JP2020117613A - Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist and resist member - Google Patents

Abstract

To provide an acid group-containing (meth)acrylate resin which has excellent alkali developability and high photo sensitivity and excellent elasticity and heat resistance in a cured product, a curable resin composition containing the same, a cured product formed of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.SOLUTION: An acid group-containing (meth)acrylate resin contains an aromatic compound (A) having a hydroxyl group, epihalohydrin (B), an unsaturated monobasic acid (C) and a polybasic anhydride (D) as essential reaction raw materials, in which the aromatic compound (A) has at least two hydroxyl groups as substituents on the aromatic group, and at least two hydroxyl groups of the aromatic compound (A) are positioned at the ortho position.SELECTED DRAWING: Figure 1

Description

The present invention has an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and having excellent elasticity and heat resistance in a cured product, a curable resin composition containing the same, and the curability described above. The present invention relates to a cured product made of a resin composition, an insulating material, a resin material for solder resist, and a resist member.

In recent years, an acid group-containing epoxy acrylate resin obtained by acrylate conversion of an epoxy resin with acrylic acid and then reaction with an acid anhydride is widely used as a resin material for a solder resist for a printed wiring board. The required performance of resin material for solder resist is that it cures with a small amount of exposure, has excellent alkali developability, and has excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in the cured product. There are various things.

As a conventionally known resin material for solder resist, active energy ray curability obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride Although a resin is known (for example, refer to Patent Document 1 below), although the cured product has excellent heat resistance, it does not satisfy the ever-increasing required properties in elasticity, and it is difficult to meet recent market demands. It wasn't enough.

Therefore, a material having excellent alkali developability and high photosensitivity and being further excellent in elasticity and heat resistance in a cured product has been demanded.

JP-A-61-243869

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

As a result of intensive studies to solve the above problems, the present inventors have found that an aromatic group-containing aromatic compound, an epihalohydrin, and an acid group-containing (meth)acrylate resin as an essential reaction raw material of a polybasic acid anhydride. The aromatic compound has at least two hydroxyl groups as a substituent on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound are located in the ortho positions with respect to each other. The present invention has been completed by finding that the above problems can be solved by using an acid group-containing (meth)acrylate resin.

That is, the present invention uses an aromatic compound (A) having a hydroxyl group, epihalohydrin (B), unsaturated monobasic acid (C), and polybasic acid anhydride (D) as essential reaction raw materials. An acid group-containing (meth)acrylate resin, wherein the aromatic compound (A) has at least two hydroxyl groups as substituents on an aromatic ring, and among the hydroxyl groups of the aromatic compound (A) An acid group-containing (meth)acrylate resin characterized in that at least two of them are positioned in ortho positions with each other, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material, and a solder resist. And a resist member.

The acid group-containing (meth)acrylate resin of the present invention has excellent alkali developability and high photosensitivity, and also has excellent elasticity and heat resistance in a cured product, and therefore an insulating material, a resin material for solder resist and a resist. It can be suitably used for members.

3 is a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 1. ^{13 is} a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 2.

The acid group-containing (meth)acrylate resin of the present invention comprises an aromatic compound (A) having a hydroxyl group, epihalohydrin (B), unsaturated monobasic acid (C), polybasic acid anhydride (D), Is used as an essential reaction raw material.

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The aromatic compound (A) having a hydroxyl group has at least two hydroxyl groups as a substituent on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are in ortho positions with respect to each other. It is located.

Examples of the aromatic compound (A) include compounds represented by the following structural formulas (1-1) to (1-7).

In the structural formulas (1-1) to (1-7), each R ¹ independently represents a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen. Any of the atoms, R ² is independently a hydrogen atom or a methyl group. Further, q is 0 or an integer of 1 or more. The position of the substituent R ¹ on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formulas (1-2) and (1-3), the substituent R ¹ may be substituted on any ring. In the structural formulas (1-4) to (1-7), it may be substituted on any ring of the benzene ring present in one molecule, and the benzene ring in one molecule is shown. It is shown that the number of the above substituents is q+2.

Among the compounds represented by the structural formulas (1-1) to (1-7), it is possible to form a cured product having excellent alkali developability and high photosensitivity, and having excellent elasticity and heat resistance. Since an acid group-containing (meth)acrylate resin is obtained, dihydroxybenzene in which q is 0 in the structural formula (1-1) and trihydroxybenzene in which q is 1 in the structural formula (1-1) are preferable. More specifically, 1,2-dihydroxybenzene having a hydroxyl group at the 1-position and 2-position (hereinafter sometimes referred to as "catechol"), 1 having a hydroxyl group at the 1-position, 2-position and 3-position , 2,3-trihydroxybenzene (hereinafter sometimes referred to as "pyrogallol") or 1,2,4-trihydroxybenzene having a hydroxyl group at the 1-position, 2-position and 4-position, and more preferred is pyrogallol. Alternatively, 1,2,4-trihydroxybenzene is particularly preferable.

In addition, as the aromatic compound (A), a novolac type phenol resin using one or more compounds represented by the structural formulas (1-1) to (1-7) as a reaction raw material is also used. be able to.

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

Examples of the epihalohydrin (B) include epichlorohydrin and epibromohydrin. These epihalohydrins (B) can be used alone or in combination of two or more kinds. Among these, epichlorohydrin is preferable from the viewpoint of easily controlling the reaction.

