TW202031703A - Acid-group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Abstract

The present invention provides an acid-group-containing (meth)acrylate resin having, as essential reaction raw materials, an amide-imide resin having an acid group and/or acid anhydride group, a hydroxyl-group-containing (meth)acrylate compound, an epoxy-group-containing (meth)acrylate compound, and a polycarboxylic acid anhydride, wherein the acid-group-containing (meth)acrylate resin is characterized in that: the amide-imide resin is a reaction product of a polyisocyanate compound and a polycarboxylic acid anhydride, or is a reaction product of a polyisocyanate compound, a polycarboxylic acid anhydride, and a hydroxyl-group-containing (meth)acrylate compound; and the hydroxyl-group-containing (meth)acrylate compound contains a (meth)acrylate compound having two hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups. The acid-group-containing (meth)acrylate resin has exceptional photosensitivity and alkaline developability and can form a cured product having exceptional heat resistance.

Description

Acid group-containing (meth)acrylate resin, curable resin composition, hardened material, insulating material, resin material for solder mask, and solder mask

The present invention relates to an acid group-containing (meth)acrylate resin with excellent sensitivity and alkali developability and excellent heat resistance in the cured product, a curable resin composition containing the same, and an insulation containing the aforementioned curable resin composition Materials, solder resist resin materials, solder resist components, and methods for manufacturing acid group-containing (meth)acrylate resins.

In recent years, among resin materials for solder resists for printed wiring boards, epoxy acrylate resins containing acid groups, which are obtained by acrylateizing epoxy resins with acrylic acid and reacting acid anhydrides, have been widely used. The performance required of the solder resist resin material includes various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance in the cured product.

As a conventionally known resin material for solder resist, active energy ray curable resins obtained by reacting a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride are known (for example Refer to Patent Document 1) below. Although the heat resistance of the cured product is excellent, it does not meet the requirements that will gradually increase in the future, and is not sufficient for the current market requirements.

Therefore, a material having excellent sensitivity and alkali developability and more excellent heat resistance in the cured product is required. [Prior Technical Literature] [Patent Literature]

Patent Document 1 　 JP 61-243869 A

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin with excellent sensitivity and alkali developability and excellent heat resistance in the cured product, a curable resin composition containing the same, A method for producing an insulating material, a solder resist resin material, a solder resist member, and an acid group-containing (meth)acrylate resin containing the aforementioned curable resin composition. [Means used to solve the problem]

The inventors of the present case have studied in detail to solve the above-mentioned problems, and found that the above-mentioned problems can be solved by using the following acid group-containing (meth)acrylate resin, thereby completing the present invention: the acid group-containing (meth)acrylic acid Ester resins are based on amide resins with acid groups and/or acid anhydride groups, hydroxyl-containing (meth)acrylate compounds, epoxy-containing (meth)acrylate compounds and polycarboxylic anhydrides as essential The acid group-containing (meth)acrylate resin of the reaction raw material is characterized by: the reaction product of the polyisocyanate compound and polycarboxylic anhydride of the aforementioned amidoimine resin or the polyisocyanate compound, polycarboxylic anhydride, and hydroxyl group-containing The reactant of (meth)acrylate, hydroxyl-containing (meth)acrylate compound used as the raw material of acid group-containing (meth)acrylate resin or used as the raw material of amide resin Either or both of the hydroxyl group-containing (meth)acrylate compounds include a (meth)acrylate compound having 2 hydroxyl groups and/or a (meth)acrylate compound having 3 hydroxyl groups.

That is, the present invention relates to an acid group-containing (meth)acrylate resin, which is based on an acid group and/or acid anhydride group-containing amide resin (A), and hydroxyl group-containing (meth)acrylic acid The ester compound (B), the epoxy group-containing (meth)acrylate compound (C), and the polycarboxylic anhydride (D) are the necessary reaction materials and the acid group-containing (meth)acrylate resin is characterized by: The aforementioned amide imine resin (A) is a reactant (A-1) of polyisocyanate compound (a1) and polycarboxylic anhydride (a2), or polyisocyanate compound (a1), polycarboxylic anhydride (a2), and The reactant (A-2) of the hydroxyl-containing (meth)acrylate compound (a3); the aforementioned hydroxyl-containing (meth)acrylate compound (B) or the aforementioned hydroxyl-containing (meth)acrylate compound (a3) Either or both of them include a (meth)acrylate compound having 2 hydroxyl groups and/or a (meth)acrylate compound having 3 hydroxyl groups; and regarding a curable resin composition containing them, the aforementioned A method for producing a cured product of a curable resin composition, an insulating material, a solder resist resin material, a solder resist member, and an acid group-containing (meth)acrylate resin. [Effects of Invention]

The acid group-containing (meth)acrylate resin of the present invention has excellent sensitivity and alkali developability, and excellent heat resistance in the cured product, so it can be ideally used in insulating materials, solder resist resin materials and solder resist components .

