions, and preferred catalysts include, for example, quaternary ammonium salts, quaternary phosphonium salts, imidazole compounds and the like. The amount of the catalyst added is preferably about 0.001 to 5% by mass with respect to the total mass of the reaction raw materials. Further, the reaction may be appropriately carried out in an organic solvent.

The softening point of the epoxy resin (A) having an oxazolidone ring structure in the molecule is preferably a value measured based on JIS K7234 and is in the range of 50 to 120 ° C. Further, the melt viscosity is based on ASTM D4287, and the value at 150 ° C. measured by an ICI viscometer is preferably in the range of 0.1 to 20 dPa · s.

Examples of the unsaturated monocarboxylic acid (B) include compounds having a (meth) acryloyl group and a carboxy group in one molecule, and examples thereof include acrylic acid and methacrylic acid. The unsaturated monocarboxylic acid (B) may be used alone or in combination of two or more.

Examples of the unsaturated monocarboxylic acid anhydride (C) include acid anhydrides of compounds having a (meth) acryloyl group and a carboxy group in one molecule, such as acrylic acid anhydrides and methacrylic acid anhydrides. Can be mentioned. The unsaturated monocarboxylic acid anhydride (C) may be used alone or in combination of two or more.

As the dicarboxylic acid anhydride (D), any acid anhydride of a compound having two carboxy groups in one molecule can be used. Specifically, 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, Examples thereof include acid anhydrides of dicarboxylic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid. The dicarboxylic acid anhydride (D) may be used alone or in combination of two or more. Among them, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. have a molecular structure in that they are acid group-containing (meth) acrylate resins having excellent heat resistance in cured products. Acid anhydrides of compounds having a cyclic structure are preferred. Further, succinic acid anhydride is preferable in that it becomes an acid group-containing (meth) acrylate resin having excellent developability.

The acid group-containing (meth) acrylate resin of the present invention includes an epoxy resin (A) having an oxazolidone ring structure in the molecule, the unsaturated monocarboxylic acid (B), the unsaturated monocarboxylic acid anhydride (C) and the like. The production method thereof is not particularly limited as long as the dicarboxylic acid anhydride (D) is used as an essential reaction raw material, and for example, either a method of reacting all of the reaction raw materials at once or a method of sequentially reacting them may be used. good. Above all, since the reaction is easy to control, the epoxy resin (A), the unsaturated monocarboxylic acid (B), and the unsaturated monocarboxylic acid anhydride (C) are first reacted, and then the dicarboxylic acid anhydride. The method of reacting (D) is preferable. In the reaction, for example, the epoxy resin (A), the unsaturated monocarboxylic acid (B), and the unsaturated monocarboxylic acid anhydride (C) are subjected to an esterification reaction catalyst, an antioxidant, and polymerization in an organic solvent. After reacting in the presence of a banning agent in a temperature range of 100 to 150 ° C. for about 5 to 12 hours, dicarboxylic acid anhydride (D) is added to the reaction system, and 1 to 1 to 120 ° C. in a temperature range of 90 to 120 ° C. It can be carried out by a method of reacting for about 5 hours.

The reaction ratio of the epoxy resin (A), the unsaturated monocarboxylic acid (B), and the unsaturated monocarboxylic acid anhydride (C) was such that the unsaturated monocarboxylic acid relative to 1 mol of the epoxy group in the epoxy resin (A). It is preferable to use the acid (B) and the unsaturated monocarboxylic acid anhydride (C) in a total range of 0.9 to 1.1 mol.

Further, since the obtained acid group-containing (meth) acrylate resin has an excellent balance between the developability and the physical properties of the cured product, the unsaturated monocarboxylic acid (B) and the unsaturated monocarboxylic acid anhydride (C) It is more preferable that the value of the molar ratio [(B) / (C)] with and to is in the range of 0.3 to 3.5.

The reaction ratio of the dicarboxylic acid anhydride (D) is preferably in the range of 0.9 to 1.1 mol with respect to 1 mol of the unsaturated monocarboxylic acid (B).