The unsaturated monobasic acid (C) means a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like. Examples of the unsaturated monobasic acid (C) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid and β-furfurylacrylic acid. Further, esterified products of unsaturated monobasic acids, acid halides, acid anhydrides and the like can also be used. These unsaturated monobasic acids (C) can be used alone or in combination of two or more kinds. In addition, among these, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elasticity and heat resistance is obtained, acrylic acid Methacrylic acid is preferred.

Examples of the polybasic acid anhydride (D) include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnazic anhydride. Acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like can be mentioned. These polybasic acid anhydrides can be used alone or in combination of two or more kinds. Further, among these, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elasticity and heat resistance is obtained, tetrahydroanhydride Phthalic acid and succinic anhydride are preferred.

The method for producing the acid group-containing (meth)acrylate resin of the present invention is not particularly limited and may be produced by any method. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction can be easily controlled, the aromatic compound (A) is reacted with the epihalohydrin (B) (step 1) and the intermediate reaction product obtained in step 1 (hereinafter, referred to as “epoxy”). Resin (I)") is reacted with the unsaturated monobasic acid (C) (step 2), and the product of step 2 is reacted with the polybasic acid anhydride (D). It is preferable to manufacture by the method of (step 3).

The step 1 is a reaction between the aromatic compound (A) and the epihalohydrin (B). From the viewpoint of the yield of the intended intermediate reaction product, that is, the epoxy resin (I), the reaction is carried out in the step 1a of reacting in the presence of a quaternary onium salt and/or a basic compound, and the step 1a. It is preferable to have the step 1b of ring-closing the obtained reaction product in the presence of a basic compound. Here, when the aromatic compound (A) is reacted with the epihalohydrin (B), a reaction in which the hydroxyl groups of the aromatic compound (A) become glycidyl ether groups respectively proceeds. At the same time, oligomerization proceeds due to the reaction between the glycidyl ether group and the unreacted hydroxyl group, or when epihalohydrin undergoes an addition reaction, various reaction products can be obtained depending on various reaction conditions such as the ring closing step thereof. However, these will be included as by-products. These by-products can be removed from the reaction system and the reaction product, but the step of taking out only a single component (for example, diglycidyl ether in the case of catechol, triglycidyl ether in the case of pyrogallol) is Since this is a complicated process industrially and is directly linked to the product cost, it is often used as an epoxy resin in a state of containing by-products within a range that does not adversely affect the obtained cured product.

Further, the single component (for example, diglycidyl ether in the case of catechol, triglycidyl ether in the case of pyrogallol) has high crystallinity, and the acid group-containing (meth)acrylate resin of the present invention, or a curable resin composition There may be handling problems when doing. From these viewpoints, it is preferable to use an epoxy resin containing a certain amount of the by-products as described above from the viewpoint of handling or the elasticity and heat resistance of the obtained cured product.

From such a viewpoint, the epoxy resin (I) obtained in the step 1 is a cyclic compound (a1) having a cyclic structure containing two adjacent oxygen atoms derived from the aromatic compound (A) as constituent atoms. It is preferable to include.

Examples of the quaternary onium salt include a quaternary ammonium salt and a quaternary phosphonium salt. These quaternary onium salts can be used alone or in combination of two or more kinds.

Examples of the quaternary ammonium salt include tetramethylammonium cation, methyltriethylammonium cation, tetraethylammonium cation, tributylmethylammonium cation, tetrabutylammonium cation, phenyltrimethylammonium cation, benzyltrimethylammonium cation, phenyltriethylammonium cation, Examples thereof include chloride salts of benzyltriethylammonium cation, benzyltributylammonium cation, tetramethylammonium cation, trimethylpropylammonium cation, tetraethylammonium cation, and bromide salts of tetrabutylammonium cation.

Examples of the quaternary phosphonium salt include bromine of tetraethylphosphonium cation, tetrabutylphosphonium cation, methyltriphenylphosphonium cation, tetraphenylphosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, and benzyltriphenylphosphonium cation. Compound salts and the like can be mentioned.

Among these quaternary onium salts, chloride salts of tetramethylammonium cation, benzyltrimethylammonium cation, benzyltriethylammonium cation, and bromide salts of tetrabutylammonium cation are preferable.

The amount of the quaternary onium salt used is such that the total mass of the aromatic compound (A) and the epihalohydrin (B) can be reduced from the viewpoint that the reaction proceeds favorably and the residue in the product can be reduced. The amount is preferably 0.15 to 5 parts by mass, more preferably 0.18 to 3 parts by mass, relative to 100 parts by mass.

Examples of the basic compound include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and the like. These basic compounds may be used alone or in combination of two or more. Of these, potassium hydroxide and sodium hydroxide are preferable.

Further, the addition amount of the basic compound is 0.01 with respect to 1 mol of the hydroxyl group contained in the aromatic compound (A), from the viewpoint that the reaction proceeds favorably and the residue in the product can be reduced. The amount is preferably 0.3 mol, more preferably 0.02 to 0.2 mol.

The quaternary onium and the basic compound may be used alone or in combination of two or more kinds.

