TWI848061B - Acid group-containing (meth) acrylate resin, curable resin composition, cured product, insulating material, solder resist resin material and solder resist component - Google Patents

Abstract

The present invention provides an acid-containing (meth)acrylate resin, a curable resin composition containing the same, a cured product composed of the aforementioned curable resin composition, an insulating material, a solder mask resin material, and a solder mask component; wherein the acid-containing (meth)acrylate resin is characterized in that the following components are used as necessary reaction raw materials: a reaction product (I) of an epoxy resin (A), an unsaturated monobasic acid (B), and a polyacid anhydride (C); an epoxy resin (D); and an unsaturated monobasic acid (E). The acid-containing (meth)acrylate resin has excellent photosensitivity and alkali developability, and can form a cured product with excellent elongation.

Description

Acid-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, solder resist resin material and solder resist component

The present invention relates to an acid-containing (meth)acrylate resin, a curable resin composition containing the same, a cured product composed of the aforementioned curable resin composition, an insulating material, a solder mask resin material, and a solder mask component; wherein the acid-containing (meth)acrylate resin has excellent alkali developability and high photosensitivity, and has excellent elongation in the cured product.

In recent years, epoxy acrylate resins containing acid groups obtained by esterifying epoxy resin with acrylic acid and then reacting with acid anhydride are widely used in solder mask resin materials for printed wiring boards. The required performance of solder mask resin materials can be listed as follows: curing with a small amount of light exposure; excellent alkali development; excellent heat resistance, strength, flexibility, stretching, dielectric properties, substrate adhesion, etc. in the cured product.

As a conventionally known solder resist resin material, an active energy ray-curable resin obtained by reacting a reaction product of a novolac-type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polyacid anhydride is known (for example, refer to the following patent document 1), but the elongation of the cured product does not meet the requirements for properties that will be gradually improved in the future, and is insufficient for the recent market requirements.

Therefore, a material with excellent alkali developability and high photosensitivity, as well as better elongation in the cured product, is required.

[Prior Art Literature] [Patent Literature]

Patent document 1 Japanese Patent Publication No. 61-243869

The problem to be solved by the present invention is to provide an acid-containing (meth)acrylate resin, a curable resin composition containing the same, a cured product composed of the aforementioned curable resin composition, an insulating material, a solder mask resin material, and a solder mask component; wherein the acid-containing (meth)acrylate resin has excellent alkali developability and high photosensitivity, and has excellent elongation in the cured product.

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems and found that the above-mentioned problems can be solved by using a (meth)acrylate resin containing an acid group, thereby completing the present invention. The characteristic of the (meth)acrylate resin containing an acid group is that the following components are used as necessary reaction raw materials: epoxy resin, unsaturated monobasic acid, and reaction product (I) of polyacid anhydride; epoxy resin; and unsaturated monobasic acid.

That is, the present invention relates to an acid-containing (meth)acrylate resin, a curable resin composition containing the same, a cured product composed of the curable resin composition, an insulating material, a solder mask resin material, and a solder mask component. The acid-containing (meth)acrylate resin is characterized in that the following components are used as necessary reaction raw materials: a reaction product (I) of an epoxy resin (A), an unsaturated monobasic acid (B), and a polyacid anhydride (C); an epoxy resin (D); and an unsaturated monobasic acid (E).

The acid-containing (meth)acrylate resin of the present invention has excellent alkali developability and high photosensitivity, and can form a cured product with excellent elongation, so it can be suitable for use in insulating materials, solder mask resin materials and solder mask components.

[Aspects for implementing the invention]

The acid-containing (meth)acrylate resin of the present invention is characterized in that the following components are used as necessary reaction raw materials: the reaction product (I) of epoxy resin (A), unsaturated monobasic acid (B), and polyacid anhydride (C); epoxy resin (D); and unsaturated monobasic acid (E).

In addition, in the present invention, "(meth)acrylate" refers to acrylate and/or methacrylate. Also, "(meth)acryl" refers to acryl and/or methacryl. Furthermore, "(meth)acrylic acid" refers to acrylic acid and/or methacrylic acid.

The reaction product (I) is obtained by reacting an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C).

Examples of the epoxy resin (A) include bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenol novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol type epoxy resins, Co-phenol novolac type epoxy resin, naphthol-cresol co-phenol novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, dibenzopyran type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. Among these, the preferred acid group-containing (meth)acrylate resins are bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, and dihydroxybenzene-type epoxy resins because they can provide an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and can form a cured product having excellent elongation.

The so-called aforementioned unsaturated monobasic acid (B) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the aforementioned acid group include: a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Examples of the aforementioned unsaturated monobasic acid (B) include: acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, etc. Furthermore, esters, acid halides, acid anhydrides, etc. of the aforementioned unsaturated monobasic acid may also be used. Such unsaturated monobasic acids may be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred because they can produce acid-containing (meth)acrylate resins with excellent alkaline developability and high photosensitivity, and can form cured products with excellent elongation.

As the aforementioned polyacid anhydride (C), for example, phthalic anhydride, succinic anhydride, trimellitic anhydride, pyrophyllic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenylsuccinic anhydride, dodecenylsuccinic anhydride, etc. These polyacid anhydrides can be used alone or in combination of two or more. Moreover, among these, tetrahydrophthalic anhydride and succinic anhydride are preferred because they can produce acid-containing (meth)acrylate resins having excellent developing properties and high photosensitivity and can form cured products having excellent elongation.

The method for producing the reaction product (I) is not particularly limited and can be produced by any method. For example, it can be produced by a method of reacting all the reaction raw materials at once or by reacting the reaction raw materials in sequence. Among them, from the perspective of easy reaction control, it is preferably produced by a method of reacting the epoxy resin (A) with the unsaturated monobasic acid (B) (step A1), and reacting the intermediate reaction product obtained in the step A1 with the polyacid anhydride (C) (step A2).

The aforementioned step A1 is a step of reacting the aforementioned epoxy resin (A) with the aforementioned unsaturated monoacid (B). The reaction is mainly to react the epoxy group of the epoxy resin (A) with the acid group of the aforementioned unsaturated monoacid (B). The reaction ratio of the reaction is preferably used in a range of 0.9 to 1.1 molar number of the acid group of the aforementioned unsaturated monoacid (B) relative to 1 mole of the epoxy group of the aforementioned epoxy resin (A), and more preferably in a range of 0.95 to 1.05, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and being able to form a cured product having excellent elongation.

The reaction of the aforementioned step A1 can be carried out by heating and stirring at a temperature of about 80~150℃. Furthermore, the reaction of the aforementioned step A1 can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; toluene, xylene, and solvent oil. naphtha) and other aromatic solvents; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, saloxaline, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc.; glycol ether solvents such as alkanediol monoalkyl ether, dialkanediol monoalkyl ether, dialkanediol monoalkyl ether acetate, etc.; methoxypropanol, cyclohexanone, methyl saloxaline, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These organic solvents can be used alone or in combination of two or more. In addition, the amount of the above-mentioned organic solvents used is preferably used in a range of about 0.1 to 5 times the total mass of the reaction raw materials in order to improve the reaction efficiency.

啉、吡啶、1,8-二吖雙環[5.4.0]十一烯-7(DBU)、1,5-二吖雙環[4.3.0]壬烯-5(DBN)、1,4-二吖雙環[2.2.2]辛烷(DABCO)、三正丁胺或者二甲基苄基胺、丁胺、辛胺、單乙醇胺、二乙醇胺、三乙醇胺、咪唑、1-甲基咪唑、2,4-二甲基咪唑、1,4-二乙基咪唑、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(N-苯基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、四甲基氫氧化銨等之胺化合物類；三辛基甲基氯化銨、三辛基甲基乙酸銨等之四級銨鹽類；三甲基膦、三丁基膦、三苯基膦等之膦類；四甲基氯化鏻、四乙基氯化鏻、四丙基氯化鏻、四丁基氯化鏻、四丁基溴化鏻、三甲基(2-羥丙基)氯化鏻、三苯基氯化鏻、苄基氯化鏻等之鏻鹽類；二月桂酸二丁基錫、三月桂酸辛基錫、二乙酸辛基錫、二乙酸二辛基錫、二新癸酸二新辛基錫、二乙酸二丁基錫、辛酸錫、1,1,3,3-四丁基-1,3-十二醯基氧二錫氧烷(1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane)等之有機錫化合物；辛酸鋅、辛酸鉍等之有機金屬化合物；辛酸錫等之無機錫化合物；無機金屬 化合物等。此等之鹼性觸媒可單獨使用，亦可併用2種以上。 As the aforementioned alkaline catalyst, for example, N-methyl

1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole Amine compounds such as 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, trioctylmethylammonium acetate Phosphine salts such as trimethylphosphine, tributylphosphine, triphenylphosphine, etc.; Phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium chloride, etc.; Dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate Tin, dibutyltin diacetate, tin octoate, 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane and other organic tin compounds; zinc octoate, bismuth octoate and other organic metal compounds; tin octoate and other inorganic tin compounds; inorganic metal compounds, etc. These alkaline catalysts can be used alone or in combination of two or more.