The selection of the organic solvent used in the reaction is appropriately selected depending on the solubility of each reaction raw material and the acid group-containing (meth) acrylate resin which is a product, and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, and methyl are selected. Examples thereof include isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate and the like. Each of these may be used alone or as a mixed solvent of two or more kinds. The amount of the organic solvent used is such that the reaction efficiency is good, so that the epoxy resin (A), the unsaturated monocarboxylic acid (B), the unsaturated monocarboxylic acid anhydride (C) and the dicarboxylic acid anhydride (D) are used. It is preferable to use the amount in the range of about 0.1 to 5 times the total mass of.

Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, and amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. These may be used alone or in combination of two or more. The amount of the catalyst added is 0.05 to 5 with respect to the total mass of the epoxy resin (A), the unsaturated monocarboxylic acid (B), the unsaturated monocarboxylic acid anhydride (C) and the dicarboxylic acid anhydride (D). It is preferable to use it in the range of mass%.

The acid value of the acid group-containing (meth) acrylate resin of the present invention is preferably in the range of 40 to 90 mgKOH / g because it has an excellent balance between developability and physical properties of the cured product. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

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

The photopolymerization initiator is, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-Methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl oxide , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one , 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and the like.

Commercially available products of these photopolymerization initiators include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651", and "Irgacure". -754, "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800", "Irgacure-1850" , "Irgacure-2959", "Irgacure-4043", "DaroCure-1173" (manufactured by Ciba Specialty Chemicals), "Lucillin TPO" (manufactured by BASF), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stoufa Chemical Co., Ltd.), "Trigonal P1" ( Akzo), "Sandray 1000" (Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop) Made) and the like.

The amount of the photopolymerization initiator added is, for example, in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth) acrylate resin of the present invention. The resin component is obtained by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, a dicarboxylic acid anhydride, and if necessary, an unsaturated monocarboxylic acid anhydride. Examples thereof include resins having a carboxyl group and a (meth) acryloyl group in the resin, various (meth) acrylate monomers, and the like.

The (meth) acrylate monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( An aliphatic mono (meth) acrylate compound such as meta) acrylate and octyl (meth) acrylate; an alicyclic mono (meth) acrylate compound such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl ( Fragrances such as meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate Mono (meth) acrylate compounds such as mono (meth) acrylate compounds: Polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains in the molecular structure of the various mono (meth) acrylate monomers. Polyoxyalkylene-modified mono (meth) acrylate compound introduced with; a lactone-modified mono (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds;

An aliphatic di (meth) acrylate compound such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. 1,4-Cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate Di (meth) acrylate compounds such as alicyclic di (meth) acrylate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; in the molecular structure of the various di (meth) acrylate compounds. A polyoxyalkylene-modified di (meth) acrylate compound into which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain has been introduced; A lactone-modified di (meth) acrylate compound with a poly) lactone structure;

An aliphatic tri (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; a polyoxyethylene chain, a polyoxypropylene chain, etc. in the molecular structure of the aliphatic tri (meth) acrylate compound. Polyoxyalkylene-modified tri (meth) acrylate compound into which a polyoxyalkylene chain such as a polyoxytetramethylene chain has been introduced; a lactone-modified tri having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound. (Meta) acrylate compound;

A tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; A tetrafunctional or higher functional polyoxyalkylene-modified poly (meth) acrylate compound in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced into the molecular structure; the aliphatic poly (meth). Examples thereof include a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the acrylate compound.

In addition, the curable resin composition of the present invention may contain various additives such as inorganic fine particles, polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers. ..

Since the acid group-containing (meth) acrylate resin of the present invention is excellent in heat resistance and strength in a cured product, for example, in the case of semiconductor devices, packages such as solder resists, interlayer insulating materials, packaging materials, underfill materials, and circuit elements are packaged. It can be used as an adhesive layer or an adhesive layer between an integrated circuit element and a circuit board. It can be suitably used for spacers and the like.