The reaction in the step 1a is a reaction in which epihalohydrin is mainly added to the hydroxyl group of the aromatic compound. The reaction temperature in step 1a is preferably 20 to 80°C, more preferably 40 to 75°C. The reaction time of the step 1a is preferably 0.5 hours or more, more preferably 1 to 50 hours.

Further, the reaction of the step 1a may be carried out in an organic solvent, if necessary. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol mono Glycol ether solvents such as alkyl ether and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dimethyl sulfone and dimethyl sulfoxide. These organic solvents may be used alone or in combination of two or more.

When the organic solvent is used, the amount thereof used is preferably in the range of 5 to 150 parts by mass, more preferably in the range of 7.5 to 100 parts by mass, relative to 100 parts by mass of epihalohydrin (B). It is more preferably in the range of 10 to 50 parts by mass.

The step 1b is a step of ring-closing the reaction product obtained in the step 1a in the presence of a basic compound, and the reaction product obtained in the step 1a as it is or unreacted epihalohydrin present in the system. Alternatively, step 1b may be performed after removing a part or all of the reaction solvent.

As the basic compound used in the step 1b, the same basic compounds as described above can be used, and the basic compounds can be used alone or in combination of two or more kinds.

The amount of the basic compound used is not particularly limited, but is preferably 0.8 to 1.5 mol, and 0.9 to 1.1 mol, relative to 1 mol of the hydroxyl group of the aromatic compound (A). It is more preferably 3 mol. It is preferable that the amount of the basic compound added is 0.8 mol or more because the ring-closing reaction of step 1b can appropriately proceed. On the other hand, it is preferable that the amount of the basic compound added is 1.5 mol or less, because side reactions can be prevented or suppressed. When the basic compound is used in step 1a, it is preferable to use the above-mentioned amount including the amount used in step 1a.

The reaction temperature in step 1b is preferably 30 to 120°C, more preferably 25 to 80°C. The reaction time is preferably 0.5 to 4 hours, more preferably 1 to 3 hours.

After performing the step 1b, the reaction product obtained can be purified, if necessary.

The cyclic compound (a1) is not particularly limited, and examples thereof include compounds represented by the following structural formula.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen. Is an atom, m is 0 or an integer of 1 to 4, and n is 0 or an integer of 1 to 3.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen. Is an atom, and m is 0 or an integer of 1 to 6.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen. Is an atom, and m is 0 or an integer of 1-8.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen. R ² is independently a hydrogen atom or a methyl group, and m is 0 or an integer of 1 to 8.

The cyclic compound (a1) may be contained alone or in combination of two or more kinds.

The content of the cyclic compound (a1) is excellent in solvent solubility, and since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent elasticity and heat resistance is obtained, the aromatic compound ( A) With respect to 100 g, it is preferably 0.040 to 0.115 mol, particularly preferably 0.050 to 0.115 mol, and most preferably 0.070 to 0.115 mol. Further, when the content of the cyclic compound is within this range, the effect of suppressing crystallization is enhanced. In addition, in this specification, the "content of the cyclic compound" is a value measured by the method described in Examples. When two or more cyclic compounds are contained, the “content of cyclic compound” is the total content thereof.

The content of the cyclic compound (a1) can be controlled by appropriately adjusting the charging ratio of the raw materials in the reaction with the epihalohydrin (B) or the ring closure step, the catalyst, the solvent species and the reaction conditions.

The step 2 is a reaction between the epoxy resin (I) obtained in the step 1 and the unsaturated monobasic acid (C). The reaction ratio is preferably such that the number of moles of the acid group of the unsaturated monobasic acid (C) is 0.7 to 1.2 with respect to 1 mole of the epoxy group of the epoxy resin (I), The range of 0.9 to 1.1 is more preferable. The reaction of the step 2 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C. In addition, the reaction of the step 2 may be carried out in an organic solvent, if necessary.

Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole and 2-ethyl. Examples include imidazole compounds such as -4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These esterification catalysts can be used alone or in combination of two or more kinds.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency becomes good.

The step 3 is a reaction between the product of the step 2 and the polybasic acid anhydride (D). The reaction is mainly to react the hydroxyl group in the product obtained in the step 2 with the polybasic acid anhydride (D). In the product of the step 2, for example, a hydroxyl group generated in the reaction of the step 2 is present. The reaction ratio of the polybasic acid anhydride (D) is preferably adjusted so that the acid value of the product (meth)acrylate resin containing an acid group is about 60 to 120 mgKOH/g. The reaction of step 3 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C. When step 2 and step 3 are carried out continuously, the esterification catalyst may not be added or may be added appropriately. Further, the reaction may be carried out in an organic solvent, if necessary. The esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds. In the present invention, the acid value 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 its molecular structure, it can be used as a curable resin composition by adding a photopolymerization initiator, for example. You can

As the photopolymerization initiator, an appropriate one may be selected and used depending on the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino). 2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-. Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.

Examples of commercial products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100". Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA". , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" ( Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop), "Runtecure-1104" (Runtec) Manufactured by the company) and the like. These photopolymerization initiators can be used alone or in combination of two or more kinds.

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

The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth)acrylate resin described above. Examples of the other resin component include a resin (E) having an acid group and a polymerizable unsaturated bond, various (meth)acrylate monomers, and the like.

