TW202229390A - (meth)acrylate resin having acid group, curable resin composition, cured product, insulating amterial and resist member - Google Patents

Abstract

The present invention provides a (meth)acrylate resin having an acid group, said (meth)acrylate resin using, as essential starting materials, (A) an epoxy resin, (B) an unsaturated monobasic acid, (C) a compound having a hydroxyl group and a carboxyl group, and (D) a polybasic acid anhydride, while being characterized in that: the compound (C) has at least two hydroxyl groups and at least one carboxyl group; and the amount of the compound (C) used is within the range of from 0.2 mole to 0.4 mole relative to 1 mole of epoxy groups in the epoxy resin (A). Since this (meth)acrylate resin having an acid group has excellent alkali developability and a cured product thereof has excellent elongatability and adhesion to a base material, this (meth)acrylate resin having an acid group is suitable for use in insulating materials, resist members and the like.

Description

(Meth)acrylate resin having acid group, curable resin composition, cured product, insulating material, and solder resist

The present invention relates to a (meth)acrylate resin having an acid group having excellent alkali developability, and having excellent elongation of a cured product and excellent adhesion to a substrate, and a curable resin composition containing the above-mentioned curable resin. The hardened product, insulating material and solder resist member composed of the composition.

In recent years, as resin materials for solder resists for printed wiring boards, acid group-containing epoxy acrylate resins obtained by acrylated epoxy resins with acrylic acid and then reacted with acid anhydrides have been widely used. The properties required for the solder resist resin material include curing with a small exposure amount, excellent alkali developability, excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. of the cured product. and other performance.

As a conventionally known resin material for solder resists, there are known active energy ray-curable resins (eg , refer to the following Patent Document 1), but in terms of elongation and substrate adhesion, it cannot satisfy more and more required properties in the future, and it is also insufficient for conventional market requirements.

Therefore, a material having excellent alkali developability and further excellent elongation of the cured product and substrate adhesion is required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-243869

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide a (meth)acrylate resin having an acid group having excellent alkali developability, and having excellent elongation of a cured product and excellent adhesion to a substrate, a curable resin composition containing the same, A cured product, an insulating material, and a solder resist member composed of the aforementioned curable resin composition. [means to solve the problem]

The inventors of the present invention have made careful studies in order to solve the above-mentioned problems, and as a result, have found that by using epoxy resins, unsaturated monoacids, compounds having hydroxyl and carboxyl groups, and polybasic acid anhydrides as necessary reaction raw materials ( The meth)acrylate resin can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention relates to a (meth)acrylate resin having an acid group, a curable resin composition containing the same, a cured product composed of the curable resin composition, an insulating material, and a solder resist member, which have an acid group. The characteristic of the base (meth)acrylate resin is to use epoxy resin (A), unsaturated monoacid (B), compound (C) having hydroxyl and carboxyl group, and polybasic acid anhydride (D) as necessary reaction raw materials. [Effect of invention]

The (meth)acrylate resin having an acid group of the present invention has excellent alkali developability, and has excellent elongation of a cured product and excellent substrate adhesion, so that it can be suitably used for insulating materials and solder resist members.

[Form for carrying out the invention]

The (meth)acrylate resin having an acid group of the present invention is characterized by comprising epoxy resin (A), unsaturated unit acid (B), compound (C) having hydroxyl and carboxyl groups, and polybasic acid anhydride (D) as Necessary reaction materials.

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

型環氧樹脂、二羥基苯型環氧樹脂、三羥基苯型環氧樹脂、

唑啶酮型環氧樹脂等。該等環氧樹脂(A)係可以單獨使用，也可以合併使用2種以上。又，該等之中，基於能夠得到具有優異鹼顯影性，且具有硬化物之伸度及基材密接性優異之具有酸基之(甲基)丙烯酸酯樹脂的觀點，較佳的是酚醛清漆型環氧樹脂，更佳的是甲酚酚醛清漆型環氧樹脂。The specific structure of the epoxy resin (A) is not particularly limited as long as it has a plurality of epoxy groups in the resin and can react with the unsaturated unit acid (B). As said epoxy resin (A), a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthyl ether type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin are mentioned, for example Epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-asol novolak epoxy resin Resin, naphthol-cresol co-acetal type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, Biphenyl Aralkyl Epoxy Resin, Phenyl Epoxy Resin, 𠮿

type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin,

oxazolidone epoxy resin, etc. These epoxy resins (A) may be used alone or in combination of two or more. In addition, among these, from the viewpoint of being able to obtain a (meth)acrylate resin having an acid group having excellent alkali developability and having excellent elongation of the cured product and excellent substrate adhesion, novolak is preferred. type epoxy resin, more preferably a cresol novolak type epoxy resin.

As said bisphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol E type epoxy resin are mentioned, for example Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.

As said hydrogenated bisphenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, Hydrogenated bisphenol S-type epoxy resin, etc.

As said biphenol type epoxy resin, 4, 4'- biphenol type epoxy resin, 2, 2'- biphenol type epoxy resin, tetramethyl-4, 4'- biphenol type epoxy resin, tetramethyl-4, 4'- biphenol type ring is mentioned, for example Oxygen resin, tetramethyl-2,2'-biphenol type epoxy resin, etc.

Examples of the above-mentioned hydrogenated biphenol-type epoxy resins include hydrogenated 4,4'-biphenol-type epoxy resins, hydrogenated 2,2'-biphenol-type epoxy resins, hydrogenated tetramethyl-4,4'- Biphenol type epoxy resin, hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, etc.

As said epoxy resin (A), the softening point is preferably 80°C or higher, more preferably 80°C or higher and 100°C or lower, and particularly preferably 85°C or higher and 100°C or lower. In addition, in this invention, a softening point is a value measured by the method based on JIS K7234 (1986).

The aforementioned unsaturated unit acid (B) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. In addition, in the present invention, "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

As said acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, for example.

Examples of the unsaturated unit acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styryl acrylic acid, and β-furfuryl acrylic acid. In addition, esters of the aforementioned unsaturated monoacids, halides, acid anhydrides, and the like can also be used. Moreover, the compound etc. which are represented by following structural formula (1) can also be used.

[在式(1)中，X表示碳數1～10之伸烷基鏈、聚氧伸烷基鏈、(聚)酯鏈、芳香族烴鏈、或(聚)碳酸酯鏈，結構中亦可具有鹵素原子、烷氧基等。Y係氫原子或甲基。]

[In formula (1), X represents an alkylene chain with 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain. It may have a halogen atom, an alkoxy group, or the like. Y is a hydrogen atom or a methyl group. ]

As said polyoxyalkylene chain, a polyoxyethylene chain, a polyoxypropylidene chain, etc. are mentioned, for example.

As said (poly)ester chain, the (poly)ester chain represented by following structural formula (X-1) is mentioned, for example.

[式(X-1)中，R ₁為碳原子數1～10之伸烷基，n為1～5之整數。]

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

As said aromatic hydrocarbon chain, a phenyl-extended chain, a naphthyl-extended chain, a biphenyl-extended chain, a phenyl naphthyl-extended chain, a binaphthyl-extended chain, etc. are mentioned, for example. Moreover, as a partial structure, the hydrocarbon chain which has aromatic rings, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, can also be used.

As said (poly)carbonate chain, the (poly)carbonate chain represented by following structural formula (X-2) is mentioned, for example.

[式(X-2)中，R ₂為碳原子數1～10之伸烷基，n為1～5的整數。]

[In formula (X-2), R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

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

These unsaturated unit acids (B) may be used alone or in combination of two or more.

As a compound (C) which has the said hydroxyl group and a carboxyl group, what is necessary is just to have at least two hydroxyl groups and at least one carboxyl group.

As a compound (C) which has the said hydroxyl group and a carboxyl group, dimethylol propionic acid, dimethylol butyric acid, etc. are mentioned, for example. The compound (C) having these hydroxyl groups and carboxyl groups may be used alone or in combination of two or more. In addition, among these, from the viewpoint of obtaining (meth)acrylate resin having an acid group having excellent alkali developability, and having excellent elongation of the cured product and excellent substrate adhesion, dihydroxyl is preferable. Methylpropionic acid.

The usage-amount of the compound (C) having a hydroxyl group and a carboxyl group is based on the viewpoint of obtaining (meth)acrylate resin having an acid group having excellent alkali developability and having excellent elongation and substrate adhesiveness of a cured product. , is preferably in the range of 0.2 to 0.4 moles, more preferably in the range of 0.25 to 0.35, relative to 1 mole of the epoxy group contained in the epoxy resin (A).

In addition, the use ratio of the epoxy resin (A), the unsaturated unit acid (B), and the compound (C) is based on the fact that excellent alkali developability can be obtained, and the elongation and substrate adhesion of the cured product are excellent. From the viewpoint of the (meth)acrylate resin having an acid group, the carboxyl group of the unsaturated unit acid (B) and the compound ( The total number of moles of carboxyl groups C) has is preferably in the range of 0.95 to 1.05.

As said polybasic acid anhydride (D), an aliphatic polybasic acid anhydride, an alicyclic polybasic acid anhydride, an aromatic polybasic acid anhydride, etc. are mentioned, for example.

Examples of the aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. acid, citraconic acid, itaconic acid, glutaric acid, anhydride of 1,2,3,4-butanetetracarboxylic acid, etc. Moreover, as said aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be any of a straight chain type and a branch type, and may have an unsaturated bond in a structure.