Further, the acid group-containing (meth) acrylate resin of the present invention is excellent in heat resistance and strength in a cured product as well as developability, and thus can be suitably used for solder resist applications. The resin material for solder resist of the present invention contains, for example, each component such as a curing agent, a curing accelerator, and an organic solvent in addition to the acid group-containing (meth) acrylate resin, a photopolymerization initiator and various additives. Become.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin. The epoxy resin used here is, for example, a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthylene ether type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin. , Bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Examples thereof include an addition reaction type epoxy resin. These may be used alone or in combination of two or more. Among these epoxy resins, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, because they are excellent in heat resistance in cured products. , Naftor-cresol co-condensed novolak type epoxy resin and other novolak type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ° C. are particularly preferable.

The curing accelerator accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, etc. Examples include amine complex salts. These may be used alone or in combination of two or more. The amount of the curing accelerator added is, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin and the curing agent, and for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, and the like. Examples thereof include cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.

In the method of obtaining a resist member using the solder resist resin material of the present invention, for example, the solder resist resin material is applied onto a substrate, and an organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C. After that, a method of exposing the unexposed portion with an ultraviolet ray or an electron beam through a photomask on which a desired pattern is formed, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing in a temperature range of about 140 to 180 ° C. can be mentioned. ..

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the examples of the present application, the acid value of the acid group-containing (meth) acrylate resin was measured by the neutralization titration method of JIS K 0070 (1992).

Production Example 1 Production of epoxy resin (A-1) having an oxazolidone ring structure in the molecule Bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation) in a four-necked flask equipped with a stirrer, thermometer, and condenser. Epoxy equivalent (188 g / equivalent) 376 g, bisphenol A 6.6 g, and tetrabutylphosphonium bromide (“TBP-BB” manufactured by Hokuko Chemical Industry Co., Ltd.) 0.08 g were charged, and the temperature was raised to 150 ° C. for 2 hours. Then, 58 g of tolylene diisocyanate (“TDI-80” manufactured by Mitsui Chemicals, Inc.) was added dropwise over 3 hours under the same temperature conditions. After the completion of the dropping, heating and stirring are continued, sampling is performed over time, and IR measurement is performed. It is confirmed that the absorption peak of the isocyanate group (around 2250 to 2280 cm ^-1 ) has disappeared, and the molecule has an oxazolidone ring structure. 431 g of epoxy resin (A-1) was obtained. The epoxy equivalent of the obtained epoxy resin (A-1) was 338 g / equivalent, the softening point measured based on JIS K7234 was 79 ° C, and the melt viscosity at 150 ° C measured by an ICI viscometer was 79 ° C. It was 6.3 dPa · s.

Production Example 2 Production of epoxy resin (A-2) having an oxazolidone ring structure in the molecule Bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation) in a four-necked flask equipped with a stirrer, thermometer, and condenser. Epoxy equivalent (188 g / equivalent) 376 g, bisphenol A 6.6 g, and tetrabutylphosphonium bromide (“TBP-BB” manufactured by Hokuko Chemical Industry Co., Ltd.) 0.08 g were charged, and the temperature was raised to 150 ° C. for 2 hours. Then, under the same temperature condition, 83 g of diphenylmethane diisocyanate (“Millionate MT-F” manufactured by Tosoh Corporation) was added over 3 hours. After the completion of the dropping, heating and stirring are continued, sampling is performed over time, and IR measurement is performed. It is confirmed that the absorption peak of the isocyanate group (around 2250 to 2280 cm ^-1 ) has disappeared, and the molecule has an oxazolidone ring structure. An epoxy resin (A-2) was obtained. The epoxy equivalent of the obtained epoxy resin (A-2) was 331 g / equivalent.