The resin (E) having an acid group and a polymerizable unsaturated bond may be any as long as it has an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond Epoxy resin having, urethane resin having acid group and polymerizable unsaturated bond, acrylic resin having acid group and polymerizable unsaturated bond, amide imide resin having acid group and polymerizable unsaturated bond, acid group and polymerizable unsaturated Examples thereof include an acrylamide resin having a bond.

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

Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include, for example, an epoxy resin, an unsaturated monobasic acid, and an acid group-containing epoxy (meth)acrylate resin that uses polybasic acid anhydride as an essential reaction raw material. , Epoxy resin, unsaturated monobasic acid, polybasic acid anhydride, and acid group- and urethane group-containing epoxy (meth)acrylate resin using polyisocyanate compound as a reaction raw material, epoxy resin, unsaturated monobasic acid, polybasic An acid group, a polyisocyanate compound, and an epoxy group-containing urethane (meth)acrylate resin containing a hydroxyl group-containing (meth)acrylate compound as a reaction raw material may be used.

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, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, and trihydroxybenzene epoxy resins. These epoxy resins can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as the above-mentioned unsaturated monobasic acid (C), and the unsaturated monobasic acid may be used alone or in combination of two or more kinds. it can.

As the polybasic acid anhydride, the same as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.

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

[In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ^{2 s} are each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural site represented by the structural formula (2) and the methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15. ]

Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate. , Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate Examples thereof include acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Further, 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 each of the various hydroxyl group-containing (meth)acrylate compounds ( It is also possible to use a modified poly)oxyalkylene or a modified lactone in which a (poly)lactone structure is introduced into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds. 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 an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the epoxy resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

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

Examples of the urethane resin having an acid group and a polymerizable unsaturated bond include, for example, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and optionally a polybasic acid anhydride, the carboxyl group. Those obtained by reacting with a polyol compound other than the containing 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 And the like.

As the polyisocyanate compound, the same polyisocyanate compound as described above can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

The hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound, and the hydroxyl group-containing (meth)acrylate compound may be used alone or in combination of two or more kinds. You can also do it.

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 kinds.

As the polybasic acid anhydride, the same as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.

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 chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds. Introduced (poly)oxyalkylene modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structures of the various polyol compounds described above. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.

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

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

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, and 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 obtained by Examples thereof include products and products obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

The acrylic resin intermediate may be obtained by copolymerizing, in addition to the (meth)acrylate compound (α), other polymerizable unsaturated group-containing compound, if necessary. The other polymerizable unsaturated group-containing compound is, for example, (meth)acrylate 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, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples thereof include aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene and chlorostyrene. These may 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 contained in the (meth)acrylate compound (α), but from the viewpoint of reactivity, it is the following combination. Is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), an isocyanate group-containing (meth)acrylate is preferably used 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), a carboxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

As the polybasic acid anhydride, the same polybasic acid anhydride (D) as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. ..

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

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

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 at least one reactive functional group 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. To be The compound having a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a hydroxyl group-containing (meth)acrylate compound or a (meth)acryloyl group-containing epoxy compound, it is preferable to have an acid anhydride group, and both an acid group and an acid anhydride group It is more preferable to have The acid value of the solid content of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g when measured 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 ring-opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH/g.

Examples of the amide-imide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as a reaction raw material.

As the polyisocyanate compound, the same polyisocyanate compound as described above can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

As the polybasic acid anhydride, the same as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.

In addition to the polyisocyanate compound and the polybasic acid anhydride, a polybasic acid can be used as a reaction raw material in combination with the amide-imide resin, if necessary.

As the polybasic acid, any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule. 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. To be 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 kinds.

The hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound, and the hydroxyl group-containing (meth)acrylate compound may be used alone or in combination of two or more kinds. You can also do it.

As the epoxy group-containing (meth)acrylate compound, other specific structures are not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and various 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, dihydroxynaphthalene diglycidyl ether, 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 it facilitates the control of the reaction, has excellent alkali developability and high photosensitivity, and has excellent elasticity and heat resistance. A glycidyl group-containing (meth)acrylate monomer is preferable because an acid group-containing (meth)acrylate resin capable of forming a cured product is obtained. The molecular weight of the glycidyl group-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, 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 amide-imide resin having an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the amide-imide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include, for example, a phenolic hydroxyl group-containing compound, an alkylene oxide and/or an alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, and a polybasic acid anhydride. And an unsaturated monobasic acid, if necessary, are reacted with each other.

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

In the structural formulas (3-1) to (3-4), R ¹ is any 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 each independently a hydrogen atom or a methyl group. Further, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0. q is an integer of 2 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and the structural formula ( In 3-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (3-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be substituted, and 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 essential. Of the reaction product used as the reaction raw material, 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) A reaction product as a raw material can also be used. In addition, 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 groups in the molecule It is also possible to use a novolac-type phenol resin as a reaction raw material.

[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 0 or an integer of 1 to 4. In formulas (x-2), (x-3) and (x-5), Z is any of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group. In formula (x-5), Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and j is an integer of 1 to 4. ]

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

In the structural formulas (4-1) to (4-4), R ⁴ is any 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 each independently a hydrogen atom or a methyl group. Further, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of structural formula (4-2), the substituent may be substituted on any ring, and In 4-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (4-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be replaced.