As the aforementioned alicyclic polybasic acid anhydride, in the present invention, an acid anhydride group bonded to an alicyclic structure is regarded as an alicyclic polybasic acid anhydride, regardless of the presence or absence of an aromatic ring in other structural parts. As said alicyclic polybasic acid anhydride, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic 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-dioxytetrahydrofuran-3-yl)-1, Anhydride of 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, etc.

As said aromatic polybasic acid anhydride, for example, phthalic acid, trimellitic acid, pyrometic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl Anhydride of tetracarboxylic acid, diphenylketone tetracarboxylic acid, etc.

These polybasic acid anhydrides (D) may be used alone or in combination of two or more. In addition, among these, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent alkali developability, and having excellent elongation of the cured product and excellent substrate adhesion, tetrahydro-ortho Phthalic anhydride, cyclohexane-1,2-dicarboxylic anhydride, succinic anhydride.

The usage-amount of the said polybasic acid anhydride (D) is based on the viewpoint of obtaining (meth)acrylate resin having an acid group which has excellent alkali developability, and has excellent elongation and substrate adhesion of the cured product. The epoxy resin (A) is 1 mol, preferably in the range of 0.35 to 1 mol, more preferably in the range of 0.45 to 0.95 mol.

There is no restriction|limiting in particular as a manufacturing method of the (meth)acrylate resin which has an acid group of this invention, It can manufacture by any method. For example, all of the reaction raw materials containing the epoxy resin (A), the unsaturated unit acid (B), the compound (C) having a hydroxyl group and a carboxyl group, and the polybasic acid anhydride (D) may be reacted all at once. It may be produced by a method of sequentially reacting the reaction raw materials. Among them, from the viewpoint of easy reaction control, it is preferable to first make the epoxy resin (A), the unsaturated unit acid (B), the epoxy resin (A), the unsaturated unit acid (B), the hydroxyl group and the The compound (C) of the carboxyl group is reacted, and then, the polybasic acid anhydride (D) is added, and the method of making it react in the temperature range of 80-140 degreeC, and producing.

Moreover, the reaction system of the said epoxy resin (A), the said unsaturated unit acid (B), the said compound (C) which has a hydroxyl group and a carboxyl group, and the said polybasic acid anhydride (D) can also be performed in an organic solvent as needed.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; and cyclic ether solvents such as tetrahydrofuran and dioxolane. ; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, etc.; Aromatic solvents such as toluene, xylene, solvent naphtha, etc.; Alicyclic solvents such as cyclohexane, methylcyclohexane, etc.; Carbide Alcohol solvents such as alcohol, silosol, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc.; Glycol ether solvent of alcohol monoalkyl ether acetate, etc.; methoxypropanol, cyclohexanone, methyl silosol, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These organic solvents may be used alone or in combination of two or more. In addition, the usage-amount of the said organic solvent is a viewpoint of making reaction efficiency favorable, and it is preferable to use it in the range of about 0.1-5 times the amount with respect to the total mass of reaction raw materials.

Examples of the basic catalyst include N-methylpyridine, 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, dimethine Ethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyl Oxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl) Amine compounds such as aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; grade 4 ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; trimethylammonium Phosphines such as tributylphosphine, tributylphosphine, triphenylphosphine, etc.; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide Phosphonium salts such as phosphonium, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenylphosphonium chloride, benzyl phosphonium chloride, etc.; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate , dioctyl tin diacetate, dioctyl tin di-neodecanoate, dibutyl tin diacetate, tin octoate, 1,1,3,3-tetrabutyl-1,3-dodecanoyl distannoxane (1 , 1,3,3-tetrabutyl-13-dodecanoyldistanoxane) and other organotin compounds; organometallic compounds such as zinc octoate, bismuth octoate, etc.; inorganic tin compounds such as tin octoate; inorganic metal compounds, etc. These alkaline catalysts may be used alone or in combination of two or more.

The usage-amount of the above-mentioned alkaline catalyst is based on the viewpoint of obtaining (meth)acrylate resin having an acid group which has excellent alkali developability, and has excellent elongation of the cured product and excellent adhesion to the substrate. The total of the oxygen resin (A), the unsaturated unit acid (B), the compound (C) having a hydroxyl group and a carboxyl group, and the polybasic acid anhydride (D) is 100 parts by mass in total, preferably in the range of 0.01 to 1.0 parts by mass, more The range of 0.05-0.8 is preferable.

The acid value of the (meth)acrylate resin having an acid group of the present invention is based on the fact that (meth)acrylic acid having an acid group having excellent alkali developability, and having excellent elongation and substrate adhesion of the cured product can be obtained From the viewpoint of the ester resin, the range of 50 to 150 mgKOH/g is preferable, and the range of 60 to 120 mgKOH/g is more preferable. In addition, in this invention, the acid value of the (meth)acrylate resin which has an acid group is the value measured by the neutralization titration method of JIS K 0070 (1992).

In the manufacture of the (meth)acrylate resin which has an acid group of this invention, a polymerization inhibitor, antioxidant, etc. can also be used as needed.

基-二苯胺、4,4'-二辛基-二苯胺、聚(2,2,4-三甲基-1,2-二氫喹啉)、苯乙烯化二苯胺、苯乙烯化二苯胺與2,4,4-三甲基戊烯之反應生成物、二苯胺與2,4,4-三甲基戊烯之反應生成物等之胺化合物；啡噻𠯤、硫二丙酸二硬脂酯、2,2-雙({[3-(十二烷硫基)丙醯基]氧基}甲基)-1,3-丙二基=雙[3-(十二烷硫基)丙酸酯]、二-十三烷-1-基=3,3'-硫烷二基二丙酸酯等之硫醚化合物；N-亞硝基二苯胺、N-亞硝基苯基萘胺、對亞硝基苯酚、亞硝基苯、對亞硝基二苯胺、α-亞硝基-β-萘酚等、N,N-二甲基對亞硝基苯胺、對亞硝基二苯胺、對亞硝基二甲胺、對亞硝基-N,N-二乙胺、N-亞硝基乙醇胺、N-亞硝基二正丁胺、N-亞硝基-N-正丁基-4-丁醇胺、N-亞硝基-二異丙醇胺、N-亞硝基-N-乙基-4-丁醇胺、5-亞硝基-8-羥基喹啉、N-亞硝基𠰌啉、N-亞硝基-N-苯基羥胺銨鹽、亞硝基苯、N-亞硝基-N-甲基-對甲苯磺醯胺、N-亞硝基-N-乙基胺基甲酸酯、N-亞硝基-N-正丙基胺基甲酸酯、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、1-亞硝基-2-萘酚-3,6-磺酸鈉、2-亞硝基-1-萘酚-4-磺酸鈉、2-亞硝基-5-甲基胺基苯酚鹽酸鹽、2-亞硝基-5-甲基胺基苯酚鹽酸鹽等之亞硝基化合物；磷酸與十八烷-1-醇之酯、亞磷酸三苯酯、3,9-二-十八烷-1-基-2,4,8,10-四氧-3,9-二磷螺[5.5]十一烷、亞磷酸參壬基苯基酯、亞磷酸-(1-甲基亞乙基)-二-4,1-伸苯基四-C12-15-烷基酯、2-乙基己基=二苯基=亞磷酸酯、亞磷酸二苯基異癸酯、三異癸基=亞磷酸酯、參(2,4-二-三級丁基苯基)亞磷酸酯等之亞磷酸酯化合物；雙(二甲基二硫胺甲酸-κ(2)S,S')鋅、二乙基二硫胺甲酸鋅、二丁基・二硫胺甲酸鋅等之鋅化合物；雙(N,N-二丁基二硫胺甲酸-S,S')鎳等之鎳化合物；1,3-二氫-2H-苯并咪唑-2-硫酮、4,6-雙(辛基硫甲基)鄰甲酚、2-甲基-4,6-雙[(辛烷-1-基氫硫基)甲基]苯酚、二月桂基硫二丙酸酯、3,3'-硫二丙酸二硬脂酯等之硫化合物等。該等聚合抑制劑係可單獨使用，也可合併使用2種以上。Examples of the aforementioned polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-biphenyl -1-Naphthol, 3-(N-Salicylyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzyl)dodecanedihydrazide , Styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline Phenolic compounds such as; hydroquinone, methylhydroquinone, p-benzoquinone, methyl p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone Quinone compounds such as; melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-diphenylamine

diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, styrenated diphenylamine Amine compounds such as reaction product with 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, etc. Fatty ester, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio) Propionate], di-tridec-1-yl=3,3'-sulfanediyl dipropionate and other sulfide compounds; N-nitroso diphenylamine, N-nitrosophenylnaphthalene Amine, p-nitrosophenol, nitrosobenzene, p-nitroso diphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl-p-nitrosoaniline, p-nitroso diphenylamine Aniline, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butylamine yl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N -Nitrosoline, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N -Ethyl carbamate, N-nitroso-N-propyl carbamate, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1- Sodium nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride , 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds; esters of phosphoric acid and octadec-1-ol, triphenyl phosphite, 3,9-di-octadecyl Alk-1-yl-2,4,8,10-tetraoxo-3,9-diphosphospiro[5.5]undecane, samnonylphenyl phosphite,-(1-methylethylene phosphite) base)-di-4,1-phenylene tetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl= Phosphite compounds such as phosphite, ginseng (2,4-di-tertiary butylphenyl) phosphite; bis(dimethyldithicarbamic acid-κ(2)S,S')zinc, Zinc compounds such as zinc diethyldithiamine, zinc dibutyl·dithicarbamate, etc.; nickel compounds such as bis(N,N-dibutyldithicarbamate-S,S') nickel; 1, 3-Dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)o-cresol, 2-methyl-4,6-bis[(octan-1-yl Sulfur compounds such as mercapto)methyl]phenol, dilauryl thiodipropionate, distearyl 3,3'-thiodipropionate, and the like. These polymerization inhibitors may be used alone or in combination of two or more.