Production Example 3 Production of epoxy resin (A-3) having an oxazolidone ring structure in the molecule Bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Corporation) in a four-necked flask equipped with a stirrer, thermometer, and condenser. Epoxy equivalent 188 g / equivalent) 376 g and tetrabutylphosphonium bromide (“TBP-BB” manufactured by Hokuko Chemical Industry Co., Ltd.) 0.13 g were charged and heated to 170 ° C. Then, under the same temperature condition, 65 g of xylylene diisocyanate (“Takenate 500” manufactured by Mitsui Chemicals, Inc.) was added dropwise over 3 hours. After the completion of the dropping, heating and stirring are continued, sampling is performed over time, and IR measurement is performed. It is confirmed that the absorption peak of the isocyanate group (around 2250 to 2280 cm ^-1 ) has disappeared, and the molecule has an oxazolidone ring structure. An epoxy resin (A-3) was obtained. The epoxy equivalent of the obtained epoxy resin (A-3) was 291 g / equivalent.

Production Example 4 Production of epoxy resin (A-4) having an oxazolidone ring structure in the molecule A cycloring-containing epoxy resin (EPICLON HP manufactured by DIC Corporation) is placed in a four-necked flask equipped with a stirrer, a thermometer, and a condenser. -7200L ”epoxy equivalent 247g / equivalent) 494g and tetrabutylphosphonium bromide (“TBP-BB” manufactured by Hokuko Kagaku Kogyo Co., Ltd.) 0.17g were charged and heated to 160 ° C. Then, under the same temperature condition, 63 g of diphenylmethane diisocyanate (“Millionate MT-F” manufactured by Tosoh Corporation) was added over 3 hours. After the completion of the dropping, heating and stirring are continued, sampling is performed over time, and IR measurement is performed. It is confirmed that the absorption peak of the isocyanate group (around 2250 to 2280 cm ^-1 ) has disappeared, and the molecule has an oxazolidone ring structure. An epoxy resin (A-4) was obtained. The epoxy equivalent of the obtained epoxy resin (A-4) was 341 g / equivalent.

Example 1 Production of Acid Group-Containing (Meta) Acrylic Resin (1) 215 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 112 parts by mass of acrylic acid and 72 parts by mass of anhydrous methacrylic acid. , 4.3 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 301 parts by mass of diethylene glycol monomethyl ether acetate and 237 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (1) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (1) was 80 mgKOH / g. The GPC chart of the acid group-containing (meth) acrylate resin (1) is shown in FIG.

Example 2 Production of Acid Group-Containing (Meta) Acrylic Resin (2) 222 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.2 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 91 parts by mass of acrylic acid and 121 parts by mass of anhydrous methacrylic acid. , 4.4 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 286 parts by mass of diethylene glycol monomethyl ether acetate and 192 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (2) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (2) was 65 mgKOH / g.

Example 3 Production of Acid Group-Containing (Meta) Acrylic Resin (3) 229 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.3 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.5 parts by mass of methquinone as a thermal polymerization inhibitor, and then 69 parts by mass of acrylic acid and 171 parts by mass of anhydrous methacrylic acid. , 4.6 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 271 parts by mass of diethylene glycol monomethyl ether acetate and 146 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (3) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (3) was 50 mgKOH / g.

Example 4 Production of Acid Group-Containing (Meta) Acrylic Resin (4) 217 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.2 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 105 parts by mass of acrylic acid and 89 parts by mass of anhydrous methacrylic acid. , 4.3 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 261 parts by mass of diethylene glycol monomethyl ether acetate and 146 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (4) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (4) was 80 mgKOH / g.

Example 5 Production of Acid Group-Containing (Meta) Acrylic Resin (5) 224 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then add 85 parts by mass of acrylic acid and 134 parts by mass of anhydrous methacrylic acid. , 4.5 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 253 parts by mass of diethylene glycol monomethyl ether acetate and 118 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (5) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (5) was 65 mgKOH / g.