The aforementioned step A2 is a step of reacting the intermediate reaction product obtained in the aforementioned step A1 with the aforementioned polyacid anhydride (C). The reaction is mainly to react the hydroxyl group of the aforementioned intermediate reaction product with the aforementioned polyacid anhydride (C). The aforementioned intermediate reaction product contains hydroxyl groups generated by the ring opening of the epoxy group of the aforementioned epoxy resin (A). The reaction ratio of the aforementioned polyacid anhydride (C) is preferably adjusted so that the acid value of the resulting reaction product (I) is about 70~160mgKOH/g.

The reaction of the aforementioned step A2 can be carried out, for example, by heating and stirring at a temperature of about 70 to 140°C in the presence of an appropriate alkaline catalyst. In addition, the reaction can also be carried out in an organic solvent as needed. Furthermore, the aforementioned alkaline catalyst and the aforementioned organic solvent can be the same as the alkaline catalyst and organic solvent mentioned above, and they can be used alone or in combination of two or more.

As the aforementioned epoxy resin (D), the aforementioned epoxy resin (A) may be used as an example. The aforementioned epoxy resin (D) may be used alone or in combination of two or more. Furthermore, the aforementioned epoxy resin (A) and the aforementioned epoxy resin (D) may be the same or different.

In addition, the epoxy equivalent of the aforementioned epoxy resin (D) is preferably less than 180 g/equivalent, and more preferably in the range of 100 to 180 g/equivalent, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity, and being able to form a cured product having excellent elongation.

As the unsaturated monobasic acid (E), the unsaturated monobasic acid (B) exemplified above can be used. The unsaturated monobasic acid (E) can be used alone or in combination of two or more. The unsaturated monobasic acid (B) and the unsaturated monobasic acid (E) can be the same or different.

The method for producing the acid group-containing (meth)acrylate resin is not particularly limited, and the resin may be produced by any method. For example, the resin may be produced by reacting all the reaction materials including the reaction product (I), the epoxy resin (D), and the unsaturated monobasic acid (E) together; or by reacting the reaction product (I) with the epoxy resin (D) (step 1a), and then reacting the product of step 1a with the unsaturated monobasic acid (E) (step 2a). Alternatively, the resin may be produced by reacting the epoxy resin (D) with the unsaturated monobasic acid (E) to obtain the reaction product (II) (step 1b), and then reacting the reaction product (II) with the reaction product (I) (step 2b). Among them, from the viewpoint of being able to obtain an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and being able to form a cured product having excellent elongation, it is preferred to produce the resin by a method of obtaining a reaction product (II) in advance and then reacting the reaction product (II) with the reaction product (I).

The aforementioned step 1a is a step of reacting the aforementioned reaction product (I) with the aforementioned epoxy resin (D). The reaction is mainly to react the acid group of the aforementioned reaction product (I) with the epoxy group of the aforementioned epoxy resin (D). The reaction ratio of the reaction is preferably used in a ratio of 0.3 to 0.8 moles of the epoxy group of the aforementioned epoxy resin (D) relative to 1 mole of the acid group of the aforementioned reaction product (I), and more preferably in a ratio of 0.4 to 0.8, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and forming a cured product having excellent elongation.

The reaction of the reaction product (I) and the epoxy resin (D) can be carried out by heating and stirring at a temperature of about 80 to 150°C in the presence of an appropriate alkaline catalyst. In addition, the reaction can also be carried out in an organic solvent as needed. Furthermore, the alkaline catalyst and the organic solvent can be the same as the alkaline catalyst and the organic solvent mentioned above, and they can be used alone or in combination of two or more.

As the aforementioned step 2a, the product obtained in the aforementioned step 1a is reacted with the aforementioned unsaturated monobasic acid (E). The reaction is mainly to react the epoxy group of the aforementioned product with the acid group of the aforementioned unsaturated monobasic acid (E). The reaction ratio of the reaction is preferably used in a ratio in the range of 0.9 to 1.1 in terms of the molar number of the acid group of the aforementioned unsaturated monobasic acid (E) relative to 1 mole of the epoxy group of the aforementioned product.

The reaction of the aforementioned step 2a can be carried out by heating and stirring at a temperature of about 80-150°C in the presence of an appropriate alkaline catalyst. When step 1a and step 2a are carried out continuously, the alkaline catalyst may not be added, or it may be added appropriately. In addition, the reaction can also be carried out in an organic solvent as needed. Furthermore, the aforementioned alkaline catalyst and the aforementioned organic solvent can be the same as the alkaline catalyst and organic solvent mentioned above, and they can be used alone or in combination of two or more.

The aforementioned step 1b is a step of producing a reaction product (II). The aforementioned reaction product (II) is obtained by reacting the aforementioned epoxy resin (D) and the aforementioned unsaturated monobasic acid (E). The reaction of the aforementioned epoxy resin (D) and the aforementioned unsaturated monobasic acid (E) can obtain an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity, and can form a cured product having excellent elongation. It is preferred to use the acid group of the aforementioned unsaturated monobasic acid (E) in a ratio of 0.25 to 0.75, and more preferably in a ratio of 0.3 to 0.7, relative to 1 mol of epoxy groups of the aforementioned epoxy resin (D).

The reaction of the aforementioned step 1b can be carried out by heating and stirring at a temperature of about 70 to 150°C. Furthermore, the reaction of the aforementioned step 1b can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used. Furthermore, the aforementioned alkaline catalyst and the aforementioned organic solvent can be the same as the alkaline catalyst and organic solvent mentioned above, and they can be used alone or in combination of two or more.

As the aforementioned reaction product (II), it is preferred to have an epoxy group and a (meth)acrylic group in the same molecule in order to obtain an acid-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and forming a cured product having excellent elongation.

As the aforementioned step 2b, it is a step of reacting the aforementioned reaction product (II) with the aforementioned reaction product (I). The reaction is mainly to react the acid group of the aforementioned reaction product (I) with the epoxy group of the aforementioned reaction product (II). The reaction ratio of the reaction is preferably used in a ratio of 0.03 to 0.4 moles of epoxy groups of the aforementioned reaction product (II) relative to 1 mole of the acid group of the aforementioned reaction product (I), and more preferably in a ratio of 0.05 to 0.4, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and forming a cured product having excellent elongation.

In addition, the reaction of the aforementioned step 2b can be carried out under heating and stirring at a temperature of about 90 to 150°C. Furthermore, the reaction of the aforementioned step 2b can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used. Furthermore, the aforementioned alkaline catalyst and the aforementioned organic solvent can be the same as the alkaline catalyst and organic solvent mentioned above, and they can be used alone or in combination of two or more.

The acid value of the acid-containing (meth)acrylate resin of the present invention is preferably in the range of 50 to 140 mgKOH/g, and more preferably in the range of 60 to 120 mgKOH/g, in order to obtain an acid-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and forming a cured product having excellent elongation. In addition, the acid value of the acid-containing (meth)acrylate resin in the present invention is the value measured by the neutralization titration method of JIS K 0070 (1992).

Furthermore, the weight average molecular weight (Mw) of the aforementioned acid group-containing (meth)acrylate resin is preferably in the range of 1,000 to 20,000. In addition, in the present invention, the weight average molecular weight (Mw) refers to the value measured by gel permeation chromatography (GPC).