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

Moreover, as a commercial item of the said polymerization inhibitor and the said antioxidant, "Q-1300", "Q-1301" by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM" by Sumitomo Chemical Co., Ltd. -S", "Sumilizer GA-80", etc.

Since the (meth)acrylate resin having an acid group of the present invention has a polymerizable (meth)acryloyl group in the molecular structure, for example, a photopolymerization initiator can be added to form a curable resin composition. form to be used.

As the above-mentioned photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl ketone, etc. Oxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenyl Ethyl ethan-1-one, diphenyl(2,4,6-trimethoxybenzyl)phosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-Trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-𠰌linepropan-1-one, 2- Photo-radical polymerization initiators such as benzyl-2-dimethylamino-1-(4-𠰌linephenyl)-1-butanone, etc.

Commercially available examples of the other photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", and "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 Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10" ", "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", " "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), etc. These photopolymerization initiators may be used alone or in combination of two or more.

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

Moreover, the said photoinitiator is a photosensitizer, such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound, etc., can be used together as needed.

The curable resin composition system of this invention may contain other resin components other than the (meth)acrylate resin which has the said acid group. As said other resin component, the resin (E) which has an acid group and a polymerizable unsaturated group, various (meth)acrylate monomers, etc. are mentioned, for example.

The resin (E) having an acid group and a polymerizable unsaturated group may be any resin as long as it has an acid group and a polymerizable unsaturated group in the resin, and examples thereof include a ring having an acid group and a polymerizable unsaturated group. Oxygen resin, urethane resin with acid group and polymerizable unsaturated group, acrylic resin with acid group and polymerizable unsaturated group, amide imide resin with acid group and polymerizable unsaturated group, Acrylamide resin with acid group and polymerizable unsaturated group, ester resin with acid group and polymerizable unsaturated group, etc.

As said acid group, what was exemplified above as an acid group is mentioned.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include epoxy (meth)acrylate having an acid group using an epoxy resin, an unsaturated monoacid, and a polybasic acid anhydride as necessary reaction raw materials. Resin; epoxy (methyl) having acid group and urethane bond using epoxy resin, unsaturated unit acid, polybasic acid anhydride, polyisocyanate compound, and (meth)acrylate compound having hydroxyl group as necessary reaction raw materials base) acrylate resin, etc.

As said epoxy resin, the thing exemplified as the above-mentioned epoxy resin (A) can be used, and the said epoxy resin system can be used individually or in combination of 2 or more types.

As the unsaturated unit acid, the same ones as those exemplified above as the unsaturated unit acid (B) can be used, and the unsaturated unit acid system may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.

Examples of the polyisocyanate compound include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Alicyclic diisocyanate compounds such as diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.; tolylene diisocyanate, diisocyanate, tetramethyl diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3,3'- Aromatic diisocyanate compounds such as dimethyl biphenyl, di-o-toluidine diisocyanate, etc.; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (2); these trimeric isocyanates Modified body, biuret modified body, allophanate modified body, etc. In addition, these polyisocyanate compounds may be used alone or in combination of two or more.

[式中，R ¹各自獨立地為氫原子、碳原子數1～6之烴基之任一者。R ²各自獨立地為碳原子數1～4之烷基。l為0或1～3之整數，m為1～15之整數。]

[In the formula, R ¹ is each independently any one of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms. R ² is each independently an alkyl group having 1 to 4 carbon atoms. l is 0 or an integer of 1-3, and m is an integer of 1-15. ]

Examples of the (meth)acrylate compound having the aforementioned hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, and trimethylol. Di(meth)acrylate (Meth)acrylate, Dipiveaerythritol di(meth)acrylate, Dipiotaerythritol tri(meth)acrylate, Dipiotaerythritol tetra(meth)acrylate, Dipiotaerythritol Alcohol penta(meth)acrylate, di-trimethylolpropane(meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate Acrylate etc. In addition, it is also possible to introduce (poly)oxyethylidene chain, (poly)oxypropylidene chain, (poly)oxytetramethylene chain into the molecular structure of the aforementioned various hydroxyl-containing (meth)acrylate compounds. A (poly)oxyalkylene modified product formed from a (poly)oxyalkylene chain such as a (poly)oxyalkylene chain, and a (poly)lactone structure introduced into the molecular structure of the aforementioned various (meth)acrylate compounds having hydroxyl groups The lactone modified body and so on. These hydroxyl-containing (meth)acrylate compounds may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the epoxy resin which has the said acid group and a polymerizable unsaturated group, It can manufacture by arbitrary methods. In the production of the epoxy resin having the aforementioned acid group and a polymerizable unsaturated group, it can be carried out in an organic solvent as required, and an alkaline catalyst can also be used as required.

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

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

Examples of the urethane resin having an acid group and a polymerizable unsaturated group include a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and, if necessary, a polyisocyanate compound. Polybasic acid anhydrides and polyhydric alcohol compounds other than the aforementioned polyhydric alcohol compounds having carboxyl groups are reacted; polyisocyanate compounds, (meth)acrylate compounds having hydroxyl groups, polybasic acid anhydrides, and polyhydric alcohol compounds other than polyhydric alcohol compounds having carboxyl groups Alcohol compounds are obtained by reacting them, and the like.

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

As the (meth)acrylate compound having a hydroxyl group, the same ones exemplified as the (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone, Two or more types may be used in combination.

As a polyol compound which has the said carboxyl group, 2, 2- dimethylol propionic acid, 2, 2- dimethylol butyric acid, 2, 2- dimethylol valeric acid, etc. are mentioned, for example. The above-mentioned polyol compound having a carboxyl group may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.

Examples of polyol compounds other than the polyol compound having a carboxyl group include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, trimethylolpropane, di-trimethylolpropane, Aliphatic polyol compounds such as neopentaerythritol and dipeoerythritol; aromatic polyol compounds such as biphenol, bisphenol, etc.; (poly)oxyethylextended chains are introduced into the molecular structures of the aforementioned various polyol compounds , (poly) oxyalkylene chain, (poly) oxytetramethylene chain, etc. (poly) oxyalkylene chain modified (poly) oxyalkylene chain; in the aforementioned various polyol compounds Lactone modified body, etc., which is formed by introducing (poly)lactone structure into the molecular structure. The polyol compounds other than the polyol compound having a carboxyl group may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the urethane resin which has the said acid group and a polymerizable unsaturated group, It can manufacture by any method. In the production of the aforementioned urethane resin having an acid group and a polymerizable unsaturated group, it can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used as needed.

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

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

Examples of the acrylic resin having an acid group and a polymerizable unsaturated group include 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. The necessary components are polymerized, and the obtained acrylic resin intermediate is further reacted with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups, thereby introducing (meth)propylene The reaction product obtained by the acyl group; the reaction product obtained by reacting the polybasic acid anhydride with the hydroxyl group in the above-mentioned reaction product, etc.

In addition to the (meth)acrylate compound (α), the above-mentioned acrylic resin intermediate system may be obtained by copolymerizing other compounds having a polymerizable unsaturated group as required. Examples of the aforementioned other compounds having a polymerizable unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Alkyl (meth)acrylate such as 2-ethylhexyl acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, etc. Alicyclic structure (meth)acrylate; (meth)acrylate with aromatic ring such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl acrylate, etc.; 3-methyl acrylate (meth)acrylates with silicon groups such as acryloyloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, chlorostyrene, etc. These systems may be used alone or in combination of two or more.

The aforementioned (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the aforementioned (meth)acrylate compound (α). A combination of the following is preferred. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate Compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound ( β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β) ). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound ( β). The aforementioned (meth)acrylate compound (β) may be used alone or in combination of two or more.

The above-mentioned polybasic acid anhydrides may be the same as those exemplified as the above-mentioned polybasic acid anhydrides (D), and the above-mentioned polybasic acid anhydrides may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the acrylic resin which has the said acid group and a polymerizable unsaturated group, It can manufacture by any method. In the production of the above-mentioned acrylic resin having an acid group and a polymerizable unsaturated group, it can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used as needed.

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

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

Examples of the amide imide resin having an acid group and a polymerizable unsaturated group include an amide imide resin having an acid group and/or an acid anhydride group, and a (meth)acrylate compound having a hydroxyl group. and/or a (meth)acrylate compound having an epoxy group, as required, 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 obtained by the reaction of the compound. In addition, the compound having the aforementioned reactive functional group may or may not have a (meth)acryloyl group.

As said amide imide resin, it may have either only an acid group or an acid anhydride group, or both may be sufficient. From the viewpoint of the reactivity and reaction control of the (meth)acrylate compound having a hydroxyl group and the epoxy compound having a (meth)acryloyl group, those having an acid anhydride group are preferred, and both an acid group and an acid anhydride group are more preferred. all possess. 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 ring-opened. On the other hand, in the presence of water or the like, the measured value is preferably in the range of 61 to 360 mgKOH/g according to the conditions of ring-opening the acid anhydride group.

