JP7192521B2 - Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Description

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

In recent years, acid group-containing epoxy acrylate resins obtained by reacting acid anhydrides after acrylated epoxy resins with acrylic acid have been widely used as resin materials for solder resists for printed wiring boards. Performance requirements for resin materials for solder resists include curing with a small amount of exposure, excellent alkali developability, and excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in the cured product. Various things are mentioned.

As a conventionally known resin material for solder resist, active energy ray-curing obtained by reacting a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride Resins are known (see, for example, Patent Document 1 below), but although they are excellent in heat resistance in cured products, they do not satisfy the ever-increasing demand for elasticity in the future. it wasn't good enough.

Therefore, there has been a demand for a material that has excellent alkali developability and high photosensitivity, and which has even better elasticity and heat resistance in a cured product.

JP-A-61-243869

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

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

That is, the present invention uses an aromatic compound (A) having a hydroxyl group, an epihalohydrin (B), an unsaturated monobasic acid (C), and a 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 the aromatic ring, and among the hydroxyl groups of the aromatic compound (A) Acid group-containing (meth)acrylate resin characterized in that at least two are located in the ortho position to each other, a curable resin composition containing the same, a cured product comprising 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 has excellent elasticity and heat resistance in a cured product. It can be suitably used for members.

13 is a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 1. FIG. 13 is a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 2. FIG.

The acid group-containing (meth)acrylate resin of the present invention comprises an aromatic compound (A) having a hydroxyl group, an epihalohydrin (B), an unsaturated monobasic acid (C), a 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)acryl" means acryl and/or methacryl.

The aromatic compound (A) having a hydroxyl group has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are ortho-positioned 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 above structural formulas (1-1) to (1-7), R ¹ is each 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 and each R ² is independently a hydrogen atom or a methyl group. Also, 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. In structural formulas (1-4) to (1-7), it indicates that any of the benzene rings present in one molecule may be substituted, and the benzene ring in one molecule It indicates that the number of substituents above is q+2.

Among the compounds represented by the above structural formulas (1-1) to (1-7), it has excellent alkali developability and high photosensitivity, and can form a cured product having excellent elasticity and heat resistance. Dihydroxybenzene in which q is 0 in Structural Formula (1-1) and trihydroxybenzene in which q is 1 in Structural Formula (1-1) are preferable because an acid group-containing (meth)acrylate resin can be obtained. More specifically, 1,2-dihydroxybenzene having hydroxyl groups at the 1 and 2 positions (hereinafter sometimes referred to as "catechol"), 1 having hydroxyl groups at the 1, 2 and 3 positions , 2,3-trihydroxybenzene (hereinafter sometimes referred to as “pyrogallol”), or 1,2,4-trihydroxybenzene having hydroxyl groups at the 1-, 2- and 4-positions is more preferred, and pyrogallol or 1,2,4-trihydroxybenzene is particularly preferred.

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

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

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

The unsaturated monobasic acid (C) refers to 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, and a phosphoric acid group. Examples of the unsaturated monobasic acid (C) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Esterified products, acid halides, acid anhydrides, etc. of the unsaturated monobasic acids can also be used. These unsaturated monobasic acids (C) can be used alone or in combination of two or more. In addition, among these, since it is possible to obtain an acid group-containing (meth)acrylate resin that has excellent alkali developability and high photosensitivity and can form a cured product having excellent elasticity and heat resistance, 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 methyl nadic anhydride. acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like. These polybasic acid anhydrides can be used alone or in combination of two or more. Also, among these, an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elasticity and heat resistance can be obtained. 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 any method may be used. For example, it may be produced by a method of reacting all of 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 is easy to control, the aromatic compound (A) and the epihalohydrin (B) are reacted (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 a method of causing (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 desired intermediate reaction product, that is, the epoxy resin (I), the reaction is carried out in the presence of a quaternary onium salt and/or a basic compound in step 1a, and It is preferable to have a step 1b in which the obtained reactant is ring-closed in the presence of a basic compound. Here, when the aromatic compound (A) and the epihalohydrin (B) are reacted, a reaction proceeds in which the hydroxyl groups of the aromatic compound (A) become glycidyl ether groups. At the same time, various reaction products are obtained depending on various reaction conditions, such as the progress of oligomerization due to the reaction of glycidyl ether groups and unreacted hydroxyl groups, or the addition reaction of epihalohydrin, and the ring closure process thereof. , these will be included as by-products. These by-products can be removed from the reaction system and reaction product, but the step of removing only a single component (for example, diglycidyl ether in the case of catechol and triglycidyl ether in the case of pyrogallol) is Industrially, this is a complicated process and is directly linked to product costs, so it is often used as an epoxy resin in a state containing by-products to the extent that it does not adversely affect the resulting cured product.