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

啉基苯基)-丁酮-1,2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮等烷基苯酮系光聚合起始劑；2,4,6-三甲基苄醯基-二苯基-膦氧化物等醯膦氧化物系光聚合起始劑；二苯甲酮化合物等分子內除氫型光聚合起始劑等。此等可各自單獨使用，亦可併用2種以上。 The aforementioned photopolymerization initiator can be selected and used appropriately according to the type of active energy rays to be irradiated. In addition, photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds can also be used in combination. Specific examples of photopolymerization initiators include: 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-

1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

[0043] Alkyl phenone-based photopolymerization initiators such as [(1,2-(4-(6-( ...

(thioxanthone)及9-氧硫

衍生物、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、二苯基(2,4,6-三甲氧基苯甲醯)氧化膦、2,4,6-三甲基苯甲醯二苯基氧化膦、雙(2,4,6-三甲基苯甲醯)苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-

啉基丙烷-1- 酮、2-苄基-2-二甲胺-1-(4-

啉基苯基)-1-丁酮等。 Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 9-oxothiophene,

(thioxanthone) and 9-oxosulfur

derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-

1-Phenylpropane-1-one, 2-benzyl-2-dimethylamine-1-(4-

1-Butanone, etc.

Examples of commercially available photopolymerization initiators include: "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad- 2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA" (manufactured by Nippon Kayaku Co., Ltd.), "VICURE-10", "VICURE-55" (manufactured by Stauffer Chemical Co., Ltd.), "TRIGONALP1" (AKZO), "SANDORAY 1000" (SANDOZ), "DEAP" (APJOHN), "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD" (WARD BLEKINSOP), "Runtecure-1104" (Runtec), etc. These photopolymerization initiators can be used alone or in combination of two or more.

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

The curable resin composition of the present invention may also contain other resin components besides the aforementioned acid group-containing (meth)acrylate resin. Examples of the aforementioned other resin components include resins (F) having acid groups and polymerizable unsaturated bonds, various (meth)acrylate monomers, etc.

As the resin (F) having an acid group and a polymerizable unsaturated bond, any resin having an acid group and a polymerizable unsaturated bond may be used, and examples thereof include epoxy resins having an acid group and a polymerizable unsaturated bond, urethane resins having an acid group and a polymerizable unsaturated bond, acrylic resins having an acid group and a polymerizable unsaturated bond, amide imide resins having an acid group and a polymerizable unsaturated bond, and acrylamide resins having an acid group and a polymerizable unsaturated bond.

Examples of the aforementioned acid groups include carboxyl, sulfonic acid, phosphoric acid, etc.

Examples of the aforementioned epoxy resins having an acid group and a polymerizable unsaturated bond include: an epoxy (meth)acrylate resin containing an acid group using an epoxy resin, an unsaturated monobasic acid, and a polyacid anhydride as necessary reaction raw materials, and an epoxy (meth)acrylate resin containing an acid group and a carbamate group using an epoxy resin, an unsaturated monobasic acid, a polyacid anhydride, a polyisocyanate compound, and a hydroxyl-containing (meth)acrylate compound as reaction raw materials.

As the aforementioned epoxy resin, the epoxy resin (A) mentioned above can be used. The aforementioned epoxy resin can be used alone or in combination of two or more.

As the unsaturated monobasic acid, those exemplified as the unsaturated monobasic acid (B) mentioned above can be used. The unsaturated monobasic acid can be used alone or in combination of two or more.

As the aforementioned polyacid anhydride, the examples of the aforementioned polyacid anhydride (C) can be used. The aforementioned polyacid anhydride can be used alone or in combination of two or more.

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

[In the formula, ^R1 is independently a hydrogen atom or a alkyl group having 1 to 6 carbon atoms. ^R2 is independently a bonding point to an alkyl group having 1 to 4 carbon atoms or to the structural part represented by the structural formula (1) through a methylene group marked with an asterisk. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15].

Examples of the hydroxyl-containing (meth)acrylate compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trihydroxymethylpropane (meth)acrylate, trihydroxymethylpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di-trihydroxymethylpropane (meth)acrylate, di-trihydroxymethylpropane di(meth)acrylate, and di-trihydroxymethylpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified products introduced with (poly)oxyethylene chains such as (poly)oxypropylene chains and (poly)oxytetramethylene chains into the molecular structure of the aforementioned various hydroxyl-containing (meth)acrylate compounds, or (poly)lactone modified products introduced with (poly)lactone structures into the molecular structure of the aforementioned various hydroxyl-containing (meth)acrylate compounds, etc. can also be used. These hydroxyl-containing (meth)acrylate compounds can be used alone or in combination of two or more.

The method for producing the aforementioned epoxy resin having an acid group and a polymerizable unsaturated bond is not particularly limited and can be produced by any method. The production of the aforementioned epoxy resin having an acid group and a polymerizable unsaturated bond can be carried out in an organic solvent as needed, and an alkaline catalyst can also be used as needed.

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

As the aforementioned alkaline catalyst, the same alkaline catalyst as the above-mentioned one can be used. The aforementioned alkaline catalyst can be used alone or in combination of two or more.

As the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond, for example, there can be cited those obtained by reacting a polyisocyanate compound, a hydroxyl-containing (meth)acrylate compound, a carboxyl-containing polyol compound, and a polyacid anhydride as required, and a polyol compound other than the aforementioned carboxyl-containing polyol compound, or those obtained by reacting a polyisocyanate compound, a hydroxyl-containing (meth)acrylate compound, a polyacid anhydride, and a polyol compound other than the carboxyl-containing polyol compound, etc.

As the aforementioned polyisocyanate compound, the same polyisocyanate compound as the above-mentioned polyisocyanate compound can be used. The aforementioned polyisocyanate compound can be used alone or in combination of two or more.

As the aforementioned hydroxyl-containing (meth)acrylate compound, the same one as the aforementioned hydroxyl-containing (meth)acrylate compound can be used. The aforementioned hydroxyl-containing (meth)acrylate compound can be used alone or in combination of two or more.

Examples of the aforementioned carboxyl-containing polyol compounds include 2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethylbutyric acid, and 2,2-dihydroxymethylpentanoic acid. The aforementioned carboxyl-containing polyol compounds may be used alone or in combination of two or more.

As the aforementioned polyacid anhydride, the examples of the aforementioned polyacid anhydride (C) can be used. The aforementioned polyacid anhydride can be used alone or in combination of two or more.

As polyol compounds other than the aforementioned carboxyl-containing polyol compounds, for example: aliphatic polyol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, trihydroxymethylpropane, ditrihydroxymethylpropane, neopentyltriol, dipentyltriol, etc.; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified products in which (poly)oxyethylene chains such as (poly)oxypropylene chains and (poly)oxytetramethylene chains are introduced into the molecular structures of the aforementioned various polyol compounds; lactone modified products in which (poly)lactone structures are introduced into the molecular structures of the aforementioned various polyol compounds, etc. The aforementioned polyol compounds other than the carboxyl-containing polyol compounds may be used alone or in combination of two or more.

The method for producing the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited and can be produced by any method. The production of the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond can also be carried out in an organic solvent as needed, and can also use an alkaline catalyst as needed.

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

As the aforementioned alkaline catalyst, the same alkaline catalyst as the above-mentioned one can be used. The aforementioned alkaline catalyst can be used alone or in combination of two or more.

Examples of the aforementioned acrylic resin having an acid group and a polymerizable unsaturated bond include: a reaction product obtained by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the obtained acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups to introduce a (meth)acryloyl group, or a reaction product obtained by reacting the hydroxyl group in the aforementioned reaction product with a polyacid anhydride.

The acrylic resin intermediate may be copolymerized with a compound containing other polymerizable unsaturated groups in addition to the (meth)acrylate compound (α) as required. The aforementioned compounds containing other polymerizable unsaturated groups include, for example: (meth) alkyl acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (meth) acrylates containing alicyclic structures such as cyclohexyl (meth) acrylate, isoborneol (meth) acrylate, and dicyclopentanyl (meth) acrylate; (meth) acrylates containing aromatic rings such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl acrylate; (meth) acrylates containing silyl groups such as 3-methacryloyloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can 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), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the aforementioned (meth)acrylate compound (α), an isocyanate group-containing (meth)acrylate is preferably used as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the aforementioned (meth)acrylate compound (α), an epoxypropyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound (β). When using an isocyanate group-containing (meth)acrylate as the aforementioned (meth)acrylate compound (α), it is preferred to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When using an epoxypropyl group-containing (meth)acrylate as the aforementioned (meth)acrylate compound (α), it is preferred to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The aforementioned (meth)acrylate compound (β) may be used alone or in combination of two or more.