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

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

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elasticity and heat resistance is obtained. .. The alkylene oxides may be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elasticity and heat resistance is obtained. .. The alkylene carbonates may 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, N-methoxyethyl(meth)acrylamide. , N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide and the like. The N-alkoxyalkyl (meth)acrylamide compounds may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.

As the unsaturated monobasic acid, the same as the above-mentioned unsaturated monobasic acid (C) can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more kinds. it can.

The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the acrylamide resin having an acid group and a polymerizable unsaturated bond 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 organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

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

The amount of the resin (E) having an acid group and a polymerizable unsaturated bond used is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the acid group-containing (meth)acrylate resin of the present invention.

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2 -Aliphatic mono(meth)acrylate compounds such as ethylhexyl(meth)acrylate and octyl(meth)acrylate; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate, etc. Acrylate compounds; Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. (Meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxy in the molecular structure of the various mono(meth)acrylate monomers A (poly)oxyalkylene-modified mono(meth)acrylate compound having a polyoxyalkylene chain such as a tetramethylene chain introduced therein; a lactone-modified mono compound having a (poly)lactone structure introduced into the molecular structure of each of the various mono(meth)acrylate compounds (Meth)acrylate compound; aliphatic such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Di(meth)acrylate compound; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane di Alicyclic di(meth)acrylate compounds such as methanol di(meth)acrylate; biphenol di(meth)acrylate, bisphe Aromatic di(meth)acrylate compounds such as nordi(meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene in the molecular structures of the various di(meth)acrylate compounds. A polyoxyalkylene-modified di(meth)acrylate compound having a (poly)oxyalkylene chain such as a chain introduced thereinto; a lactone-modified di(meth) having a (poly)lactone structure introduced into the molecular structure of each of the various di(meth)acrylate compounds ) Acrylate compound; Aliphatic tri(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyethylene chain in the molecular structure of the aliphatic tri(meth)acrylate compound. A (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a (poly)oxypropylene chain or a (poly)oxytetramethylene chain; a molecule of the aliphatic tri(meth)acrylate compound Lactone-modified tri(meth)acrylate compound having a (poly)lactone structure introduced therein; tetra- or higher-functional such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain or the like (poly) in the molecular structure of the aliphatic poly(meth)acrylate compound A tetra- or higher functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced; a tetra-functional or higher functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples thereof include modified poly(meth)acrylate compounds. The various (meth)acrylate monomers may be used alone or in combination of two or more.

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

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin. 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, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, and trihydroxybenzene epoxy resins. These epoxy resins can be used alone or in combination of two or more kinds. In addition, among these, a curable resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elasticity and heat resistance is obtained, and therefore, a phenol novolac epoxy resin , Cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin and other novolac type epoxy resins are preferable, and the softening point is Those in the range of 20 to 120° C. are particularly preferable.

The curing accelerator is for promoting a curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, Examples thereof include amine complex salts. These curing accelerators can be used alone or in combination of two or more kinds. Further, the addition amount of the curing accelerator is preferably within a range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

As the organic solvent, those similar to the above-mentioned organic solvents can be used, and these organic solvents can be used alone or in combination of two or more kinds.

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

As a source of ultraviolet rays, ultraviolet lamps are generally used in terms of practicality and economy. Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.

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 within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.

Irradiation with the active energy ray may be performed in one step or in two or more steps.

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

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

The resist member of the present invention is, for example, a photomask on which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100°C. Through exposure with an active energy ray, the unexposed area is developed with an alkaline aqueous solution, and then heat-cured 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 described in more detail with reference to Examples and Comparative Examples.

In this example, the weight average molecular weight (Mw) was measured by the gel permeation chromatography (GPC) method under the following conditions.

<GPC measurement conditions>
Measuring device: Tosoh Corporation "HLC-8220 GPC",
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G4000HXL”
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 rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 Model II Version 4.10”.

(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
"F-10" manufactured by Tosoh Corporation
Tosoh Corporation "F-20"
"F-40" manufactured by Tosoh Corporation
Tosoh Corporation "F-80"
Tosoh Corporation "F-128"
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content, filtered through a microfilter (50 μl).

In this example, ¹³ C-NMR was measured under the following conditions.

< ¹³ C-NMR measurement conditions>
Device: JEM-ECA500 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30° pulse Sample concentration: 30 wt%
Number of times of integration: 4000 times Standard of chemical shift: Peak of dimethyl sulfoxide: 39.5 ppm

In the examples of the present application, the content X (mol) of the cyclic compound in the epoxy resin was calculated by the following formula.

In the above formula, X is the cyclic compound content (mol) per 100 g of the epoxy resin, (A) is the cyclic compound (mol) per 1 mol of the aromatic ring, and (B) is the epoxy group (1) per the aromatic ring ( mol) and (C) is an epoxy equivalent (g/equivalent).

(Synthesis Example 1: Synthesis of epoxy resin (1))
Process 1a
165 g (1.50 mol) of catechol and 1388 g (15 mol) of epichlorohydrin were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introducing tube, and a stirrer, and the temperature was raised to 50°C. Then, 11.2 g (0.06 mol) of benzyltrimethylammonium chloride was added, and the mixture was stirred at 50° C. for 15 hours.