In addition, the single component (e.g., 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 or curable resin composition of the present invention Handling problems may also arise when From these points of view, it is preferable to use an epoxy resin containing a certain amount of by-products as described above from the point of view of handling, or from the point of view of elasticity and heat resistance of the resulting 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. preferably included.

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

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

Examples of the quaternary phosphonium salts include tetraethylphosphonium cation, tetrabutylphosphonium cation, methyltriphenylphosphonium cation, tetraphenylphosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, and bromine of benzyltriphenylphosphonium cation. compound salts and the like.

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

The amount of the quaternary onium salt to be used is the total mass of the aromatic compound (A) and the epihalohydrin (B), from the viewpoint that the reaction proceeds well and the residue in the product can be reduced. It is preferably 0.15 to 5 parts by mass, more preferably 0.18 to 3 parts by mass, per 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 can be used alone or in combination of two or more. Moreover, among these, potassium hydroxide and sodium hydroxide are preferable.

Further, the amount of the basic compound to be added is 0.01 per 1 mol of the hydroxyl group of the aromatic compound (A), from the viewpoint that the reaction proceeds well and the residue in the product can be reduced. It is preferably from 0.3 mol, more preferably from 0.02 to 0.2 mol.

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

The reaction of step 1a is mainly a reaction in which epihalohydrin is 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 in step 1a is preferably 0.5 hours or more, more preferably 1 to 50 hours.

Moreover, 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, and propylene glycol monomethyl ether; glycol ether solvents such as alkyl ethers and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dimethyl sulfone; These organic solvents can be used alone or in combination of two or more.

When the organic solvent is used, the amount 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, based on 100 parts by mass of the epihalohydrin (B). Preferably, 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. or part or all of the reaction solvent may be removed before step 1b.

As the basic compound used in 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.

The amount of the basic compound used is not particularly limited, but it is preferably 0.8 to 1.5 mol, and preferably 0.9 to 1.5 mol, per 1 mol of the hydroxyl group of the aromatic compound (A). More preferably 3 mol. It is preferable that the addition amount of the basic compound is 0.8 mol or more because the ring closure reaction in step 1b can proceed favorably. On the other hand, when the amount of the basic compound added is 1.5 mol or less, it is preferable because side reactions can be prevented or suppressed. When a basic compound is used in step 1a, it is preferable to use the above 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, etc., if necessary.

Examples of the cyclic compound (a1) include, but are not limited to, compounds represented by the following structural formulas.

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 any atom, m is 0 or an integer of 1-4, and n is 0 or an integer of 1-3.

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 any atom, and m is 0 or an integer of 1-6.

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 any 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 each R ² is independently a hydrogen atom or a methyl group, and m is 0 or an integer of 1-8.

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

The content of the cyclic compound (a1) is excellent in solvent solubility, and an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent elasticity and heat resistance is obtained. A) per 100 g, preferably 0.040 to 0.115 mol, particularly preferably 0.050 to 0.115 mol, most preferably 0.070 to 0.115 mol. In addition, 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 a cyclic compound" is the value measured by the method as described in an Example. Moreover, when two or more kinds of cyclic compounds are included, the "content of cyclic compounds" is the total content thereof.

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

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 in a range in which the number of moles of acid groups of the unsaturated monobasic acid (C) per 1 mole of epoxy groups of the epoxy resin (I) is 0.7 to 1.2. A range of 0.9 to 1.1 is more preferable. The reaction of step 2 can be carried out, for example, in the presence of a suitable esterification catalyst, with heating and stirring at a temperature of about 80 to 140°C. Moreover, 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, 2-ethyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole and other imidazole compounds. These esterification catalysts can be used alone or in combination of two or more.

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

The step 3 is a reaction of the product of the step 2 and the polybasic acid anhydride (D). The reaction mainly involves reacting the hydroxyl groups in the product obtained in step 2 with the polybasic acid anhydride (D). The product of step 2 contains, for example, hydroxyl groups generated in the reaction of step 2, and the like. The reaction ratio of the polybasic acid anhydride (D) is preferably adjusted so that the resulting acid group-containing (meth)acrylate resin has an acid value of about 60 to 120 mgKOH/g. The reaction in step 3 can be carried out, for example, in the presence of a suitable esterification catalyst, with heating and stirring at a temperature of about 80 to 140°C. When step 2 and step 3 are performed continuously, the esterification catalyst may not be added, or may be added as appropriate. Moreover, you may carry out reaction in an organic solvent as needed. The same esterification catalyst and organic solvent as those described above can be used as the esterification catalyst and organic solvent, and they can be used alone or in combination of two or more. 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. can be done.