The aforementioned polyacid anhydride can be used as an example of the aforementioned polyacid anhydride (C). The aforementioned polyacid anhydride can be used alone or in combination of two or more.

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited and can be produced by any method. The production of the acrylic resin having an acid group and a polymerizable unsaturated bond can be carried out in an organic solvent as required, or an alkaline catalyst can be used as required.

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

As the aforementioned alkaline catalyst, the same alkaline catalyst as the above-mentioned one can be used. The aforementioned alkaline catalyst can be used alone or in combination of two or more.

As the aforementioned amide-imide resin having an acid group and a polymerizable unsaturated bond, for example, there can be cited: a compound obtained by reacting an amide-imide resin having an acid group and/or an acid anhydride group, a hydroxyl-containing (meth)acrylate compound and/or an epoxy-containing (meth)acrylate compound, and a compound having one or more reactive functional groups selected from the group including a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group as required. In addition, the compound having the aforementioned reactive functional group may or may not have a (meth)acryloyl group. .

The amide imide resin may have only one of an acid group or an anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a hydroxyl-containing (meth)acrylate compound or a (meth)acryloyl-containing epoxide, it is preferred to have an anhydride group, and it is more preferred to have both an acid group and an anhydride group. The acid value of the amide imide resin is preferably in the range of 60 to 350 mgKOH/g when measured under neutral conditions, i.e., when the anhydride group is not ring-opened. On the other hand, the measured value under conditions such as the presence of water and when the anhydride group is ring-opened is preferably in the range of 61 to 360 mgKOH/g.

Examples of the aforementioned amide imide resin include those obtained using polyisocyanate compounds and polyacid anhydrides as reaction raw materials.

As the aforementioned polyisocyanate compound, the same polyisocyanate compound as the above-mentioned polyisocyanate compound can be used. The aforementioned polyisocyanate compound can be used alone or in combination of two or more.

As the aforementioned polyacid anhydride, the examples of the aforementioned polyacid anhydride (C) can be used. The aforementioned polyacid anhydride can be used alone or in combination of two or more.

Furthermore, the aforementioned amide imide resin may also be used in combination with a polyacid as a reaction raw material in addition to the aforementioned polyisocyanate compound and polyacid anhydride as needed.

As the aforementioned polyacid, any compound having two or more carboxyl groups in one molecule may be used. Examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, hexaconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2. 1] heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the aforementioned polyacid, for example, a copolymer of a covalent diene vinyl monomer and acrylonitrile, that is, a polymer having a carboxyl group in its molecule can also be used. These polyacids can be used alone or in combination of two or more.

As the aforementioned hydroxyl-containing (meth)acrylate compound, the same one as the aforementioned hydroxyl-containing (meth)acrylate compound can be used. The aforementioned hydroxyl-containing (meth)acrylate compound can be used alone or in combination of two or more.

Examples of the aforementioned epoxy-containing (meth)acrylate compounds include: (meth)acrylate monomers containing epoxypropyl groups such as epoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate epoxypropyl ether, and epoxyhexylmethyl (meth)acrylate; mono(meth)acrylates of epoxypropyl ether compounds such as dihydroxyphenyl diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy-containing (meth)acrylate compounds may be used alone or in combination of two or more.

The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated bond is not particularly limited and can be produced by any method. The production of the amide-imide resin having an acid group and a polymerizable unsaturated bond can be carried out in an organic solvent as required, or an alkaline catalyst can be used as required.

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

As the aforementioned alkaline catalyst, the same alkaline catalyst as the above-mentioned one can be used. The aforementioned alkaline catalyst can be used alone or in combination of two or more.

Examples of the aforementioned acrylamide resin having an acid group and a polymerizable unsaturated bond include: those obtained by reacting a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkyl carbonate, an N-alkoxyalkyl (meth) acrylamide compound, a polyacid anhydride, and an unsaturated monoacid as required.

The aforementioned compound containing a phenolic hydroxyl group refers to a compound having at least two phenolic hydroxyl groups in the molecule. Examples of the aforementioned compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).

In the above structural formulas (2-1) to (2-4), ^R1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and ^R2 is independently a hydrogen atom or a methyl group. In addition, p is an integer greater than or equal to 0 or 1, preferably an integer greater than or equal to 0 or 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer greater than or equal to 2, preferably 2 or 3. In addition, regarding the position of the substituent on the aromatic ring in the above structural formula, it is arbitrary, which means that, for example, in the naphthalene ring of structural formula (2-2), the substitution can be made on any ring, in structural formula (2-3), the substitution can be made on any ring of the benzene ring present in one molecule, and in structural formula (2-4), the substitution can be made on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is shown as p and q.

Furthermore, as the aforementioned phenolic hydroxyl-containing compound, for example, a reaction product of a compound having one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) as essential reaction raw materials, and a reaction product of a compound having at least two phenolic hydroxyl groups in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) as essential reaction raw materials can also be used. Furthermore, a novolac-type phenolic resin using one or more compounds having one phenolic hydroxyl group in the molecule as reaction raw materials, and a novolac-type phenolic resin using one or more compounds having at least two phenolic hydroxyl groups in the molecule as reaction raw materials can also be used.

[In formula (X-1), h is 0 or 1. In formulas (X-2) to (X-5), ^R3 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 of 1 to 4. In formulas (X-2), (X-3) and (X-5), Z is any one of a vinyl group, a halogenmethyl group, a hydroxymethyl 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].

Examples of the compounds having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).

In the above structural formulas (3-1) to (3-4), ^R4 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and ^R5 is independently a hydrogen atom or a methyl group. In addition, p is an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and most preferably 0. In addition, the position of the substituent on the aromatic ring in the above structural formula is arbitrary, which means that, for example, in the naphthyl ring of the structural formula (3-2), the substitution can be made on any ring of the benzene ring present in one molecule in the structural formula (3-3), and in the structural formula (3-4), the substitution can be made on any ring of the benzene ring present in one molecule.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above structural formulas (2-1) to (2-4) can be used.

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

As the aforementioned oxirane, for example, ethylene oxide, propylene oxide, butylene oxide, pentene oxide, etc. can be listed. Among these, ethylene oxide or propylene oxide is preferred because it can obtain a curable resin composition having excellent alkali developability and high photosensitivity, and can form a cured product with excellent elongation. The aforementioned oxirane can be used alone or in combination of two or more.

As the aforementioned alkyl carbonate, for example, ethyl carbonate, propyl carbonate, butyl carbonate, pentyl carbonate, etc. can be listed. Among them, ethyl carbonate or propyl carbonate is preferred because it can obtain a curable resin composition having excellent alkali developability and high photosensitivity, and can form a cured product having excellent elongation. The aforementioned alkyl carbonate can be used alone or in combination of two or more.

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

As the aforementioned polyacid anhydride, the examples of the aforementioned polyacid anhydride (C) can be used. The aforementioned polyacid anhydride can be used alone or in combination of two or more.

As the aforementioned unsaturated monobasic acid, those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used. The aforementioned unsaturated monobasic acid can be used alone or in combination of two or more.

The method for producing the aforementioned acrylamide resin having an acid group and a polymerizable unsaturated bond is not particularly limited and can be produced by any method. The production of the aforementioned acrylamide resin having an acid group and a polymerizable unsaturated bond can be carried out in an organic solvent as required, and an alkaline catalyst or an acidic catalyst can be used as required.

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

As the aforementioned alkaline catalyst, the same alkaline catalyst as the above-mentioned one can be used. The aforementioned alkaline catalyst can be used alone or in combination of two or more.

Examples of the aforementioned 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, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These acidic catalysts may be used alone or in combination of two or more.