[Form to implement the invention]

The acid group-containing (meth)acrylate resin of the present invention is characterized by having an acid group and/or acid anhydride group amide resin (A) and a hydroxyl group-containing (meth)acrylate compound (B ), epoxy-containing (meth)acrylate compound (C) and polycarboxylic acid anhydride (D) as essential reaction materials.

In addition, in the present invention, "(meth)acrylate" means acrylate and/or methacrylate. In addition, "(meth)acryloyl group" means an acrylic acid group and/or a methacryloyl group. Furthermore, "(meth)acrylic acid" refers to acrylic acid and/or methacrylic acid.

As the aforementioned amide resin (A) having an acid group and/or an acid anhydride group, it may have only either an acid group or an acid anhydride group, or both. Among them, it is preferable to have an acid anhydride group from the viewpoint of reactivity with the aforementioned hydroxyl group-containing (meth)acrylate compound (B) and the aforementioned epoxy group-containing (meth)acrylate compound (C) and reaction control. , Preferably has both an acid group and an acid anhydride group.

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

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

As the aforementioned amide imide resin (A), [1] the reactant (A-1) of polyisocyanate compound (a1) and polycarboxylic anhydride (a2) (hereinafter sometimes referred to as "amide amide resin" (A-1)''), or (2) the reactant (A-2) of polyisocyanate compound (a1), polycarboxylic anhydride (a2) and hydroxyl-containing (meth)acrylate compound (a3) (there are below It is called amide resin (A-2)).

[1] The amide resin (A-1) will be described.

The aforementioned amide imine resin (A-1) is obtained by reacting a polyisocyanate compound (a1) and a polycarboxylic anhydride (a2).

Examples of the polyisocyanate compound (a1) include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethyl Aliphatic diisocyanate compounds such as hexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate , Diisocyanate, tetramethyl diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl diisocyanate Aromatic diisocyanate compounds such as benzene and o-tolidine diisocyanate (o-tolidine diisocyanate); polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); these trimer isocyanates Cyanic acid modified material, biuret modified material, allophanate modified material, etc. Moreover, these polyisocyanate compounds may be used individually or in combination of 2 or more types. These polyisocyanate compounds (a1) are preferably non-trimeric (meth)acrylate resins in view of obtaining an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance. Polyisocyanate modifier.

[式(1)中，R¹ 分別獨立為氫原子、或碳原子數1~6之烴基的任一者。R² 分別獨立為碳原子數1~4的烷基、或與以結構式(1)所表示的結構部位透過標註*符號之亞甲基而連結之鍵結點的任一者。l為0或1~3的整數，m為1~15的整數]。

[In formula (1), R ^{1 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ^{2 is} each independently an alkyl group having 1 to 4 carbon atoms, or any one of the bonding points connected to the structural part represented by the structural formula (1) through the methylene group marked with the * symbol. l is 0 or an integer from 1 to 3, m is an integer from 1 to 15].

Among these, from the viewpoint of becoming an acid group-containing (meth)acrylate resin having excellent solvent solubility, the aforementioned alicyclic diisocyanate compound or a modified product thereof is preferred, and the alicyclic diisocyanate compound is preferred. Isocyanate. In addition, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, the aforementioned aliphatic diisocyanate compound or The modified product is preferably an aliphatic diisocyanate. Furthermore, relative to the total mass of the polyisocyanate compound (a1), the ratio of the total mass of the alicyclic diisocyanate compound or its modification to the total mass of the aliphatic diisocyanate compound or its modification is preferably 70% by mass or more , More preferably 90% by mass or more. In addition, when the alicyclic diisocyanate compound or its modified product is used in combination with the aliphatic diisocyanate compound or its modified product, the mass ratio of the two is preferably in the range of 20/80 to 80/20.

As said polycarboxylic acid anhydride (a2), aliphatic polycarboxylic acid anhydride, alicyclic polycarboxylic acid anhydride, aromatic polycarboxylic acid anhydride, etc. are mentioned, for example.

Examples of the aliphatic polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and maleic acid. , Fumaric acid, citraconic acid, itaconic acid, glutaconic acid, anhydrides of 1,2,3,4-butanetetracarboxylic acid, etc. In addition, as the aliphatic polycarboxylic acid anhydride, the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.

As the aforementioned alicyclic polycarboxylic acid anhydride, in the present invention, an alicyclic structure having an anhydride group bonded to it is used as the alicyclic polycarboxylic acid anhydride, regardless of whether other structural parts have an aromatic ring. Examples of the alicyclic polycarboxylic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and 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 anhydride, etc.