Process 1b
1000 mL of distilled water was poured into the reaction solution obtained in the step 1a and stirred, and the upper layer was removed after standing. 318 g of 48% sodium hydroxide aqueous solution was added dropwise over 2.5 hours, and the mixture was stirred for 1 hour.

400 mL of distilled water was poured into the obtained solution, and the solution was left to stand. The lower layer saline was removed, and epichlorohydrin was distilled and recovered at 120°C. Then, 566 g of methyl isobutyl ketone (hereinafter, abbreviated as “MIBK”) and 167 g of water were sequentially added, and the mixture was washed at 80° C. with water. After removing the lower layer of washing water, dehydration and filtration were performed, and MIBK was desolvated at 150° C. to produce an epoxy resin (1). When the obtained epoxy resin was visually observed, it was liquid.

The epoxy equivalent of this epoxy resin (1) was 138 g/equivalent, and the viscosity at 25° C. was 190 mPa·s. In the present invention, the epoxy equivalent is a value measured according to JIS K 7236:2009, and the viscosity is a value measured by "TV-22" manufactured by Toki Sangyo Co., Ltd.

In addition, the cyclic compound content (mol) per 100 g of this epoxy resin (1) is the aromatic ring corresponding to the ipso (ipso) position of catechol around 130 to 150 ppm in the above formula (A) in ¹³ C-NMR measurement. And the peak derived from the cyclic compound around 60 ppm is calculated by the integral ratio, and (B) is a peak derived from the aromatic ring corresponding to the ipso (ipso) position of catechol around 130 to 150 ppm, and 50 ppm. It was calculated from the integral ratio of peaks derived from the nearby epoxy groups. As a result, the content of the cyclic compound was 0.071 mol/100 g. The result of ¹³ C-NMR measurement [chart] is shown in FIG. 1.

(Synthesis Example 2: Synthesis of epoxy resin (2))
Epoxy resin in the same manner as in Synthesis Example 1 except that 165 g (1.50 mol) of catechol in Synthesis Example 1 was changed to 126 g (1.00 mol) of pyrogallol, 566 g of MIBK was changed to 500 g, and 167 g of water was changed to 147 g. (2) was produced. When the obtained epoxy resin was visually observed, it was liquid. The epoxy equivalent of this epoxy resin (2) was 128 g/equivalent, and the viscosity at 25° C. was 3100 mPa.s. It was s. The cyclic compound content per 100 g of this epoxy resin (2) was 0.086 mol/100 g. The result of ¹³ C-NMR measurement [chart] is shown in FIG. 2.

(Synthesis Example 3: Synthesis of epoxy resin (3))
An epoxy resin was produced in conformity with the Experimental section described in Non-Patent Document (Tetrahedron, 2013, 69, 1345-1353). A flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introducing tube, and a stirrer was charged with 126 g (1.00 mol) of 1,2,3-trihydroxybenzene and 1111 g (12 mol) of epichlorohydrin and placed at 100°C. It was heated up to. 11.4 g (0.05 mol) of benzyltriethylammonium chloride was added thereto, and the mixture was heated and stirred at 100° C. for 1 hour. Then, the temperature was lowered to 30° C., 780 g of 20% NaOH aqueous solution was added dropwise thereto over 2.5 hours, and the mixture was further stirred for 1 hour and then allowed to stand. Thereafter, the same operation as in Synthesis Example 1 was performed to produce an epoxy resin (3). When the obtained epoxy resin was visually observed, it was liquid.

The epoxy equivalent of this epoxy resin (3) was 184 g/equivalent, and the viscosity at 25° C. was 53300 mPa·s. The cyclic compound content per 100 g of this epoxy resin (3) was 0.120 mol/100 g.

(Synthesis Example 4: Synthesis of epoxy resin (4))
Epoxy resin (4) was produced by refining the epoxy resin produced in Synthesis Example 3 by recrystallization using MIBK as a good solvent and hexane as a poor solvent. The epoxy equivalent of this epoxy resin (4) was 107 g/equivalent. The cyclic compound content per 100 g of this epoxy resin (4) was 0.039 mol/100 g. The viscosity could not be measured because the obtained epoxy resin (4) was solid.

(Example 1: Preparation of acid group-containing acrylate resin (1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 53 parts by mass of diethylene glycol monomethyl ether acetate, 138 parts by mass of epoxy resin (1), 0.2 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methoquinone, and acrylic. 73 parts by mass of acid and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 100° C. for 20 hours while blowing air. Next, 56 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 3 hours to obtain the target acid group-containing acrylate resin (1). The acid value of the solid content of this acid group-containing acrylate resin (1) was 80 mgKOH/g, and the weight average molecular weight was 650.

(Example 2: Preparation of acid group-containing acrylate resin (2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 50 parts by mass of diethylene glycol monomethyl ether acetate, 128 parts by mass of epoxy resin (2), 0.2 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methquinone, acryl. 73 parts by mass of acid and 1.0 part by mass of triphenylphosphine were added and reacted at 100° C. for 20 hours while blowing air. Next, 53 parts by mass of tetrahydrophthalic anhydride and 35 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (2). The acid value of the solid content of the acid group-containing acrylate resin (2) was 80 mgKOH/g, and the weight average molecular weight was 930.