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

Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; cyclohexyl(meth)acrylate, isoborneol(meth)acrylate, and adamantane(meth)acrylate; esters; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, phenyl(meth)acrylate, phenylbenzyl(meth)acrylate, phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxy(meth)acrylate, Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as benzyl acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the aforementioned various mono(meth)acrylate monomers; Lactone-modified mono(meth)acrylate compounds with a (poly)lactone structure introduced into the molecular structure; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate alicyclic di(meth)acrylate compounds such as dicyclopentyl di(meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate, bisphenol di(meth)acrylate; (poly)oxyalkyl chains such as (poly)oxyethyl chains, (poly)oxypropyl chains, (poly)oxytetramethylene chains are introduced into the molecular structure of the aforementioned di(meth)acrylate compounds; di(meth)acrylate compounds modified with polyoxyalkylene; di(meth)acrylate compounds modified with lactone structure introduced into the molecular structure of the aforementioned di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trihydroxymethylpropane tri(meth)acrylate and glycerol tri(meth)acrylate; di(meth)acrylate compounds modified with polyoxyalkylene chain and polyoxypropylene chain introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compounds; (poly)oxyalkylene-modified tri(meth)acrylate compounds containing (poly)oxyalkylene chains such as (poly)oxytetramethylene chains, (poly)oxytetramethylene chains, etc.; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compounds; aliphatic poly(meth)acrylates having four or more functional groups such as neopentylthol tetra(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, dipentylthol hexa(meth)acrylate, etc. Acrylate compounds; (poly)oxyalkyl modified poly(meth)acrylate compounds with more than four functional groups, such as (poly)oxyethyl chains, (poly)oxypropyl chains, (poly)oxytetramethylene chains, etc., introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds; (poly)lactone modified poly(meth)acrylate compounds with more than four functional groups, such as (poly)lactone structures, introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds, etc. The aforementioned various (meth)acrylate monomers may be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention may contain various additives such as curing agent, curing accelerator, organic solvent, inorganic microparticles, polymer microparticles, pigment, defoaming agent, viscosity regulator, leveling agent, flame retardant, storage stabilizer, etc. as needed.

As the aforementioned hardener, there is no particular limitation as long as it has a functional group that can react with the carboxyl group in the aforementioned acid group-containing (meth)acrylate resin, and examples thereof include epoxy resins. Examples of the aforementioned epoxy resins include bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenol novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol copolymer type epoxy resins, and the like. Novolac type epoxy resin, naphthol-cresol co-novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, dibenzopyran type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. Among these, the curable resin composition that can form a cured product having excellent alkali developability and high photosensitivity and excellent elongation is preferably a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a biphenol novolac type epoxy resin, a naphthol novolac type epoxy resin, a naphthol-phenol co-reduction novolac type epoxy resin, a naphthol-cresol co-reduction novolac type epoxy resin, etc. Novolac type epoxy resins are particularly preferred, and those having a softening point in the range of 20 to 120°C are particularly preferred.

As the aforementioned hardening accelerator, it is a thing which promotes the hardening reaction of the aforementioned hardener. When epoxy resin is used as the aforementioned hardener, phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acid, amine salts, etc. can be listed. Such hardening accelerators can be used alone or in combination of two or more. In addition, the addition amount of the aforementioned hardening accelerator is preferably used in the range of 1 to 10 parts by mass relative to 100 parts by mass of the aforementioned hardener.

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

The cured product of the present invention can be obtained by irradiating the aforementioned curable resin composition with active energy rays. Examples of the aforementioned active energy rays include ultraviolet rays, electron rays, ionizing radiation such as α rays, β rays, and γ rays. In addition, when ultraviolet rays are used as the aforementioned active energy rays, in order to more efficiently perform the curing reaction of ultraviolet rays, the irradiation can also be performed in an inert gas environment such as nitrogen, or in an air environment.

As a source of ultraviolet light, from the perspective of practicality and economy, ultraviolet lamps are generally used. Specifically, they include: low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

The cumulative light intensity of the active energy ray is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , and more preferably 50 to 1,000 mJ/cm ² . The cumulative light intensity within the above range is preferred because it can prevent or suppress the generation of uncured portions.

Furthermore, the aforementioned active energy ray irradiation can be carried out in one stage or in two or more stages.

Furthermore, the cured product of the present invention has excellent tensile strength and can be used as, for example, solder resist, interlayer insulation material, packaging material, underfill material, circuit component packaging bonding layer, or integrated circuit component and circuit substrate bonding layer in semiconductor device applications. In addition, it can be used as thin film transistor protective film, liquid crystal color filter protective film, color filter pigment photoresist, black matrix photoresist, spacer, etc. in thin display applications represented by LCD and OELD. Among these, it can be particularly ideally used for solder resist applications.

The solder mask resin material of the present invention is composed of the aforementioned curable resin composition.

The solder resist component of the present invention can be obtained, for example, by the following method: the aforementioned solder resist resin material is applied to the substrate, the organic solvent is evaporated and dried in a temperature range of about 60 to 100°C, then exposed with active energy rays through a photomask having a desired pattern, the unexposed portion is developed with an alkaline aqueous solution, and then heated and hardened at a temperature range of about 140 to 200°C.

As the aforementioned substrate, there can be cited, for example, metal foils such as copper foil and aluminum foil.

[Implementation example]

The following examples and comparative examples are given to illustrate the present invention in more detail.

The acid value of the acid group-containing (meth)acrylate resin in this embodiment is measured by the neutralization titration method of JIS K 0070 (1992).

The molecular weight of the acid-containing (meth)acrylate resin in this embodiment is measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by TOSOH Co., Ltd., column: protective column "HXL-L" manufactured by Tosoh Co., Ltd.

+Tosoh Co., Ltd. "TSK-GEL G2000HXL"

+Tosoh Co., Ltd. "TSK-GEL G2000HXL"

+Tosoh Co., Ltd. "TSK-GEL G3000HXL"

+Tosoh Co., Ltd. "TSK-GEL G4000HXL"

Detector: RI (differential refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by TOSOH Co., Ltd.

Measurement conditions: column temperature 40℃

Expand solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of the aforementioned "GPC-8020 Model II Version 4.10", the molecular weight uses the following known monodisperse polystyrene.

(Using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: A tetrahydrofuran solution converted to 1.0 mass % of the resin solid content was filtered through a microfilter (50μL)

(Synthesis Example 1: Preparation of reaction product (II-1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 376 parts by mass of a bisphenol A epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent 188 g/equivalent, hereinafter referred to as "bisphenol A epoxy resin (1)") were charged, 0.22 parts by mass of dibutyl hydroxytoluene as an antioxidant and 0.22 parts by mass of p-hydroxyanisole (methoquinone) as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.22 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100°C for 10 hours while blowing air. Then, after confirming that the acid value is less than 1 mgKOH/g, 0.22 parts by mass of oxalic acid is added and stirred at 70°C for 3 hours to obtain a reaction product (II-1). The epoxy equivalent of this reaction product (II-1) is 478 g/equivalent. In addition, the molar number of the acid group of acrylic acid is 0.5 per 1 mol of epoxy group of bisphenol A type epoxy resin (1).

(Synthesis Example 2: Preparation of reaction product (II-2))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of a bisphenol A epoxy resin ("EPICLON 850CRP" manufactured by DIC Corporation, epoxy equivalent 173 g/equivalent, hereinafter referred to as "bisphenol A epoxy resin (2)") were charged, 0.21 parts by mass of dibutyl hydroxytoluene as an antioxidant and 0.21 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100°C for 10 hours while blowing air. Then, after confirming that the acid value is less than 1 mgKOH/g, 0.21 parts by mass of oxalic acid is added and stirred at 70°C for 3 hours to obtain a reaction product (II-2). The epoxy equivalent of this reaction product (II-2) is 450 g/equivalent. In addition, the molar number of the acid group of acrylic acid is 0.5 per 1 mol of epoxy group of bisphenol A type epoxy resin (2).

(Synthesis Example 3: Preparation of reaction product (II-3))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of bisphenol A epoxy resin (2) was charged, 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.18 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, 22 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 100°C for 5 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.18 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain a reaction product (II-3). The epoxide equivalent of this reaction product (II-3) was 241 g/equivalent. Furthermore, the molar number of the acid groups in acrylic acid is 0.15 per 1 mol of the epoxy groups in the bisphenol A type epoxy resin (2).