Examples of the aforementioned aromatic polycarboxylic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, and biphenyl tricarboxylic acid. Acid, biphenyl tetracarboxylic acid, anhydride of benzophenone tetracarboxylic acid, etc.

These polycarboxylic anhydrides (a2) may be used alone or in combination of two or more kinds. In addition, among these, in view of obtaining an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, the aforementioned alicyclic resin is preferred Polycarboxylic acid anhydride or the aforementioned aromatic polycarboxylic acid anhydride. In addition, in view of obtaining an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, it is preferable to use a carboxyl group and an acid anhydride group in the molecular structure. Of the two tricarboxylic anhydrides, cyclohexane tricarboxylic anhydride or trimellitic anhydride is particularly preferred. At this time, the content of the tricarboxylic acid anhydride in the polycarboxylic acid anhydride (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.

Moreover, as the said amide imine resin (A-1), in addition to the said polyisocyanate compound (a1) and the said polycarboxylic anhydride (a2), you may use together other compounds as a reaction raw material as needed. When the aforementioned other compounds are used in combination, from the perspective of fully exerting the effects achieved by the present invention, the polyisocyanate compound (a1) and the aforementioned polycarboxylic anhydride (a2) in the reaction raw material of the aforementioned amidoimide resin (A-1) The total content is preferably 80% by mass or more, more preferably 85% by mass.

As said other compound, polycarboxylic acid etc. are mentioned, for example.

As the aforementioned polycarboxylic acid, any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule. Examples 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, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butane tetracarboxylic acid Acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid 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. Furthermore, as the aforementioned polycarboxylic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, that is, a polymer having a carboxyl group in its molecule, can also be used. These polycarboxylic acids (a2) may be used alone or in combination of two or more kinds.

As a copolymer of the aforementioned conjugated diene vinyl monomer and acrylonitrile, that is, a polymer having a carboxyl group in the molecule, for example, butadiene-acrylonitrile represented by the following structural formula (2-1) A polymer having a carboxyl group in the copolymer, or a half ester of a polymer having a hydroxyl group in the molecule of the butadiene-acrylonitrile copolymer represented by the following structural formula (2-2) and a polybasic acid anhydride such as maleic anhydride. In addition, the position of the carboxyl group may be at any position on the side chain or terminal of the molecule, but is preferably the terminal.

[結構式(2-1)中，X為1~50的整數，Y為1~50的整數，Z為1~20的整數]。

[In the structural formula (2-1), X is an integer from 1 to 50, Y is an integer from 1 to 50, and Z is an integer from 1 to 20].

[結構式(2-2)中，X為1~50的整數，Y為1~50的整數，Z為1~20的整數]。

[In the structural formula (2-2), X is an integer from 1 to 50, Y is an integer from 1 to 50, and Z is an integer from 1 to 20].

The acid value of the aforementioned amidoimide resin (A-1) is derived from an acid group-containing (meth)acrylate resin that has excellent sensitivity and alkali developability and can form a cured product with excellent heat resistance. Look, the measured value under neutral conditions, that is, without ring-opening the acid anhydride group, is preferably in the range of 60~350mgKOH/g, and in the presence of water, etc., the condition for ring-opening the acid anhydride group The measured value below is preferably in the range of 61~360mgKOH/g. In addition, the acid value in the present invention is a value measured by the neutralization titration method in JIS K 0070 (1992).

It does not specifically limit as a manufacturing method of the said amide imine resin (A-1), It can manufacture by any method. For example, it can be produced by the same method as general amide resin. Specifically, it can be exemplified by using 0.8-3.5 mol of the aforementioned polycarboxylic anhydride (a2) with respect to 1 mol of the isocyanate group possessed by the aforementioned polyisocyanate compound (a1) under a temperature condition of about 100-180°C A method of stirring and mixing to make it react.

The reaction can be carried out in an organic solvent as required, and an alkaline catalyst can also be used as required.

Examples of the aforementioned organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate and ethyl acetate. Ester solvents such as esters and butyl acetate; aromatic solvents such as toluene, xylene, and naphtha; cyclohexane, methylcyclohexane, and other alicyclic solvents; carbitol, xyloxol, methanol, isopropanol Alcohol solvents such as, butanol, propylene glycol monomethyl ether; glycol ether solvents such as alkane glycol monoalkyl ether, dialkyl glycol monoalkyl ether, dialkyl glycol monoalkyl ether acetate, etc.; methoxypropane Alcohol, cyclohexanone, methyl celoxol, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These organic solvents may be used alone or in combination of two or more kinds. In addition, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials in terms of improving 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)、三正丁胺或二甲基苄胺、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、四甲基氫氧化銨等胺化合物類；三辛基甲基氯化銨、三辛基甲基乙酸銨等四級銨鹽類；三甲膦、三丁膦、三苯膦等膦類；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-1,3-十二醯基二錫氧烷等有機錫化合物；辛酸鋅、辛酸鉍等有機金屬化合物；辛酸錫等無機錫化合物；無機金屬化合物等。此等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