As for the photopolymerization initiator, an appropriate one may be selected and used according to 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 photopolymerization initiators include 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- acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds; Each of these may be used alone, or two or more of them may be used in combination.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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- one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and the like.

Commercially available products of the other photopolymerization initiators include, for example, "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-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 Stouffer Chemical), “Trigonal P1” (manufactured by Akzo), “Sunray 1000” ( Sands), "Deep" (Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Ward Blenkinsop), "Runtecure-1104" (Runtec company) and the like. These photopolymerization initiators can be used alone or in combination of two or more.

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

The curable resin composition of the present invention may contain resin components other than the acid group-containing (meth)acrylate resin described above. Examples of the other resin components 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 resin having an acid group and a polymerizable unsaturated bond. epoxy resin, 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 bond Examples include acrylamide resins having bonds.

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

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

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 novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resins, biphenylaralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more.

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

As the polybasic acid anhydride, those similar to the polybasic acid anhydride (D) described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can.

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

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

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

Examples of the hydroxyl group-containing (meth)acrylate compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol (meth)acrylate. , pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth) Acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and the like. In addition, a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds ( Poly)oxyalkylene modified products and lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl group-containing (meth)acrylate compounds can 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 any method may be used. 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 solvent as described above can be used, and the organic solvent can be used alone or in combination of two or more.

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-( 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium acetate, etc. ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; Phosphonium salts such as chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; Organic tin 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; etc. These basic catalysts can be used alone or in combination of two or more.

Examples of the urethane resin having an acid group and a polymerizable unsaturated bond include, 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 contained polyol compound, or reacting with a polyol compound other than a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a 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.

As the hydroxyl group-containing (meth)acrylate compound, the same hydroxyl group-containing (meth)acrylate compound as described above can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more. You can also

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 compounds can be used alone or in combination of two or more.

As the polybasic acid anhydride, those similar to the polybasic acid anhydride (D) described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can.

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

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

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

As the acrylic resin having an acid group and a polymerizable unsaturated bond, for example, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group is polymerized as an essential component. A reaction obtained by introducing a (meth)acryloyl group by further reacting the acrylic resin intermediate obtained by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups products, and those obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be obtained by copolymerizing the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. The other polymerizable unsaturated group-containing compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like (meth) Alkyl acrylic ester; Alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene; These can be used alone or in combination of two or more.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α). From the viewpoint of reactivity, the following combinations are preferred: is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more.

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

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

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

Examples of the amideimide resin having an acid group and a polymerizable unsaturated bond include, for example, 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 Those obtained by reacting a compound with, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. be done. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

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

Examples of the amide-imide resin include those obtained by reacting a polyisocyanate compound and a polybasic acid anhydride as starting materials.

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.

As the polybasic acid anhydride, those similar to the polybasic acid anhydride (D) described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can.

Moreover, the amide-imide resin can also use polybasic acid together as a reaction raw material other than the said polyisocyanate compound and polybasic acid anhydride if needed.

Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid. 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, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. be done. As the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth)acrylate compound, the same hydroxyl group-containing (meth)acrylate compound as described above can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more. You can also

As the epoxy group-containing (meth)acrylate compound, a wide variety of compounds can be used without any particular limitation as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure. . For example, glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, Examples include mono(meth)acrylated diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can 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 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 preferred because an acid group-containing (meth)acrylate resin capable of forming a cured product can be obtained. Moreover, 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, 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 any method may be used. 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 solvent as described above can be used, and the organic solvent can be used alone or in combination of two or more.

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

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include, 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, if necessary, those obtained by reacting an unsaturated monobasic acid.

The phenolic hydroxyl group-containing compound is 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) above, R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. , R ² are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more 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. For example, the naphthalene ring of structural formula (3-2) may be substituted on any ring, and the structural formula ( In 3-3), any benzene ring present in one molecule may be substituted, and in structural formula (3-4), any benzene ring present in one molecule may be substituted. It indicates that it may be substituted, and indicates that the number of substituents in one molecule is p and q.