(Synthesis Example 4: Preparation of reaction product (II-4))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of bisphenol A epoxy resin (2) was charged, 0.19 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.19 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, 43 parts by mass of acrylic acid and 0.19 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 100°C for 8 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.19 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain a reaction product (II-4). The epoxide equivalent of this reaction product (II-4) was 301 g/equivalent. Furthermore, the molar number of the acid group of acrylic acid is 0.3 per 1 mol of the epoxy group of the bisphenol A type epoxy resin (2).

(Synthesis Example 5: Preparation of reaction product (II-5))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of bisphenol A epoxy resin (2) were charged, 0.22 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.22 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, 101 parts by mass of acrylic acid and 0.44 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 100°C for 10 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.22 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain a reaction product (II-5). The epoxide equivalent of this reaction product (II-5) was 785 g/equivalent. Furthermore, the molar number of the acid groups in acrylic acid is 0.7 per 1 mol of the epoxy groups in the bisphenol A type epoxy resin (2).

(Synthesis Example 6: Preparation of reaction product (II-6))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of bisphenol A epoxy resin (2) was charged, 0.23 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.23 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, 122 parts by mass of acrylic acid and 0.46 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 100°C for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.23 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain a reaction product (II-6). The epoxy equivalent of this reaction product (II-6) was 1603 g/equivalent. Furthermore, the molar number of the acid groups in acrylic acid is 0.85 per 1 mol of the epoxy groups in the bisphenol A type epoxy resin (2).

(Synthesis Example 7: Preparation of reaction product (II-7))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 318 parts by mass of bisphenol F epoxy resin ("EPICLON 830CRP" manufactured by DIC Corporation, epoxy equivalent 159 g/equivalent, hereinafter referred to as "bisphenol F epoxy resin (1)") were charged, 0.2 parts by mass of dibutyl hydroxytoluene as an antioxidant and 0.2 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100°C for 10 hours while blowing air. Then, after confirming that the acid value is less than 1 mgKOH/g, 0.2 parts by mass of oxalic acid is added and stirred at 70°C for 3 hours to obtain a reaction product (II-7). The epoxy equivalent of this reaction product (II-7) is 421 g/equivalent. In addition, the molar number of the acid group of acrylic acid is 0.5 per 1 mol of epoxy group of bisphenol F type epoxy resin (1).

(Synthesis Example 8: Preparation of reaction product (II-8))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 282 parts by mass of a naphthalene epoxy resin ("EPICLON 4032D" manufactured by DIC Corporation, epoxy equivalent 141 g/equivalent, hereinafter referred to as "naphthalene epoxy resin (1)") was charged, 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.18 parts by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine were added. While blowing air, an esterification reaction was carried out at 100°C for 10 hours. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.18 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain a reaction product (II-8). The epoxy equivalent of the reaction product (II-8) is 388 g/equivalent. In addition, the molar number of the acid group of acrylic acid is 0.5 per 1 mol of the epoxy group of the naphthalene-type epoxy resin (1).

(Synthesis Example 9: Preparation of Acid-containing Acrylic Resin (P))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was placed, 428 parts by mass of o-cresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214 g/equivalent) was dissolved, 4 parts by mass of dibutyl hydroxytoluene and 0.4 parts by mass of p-hydroxyanisole were added, and then 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 120°C for 10 hours while blowing air. Subsequently, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110°C for 2.5 hours to obtain the target acid group-containing acrylic resin (P). The solid acid value of this acid-containing acrylic resin (P) is 85 mgKOH/g, and the weight average molecular weight is 8540.

(Example 1: Preparation of acid-containing acrylic resin (1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 162 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-1). Then, 97 parts by weight of bisphenol A epoxy resin (2) was added and reacted at 110°C for 2 hours, and then 20 parts by weight of acrylic acid was added and reacted at 120°C for 3 hours to obtain the target acid group-containing acrylate resin (1). The solid acid value of this acid group-containing acrylate resin (1) is 89 mgKOH/g, and the weight average molecular weight is 5670. In addition, the molar number of epoxy groups in bisphenol A epoxy resin (2) is 0.56 per 1 mole of acid groups in the reaction product (I-1).

(Example 2: Preparation of acid-containing acrylic resin (2))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 200 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-2). Then, 138 parts by weight of bisphenol A epoxy resin (2) was added and reacted at 110°C for 2 hours, and then 28 parts by weight of acrylic acid was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylate resin (2). The solid acid value of this acid group-containing acrylate resin (2) was 69 mgKOH/g, and the weight average molecular weight was 6070. In addition, the molar number of epoxy groups in bisphenol A epoxy resin (2) was 0.80 per 1 mole of acid groups in the reaction product (I-2).

(Example 3: Preparation of acid-containing acrylic resin (3))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-3). Then, 49 parts by weight of bisphenol A epoxy resin (2) was added and reacted at 110°C for 2 hours, and then 10 parts by weight of acrylic acid was added and reacted at 120°C for 3 hours to obtain the target acid group-containing acrylate resin (3). The solid acid value of this acid group-containing acrylate resin (3) is 115 mgKOH/g, and the weight average molecular weight is 5180. In addition, the molar number of epoxy groups in bisphenol A epoxy resin (2) is 0.28 relative to 1 mole of acid groups in the reaction product (I-3).

(Example 4: Preparation of acid-containing acrylic resin (4))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 223 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-4). Then, 153 parts by weight of bisphenol A epoxy resin (2) was added and reacted at 110°C for 2 hours, and then 31 parts by weight of acrylic acid was added and reacted at 120°C for 6 hours to obtain the target acid group-containing acrylate resin (4). The solid acid value of this acid group-containing acrylate resin (4) is 63 mgKOH/g, and the weight average molecular weight is 6410. In addition, the molar number of epoxy groups in bisphenol A epoxy resin (2) is 0.89 relative to 1 mole of acid groups in the reaction product (I-4).

(Example 5: Preparation of acid-containing acrylic resin (5))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 177 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-5). Then, 124 parts by weight of the reaction product (II-1) obtained in Synthesis Example 1 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (5). The solid acid value of this acid group-containing acrylic resin (5) is 87 mgKOH/g, and the weight average molecular weight is 5090. In addition, the molar number of epoxy groups in the reaction product (II-1) is 0.26 per 1 mole of acid groups in the reaction product (I-5).

(Example 6: Preparation of acid-containing acrylic resin (6))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 162 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-6). Then, 117 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (6). The solid acid value of this acid group-containing acrylic resin (6) is 87 mgKOH/g, and the weight average molecular weight is 4920. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.26 per 1 mole of acid groups in the reaction product (I-6).

(Example 7: Preparation of acid-containing acrylic resin (7))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 200 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-7). Then, 167 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 7 hours to obtain the target acid group-containing acrylic resin (7). The solid acid value of this acid group-containing acrylic resin (7) is 68 mgKOH/g, and the weight average molecular weight is 5880. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.37 per 1 mole of acid groups in the reaction product (I-7).

(Example 8: Preparation of acid-containing acrylic resin (8))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-8). Then, 59 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 3 hours to obtain the target acid group-containing acrylic resin (8). The solid acid value of this acid group-containing acrylic resin (8) is 116 mgKOH/g, and the weight average molecular weight is 5020. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.13 per 1 mole of acid groups in the reaction product (I-8).

(Example 9: Preparation of acid-containing acrylic resin (9))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 223 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-9). Then, 185 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 6 hours to obtain the target acid group-containing acrylic resin (9). The acid value of the acid group-containing acrylic resin (9) was 63 mgKOH/g and the weight average molecular weight was 6290. In addition, the molar number of epoxy groups in the reaction product (II-2) was 0.41 per 1 mole of acid groups in the reaction product (I-9).

(Example 10: Preparation of acid-containing acrylic resin (10))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 165 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-10). Then, 63 parts by weight of the reaction product (II-3) obtained in Synthesis Example 3 was added and reacted at 120°C for 6 hours to obtain the target acid group-containing acrylic resin (10). The solid acid value of this acid group-containing acrylic resin (10) is 98 mgKOH/g, and the weight average molecular weight is 6030. In addition, the molar number of epoxy groups in the reaction product (II-3) is 0.26 per 1 mole of acid groups in the reaction product (I-10).