As said amide imide resin, the thing obtained by using a polyisocyanate compound and a polybasic acid anhydride as a reaction raw material is mentioned, for example.

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

As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.

Moreover, in addition to the said polyisocyanate compound and a polybasic acid anhydride, the said amide imide resin can also use together a polybasic acid as a reaction raw material as needed.

As the aforementioned polybasic acid, any one 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, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaric 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-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyrometic acid, naphthalene Dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the aforementioned polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, and a polymer having a carboxyl group in the molecule can be used. These polybasic acid systems may be used alone or in combination of two or more.

As the (meth)acrylate compound having a hydroxyl group, the same ones exemplified as the (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone, Two or more types may be used in combination.

As a (meth)acrylate compound which has the said epoxy group, if it has a (meth)acryloyl group and an epoxy group in a molecular structure, it will not specifically limit, Various compounds can be used. For example, (meth)acrylates having glycidyl groups such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylates can be mentioned. Acrylate monomers; mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthyl diglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. compounds, etc. These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more. Among them, the (meth)acrylate compound having one epoxy group is preferable from the viewpoint of easy control of the reaction, and it is possible to obtain excellent alkali developability and can form a compound having excellent elongation. From the viewpoint of the curable resin composition of the cured product of degree and substrate adhesion, a (meth)acrylate monomer having a glycidyl group is preferred. Moreover, it is preferable that the molecular weight system of the (meth)acrylate monomer which has the said glycidyl group is 500 or less. Furthermore, the ratio of the (meth)acrylate monomer having a glycidyl group to the total mass of the (meth)acrylate compound having an epoxy group is preferably 70% by mass or more, more preferably 90% by mass above.

It does not specifically limit as a manufacturing method of the amide imide resin which has the said acid group and a polymerizable unsaturated group, It may manufacture by any method. In the production of the above-mentioned amide imide resin having an acid group and a polymerizable unsaturated group, it can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used as needed.

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

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

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group include a compound having a phenolic hydroxyl group, an alkylene oxide, an alkylene carbonate, and an N-alkoxyalkyl (meth)propylene. It is obtained by reacting amide compound, polybasic acid anhydride, and unsaturated unit acid according to need.

The compound which has the said phenolic hydroxyl group means the compound which has at least 1 phenolic hydroxyl group in a molecule|numerator. As a compound which has at least one phenolic hydroxyl group in the said molecule|numerator, the compound represented by following structural formula (3-1) - (3-4) is mentioned, for example.

In the above structural formulas (3-1) to (3-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom , R ² is each independently a hydrogen atom or a methyl group. Moreover, p is an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1. In addition, the position of the substituent on the aromatic ring in the above structural formula is arbitrary, for example, it is shown that: in the naphthalene ring of the structural formula (3-2), it can be substituted on any ring, and in the structural formula (3-3), it can be substituted on any ring. ) may be substituted on any ring of the benzene ring existing in one molecule, and in structural formula (3-4), it may be substituted on any ring of the benzene ring existing in one molecule. The numbers of substituents in one molecule are shown as p and q.

In addition, as the compound having a phenolic hydroxyl group, for example, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulae (x-1) to (x-5) can also be used. The compounds are reaction products of necessary reaction raw materials, etc. Moreover, the novolak-type phenol resin etc. which use one or two or more types of the compound which has at least 1 phenolic hydroxyl group in a molecule|numerator as a reaction raw material can also be used.

[式(x-1)中，h為0或1。式(x-2)～(x-5)中，R ³為碳原子數1～20之烷基、碳原子數1～20之烷氧基、芳基、鹵素原子之任一者，i為0或1～4之整數。式(x-2)、(x-3)及(x-5)中，Z為乙烯基、鹵化甲基、羥甲基、烷氧基甲基之任一者。式(x-5)中，Y為碳原子數1～4之伸烷基、氧原子、硫原子、羰基之任一者，j為1～4之整數。]

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

These compounds having a phenolic hydroxyl group may be used alone or in combination of two or more.

As said alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, pentene oxide, etc. are mentioned, for example. Among these, ethylene oxide or propylene oxide is preferable from the viewpoint of obtaining a curable resin composition which has excellent alkali developability and can form a cured product having excellent elongation and substrate adhesion. The aforementioned alkylene oxides may be used alone or in combination of two or more.

As said alkylene carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, butylene carbonate, etc. are mentioned, for example. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of obtaining a curable resin composition that has excellent alkali developability and can form a cured product having excellent elongation and substrate adhesion. ester. The above 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 and N-ethoxymethyl(meth)acrylamide. Amine, N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-butyl Oxyethyl (meth) acrylamide, etc. The above-mentioned N-alkoxyalkyl (meth)acrylamide compounds may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.

As the unsaturated unit acid, the same ones as those exemplified above as the unsaturated unit acid (B) can be used, and the unsaturated unit acid system may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the acrylamide resin which has the said acid group and a polymerizable unsaturated group, It can manufacture by any method. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group can be carried out in an organic solvent as required, and an alkaline catalyst and an acidic catalyst can be used as required.

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

As the alkaline catalyst, the same ones as those exemplified above as the alkaline catalyst can be used, and the alkaline catalysts may 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, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid, etc. In addition, a solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalyst systems may be used alone or in combination of two or more.

As an ester resin which has the said acid group and a polymerizable unsaturated group, the thing obtained by making the compound which has a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an unsaturated unit acid, and a polybasic acid anhydride react is mentioned, for example.

As the compound having the phenolic hydroxyl group, the same ones as those exemplified above as the compound having the phenolic hydroxyl group can be used, and the compound having the phenolic hydroxyl group may be used alone or in combination of two or more.

As the said alkylene oxide, the thing exemplified as the above-mentioned alkylene oxide can be used. Among these, ethylene oxide or propylene oxide is preferable from the viewpoint of obtaining a curable resin composition which has excellent alkali developability and can form a cured product having excellent elongation and substrate adhesion. The aforementioned alkylene oxides may be used alone or in combination of two or more.

As the alkylene carbonate, the same ones as those exemplified as the alkylene carbonate above can be used. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of obtaining a curable resin composition that has excellent alkali developability and can form a cured product having excellent elongation and substrate adhesion. ester. The above alkylene carbonates may be used alone or in combination of two or more.

As the unsaturated unit acid, the same ones as those exemplified above as the unsaturated unit acid (B) can be used, and the unsaturated unit acid system may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the ester resin which has the said acid group and a polymerizable unsaturated group, It can manufacture by arbitrary methods. In the production of the above-mentioned ester resin having an acid group and a polymerizable unsaturated group, it can be carried out in an organic solvent as required, and an alkaline catalyst and an acidic catalyst can also be used as required.

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

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

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

The usage-amount of the resin (E) which has the said acid group and a polymerizable unsaturated group is the range of 10-900 mass parts with respect to 100 mass parts of (meth)acrylate resins which have an acid group of this invention.

Examples of the aforementioned various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Aliphatic mono(meth)acrylate compounds such as amyl meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc.; (methyl) ) Alicyclic mono(meth)acrylate compounds such as cyclohexyl acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate, etc.; glycidyl (meth)acrylate, tetrahydroacrylate Heterocyclic mono(meth)acrylate compounds such as furfuryl ester; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate , phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxy (meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenylbenzyl ester, phenylphenoxyethyl (meth)acrylate, etc.; mono(meth)acrylates of the aforementioned types (Poly)oxyalkylene chains formed by introducing polyoxyalkylene chains such as (poly)oxyethylidene chains, (poly)oxypropylidene chains, (poly)oxytetramethylene chains, etc., into the molecular structure of monomers. Alkyl-modified mono(meth)acrylate compound; Lactone-modified mono(meth)acrylate obtained by introducing (poly)lactone structure into the molecular structure of the aforementioned various mono(meth)acrylate compounds Compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Aliphatic di(meth)acrylates such as meth)acrylates; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol Alicyclic di(meth)acrylate compounds such as di(meth)acrylate, dicyclopentenyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc.; diphenol di Aromatic di(meth)acrylate compounds such as (meth)acrylates and bisphenol di(meth)acrylates; (poly)oxygen is introduced into the molecular structure of the aforementioned various di(meth)acrylate compounds Polyoxyalkylene modified di(meth)acrylates formed from (poly)oxyalkylene chains such as ethylidene chains, (poly)oxypropylidene chains, (poly)oxytetramethylene chains, etc. Compound; Lactone-modified di(meth)acrylate compound obtained by introducing (poly)lactone structure into the molecular structure of the aforementioned various di(meth)acrylate compounds; Trimethylolpropane tri(methyl) ) aliphatic tri(meth)acrylate compounds such as acrylates, glycerol tri(meth)acrylates, etc.; (poly)oxyethylene is introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compounds (Poly)oxyalkylene modified tri(meth)acrylate formed from (poly)oxyalkylene chain such as radical chain, (poly)oxypropylidene chain, (poly)oxytetramethylene chain, etc. Compounds; in the aforementioned lipids Lactone-modified tri(meth)acrylate compound formed by introducing (poly)lactone structure into the molecular structure of aliphatic tri(meth)acrylate compound; neotaerythritol tetra(meth)acrylate, dimethacrylate - Trimethylolpropane tetra(meth)acrylate, dipivalerythritol hexa(meth)acrylate and other tetrafunctional aliphatic poly(meth)acrylate compounds; in the aforementioned aliphatic poly(meth)acrylate (poly)oxyalkylene chains such as (poly)oxyethylidene chains, (poly)oxypropylidene chains, (poly)oxytetramethylene chains, etc. are introduced into the molecular structure of acrylate compounds A (poly)oxyalkylene modified poly(meth)acrylate compound having more than 4 functions; a tetrafunctional compound obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound The lactone-modified poly(meth)acrylate compounds and the like above.