Example 6 Production of Acid Group-Containing (Meta) Acrylic Resin (6) 230 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -1) Dissolve 676 parts by mass, add 2.3 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.5 parts by mass of methquinone as a thermal polymerization inhibitor, and then 65 parts by mass of acrylic acid and 180 parts by mass of anhydrous methacrylic acid. , 4.6 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 246 parts by mass of diethylene glycol monomethyl ether acetate and 90 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (5) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (5) was 50 mgKOH / g.

Example 7 Production of Acid Group-Containing (Meta) Acrylic Resin (7) 212 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -2) Dissolve 662 parts by mass, add 2.1 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 110 parts by mass of acrylic acid and 75 parts by mass of anhydrous methacrylic acid. , 4.2 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 371 parts by mass of diethylene glycol monomethyl ether acetate and 234 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (7) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (7) was 80 mgKOH / g.

Example 8 Production of Acid Group-Containing (Meta) Acrylic Resin (8) 195 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -3) Dissolve 582 parts by mass, add 2.0 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 101 parts by mass of acrylic acid and 98 parts by mass of anhydrous methacrylic acid. , 3.9 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 340 parts by mass of diethylene glycol monomethyl ether acetate and 213 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (8) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (8) was 80 mgKOH / g.

Example 9 Production of Acid Group-Containing (Meta) Acrylic Resin (9) 219 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin (A) obtained above was placed. -4) Dissolve 682 parts by mass, add 2.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, and then 104 parts by mass of acrylic acid and 92 parts by mass of anhydrous methacrylic acid. , 4.4 parts by mass of triphenylphosphine was added, and the esterification reaction was carried out at 120 ° C. for 8 hours while blowing air. Then, 331 parts by mass of diethylene glycol monomethyl ether acetate and 144 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (9) solution. The solid acid value of the acid group-containing (meth) acrylate resin (9) was 80 mgKOH / g.

Comparative Production Example 1 Production of Acid Group-Containing (Meta) Acrylic Resin (1') An orthocresol novolac type epoxy was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler by placing 157 parts by mass of diethylene glycol monoethyl ether acetate. Dissolve 430 parts by mass of resin ("EPICLON N-695" made by DIC Co., Ltd., epoxy equivalent 215 g / equivalent), and add 1.6 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor. After the addition, 101 parts by mass of acrylic acid, 98 parts by mass of anhydrous methacrylic acid, and 3.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120 ° C. for 8 hours while blowing air. Next, 280 parts by mass of diethylene glycol monoethyl ether acetate and 182 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (1') solution. The solid acid value of the acid group-containing (meth) acrylate resin (1') was 85 mgKOH / g.

Examples 10-18 and Comparative Example 1
A curable resin composition was prepared according to the following procedure, and various evaluation tests were performed. The results are shown in Table 1.

◆ Evaluation of photosensitivity and drying control range ・ Preparation of curable resin composition 100 g of acid group-containing (meth) acrylate resin obtained at the above, "LumiCure DPA-600T" manufactured by Toa Synthetic Co., Ltd. (dipentaerythritol pentaacrylate and di) 10 g of a composition containing pentaerythritol hexaacrylate at a molar ratio of 40/60), 24 g of orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, and 2-methyl as a photopolymerization initiator. -1- (4-Methylthiophenyl) -2-morpholinopropane-1-one ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 5 g, 2-ethyl-4-methylimidazole 0.5 g as a curing accelerator, organic 13 g of diethylene glycol monoethyl ether acetate as a solvent and 0.65 g of phthalocyanine green as a pigment were blended and kneaded with a roll mill to obtain a curable resin composition.

-Measurement of photosensitivity The curable resin composition was applied onto a glass substrate with a 50 μm applicator and dried at 80 ° C. for 30 minutes. Next, Kodak's step tablet No. Ultraviolet rays of 500 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.

-Measurement of Drying Control Width A curable resin composition was applied onto a glass substrate with a 50 μm applicator, and samples having different drying times at 80 ° C. were prepared in 10-minute increments from a drying time of 30 minutes to 100 minutes. These were developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds, and the drying time of the sample at 80 ° C., which did not leave a residue, was evaluated as the drying control range. The longer the drying control width, the better the alkaline developability.