(Example 11: Preparation of acid-containing acrylic resin (11))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 175 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-11). Next, 78 parts by weight of the reaction product (II-4) obtained in Synthesis Example 4 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (11). The solid acid value of this acid group-containing acrylic resin (11) is 95 mgKOH/g, and the weight average molecular weight is 5890. In addition, the molar number of epoxy groups in the reaction product (II-4) is 0.26 per 1 mole of acid groups in the reaction product (I-11).

(Example 12: Preparation of acid-containing acrylic resin (12))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 249 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-12). Next, 204 parts by weight of the reaction product (II-5) obtained in Synthesis Example 5 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (12). The acid value of the solid component of the acid group-containing acrylic resin (12) was 75 mgKOH/g, and the weight average molecular weight was 5310. In addition, the molar number of epoxy groups in the reaction product (II-5) was 0.26 per 1 mole of acid groups in the reaction product (I-12).

(Example 13: Preparation of acid-containing acrylic resin (13))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 298 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-13). Next, 289 parts by weight of the reaction product (II-6) obtained in Synthesis Example 6 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (13). The solid acid value of this acid group-containing acrylic resin (13) is 73 mgKOH/g, and the weight average molecular weight is 5060. In addition, the molar number of epoxy groups in the reaction product (II-6) is 0.18 per 1 mole of acid groups in the reaction product (I-13).

(Example 14: Preparation of acid-containing acrylic resin (14))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 169 parts by mass of bisphenol F epoxy resin ("EPICLON 830-S" manufactured by DIC Corporation, epoxy equivalent 169 g/equivalent, hereinafter referred to as "bisphenol F epoxy resin (2)"), 42 parts by mass of bisphenol F, and 0.4 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 84 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-hydroxyanisole, 42 parts by mass of acrylic acid, and 1.3 parts by mass of triphenylphosphine were added, and reacted at 120°C for 7 hours while blowing in air. Then, 100 parts by weight of succinic anhydride and 154 parts by weight of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-14). Then, 110 parts by weight of the reaction product (II-7) obtained in Synthesis Example 7 was added, and the mixture was reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (14). The solid acid value of the acid group-containing acrylic resin (14) was 94 mgKOH/g, and the weight average molecular weight was 4880. In addition, the molar number of epoxy groups in the reaction product (II-7) was 0.26 per 1 mole of acid groups in the reaction product (I-14).

(Example 15: Preparation of acid-containing acrylic resin (15))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 161 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-15). Then, 115 parts by weight of the reaction product (II-7) obtained in Synthesis Example 7 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (15). The solid acid value of this acid group-containing acrylic resin (15) is 86 mgKOH/g, and the weight average molecular weight is 4890. In addition, the molar number of epoxy groups in the reaction product (II-7) is 0.26 per 1 mole of acid groups in the reaction product (I-15).

(Example 16: Preparation of acid-containing acrylic resin (16))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 152 parts by mass of tetrahydrophthalic anhydride and 197 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 4 hours to obtain a reaction product (I-16). Then, 108 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (16). The acid value of the acid group-containing acrylic resin (16) was 83 mgKOH/g and the weight average molecular weight was 5010. In addition, the molar number of epoxy groups in the reaction product (II-2) was 0.24 per 1 mole of acid groups in the reaction product (I-16).

(Example 17: Preparation of acid-containing acrylic resin (17))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 169 parts by mass of bisphenol F type epoxy resin (2), 42 parts by mass of bisphenol F, and 0.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 84 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-hydroxyanisole, 42 parts by mass of acrylic acid, and 1.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 7 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 158 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-17). Then, 117 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (17). The solid acid value of this acid group-containing acrylic resin (17) is 92 mgKOH/g, and the weight average molecular weight is 49,000. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.26 per 1 mole of acid groups in the reaction product (I-17).

(Example 18: Preparation of acid-containing acrylic resin (18))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 141 parts by mass of naphthalene epoxy resin (1), 35 parts by mass of 2,7-dihydroxynaphthalene, and 0.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 72 parts by mass of diethylene glycol monomethyl ether acetate, 0.4 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-hydroxyanisole, 40 parts by mass of acrylic acid, and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 7 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 161 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-18). Then, 116 parts by weight of the reaction product (II-8) obtained in Synthesis Example 8 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (18). The solid acid value of this acid group-containing acrylic resin (18) is 94 mgKOH/g, and the weight average molecular weight is 4750. In addition, the molar number of epoxy groups in the reaction product (II-8) is 0.3 per 1 mole of acid groups in the reaction product (I-18).

(Example 19: Preparation of acid-containing acrylic resin (19))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 165 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-19). Then, 101 parts by weight of the reaction product (II-8) obtained in Synthesis Example 8 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylic resin (19). The acid value of the solid component of the acid group-containing acrylic resin (19) was 90 mgKOH/g, and the weight average molecular weight was 4870. In addition, the molar number of epoxy groups in the reaction product (II-8) was 0.26 per 1 mole of acid groups in the reaction product (I-19).

(Example 20: Preparation of acid-containing acrylic resin (20))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and reacted at 140°C for 2 hours in a nitrogen atmosphere. Then, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and reacted at 120°C for 6 hours while blowing air. Then, 100 parts by mass of succinic anhydride and 77 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 3 hours to obtain a reaction product (I-20). Then, 18 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 3 hours to obtain the target acid group-containing acrylic resin (20). The solid acid value of this acid group-containing acrylic resin (20) is 140 mgKOH/g, and the weight average molecular weight is 4760. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.04 per 1 mole of acid groups in the reaction product (I-20).

(Example 21: Preparation of acid-containing acrylic resin (21))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 46 parts by mass of acrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 77 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-21). Next, 23 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 and 35 parts by weight of bisphenol A type epoxy resin (2) were added and reacted at 120°C for 5 hours to obtain the target acid group-containing acrylate resin (21). The acid value of the solid component of this acid group-containing acrylate resin (20) is 100 mgKOH/g, and the weight average molecular weight is 8200. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.05 relative to 1 mole of acid groups in the reaction product (I-21).

(Example 22: Preparation of acid-containing methacrylate resin (1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 140°C for 2 hours in a nitrogen atmosphere. Subsequently, 92 parts by mass of diethylene glycol monomethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 55 parts by mass of methacrylic acid, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 6 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 162 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours to obtain a reaction product (I-22). Then, 117 parts by weight of the reaction product (II-2) obtained in Synthesis Example 2 was added and reacted at 120°C for 5 hours to obtain the target acid group-containing methacrylate resin (1). The solid acid value of this acid group-containing methacrylate resin (1) is 86 mgKOH/g, and the weight average molecular weight is 4840. In addition, the molar number of epoxy groups in the reaction product (II-2) is 0.26 per 1 mole of acid groups in the reaction product (I-22).

(Comparative Example 1: Production of Acid-containing Acrylic Resin (C1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 87 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 72 parts by mass of acrylic acid, and 1.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 8 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 241 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours. Subsequently, 150 parts by mass of bisphenol A epoxy resin (1) was added, and the mixture was reacted at 120°C for 8 hours. Then, 72 parts by weight of succinic anhydride was added and reacted at 110°C for 3 hours to obtain the target acid-containing acrylic resin (C1). The solid acid value of this acid-containing acrylic resin (C1) is 91 mgKOH/g.

(Comparative Example 2: Production of Acid-containing Acrylic Resin (C2))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 87 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 parts by mass of dibutyl hydroxytoluene, 0.3 parts by mass of p-hydroxyanisole, 72 parts by mass of acrylic acid, and 1.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 8 hours while blowing air. Subsequently, 100 parts by mass of succinic anhydride and 232 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 3 hours. Subsequently, 135 parts by mass of bisphenol F epoxy resin (2) was added, and the mixture was reacted at 120°C for 8 hours. Then, 72 parts by weight of succinic anhydride was added and reacted at 110°C for 3 hours to obtain the target acid-containing acrylic resin (C2). The solid acid value of this acid-containing acrylic resin (C2) is 94 mgKOH/g.