(Example 3: Preparation of acid group-containing acrylate resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 50 parts by mass of diethylene glycol monomethyl ether acetate, 128 parts by mass of epoxy resin (2), 0.2 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methquinone, acryl. 73 parts by mass of acid and 1.0 part by mass of triphenylphosphine were added and reacted at 100° C. for 20 hours while blowing air. Next, 32 parts by mass of succinic anhydride and 28 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (3). The acid value of the solid content of the acid group-containing acrylate resin (3) was 80 mgKOH/g, and the weight average molecular weight was 860.

(Example 4: Preparation of acid group-containing acrylate resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 64 parts by mass of diethylene glycol monomethyl ether acetate, 184 parts by mass of epoxy resin (3), 0.3 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methoquinone, and acrylic. 73 parts by mass of acid and 1.3 parts by mass of triphenylphosphine were added and reacted at 100° C. for 20 hours while blowing air. Then, 68 parts by mass of tetrahydrophthalic anhydride and 62 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (4). The acid value of the solid content of the acid group-containing acrylate resin (4) was 80 mgKOH/g, and the weight average molecular weight was 1010.

(Example 5: Preparation of acid group-containing acrylate resin (5))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 45 parts by mass of diethylene glycol monomethyl ether acetate, 107 parts by mass of epoxy resin (4), 0.2 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methoquinone, acryl. 73 parts by mass of acid and 0.9 parts by mass of triphenylphosphine were added and reacted at 100° C. for 20 hours while blowing air. Next, 48 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (5). The acid value of the solid content of the acid group-containing acrylate resin (5) was 80 mgKOH/g, and the weight average molecular weight was 910.

(Comparative Example 1: Preparation of acid group-containing acrylate resin (C1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, resorcin-type epoxy resin (CVC Thermoset Specialties Co., Ltd. "ERISYS RDGE-H", epoxy equivalent 129 g/equivalent) 129 parts by mass, dibutyl hydroxytoluene 0.2 parts by mass. Parts, metoquinone 0.1 parts by mass, acrylic acid 73 parts by mass and triphenylphosphine 1.0 part by mass were added, and the mixture was reacted at 100° C. for 20 hours while blowing air. Next, 53 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (C1). The acid value of the solid content of this acid group-containing acrylate resin (C1) was 80 mgKOH/g, and the weight average molecular weight was 1140.

(Comparative Example 2: Preparation of acid group-containing acrylate resin (C2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, phenyl glycidyl ether (“Denacol EX-141” manufactured by Nagase Chemmutex Co., Ltd., epoxy equivalent 151 g/equivalent) 151 parts by mass, dibutylhydroxytoluene 0.2 Mass parts, metoquinone 0.1 mass parts, acrylic acid 73 mass parts, and triphenylphosphine 1.1 mass parts were added, and it was made to react at 120 degreeC for 8 hours, blowing in air. Next, 59 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 3 hours to obtain a target acid group-containing acrylate resin (C2). The acid value of the solid content of the acid group-containing acrylate resin (C2) was 80 mgKOH/g, and the weight average molecular weight was 580.

(Example 6: Preparation of curable resin composition (1))
The acid group-containing acrylate resin (1) obtained in Example 1, orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, dipentaerythritol hexaacrylate, and diethylene glycol monoethyl ether acetate. , A photopolymerization initiator (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green were mixed in a mass part shown in Table 1 and kneaded with a roll mill to obtain a curable resin. A composition (1) was obtained.

(Examples 7 to 10: Preparation of curable resin compositions (2) to (5))
The same as Example 6 except that the acid group-containing acrylate resins (2) to (5) obtained in Examples 2 to 5 were used instead of the acid group-containing acrylate resin (1) used in Example 6. Then, curable resin compositions (2) to (5) were obtained.

(Comparative Examples 3 and 4: Preparation of curable resin compositions (C3) and (C4))
Example 6 except that the acid group-containing acrylate resins (C1) and (C2) obtained in Comparative Example 1 and Comparative Example 2 were used in place of the acid group-containing acrylate resin (1) used in Example 6. In the same manner, curable resin compositions (C3) and (C4) were obtained.

The following evaluation was performed using the curable resin compositions (1) to (5), (C3) and (C4) obtained in the above Examples and Comparative Examples.

[Evaluation method of light sensitivity]
The curable resin composition obtained in each of the examples and comparative examples was applied on a glass substrate with an applicator so as to have a film thickness of 50 μm, and then dried at 80° C. for 30 minutes each. Then, the step tablet No. manufactured by Kodak Co., Ltd. Ultraviolet rays of 1000 mJ/cm ² were radiated through the No. ² using a metal halide lamp. This was developed with a 1% by mass aqueous solution of sodium carbonate for 180 seconds, and the number of remaining steps was evaluated. The higher the number of remaining steps, the higher the photosensitivity.

[Evaluation method of alkali developability]
The curable resin composition obtained in each of the examples and comparative examples was applied on a glass substrate using an applicator so that the film thickness was 50 μm, and then at 80° C. for 60 minutes to 130 minutes at intervals of 10 minutes. And dried to prepare samples having different drying times. These were developed with a 1% sodium carbonate aqueous solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample in which no residue remained on the substrate was evaluated as the drying control width. It should be noted that the longer the dry control width, the better the alkali developability.