In addition to the above-mentioned other (meth)acrylate monomers, (methyl) compounds containing phenol compounds, cyclic carbonate compounds, cyclic ether compounds, and unsaturated unit carboxylic acids as essential reaction raw materials can be used. Acrylate monomer.

Examples of the phenolic compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, and 4-allylortho Hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalene diol, 1,5-naphthalene diol, 2,6-Naphthalene diol, 2,7-naphthalene diol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether diol, polyextended naphthyl ether diol, phenol novolak resin, cresol novolak Resins, bisphenol novolak type resins, naphthol novolak type resins, phenol aralkyl type resins, naphthol aralkyl type resins, phenol resins having a cyclic ring structure, etc.

As said cyclic carbonate compound, ethylene carbonate, propylidene carbonate, butylene carbonate, butylene carbonate, etc. are mentioned, for example. These cyclic carbonate compounds may be used alone or in combination of two or more.

As said cyclic ether compound, ethylene oxide, propylene oxide, tetrahydrofuran, etc. are mentioned, for example. These cyclic ether compounds may be used alone or in combination of two or more.

As the unsaturated monocarboxylic acid, the same ones as those exemplified above as the unsaturated monoacid (B) can be used.

It is preferable that content of the said other (meth)acrylate monomer is 90 mass % or less in the curable resin composition of this invention.

In addition, the curable resin composition of the present invention may contain a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a homogenizer, etc., as required. Various additives such as leveling agent, flame retardant, preservation stabilizer, etc.

As said hardening|curing agent, an epoxy resin, a polybasic acid, an unsaturated unit acid, an amine compound, an amide compound, an azo compound, an organic peroxide, a polyhydric alcohol compound, an epoxy resin etc. are mentioned, for example.

As said epoxy resin, the thing exemplified as the above-mentioned epoxy resin (A) can be used, and the said epoxy resin system can be used individually or in combination of 2 or more types.

As said polybasic acid, 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, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaric acid, 1,2,3,4-butanetetracarboxylic acid, cyclo Hexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2, 5-Dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyrometic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetra Formic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, etc. In addition, as the aforementioned polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, and a polymer having a carboxyl group in the molecule can be used. These polybasic acid systems may be used alone or in combination of two or more.

As the unsaturated unit acid, the same ones as those exemplified above as the unsaturated unit acid (B) can be used, and the unsaturated unit acid system may be used alone or in combination of two or more.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylamine, isophoronediamine, imidazole, and BF3-amine complexes , guanidine derivatives, etc. These amine compounds may be used alone or in combination of two or more.

As said amide-type compound, dicyandiamide, the polyamide resin synthesized from the dimer of linolenic acid, and ethylenediamine, etc. are mentioned, for example. These amide compounds may be used alone or in combination of two or more.

As said azo compound, azobisisobutyronitrile etc. are mentioned, for example.

Examples of the aforementioned organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, Alkyl peroxycarbonates, etc. These organic peroxides may be used alone or in combination of two or more.

As said polyol compound, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, 3-Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerol, glycerol mono(meth)acrylate, trimethylolethane, trimethylolethane Methylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, neotaerythritol mono(meth)acrylate, neotaerythritol di(meth)acrylate base) polyol monomers such as acrylates; by the aforementioned polyol monomers, and succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaric acid, 1,4-cyclohexanedicarboxylic acid and other dicarboxylic acids Polyester polyol obtained by co-condensation; by the polycondensation reaction of the aforementioned polyol monomer with various lactones such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone, etc. The lactone-type polyester polyol obtained is obtained by combining the above-mentioned polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, etc. Polyether polyols obtained by ring polymerization, etc. These polyol compounds may be used alone or in combination of two or more.

As said epoxy resin, the thing exemplified as the above-mentioned epoxy resin (A) can be used, and the said epoxy resin system can be used individually or in combination of 2 or more types.

The said hardening accelerator is what accelerates a hardening reaction, for example, phosphorus type compound, amine type compound, imidazole, organic acid metal salt, Lewis acid, amine complex salt, etc. are mentioned. These hardening accelerators may be used alone or in combination of two or more. Moreover, it is preferable to use the range of 0.01-10 mass % of the addition amount of the said hardening accelerator in the solid content of the said curable resin composition, for example.

羧基-5'-甲基苯基)苯并三唑、2-(2'-鄰硝基苄氧基-5'-甲基苯基)苯并三唑、2-𠮿

羧基-4-十二烷氧基二苯甲酮、2-鄰硝基苄氧基-4-十二烷氧基二苯甲酮等。該等紫外線吸收劑係可單獨使用，也可合併使用2種以上。As said ultraviolet absorber, for example, 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2 ,4-Dimethylphenyl)-1,3,5-tris𠯤, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl ]-4,6-Bis(2,4-Dimethylphenyl)-1,3,5-Tris 𠯤 and other tertiary 𠯤 derivatives, 2-(2'-𠮿

Carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-𠮿

Carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers may be used alone or in combination of two or more.

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

As said inorganic filler, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. are mentioned, for example.

As the aforementioned pigments, well-known and conventional inorganic pigments and organic pigments can be used.

As said inorganic pigment, a white pigment, antimony red, iron oxide red (Bengala), cadmium red, cadmium yellow, cobalt blue, cyanine blue, ultramarine blue, carbon black, graphite, etc. are mentioned, for example. These inorganic pigments may be used alone or in combination of two or more.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and hollow resin particles. , zinc sulfide, etc.

𠯤顏料、酞青顏料、蒽嘧啶顏料、蒽嵌蒽醌(anthanthrone)顏料、陰丹士林顏料、黃士酮顏料、苝顏料、二酮吡咯并吡咯顏料、迫位酮(perinone)顏料、喹啉黃(quinophthalone)顏料、蒽醌顏料、硫靛顏料、苯并咪唑酮顏料、偶氮顏料等。該等有機顏料係可單獨使用，也可合併使用2種以上。Examples of the organic pigments include quinacridone pigments, quinacridone quinone pigments,

Pigments Quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments may be used alone or in combination of two or more.

Examples of the flame retardant include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and inorganic phosphorus compounds such as amide phosphate; phosphate ester compounds, phosphonic acid compounds, Phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-(2, 5-dihydrooxyphenyl)-10H-9-oxo-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydrooxynaphthyl)-10H-9-oxo-10- Cyclic organophosphorus compounds such as phosphaphenanthrene-10-oxides, and organophosphorus compounds such as derivatives thereof reacted with compounds such as epoxy resins and phenol resins; trisamine compounds, cyanuric acid compounds, Nitrogen-based flame retardants such as isocyanuric acid compounds, thiocyanate, etc.; polysiloxane-based flame retardants such as polysiloxane oil, polysiloxane rubber, polysiloxane resin, etc.; metal hydroxides, metal oxides , Inorganic flame retardants of metal carbonate compounds, metal powders, boron compounds, low melting point glass, etc. These flame retardants may be used alone or in combination of two or more. Moreover, when using these flame retardants, the range of 0.1-20 mass % in the whole resin composition is preferable.

The cured product of the present invention can be obtained by irradiating the aforementioned curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Moreover, when using an ultraviolet-ray as the said active energy ray, on the premise that the hardening reaction by ultraviolet-ray is performed effectively, it can irradiate in inert gas atmosphere, such as nitrogen gas, and it can also irradiate in air environment.

As an ultraviolet generating source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, LED, etc. are mentioned.

The cumulative light intensity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , more preferably 0.5 to 10 kJ/m ² . When the accumulated light amount is in the above-mentioned range, it is preferable because the generation of the unhardened portion can be prevented or suppressed.

In addition, the irradiation of the above-mentioned active energy rays may be performed in a single stage, or may be performed in two or more stages.

In addition, the cured product of the present invention has high photosensitivity and excellent alkali developability, and is excellent in elongation and dielectric properties, so it is suitable for use as, for example, a solder resist, an interlayer insulating material, a packaging material, and an underfill material in semiconductor device applications. , the packaging bonding layer of circuit components, etc., and the bonding layer of integrated circuit and circuit substrate to be used. In addition, thin film transistor protective films, liquid crystal color filter protective films, pigment solder resists for color filters, black matrix solder resists, spacers, etc. . Among these, it can be suitably used especially for a solder resist application.

The resin material for solder resists of this invention contains the said curable resin composition.

The solder resist member of the present invention can be obtained, for example, by applying the aforementioned resin material for solder resist on a base material, volatilizing and drying an organic solvent at a temperature range of about 60 to 100° C., and then forming a desired pattern by forming a desired pattern. The mask is exposed to active energy rays, the unexposed portion is developed with an aqueous alkaline solution, and further heated and cured in a temperature range of about 140 to 200°C.