◆ Evaluation of heat resistance, elongation, and stress of cured product ・ Preparation of curable resin composition 100 g of acid group-containing (meth) acrylate resin obtained at the above, orthocresol novolac type epoxy resin (manufactured by DIC Co., Ltd.) as a curing agent EPICLON N-680 ”) 24 g, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 5 g, organic A curable resin composition was obtained by blending 13 g of diethylene glycol monoethyl ether acetate as a solvent.

-Preparation of cured product The curable resin composition was applied onto a glass substrate with a 50 μm applicator 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, the cured product was heated at 160 ° C. for 1 hour to peel off the cured product from the glass substrate to obtain a cured product.

-Evaluation of heat resistance of the cured product A 6 mm x 40 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, temperature rise rate 3). The heat resistance was evaluated using the temperature at which the elastic modulus change was maximum (tanδ change rate was the largest) as the glass transition temperature (Tg) using ° C./min.

-Measurement of elongation and stress of the cured product A 10 mm x 80 mm test piece is cut out from the cured product, and a tensile test of the test piece is performed under the following conditions using the precision universal testing machine Autograph "AG-IS" manufactured by Shimadzu Corporation. gone. The elongation (%) until the test piece broke and the maximum stress (MPa) were measured.
Measurement conditions: temperature 23 ° C, humidity 50%, distance between marked lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm / min

◆ Thermal cycle test evaluation of cured product / Preparation of curable resin composition 100 g of acid group-containing (meth) acrylate resin obtained at the above, "LumiCure DPA-600T" manufactured by Toa Synthetic Co., Ltd. (dipentaerythritol pentaacrylate and dipenta) 10 g of a composition containing erythritol hexaacrylate at a molar ratio of 40/60), 24 g of an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, and 2-methyl- as a photopolymerization initiator. A curable resin composition is prepared by blending 5 g of 1- (4-methylthiophenyl) -2-morpholinopropane-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals) and 13 g of diethylene glycol monoethyl ether acetate as an organic solvent. Obtained.

-Preparation of cured product The curable resin composition was applied onto an aluminum substrate with a 50 μm applicator 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 product.

-Thermal cycle test For the cured product formed on the aluminum substrate, a thermal cycle test in which the following 1 to 3 are repeated is performed for 200 cycles, and the cured product without cracks is evaluated as A, and the cured product with cracks is evaluated as B. bottom.
1: 150 ° C, 30 minutes → 2: 25 ° C, 1 minute → 3: -40 ° C, 30 minutes

Claims (7)

An acid containing an epoxy resin (A) having an oxazolidone ring structure in the molecule, an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid anhydride (D) as essential reaction raw materials. A group-containing (meth) acrylate resin
The epoxy resin (A) is a reaction product containing an epoxy resin (a1), which is a polyglycidyl etherified product of a phenolic hydroxyl group-containing compound, and a polyisocyanate compound (a2) as essential reaction raw materials.
The phenolic hydroxyl group-containing compound is bisphenol A.
The polyisocyanate compound (a2) is tolylene diisocyanate or diphenylmethane diisocyanate .
The molar ratio [(B) / (C)] of the unsaturated monocarboxylic acid (B) to the unsaturated monocarboxylic acid anhydride (C) is {(105 / 72.06) / (89/154. 16)} to 3.5, an acid group-containing acrylate resin. The acid group-containing (meth) acrylate resin according to claim 1 , wherein the epoxy equivalent of the epoxy resin (A) is in the range of 180 to 331 g / equivalent. A curable resin composition containing the acid group-containing (meth) acrylate resin according to claim 1 or 2 , and a photopolymerization initiator. A cured product of the curable resin composition according to claim 3 . An insulating material comprising the curable resin composition according to claim 3 . A resin material for a solder resist comprising the curable resin composition according to claim 3 . A resist member made of the resin material for solder resist according to claim 6 .

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