The compositions and evaluation results of the curable resin compositions (1) to (5) produced in Examples 6 to 10 and the curable resin compositions (C3) and (C4) produced in Comparative Examples 3 and 4 are shown in the table. 1 is shown.

(Example 11: Preparation of curable resin composition (6))
The acid group-containing acrylate resin (1) obtained in Example 1, an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1-(4 as a photopolymerization initiator. -Methylthiophenyl)-2-morpholinopropan-1-one ("Omnirad-907" manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent in an amount of parts by mass shown in Table 2 to prepare a curable resin composition ( 6) was obtained.

(Examples 12 to 15: Preparation of curable resin compositions (7) to (10))
The same as Example 11 except that the acid group-containing acrylate resins (2) to (5) obtained in Examples 2 to 5 were used instead of the acid group-containing acrylate resin (1) used in Example 11. Then, curable resin compositions (12) to (15) were obtained.

(Comparative Examples 5 and 6: Preparation of curable resin compositions (C5) and (C6))
Example 11 except that the acid group-containing acrylate resins (C1) and (C2) obtained in Comparative Example 1 and Comparative Example 2 were used instead of the acid group-containing acrylate resin (1) used in Example 11. In the same manner, curable resin compositions (C5) and (C6) were obtained.

The following evaluations were carried out using the curable resin compositions (6) to (10), (C5) and (C6) obtained in the above Examples and Comparative Examples.

[Heat resistance evaluation method]
<Creation of test pieces>
The curable resin composition obtained in the examples and comparative examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) with a 50 μm applicator and dried at 80° C. for 30 minutes. It was After irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece (cured product).

The test piece was cut into a size of 6 mm×40 mm, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, heating rate 3° C./min) was used. The glass transition temperature (Tg) was evaluated as the temperature at which the change in elastic modulus was maximum (the change rate of tan δ was the largest).

[Method of measuring elasticity]
The elasticity was measured based on a tensile test.
<Preparation of test piece 2>
The curable resin composition obtained in each of the examples and comparative examples was applied onto glass with a 50 μm applicator, and dried at 80° C. for 30 minutes. After irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour. The cured product was peeled from the glass to obtain a test piece 2 (cured product).

<Tensile test>
The test piece 2 was cut into a size of 10 mm×80 mm, and a tensile test of the test piece was performed under the following measurement conditions using a precision universal tester Autograph “AG-IS” manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

Measurement conditions: temperature 23°C, humidity 50%, marked line distance 20 mm, fulcrum distance 20 mm, pulling speed 10 mm/min

The compositions and evaluation results of the curable resin compositions (6) to (10) produced in Examples 11 to 15 and the curable resin compositions (C5) and (C6) produced in Comparative Example 5 and Comparative Example 6 are shown in the table. 2 shows.

In addition, the "curing agent" in Tables 1 and 2 shows an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214).

"Organic solvent" in Tables 1 and 2 indicates diethylene glycol monomethyl ether acetate.

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

Examples 6 to 15 shown in Tables 1 and 2 are examples of curable resin compositions using the acid group-containing acrylate resin of the present invention. It was confirmed that this curable resin composition has excellent photosensitivity and alkali developability, and that it has excellent elasticity and heat resistance in the cured product.

On the other hand, Comparative Examples 3 to 6 are examples of curable resin compositions that do not use the acid group-containing acrylate resin of the present invention. It was confirmed that this curable resin composition had insufficient photosensitivity and remarkably insufficient elasticity in the cured product.

Claims (12)

An aromatic compound (A) having a hydroxyl group,
Epihalohydrin (B),
Unsaturated monobasic acid (C),
Polybasic acid anhydride (D),
An acid group-containing (meth)acrylate resin using as an essential reaction raw material,
The aromatic compound (A) has at least two hydroxyl groups as a substituent on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are located in the ortho positions relative to each other. Characteristic acid group-containing (meth)acrylate resin. An intermediate reaction product of the aromatic compound (A) and the epihalohydrin (B),
The acid group-containing (meth)acrylate resin according to claim 1, which is a reaction product of the unsaturated monobasic acid (C) and the polybasic acid anhydride (D). The acid group-containing (meth) according to claim 2, wherein the intermediate reaction product contains a cyclic compound (a1) having a cyclic structure containing two adjacent oxygen atoms derived from the aromatic compound (A) as constituent atoms. Acrylate resin. The acid group-containing (meth)acrylate resin according to claim 3, wherein the content of the cyclic compound (a1) is in the range of 0.040 to 0.115 mol with respect to 100 g of the intermediate reaction product. The aromatic compound (A) is one or more selected from the group consisting of 1,2-dihydroxybenzene, 1,2,3-trihydroxybenzene, and 1,2,4-trihydroxybenzene. The acid group-containing (meth)acrylate resin described. 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 6, further comprising an organic solvent and a curing agent. The curing according to claim 6, further comprising a resin (E) having an acid group and a polymerizable unsaturated bond other than the acid group-containing (meth)acrylate resin according to any one of claims 1 to 5. Resin composition. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 6 to 8. An insulating material comprising the curable resin composition according to any one of claims 6 to 8. A resin material for a solder resist, comprising the curable resin composition according to claim 6. A resist member comprising the resin material for solder resist according to claim 11.