As said base material, the laminated board etc. which affix metal, such as copper and aluminum, are mentioned, for example. [Example]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. In addition, this invention is not limited to the Example enumerated below.

(Synthesis example 1: Preparation of resin (1) having acid group and polymerizable unsaturated group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 392 parts by mass of diethylene glycol monomethyl ether acetate and 244 parts by mass of isophorone diisocyanate modified isocyanate (EVONIK) were added. The company made "VESTANAT T-1890/100", isocyanate group content 17.2 mass %), 192 mass parts of trimellitic anhydride, and 1.0 mass parts of dibutylhydroxytoluene were dissolved. The reaction was carried out at 160° C. for 5 hours under a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1 mass % or less. The acid value of the solid content measured under the non-ring-opening condition of the acid anhydride group was 160 mgKOH/g. Add 0.3 parts by mass of methoxyphenol and 172 parts by mass of a neopentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., the content of neotaerythritol triacrylate is about 67%, and the hydroxyl value is 159.7 mgKOH/g) and 3.6 parts by mass of triphenylphosphine were allowed to react at 110° C. for 5 hours while blowing in air. Next, 163 parts by mass of glycidyl methacrylate was added, and the reaction was carried out at 110° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added, and the reaction was carried out at 110° C. for 5 hours to obtain a nonvolatile content of 62 mass % with acid groups and polymerizability Resin (1) of unsaturated group. The acid value of the solid content of the resin (1) having an acid group and a polymerizable unsaturated group was 79 mgKOH/g. In addition, the acid value is a value measured by neutralization titration method according to JIS K 0070 (1992).

(Synthesis example 2: Preparation of resin (2) having acid group and polymerizable unsaturated group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 123 parts by mass of diethylene glycol monomethyl ether acetate was added, and the o-cresol novolak type epoxy resin "EPICLON N-680" (DIC Co., Ltd. manufactured by the company, softening point 86°C, epoxy equivalent: 214 g/eq) (hereinafter, abbreviated as "epoxy resin (1)") was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of After the methoxyphenol, 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the reaction was performed at 120° C. for 10 hours while blowing in air. Next, 72 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acid group and a polymerizable unsaturated group. of resin (2). The nonvolatile content of the resin (2) having an acid group and a polymerizable unsaturated group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g.

(Example 1: Preparation of Acrylate Resin (1) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added After dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were added, and air was blown into the The reaction was carried out at 120°C for 12 hours. Next, 78 parts by mass of diethylene glycol monomethyl ether acetate and 82 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (1 ). The nonvolatile content of the acrylate resin (1) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.54, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 2: Preparation of Acrylate Resin (2) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, and 214 parts by mass of o-cresol novolak epoxy resin "EPICLON N-698 ” (manufactured by DIC Co., Ltd., softening point: 99°C, epoxy equivalent: 214 g/eq) to dissolve, and after adding 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were allowed to react at 120° C. for 12 hours while blowing in air. Next, 78 parts by mass of diethylene glycol monomethyl ether acetate and 82 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (2 ). The nonvolatile content of the acrylate resin (2) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the molar number of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the o-cresol novolak epoxy resin, which is 0.3 relative to the o-cresol novolak epoxy resin possessed. 1 mole of epoxy group, the number of moles of tetrahydrophthalic anhydride is 0.54, relative to 1 mole of epoxy group of o-cresol novolac epoxy resin, acrylic acid and dimethylolpropionic acid The total number of moles of carboxyl groups contained was 1.0.

(Example 3: Preparation of Acrylate Resin (3) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 128 parts by mass of diethylene glycol monomethyl ether acetate was added, and 207 parts by mass of o-cresol novolak epoxy resin "EPICLON N- 660” (manufactured by DIC Co., Ltd., softening point: 65°C, epoxy equivalent: 207 g/eq) was dissolved, 0.9 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoxyphenol were added, and then 50 parts by mass of Parts of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were allowed to react at 120° C. for 12 hours while blowing in air. Next, 42 parts by mass of diethylene glycol monomethyl ether acetate and 81 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (3 ). The nonvolatile content of the acrylate resin (3) having an acid group was 69% by mass, and the acid value of the solid content was 81 mgKOH/g. In addition, the molar number of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the o-cresol novolak epoxy resin, which is 0.3 relative to the o-cresol novolak epoxy resin possessed. 1 mole of epoxy group, the mole number of tetrahydrophthalic anhydride is 0.53, relative to 1 mole of epoxy group of o-cresol novolac epoxy resin, acrylic acid and dimethylolpropionic acid The total number of moles of carboxyl groups contained was 1.0.

(Example 4: Preparation of Acrylate Resin (4) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 128 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 58 parts by mass of acrylic acid, 27 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 75 parts by mass of diethylene glycol monomethyl ether acetate and 79 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (4 ). The nonvolatile content of the acrylate resin (4) having an acid group was 65% by mass, and the acid value of the solid content was 79 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.2 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.52, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 5: Preparation of Acrylate Resin (5) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 133 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. 43 parts by mass of acrylic acid, 54 parts by mass of dimethylolpropionic acid, and 1.6 parts by mass of triphenylphosphine were added after 0.2 parts by mass of methoxyphenol, and blowing in air The reaction was carried out at 120°C for 12 hours. Next, 79 parts by mass of diethylene glycol monomethyl ether acetate and 84 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (5 ). The nonvolatile content of the acrylate resin (5) having an acid group was 65% by mass, and the acid value of the solid content was 79 mgKOH/g. Moreover, the number of moles of dimethylolpropionic acid is 0.4 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and the number of moles relative to 1 mole of epoxy group possessed by the epoxy resin (1) is , the molar number of tetrahydrophthalic anhydride is 0.55, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 6: Preparation of Acrylate Resin (6) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 119 parts by mass of diethylene glycol monomethyl ether acetate was added, and 188 parts by mass of the novolak-type epoxy resin "EPICLON N-775" ( Manufactured by DIC Co., Ltd., softening point: 74°C, epoxy equivalent: 188 g/eq) to dissolve, add 0.8 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoxyphenol, and then add 50 parts by mass of acrylic acid 40 parts by mass of dimethylolpropionic acid and 1.4 parts by mass of triphenylphosphine were allowed to react at 120° C. for 10 hours while blowing in air. Next, 71 parts by mass of diethylene glycol monomethyl ether acetate and 75 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (6 ). The nonvolatile content of the acrylate resin (6) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy groups possessed by the novolak type epoxy resin, and 1 mole relative to the epoxy group possessed by the novolak type epoxy resin. Molar, the molar number of tetrahydrophthalic anhydride is 0.49, with respect to 1 mole of epoxy group possessed by novolac epoxy resin, the total amount of carboxyl groups possessed by acrylic acid and dimethylolpropionic acid The molar number is 1.0.

(Example 7: Preparation of Acrylate Resin (7) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 113 parts by mass of diethylene glycol monomethyl ether acetate was added, and 173 parts by mass of naphthalene type epoxy resin "EPICLON HP-4710" (DIC Corporation) Co., Ltd., softening point 99°C, epoxy equivalent: 173 g/eq) was dissolved, after adding 0.8 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoxyphenol, adding 50 parts by mass of acrylic acid, 40 parts by mass A mass part of dimethylolpropionic acid and 1.3 parts by mass of triphenylphosphine were allowed to react at 120° C. for 10 hours while blowing in air. Next, 67 parts by mass of diethylene glycol monomethyl ether acetate and 71 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (7 ). The nonvolatile content of the acrylate resin (7) having an acid group was 65% by mass, and the acid value of the solid content was 81 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mole of epoxy groups possessed by the naphthalene-type epoxy resin, and the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy groups possessed by the naphthalene-type epoxy resin. The molar number of hydrogen phthalic anhydride was 0.47, and the total molar number of carboxyl groups contained in acrylic acid and dimethylolpropionic acid relative to 1 mol of epoxy groups contained in the naphthalene-type epoxy resin was 1.0.

(Example 8: Preparation of Acrylate Resin (8) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 62 parts by mass of diethylene glycol monomethyl ether acetate and 53 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (8 ). The nonvolatile content of the acrylate resin (8) having an acid group was 65% by mass, and the acid value of the solid content was 57 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.35, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 9: Preparation of Acrylate Resin (9) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added After dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were added, and air was blown into the The reaction was carried out at 120°C for 12 hours. Next, 60 parts by mass of diethylene glycol monomethyl ether acetate and 49 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (9 ). The nonvolatile content of the acrylate resin (9) having an acid group was 65% by mass, and the acid value of the solid content was 51 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.32, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 10: Preparation of Acrylate Resin (10) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 169 parts by mass of diethylene glycol monomethyl ether acetate and 144 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (10 ). The nonvolatile content of this acrylate resin (10) having an acid group was 60% by mass, and the acid value of the solid content was 121 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.95, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 11: Preparation of Acrylate Resin (11) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added After dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were added, and air was blown into the The reaction was carried out at 120°C for 12 hours. Next, 174 parts by mass of diethylene glycol monomethyl ether acetate and 152 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (11 ). The nonvolatile content of the acrylate resin (11) having an acid group was 60% by mass, and the acid value of the solid content was 125 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 1.0, relative to 1 mole of epoxy group possessed by epoxy resin (1), the total molar number of carboxyl groups possessed by acrylic acid and dimethylolpropionic acid is 1.0.