Further, as the phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) are essential. or a reaction product used as a reaction raw material, or 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 used as a raw material can also be used. In addition, a novolac-type phenolic resin that uses 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. A novolak-type phenol resin or the like used as a reaction raw material can also be used.

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

[In formula (x−1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, i is an integer of 0 or 1-4. In formulas (x-2), (x-3) and (x-5), Z is a vinyl group, a halomethyl group, a hydroxymethyl group or 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) above, R ⁴ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. , R ⁵ are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, the naphthalene ring of structural formula (4-2) may be substituted on any ring, and the structural formula ( In 4-3), any benzene ring present in one molecule may be substituted, and in structural formula (4-4), any benzene ring present in one molecule may be substituted. Indicates that substitution is allowed.

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.

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

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

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

As the polybasic acid anhydride, those similar to the polybasic acid anhydride (D) described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can.

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

The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. 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 if necessary, a basic catalyst and an acidic catalyst may be used.

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

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

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

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

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2 - aliphatic mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate Acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds of: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxy in the molecular structure of the various mono (meth) acrylate monomers (Poly)oxyalkylene-modified mono(meth)acrylate compounds into which polyoxyalkylene chains such as tetramethylene chains are introduced; (Meth)acrylate compounds; aliphatics 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 compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecanedi Alicyclic di(meth)acrylate compounds such as methanol di(meth)acrylate; Aromatic di(meth)acrylate compounds such as nord di(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene in the molecular structure of the various di(meth)acrylate compounds polyoxyalkylene-modified di(meth)acrylate compound into which a (poly)oxyalkylene chain such as a chain is introduced; ) acrylate compound; aliphatic tri(meth)acrylate compounds 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 , (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with (poly)oxyalkylene chain; molecule of the aliphatic tri(meth)acrylate compound Lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the structure; tetrafunctional or higher such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Aliphatic poly (meth) acrylate compound; in the molecular structure of the aliphatic poly (meth) acrylate compound (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain such as (poly) Tetra- or more functional (poly)oxyalkylene-modified poly(meth)acrylate compound into which an oxyalkylene chain is introduced; Tetra- or more-functional lactone into which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound A modified poly(meth)acrylate compound and the like can be mentioned. The various (meth)acrylate monomers can be used alone or in combination of two or more.

The curable resin composition of the present invention may optionally contain a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, Various additives such as storage stabilizers can also be contained.

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 epoxy resins. 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 novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resins, biphenylaralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more. In addition, among these, a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elasticity and heat resistance can be obtained. , Cresol novolak type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, etc. are preferred, and the softening point is Those in the range of 20 to 120° C. are particularly preferred.

The curing accelerator accelerates the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, imidazole, an organic acid metal salt, a Lewis acid, Amine complex salts and the like can be mentioned. These curing accelerators can be used alone or in combination of two or more. Moreover, the amount of the curing accelerator added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

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

The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, 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 perform the curing reaction using the ultraviolet rays.

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

The integrated amount of active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , more preferably 50 to 1,000 mJ/cm ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.

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

In addition, since the cured product of the present invention has excellent elasticity and heat resistance, for example, in semiconductor device applications, solder resists, interlayer insulating materials, packaging materials, underfill materials, package adhesive layers such as circuit elements, It can be suitably used as an adhesive layer between an integrated circuit element and a circuit board. In addition, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like in thin display applications such as LCDs and OELDs. Among these, it can be preferably used for solder resist applications.

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

The resist member of the present invention is, for example, a photomask in which the desired pattern is formed after applying the solder resist resin material on a substrate and volatilizing and drying the organic solvent at a temperature range of about 60 to 100 ° C. It can be obtained by exposing to active energy rays through a ray, developing an unexposed portion with an alkaline aqueous solution, and further curing by heating at a temperature in the range of about 140 to 200°C.

Examples of the substrate include metal foil such as copper foil and aluminum foil.

The present invention will be described in more detail below with examples and comparative examples.

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

<GPC measurement conditions>
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".

(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A 1.0% by mass tetrahydrofuran solution 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: JNM-ECA500 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30° pulse Sample concentration: 30 wt%
Accumulation times: 4000 times Chemical shift standard: 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 per 1 mol of the aromatic ring ( mol) and (C) is the epoxy equivalent weight (g/equivalent).