(Comparative Example 3: Production of Acid-containing Acrylic Resin (C3))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A epoxy resin (1), 133 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 parts by mass of dibutyl hydroxytoluene, 0.2 parts by mass of p-hydroxyanisole, 72 parts by mass of acrylic acid, and 1.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120°C for 8 hours while blowing air. Then, 50 parts by mass of succinic anhydride was added, and the mixture was reacted at 110°C for 3 hours to obtain the target acid group-containing acrylate resin (C3). The solid acid value of the acid group-containing acrylate resin (C3) was 94 mgKOH/g.

(Example 23: Preparation of hardening resin composition (1))

The acid-containing acrylic resin (1) obtained in Example 1, o-cresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, dipentatriol hexaacrylate, diethylene glycol monoethyl ether acetate, photopolymerization initiator ("Omnirad 907" manufactured by IGM Corporation), 2-ethyl-4-methylimidazole, and phthalocyanine green were mixed in the mass proportions shown in Table 1 and kneaded by a roll mill to obtain a curable resin composition (1).

(Examples 24 to 42: Preparation of curable resin compositions (2) to (22))

Except for using the acid-containing acrylic resin (2) to (21) obtained in Examples 2 to 21 or the acid-containing methacrylate resin (1) obtained in Example 22 instead of the acid-containing acrylic resin (1) used in Example 23, the curable resin composition (2) to (22) is obtained in the same manner as in Example 23.

(Example 43: Preparation of hardening resin composition (23))

The curable resin composition (23) is obtained in the same manner as in Example 23, except that the acid-containing acrylic resin obtained in Example 6 and the acid-containing acrylic resin (P) obtained in Synthesis Example 9 are used instead of the acid-containing acrylic resin (1) used in Example 23.

(Comparative Examples 4~6: Preparation of hardening resin compositions (C4)~(C6))

Except for using the acid-containing acrylic resins (C1) to (C3) obtained in Comparative Examples 1 to 3 to replace the acid-containing acrylic resin (1) used in Example 21, the curable resin compositions (C4) to (C6) are obtained in the same manner as in Example 22.

The following evaluations were performed using the curable resin compositions (1) to (23) and (C4) to (C6) obtained in the above-mentioned Examples and Comparative Examples.

[Evaluation method of light sensitivity]

The curable resin composition obtained in each example and comparative example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 30 minutes. Then, 1000 mJ/cm2 of ultraviolet light was irradiated using a metal halide lamp through STEPTABLET No. ² manufactured by KODAK. It was developed for 180 seconds with a 1 mass % sodium carbonate aqueous solution, and the number of remaining segments was evaluated. In addition, the more the number of remaining segments, the higher the photosensitivity.

[Evaluation method of alkali developing properties]

The hardening resin composition obtained in each embodiment and comparative example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 30 minutes, 40 minutes, 50 minutes, and 60 minutes, respectively, to produce samples with different drying times. These were developed at 30°C for 180 seconds with a 1% sodium carbonate aqueous solution, and the drying time at 80°C for the sample with no residue left on the substrate was evaluated as the drying management range. In addition, the longer the drying management range, the better the alkaline development property.

The compositions and evaluation results of the hardening resin compositions (1) to (23) prepared in Examples 21 to 43 and the hardening resin compositions (C4) to (C6) prepared in Comparative Examples 4 to 6 are shown in Tables 1 and 2.

(Example 44: Preparation of hardening resin composition (24))

啉基丙-1-酮(IGM公司製「Omnirad-907」)、作為有機溶劑的二乙二醇單甲醚乙酸酯，得到硬化性樹脂組成物(24)。 The acid group-containing acrylate resin (1) obtained in Example 1, an o-cresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a hardener, and 2-methyl-1-(4-methylthiophenyl)-2-(4-methylthiophenyl)-3-(4-methylthiophenyl) ...3-(4-methylthiophenyl)-3-(4-methylthiophenyl)-3-(4-methylthiophenyl)-3-(4-methylthiophenyl)-3

By adding 1-oxopropanone ("Omnirad-907" manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent, a curable resin composition (24) was obtained.

(Examples 45 to 65: Preparation of hardening resin compositions (25) to (45))

The curable resin compositions (25) to (45) are obtained in the same manner as in Example 42, except that the acid-containing acrylic resins (2) to (21) obtained in Examples 2 to 21 or the acid-containing methacrylic resin (1) obtained in Example 22 are used instead of the acid-containing acrylic resin (1) used in Example 43.

(Example 66: Preparation of hardening resin composition (46))

The curable resin composition (46) is obtained in the same manner as in Example 44, except that the acid-containing acrylic resin obtained in Example 6 and the acid-containing acrylic resin (P) obtained in Synthesis Example 9 are used instead of the acid-containing acrylic resin (1) used in Example 44.

(Comparative Examples 7~9: Preparation of hardening resin compositions (C7)~(C9))

Except that the acid-containing acrylic resins (C1) to (C3) obtained in Comparative Examples 1 to 3 are used instead of the acid-containing acrylic resin (1) used in Example 44, the curable resin compositions (C7) to (C9) are obtained in the same manner as in Example 44.

The following evaluations were performed using the curable resin compositions (22) to (42) and (C7) to (C9) obtained in the above-mentioned Examples and Comparative Examples.

[Measurement method of tensile strength]

The determination of elongation is based on the tensile test.

<Preparation of test pieces>

The curable resin composition obtained in the Examples and Comparative Examples was applied to a glass substrate using a 50 μm applicator and dried at 80°C for 30 minutes. After irradiation with 1000 mJ/ ^cm2 of ultraviolet light using a metal halide lamp, it was heated at 160°C for 1 hour. The cured product was peeled off from the glass substrate to obtain a test piece (cured product).

<Tensile test>

Cut the above-mentioned test piece 2 into a size of 10mm×80mm, and use the precision universal testing machine AUTOGRAPH "AG-IS" manufactured by Shimadzu Corporation to perform a tensile test on the test piece under the following test conditions. Measure the tensile degree (%) of the test piece until it breaks, and evaluate it according to the following criteria.

Test conditions: temperature 23℃, humidity 50%, marking distance 20mm, support distance 20mm, stretching speed 10mm/min

Furthermore, the "hardener" in Tables 1 to 4 represents an o-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214 g/equivalent).

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

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

Examples 21 to 66 shown in Tables 1 to 4 are examples of curable resin compositions using the acid-containing (meth)acrylate resin of the present invention. This curable resin composition has excellent photosensitivity and alkali developability, and it can be confirmed that the cured product has excellent elongation.

On the other hand, Comparative Examples 4 to 9 are examples of curable resin compositions that do not use the acid-containing (meth)acrylate resin of the present invention. It can be confirmed that the photosensitivity of this curable resin composition is obviously insufficient, and the elongation of the cured product is also insufficient.

Claims (9)

A (meth)acrylate resin containing an acid group, which uses the following components as necessary reaction raw materials: a reaction product (I) of an epoxy resin (A), an unsaturated monobasic acid (B), and a polyacid anhydride (C); and a reaction product (II) of an epoxy resin (D) and an unsaturated monobasic acid (E); the (meth)acrylate resin containing an acid group is characterized in that: relative to 1 mol of the reaction product (I) The molar number of the epoxy group of the reaction product (II) is in the range of 0.05-0.4. The reaction product (II) has an epoxy group and a (meth)acrylic group in the same molecule. The molar number of the acid group of the unsaturated monobasic acid (E) is in the range of 0.25-0.75 relative to 1 mole of the epoxy group of the epoxy resin (D). The acid-containing (meth)acrylate resin of claim 1, wherein the epoxy equivalent of the epoxy resin (D) is less than 180 g/equivalent. A curable resin composition characterized by containing an acid group-containing (meth)acrylate resin as claimed in claim 1 or 2 and a photopolymerization initiator. The hardening resin composition of claim 3 further contains an organic solvent and a hardener. The curable resin composition of claim 3 further contains a resin (F) having an acid group and a polymerizable unsaturated bond other than the acid group-containing (meth)acrylate resin of claim 1 or 2. A hardened material characterized in that it is a hardening reaction product of a hardening resin composition as described in any one of claims 3 to 5. An insulating material characterized in that it is composed of a hardening resin composition as described in any one of claims 3 to 5. A solder resist resin material, characterized in that it is composed of a curable resin composition as described in any one of claims 3 to 5. A solder resist component, characterized in that it is composed of a solder resist resin material as claimed in claim 8.