(Example 12: Preparation of Acrylate Resin (12) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 177 parts by mass of diethylene glycol monomethyl ether acetate and 157 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (12 ). The nonvolatile content of the acrylate resin (12) having an acid group was 60% by mass, and the acid value of the solid content was 127 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 1.03, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid with respect to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 13: Preparation of Acrylate Resin (13) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added After dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were added, and air was blown into the The reaction was carried out at 120°C for 12 hours. Next, 78 parts by mass of diethylene glycol monomethyl ether acetate and 83 parts by mass of cyclohexane-1,2-dicarboxylic acid anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain acrylic acid having an acid group Ester resin (13). The nonvolatile content of the acrylate resin (13) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of cyclohexane-1,2-dicarboxylic acid anhydride is 0.54, relative to 1 molar of epoxy group possessed by epoxy resin (1), the carboxyl group possessed by acrylic acid and dimethylolpropionic acid The total number of moles is 1.0.

(Example 14: Preparation of Acrylate Resin (14) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 131 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 60 parts by mass of diethylene glycol monomethyl ether acetate and 49 parts by mass of succinic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin (14) having an acid group. The nonvolatile content of this acid group-containing acrylate resin (14) was 65% by mass, and the acid value of the solid content was 79 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of succinic anhydride is 0.49, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid is 1.0 with respect to 1 mole of epoxy group of epoxy resin (1).

(Example 15: Preparation of Acrylate Resin (15) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 129 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 48 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, blowing in air, The reaction was carried out at 120°C for 10 hours. Next, 81 parts by mass of diethylene glycol monomethyl ether acetate and 88 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (15 ). The nonvolatile content of this acid group-containing acrylate resin (15) was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (15), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.58, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 0.96.

(Example 16: Preparation of Acrylate Resin (16) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 128 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 45 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, blowing air in The reaction was carried out at 120°C for 9 hours. Next, 82 parts by mass of diethylene glycol monomethyl ether acetate and 91 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (16 ). The nonvolatile content of this acid group-containing acrylate resin (16) was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (16), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.60, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 0.93.

(Example 17: Preparation of Acrylate Resin (17) with Acid Group) In a flask equipped with a thermometer, a stirrer and a reflux cooler, 132 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) were dissolved, and 0.9 parts by mass was added to the flask. After dibutylhydroxytoluene and 0.2 parts by mass of methoxyphenol, 53 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine were added, and air was blown into the The reaction was carried out at 120°C for 11 hours. Next, 76 parts by mass of diethylene glycol monomethyl ether acetate and 79 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (17 ). The nonvolatile content of this acid group-containing acrylate resin (17) was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.52, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.04.

(Example 18: Preparation of Acrylate Resin (18) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 133 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 55 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 75 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (18 ). The nonvolatile content of this acrylate resin (18) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (18), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.5, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.07.

(Example 19: Preparation of Acrylate Resin (19) with Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 132 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 50 parts by mass of acrylic acid, 44 parts by mass of dimethylolbutyric acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 79 parts by mass of diethylene glycol monomethyl ether acetate and 84 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (19 ). The nonvolatile content of this acid group-containing acrylate resin (19) was 65% by mass, and the acid value of the solid content was 81 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy groups possessed by the epoxy resin (19), and relative to 1 mole of epoxy groups possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.55, and the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid relative to 1 mole of epoxy group possessed by epoxy resin (1) is 1.0.

(Example 20: Preparation of methacrylate resin (1) having an acid group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 135 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 60 parts by mass of methacrylic acid, 40 parts by mass of dimethylolpropionic acid, and 1.6 parts by mass of triphenylphosphine, blowing in air, The reaction was carried out at 120°C for 10 hours. Next, 80 parts by mass of diethylene glycol monomethyl ether acetate and 84 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain a methacrylate resin having an acid group (1). The nonvolatile content of this methacrylate resin (1) having an acid group was 65 mass %, and the acid value of the solid content was 79 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.3 relative to 1 mole of epoxy group possessed by the epoxy resin (1), and relative to 1 mole of epoxy group possessed by the epoxy resin (1) , the molar number of tetrahydrophthalic anhydride is 0.55, relative to 1 molar of epoxy group possessed by epoxy resin (1), the total molar molar of carboxyl group possessed by methacrylic acid and dimethylolpropionic acid The number of ears is 1.0.

(Comparative Example 1: Preparation of Acrylate Resin (R1) having an Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 125 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 0.9 parts by mass was added. After adding 65 parts by mass of acrylic acid, 13 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, blowing air in The reaction was carried out at 120°C for 12 hours. Next, 74 parts by mass of diethylene glycol monomethyl ether acetate and 78 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (R1 ). The nonvolatile content of the acrylate resin (R1) having an acid group was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.1 relative to 1 mole of epoxy groups possessed by the epoxy resin (1), and relative to 1 mole of epoxy groups possessed by the epoxy resin (1) , the total molar number of carboxyl groups of acrylic acid and dimethylolpropionic acid is 1.0.

(Comparative Example 2: Preparation of Acrylate Resin (R2) having an Acid Group) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 136 parts by mass of diethylene glycol monomethyl ether acetate was added, 214 parts by mass of epoxy resin (1) was dissolved, and 1.0 parts by mass was added After adding 36 parts by mass of acrylic acid, 67 parts by mass of dimethylolpropionic acid, and 1.5 parts by mass of triphenylphosphine, after blowing in air, The reaction was carried out at 120°C for 12 hours. Next, 81 parts by mass of diethylene glycol monomethyl ether acetate and 85 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110° C. for 3 hours to obtain an acrylate resin having an acid group (R2 ). The nonvolatile content of this acid group-containing acrylate resin (R2) was 65% by mass, and the acid value of the solid content was 80 mgKOH/g. In addition, the number of moles of dimethylolpropionic acid is 0.5 relative to 1 mole of epoxy group contained in the epoxy resin (1), and the number of moles relative to 1 mole of epoxy group contained in the epoxy resin (1) is , the total molar number of carboxyl groups of methacrylic acid and dimethylolpropionic acid is 1.0.

(Example 21: Preparation of curable resin composition (1)) According to the mass parts shown in Table 1 and Table 2, the acrylate resin (1) having an acid group obtained in Example 1 and the o-cresol novolac epoxy resin (DIC Co., Ltd.) as a hardener were blended. "EPICLON N-680" manufactured by IGM), dipivaloerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, photopolymerization initiator ("Omnirad 907" manufactured by IGM Corporation), 2-ethyl-4- Methyl imidazole and phthalocyanine green were kneaded with a roll mill to obtain a curable resin composition (1).

(Examples 22 to 42: Preparation of curable resin compositions (2) to (22)) Curable resin compositions (2) to (22) were obtained in the same manner as in Example 21 according to the compositions and blending shown in Tables 1 and 2.

(Comparative Examples 3 and 4: Preparation of Curable Resin Compositions (R1) and (R2)) According to the composition and compounding shown in Table 2, in the same manner as in Example 21, curable resin compositions (R1) and (R2) were obtained.

The following evaluations were performed using the curable resin compositions (2) to (22), (R1) and (R2) obtained in the above-mentioned Examples and Comparative Examples.

[Evaluation method of alkali developability] After applying the curable resin composition obtained in each Example and Comparative Example on a glass substrate using a coater so that the film thickness would be 50 μm, it was dried at 80° C. for 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, and 140 minutes to produce samples with 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 with no residue remaining on the substrate was evaluated as a drying control range. In addition, the longer the drying control range is, the better the alkali developability is shown.

The compositions of the curable resin compositions (2) to (22) produced in Examples 21 to 42 and the curable resin compositions (R1) and (R2) produced in Comparative Examples 3 and 4 and the evaluation results are shown in Table 1 and Table 2.

[Table 1] Table 1 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Curable resin composition (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) Composition (parts by mass) Acrylate resin with acid group(1) 65 Acrylate resin with acid group (2) 65 Acrylate resin with acid group(3) 69 Acrylate resin with acid group(4) 65 Acrylate resin with acid group(5) 65 Acrylate resin with acid group(6) 65 Acrylate resin with acid group(7) 65 Acrylate resin with acid group(8) 65 Acrylate resin with acid group(9) 65 Acrylate resin with acid group(10) 60 Acrylate resin with acid group(11) 60 Acrylate resin with acid group(12) 60 hardener 19.7 19.7 21.1 19.4 19.4 19.7 19.9 14.0 12.5 27.4 28.3 28.8 Organic solvents 10.6 10.6 11.4 10.4 10.4 10.6 10.7 7.5 6.7 14.8 15.3 15.5 photopolymerization initiator 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 Dipivalerythritol hexaacrylate 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 2-Ethyl-4-methyl-imidazole 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.3 0.3 0.5 0.6 0.6 Phthalocyanine Green 0.5 0.5 0.5 0.4 0.4 0.5 0.5 0.4 0.4 0.5 0.5 0.5 Evaluation Alkali developability [dry control width (min)] 120 100 140 100 110 100 110 100 90 140 130 110

[Table 2] Table 2 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Comparative Example 3 Comparative Example 4 Curable resin composition (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (R1) (R2) Composition (parts by mass) Acrylate resin with acid group(1) 65 65 Acrylate resin with acid group(13) 65 Acrylate resin with acid group(14) 65 Acrylate resin with acid group(15) 65 Acrylate resin with acid group(16) 65 Acrylate resin with acid group(17) 65 Acrylate resin with acid group(18) 65 Acrylate resin with acid group(19) 65 Methacrylate resin with acid group (1) 65 Resin with acid group and polymerizable unsaturated group (1) 10 Resin with acid group and polymerizable unsaturated group (2) 10 Acrylate resin with acid group (R1) 65 Acrylate resin with acid group (R2) 65 hardener 19.7 19.4 19.7 19.7 19.7 19.7 19.9 19.4 22.6 22.7 19.7 19.7 Organic solvents 10.6 10.4 10.6 10.6 10.6 10.6 10.7 10.4 12.2 12.2 10.6 10.6 photopolymerization initiator 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.75 3.75 3.25 3.25 Dipivalerythritol hexaacrylate 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 7.5 7.5 6.5 6.5 2-Ethyl-4-methyl-imidazole 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.5 0.5 0.4 0.4 Phthalocyanine Green 0.5 0.4 0.5 0.5 0.5 0.5 0.5 0.4 0.5 0.5 0.5 0.5 Evaluation Alkali developability [dry control width (min)] 120 140 100 90 130 100 110 130 100 100 80 -

In addition, "-" in Table 2 means that it cannot develop.