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

Step 1b
1000 mL of distilled water was poured into the reaction liquid obtained in the step 1a, and the mixture was stirred, left to stand, and then the upper layer was removed. 318 g of a 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 resulting solution and left to stand. The lower layer of saline was removed, and epichlorohydrin was recovered by distillation at 120°C. Then, 566 g of methyl isobutyl ketone (hereinafter abbreviated as "MIBK") and 167 g of water were sequentially added and washed with water at 80°C. After removing the washing water of the lower layer, dehydration and filtration were performed, and MIBK was desolvated at 150° C. to produce epoxy resin (1). In addition, when the obtained epoxy resin was visually observed, it was found to be liquid.

This epoxy resin (1) had an epoxy equivalent weight of 138 g/equivalent and a viscosity at 25° C. of 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 with "TV-22" manufactured by Toki Sangyo Co., Ltd.

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

(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 step (1) of 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. In addition, when the obtained epoxy resin was visually observed, it was found to be liquid. This epoxy resin (2) has an epoxy equivalent weight of 128 g/equivalent and a viscosity at 25° C. of 3100 mPa.s. was s. Moreover, 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.

(Synthesis Example 3: Synthesis of epoxy resin (3))
An epoxy resin was produced according to the Experimental section described in Non-Patent Document (Tetrahedron, 2013, 69, 1345-1353). 126 g (1.00 mol) of 1,2,3-trihydroxybenzene and 1111 g (12 mol) of epichlorohydrin were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, and heated to 100°C. The temperature was raised 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. After that, the temperature was lowered to 30° C., 780 g of a 20% NaOH aqueous solution was added dropwise over 2.5 hours, and the mixture was stirred for 1 hour and allowed to stand still. After that, the same operation as in Synthesis Example 1 was performed to produce an epoxy resin (3). In addition, when the obtained epoxy resin was visually observed, it was found to be liquid.

The epoxy equivalent of this epoxy resin (3) was 184 g/equivalent, and the viscosity at 25° C. was 53300 mPa·s. Moreover, the content of the cyclic compound 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 purifying 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. Moreover, 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))
53 parts by weight of diethylene glycol monomethyl ether acetate, 138 parts by weight of epoxy resin (1), 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methoquinone, acrylic 73 parts by mass of acid and 1.1 parts by mass of triphenylphosphine were added and reacted at 100° C. for 20 hours while blowing air. Then, 56 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 3 hours to obtain the desired acid group-containing acrylate resin (1). The acid group-containing acrylate resin (1) had a solid content acid value of 80 mgKOH/g and a weight average molecular weight of 650.

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

(Example 3: Preparation of acid group-containing acrylate resin (3))
In a flask equipped with a thermometer, stirrer and reflux condenser, 50 parts by weight of diethylene glycol monomethyl ether acetate, 128 parts by weight of epoxy resin (2), 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methoquinone, acrylic 73 parts by mass of acid and 1.0 part by mass of triphenylphosphine were added, and the mixture was 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 the desired acid group-containing acrylate resin (3). The acid group-containing acrylate resin (3) had a solid content acid value of 80 mgKOH/g and a weight average molecular weight of 860.

(Example 4: Preparation of acid group-containing acrylate resin (4))
64 parts by weight of diethylene glycol monomethyl ether acetate, 184 parts by weight of epoxy resin (3), 0.3 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methoquinone, 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. Next, 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 the desired acid group-containing acrylate resin (4). The acid group-containing acrylate resin (4) had a solid content acid value of 80 mgKOH/g and a weight average molecular weight of 1,010.

(Example 5: Preparation of acid group-containing acrylate resin (5))
45 parts by weight of diethylene glycol monomethyl ether acetate, 107 parts by weight of epoxy resin (4), 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methoquinone, acrylic 73 parts by mass of an 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 the desired acid group-containing acrylate resin (5). The acid group-containing acrylate resin (5) had a solid content acid value of 80 mgKOH/g and a weight average molecular weight of 910.

(Comparative Example 1: Preparation of acid group-containing acrylate resin (C1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 129 parts by mass of a resorcinol-type epoxy resin (“ERISYS RDGE-H” manufactured by CVC Thermoset Specialties, epoxy equivalent: 129 g/equivalent), and 0.2 mass of dibutylhydroxytoluene. 0.1 parts by mass of methoquinone, 73 parts by mass of acrylic acid and 1.0 parts by mass of triphenylphosphine 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 the desired acid group-containing acrylate resin (C1). The acid group-containing acrylate resin (C1) had a solid content acid value of 80 mgKOH/g and a weight average molecular weight of 1,140.