(Example 43: Preparation of curable resin composition (23)) According to the mass parts shown in Table 3, the acrylate resin (1) having an acid group obtained in Example 1, and the o-cresol novolak type epoxy resin (“EPICLON” manufactured by DIC Co., Ltd.) as a hardener were blended. N-680”), 2-methyl-1-(4-methylthiophenyl)-2-𠰌linepropan-1-one (“Omnirad 907” manufactured by IGM Resins) as a photopolymerization initiator, As the organic solvent, diethylene glycol monomethyl ether acetate, a curable resin composition (22) was obtained.

(Examples 44 to 64: Preparation of curable resin compositions (24) to (44)) Curable resin compositions (24) to (44) were obtained in the same manner as in Example 43 according to the compositions and blending shown in Tables 3 and 4.

(Comparative Examples 5 and 6: Preparation of Curable Resin Compositions (R3) and (R4)) According to the composition and compounding shown in Table 4, in the same manner as in Example 43, curable resin compositions (R3) and (R4) were obtained.

The following evaluations were performed using the curable resin compositions (23) to (44), (R3) and (R4) obtained in the above-mentioned Examples and Comparative Examples.

[Method of measuring elongation] The elongation was measured by a tensile test. <Preparation of Test Piece 1> The curable resin compositions obtained in Examples and Comparative Examples were coated on copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm coater. After irradiating the ultraviolet-ray of 1000mJ/cm< ² > 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 1 (cured product).

<tensile test> The aforementioned test piece 1 was cut into a size of 10 mm×80 mm, and a tensile test of the test piece 1 was carried out under the following measurement conditions using a precision universal testing machine Autograph "AG-IS" manufactured by Shimadzu Corporation. The elongation (%) until the test piece was broken was measured and evaluated according to the following criteria.

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

[Evaluation method of substrate adhesiveness] The evaluation of substrate adhesiveness was performed by the measurement of peeling strength. <Preparation of Test Piece 2> The curable resin compositions obtained in the Examples and Comparative Examples were coated on copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm coater. After irradiating the ultraviolet-ray of 1000mJ/cm< ² > using a metal halide lamp, it heated at 160 degreeC for 1 hour, and obtained the test piece 2 (hardened material).

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

The compositions and The evaluation results are shown in Tables 3 and 4.

[table 3] table 3 Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Example 53 Example 54 Curable resin composition (twenty three) (twenty four) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) Composition (parts by mass) Acrylate resin with acid group(1) 65 Acrylate resin with acid group (2) 65 Acrylate resin with acid group(3) 69 Acrylate resin with acid group(4) 65 Acrylate resin with acid group(5) 65 Acrylate resin with acid group(6) 65 Acrylate resin with acid group(7) 65 Acrylate resin with acid group(8) 65 Acrylate resin with acid group(9) 65 Acrylate resin with acid group(10) 60 Acrylate resin with acid group(11) 60 Acrylate resin with acid group(12) 60 hardener 19.7 19.7 21.1 19.4 19.4 19.7 19.9 14.0 12.5 27.4 28.3 28.8 Organic solvents 10.6 10.6 11.4 10.4 10.4 10.6 10.7 7.5 6.7 14.8 15.3 15.5 photopolymerization initiator 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 Evaluation Elongation (%) 6.7 5.3 5.8 3.8 6.2 5.8 5.3 6.2 5.8 6.1 5.8 5.6 Adhesion (N/cm) 1.458 1.051 1.145 0.981 1.215 1.089 0.994 1.284 1.062 1.192 1.041 0.991

[Table 4] Table 4 Example 55 Example 56 Example 57 Example 58 Example 59 Example 60 Example 61 Example 62 Example 63 Example 64 Comparative Example 5 Comparative Example 6 Curable resin composition (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (R3) (R4) Composition (parts by mass) Acrylate resin with acid group(1) 65 65 Acrylate resin with acid group(13) 65 Acrylate resin with acid group(14) 65 Acrylate resin with acid group(15) 65 Acrylate resin with acid group(16) 65 Acrylate resin with acid group(17) 65 Acrylate resin with acid group(18) 65 Acrylate resin with acid group(19) 65 Methacrylate resin with acid group (1) 65 Resin with acid group and polymerizable unsaturated group (1) 10 Resin with acid group and polymerizable unsaturated group (2) 10 Acrylate resin with acid group (R1) 65 Acrylate resin with acid group (R2) 65 hardener 19.7 19.4 19.7 19.7 19.7 19.7 19.9 19.4 22.6 22.7 19.7 19.7 Organic solvents 10.6 10.4 10.6 10.6 10.6 10.6 10.7 10.4 12.2 12.2 10.6 10.6 photopolymerization initiator 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.75 3.75 3.25 3.25 Evaluation Elongation (%) 6.8 6.9 6.1 5.8 6.2 5.9 6.0 6.2 6.0 6.1 2.2 3.4 Adhesion (N/cm) 1.354 1.411 1.124 1.005 1.099 0.998 1.052 1.259 1.512 1.255 0.772 0.972

In addition, the description of the mass part of the acrylate resin which has an acid group, the methacrylate resin which has an acid group, and the resin which has an acid group and a polymerizable unsaturated group in Tables 1-4 belongs to a solid content value.

The "hardener" in Tables 1 to 4 represents an o-cresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

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

The "photopolymerization initiator" in Tables 1 to 4 represents "Omnirad-907" manufactured by IGM Resins.

Examples 21 to 42 shown in Tables 1 and 2 are examples of curable resin compositions using the acrylate resin having an acid group of the present invention. It was confirmed that these curable resin compositions have excellent alkali developability.

Moreover, Examples 43-64 shown in Table 3 and Table 4 are examples of the curable resin composition using the acrylate resin which has an acid group of this invention. It was confirmed that the cured products of these curable resin compositions had excellent elongation and adhesion.

On the other hand, Comparative Examples 3 and 4 use the compound (C) having a hydroxyl group and a carboxyl group defined in the present invention. An example of a curable resin composition having an acid group outside the range of 0.4 mol. It was confirmed that the alkali developability of these curable resin compositions was insufficient.

Moreover, in Comparative Examples 5 and 6, the compound (C) having a hydroxyl group and a carboxyl group defined in the present invention was used in an amount of 0.2 to 0.4 mol with respect to 1 mol of the epoxy group of the epoxy resin (A). An example of a curable resin composition of an acrylate resin having an acid group outside the ear range. It was confirmed that the elongation and substrate adhesiveness of these curable resin compositions were remarkably insufficient.

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Claims (10)

A (meth)acrylate resin with an acid group, which is based on Epoxy resin (A), Unsaturated unit acid (B), Compounds (C) with hydroxyl and carboxyl groups, The polybasic acid anhydride (D) is a (meth)acrylic resin with an acid group that is an essential raw material, It is characterized by, The compound (C) has at least two hydroxyl groups and at least one carboxyl group, The usage-amount of this compound (C) is the range of 0.2-0.4 mol with respect to 1 mol of epoxy groups of this epoxy resin (A). The (meth)acrylate resin having an acid group according to claim 1, wherein the compound (C) is dimethylolpropionic acid and/or dimethylolbutyric acid. The (meth)acrylate resin having an acid group as claimed in claim 1 or 2, wherein the unsaturated unit acid (B) and the The total number of moles of carboxyl groups contained in the compound (C) is in the range of 0.95 to 1.05 moles. The (meth)acrylate resin having an acid group according to any one of claims 1 to 3, wherein the polybasic acid anhydride (D) is 1 mole of the epoxy group possessed by the epoxy resin (A) The usage amount is in the range of 0.35 to 1 mole. The (meth)acrylate resin having an acid group according to any one of claims 1 to 4, wherein the epoxy resin (A) has a softening point of 80°C or higher. A curable resin composition characterized by comprising the (meth)acrylate resin having an acid group according to any one of claims 1 to 5, and a photopolymerization initiator. The curable resin composition according to claim 6, further comprising a resin having an acid group and a polymerizable unsaturated group other than the (meth)acrylate resin having an acid group. A hardened product, which is the hardened product of the curable resin composition of claim 6 or 7. An insulating material characterized by comprising the hardened material of claim 8. A solder resist member is characterized by comprising the hardened material of claim 8.