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

(Example 6: Preparation of curable resin composition (1))
Acid group-containing acrylate resin (1) obtained in Example 1, ortho-cresol novolac type epoxy resin (manufactured by DIC Corporation "EPICLON N-680") 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 are blended in the parts by mass shown in Table 1, and kneaded by a roll mill to form a curable resin. A composition (1) was obtained.

(Examples 7 to 10: Preparation of curable resin compositions (2) to (5))
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. to obtain curable resin compositions (2) to (5).

(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 Examples 1 and 2 were used instead of the acid group-containing acrylate resin (1) used in Example 6. Curable resin compositions (C3) and (C4) were obtained in the same manner.

The following evaluations were performed using the curable resin compositions (1) to (5), (C3) and (C4) obtained in the above examples and comparative examples.

[Method for evaluating photosensitivity]
Each of the curable resin compositions obtained in Examples and Comparative Examples was applied onto a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Next, Kodak Step Tablet No. 2 was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp. This was developed with a 1% by mass sodium carbonate aqueous solution for 180 seconds, and the number of remaining steps was evaluated. Note that the photosensitivity is higher as the number of remaining steps is larger.

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

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

(Example 11: Preparation of curable resin composition (6))
Acid group-containing acrylate resin (1) obtained in Example 1, ortho-cresol novolac type epoxy resin (manufactured by DIC Corporation "EPICLON N-680") as a curing agent, 2-methyl-1-(4 -Methylthiophenyl)-2-morpholinopropan-1-one ("Omnirad-907" manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent are blended in the parts by mass shown in Table 2 to form a curable resin composition ( 6) was obtained.

(Examples 12 to 15: Preparation of curable resin compositions (7) to (10))
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. to obtain curable resin compositions (12) to (15).

(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 Examples 1 and 2 were used instead of the acid group-containing acrylate resin (1) used in Example 11. Curable resin compositions (C5) and (C6) were obtained in the same manner.

The following evaluations were performed using the curable resin compositions (6) to (10), (C5) and (C6) obtained in the above examples and comparative examples.

[Heat resistance evaluation method]
<Preparation of test piece>
The curable resin compositions obtained in Examples and Comparative Examples were applied on 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. rice field. After irradiating ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, it was heated at 160° C. for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece (cured product).

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

[Method for measuring elasticity]
Elasticity measurements were based on tensile tests.
<Production of test piece 2>
The curable resin compositions obtained in Examples and Comparative Examples were applied on glass with a 50 μm applicator and dried at 80° C. for 30 minutes. After irradiating ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, it was heated at 160° C. for 1 hour. The cured product was peeled off from the glass to obtain 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 was performed on the test piece under the following measurement conditions using a precision universal testing machine Autograph “AG-IS” manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece breaks was measured and evaluated according to the following criteria.

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

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

The "curing agent" in Tables 1 and 2 indicates 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 the cured product thereof has excellent elasticity and heat resistance.

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 was insufficient in photosensitivity and remarkably insufficient in elasticity of the cured product.

Claims (10)

an aromatic compound (A) having a hydroxyl group;
epihalohydrin (B);
an unsaturated monobasic acid (C);
a polybasic acid anhydride (D);
An acid-group-containing (meth)acrylate resin having as an essential reaction raw material,
The aromatic compound (A) has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are positioned ortho to each other , , 2-dihydroxybenzene and 1,2,3-trihydroxybenzene, at least one selected from the group consisting of
The unsaturated monobasic acid (C) is a compound having a carboxyl group and a polymerizable unsaturated bond in one molecule,
A reaction product of the intermediate reaction product of the aromatic compound (A) and the epihalohydrin (B) and the unsaturated monobasic acid (C) is further reacted with the polybasic acid anhydride (D). An acid group-containing (meth)acrylate resin characterized by comprising: The acid group-containing (meta) according to claim 1 , 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. 3. The acid group-containing (meth)acrylate resin according to claim 2 , wherein the content of said cyclic compound (a1) is in the range of 0.040 to 0.115 mol per 100 g of said intermediate reaction product. A curable resin composition comprising the acid group-containing (meth)acrylate resin according to any one of claims 1 to 3 and a photopolymerization initiator. 5. The curable resin composition according to claim 4 , further comprising an organic solvent and a curing agent. Curing according to claim 4 , 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 3 . elastic resin composition. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 4 to 6 . An insulating material comprising the curable resin composition according to any one of claims 4 to 6 . A resin material for a solder resist, comprising the curable resin composition according to any one of claims 4 to 6 . A resist member comprising the solder resist resin material according to claim 9 .

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