Morpholine, pyridine, 1,8-diazbicyclo[5.4.0]undecene-7(DBU), 1,5-diazbicyclo[4.3.0]nonene-5(DBN), 1,4-bis Acridine bicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4 -Dimethylimidazole, 1,4-Diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyl Trimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylhydrogen Amine compounds such as ammonium oxide; quaternary ammonium salts such as trioctyl methyl ammonium chloride and trioctyl methyl ammonium acetate; phosphines such as trimethyl phosphine, tributyl phosphine, and triphenyl phosphine; tetramethyl phosphonium chloride , Tetraethyl phosphonium chloride, tetrapropyl phosphonium chloride, tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenyl phosphonium chloride, Phosphonium salts such as benzyl phosphonium chloride; dibutyl tin dilaurate, octyl tin trilaurate, octyl tin diacetate, dioctyl tin diacetate, dioctyl tin dineodecanoate, dibutyl tin diacetate, caprylic acid Tin, 1,1,3,3-tetrabutyl-1,3-dodecyl distannoxane and other organotin compounds; zinc octoate, bismuth octoate and other organic metal compounds; tin octoate and other inorganic tin compounds; inorganic metals Compound etc. These alkaline catalysts may be used alone or in combination of two or more kinds.

[2] The amide resin (A-2) will be described.

The aforementioned amide imine resin (A-2) is obtained by reacting a polyisocyanate compound (a1), a polycarboxylic anhydride (a2), and a hydroxyl group-containing (meth)acrylate compound (a3).

As said polyisocyanate compound (a1), the thing similar to the said polyisocyanate compound (a1) can be used, and the said polyisocyanate compound may be used individually or in combination of 2 or more types.

As said polycarboxylic acid anhydride (a2), the same thing as the said polycarboxylic acid anhydride (a2) can be used.

The amount of the aforementioned polycarboxylic anhydride (a2) used is relative to the aforementioned point of view that an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product with excellent heat resistance can be obtained. The isocyanate group contained in the polyisocyanate compound (a1) is preferably 1 mol, preferably in the range of 0.8 to 3.5 mol.

As the aforementioned hydroxyl-containing (meth)acrylate compound (a3), as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in the molecular structure, other specific structures are not particularly limited, and various types can be used. Compound. As an example, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate , Neopentaerythritol (meth)acrylate, Neopentaerythritol di(meth)acrylate, Neopentaerythritol tri(meth)acrylate, Dineopentaerythritol (meth)acrylate, Dixin Pentyleneerythritol di(meth)acrylate, dineopentaerythritol tri(meth)acrylate, dineopentaerythritol tetra(meth)acrylate, dineopentaerythritol penta(meth)acrylate, Di-trimethylolpropane (meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, etc. In addition, it can also be used to introduce (poly)oxyethylene chain, (poly)oxyethylene chain, (poly)oxytetramethylene chain into the molecular structure of the aforementioned various hydroxyl-containing (meth)acrylate compounds (Poly)oxyalkylene modified products with (poly)oxyalkylene chains, or lactone modified products with a (poly)lactone structure introduced into the molecular structure of the aforementioned various hydroxyl-containing (meth)acrylate compounds Wait. These hydroxyl group-containing (meth)acrylate compounds (a3) may be used alone or in combination of two or more kinds.

In addition, as the aforementioned amidoimide resin (A-2), in addition to the aforementioned polyisocyanate compound (a1), the aforementioned polycarboxylic anhydride (a2), and the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) as necessary , Other compounds can also be used together as reaction raw materials. When the aforementioned other compounds are used in combination, from the perspective of fully exerting the effects achieved by the present invention, the aforementioned polyisocyanate compound (a1), the aforementioned polycarboxylic anhydride (a2), and the aforementioned reaction raw material of the amide imide resin (A-2) The total content of the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) is preferably 80% by mass or more, more preferably 85% by mass.

As said other compound, polycarboxylic acid etc. are mentioned, for example.

As the aforementioned polycarboxylic acid, the same as the aforementioned polycarboxylic acid can be used. The aforementioned polycarboxylic acid may be used alone or in combination of two or more kinds.

The acid value of the aforementioned amidoimide resin (A-2) is derived from an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance It can be seen that the measured value under neutral conditions, that is, without ring-opening the anhydride group, is preferably in the range of 60~350mgKOH/g, and in the presence of water, the The measured value under the conditions is preferably in the range of 61~360mgKOH/g.

There is no restriction|limiting in particular as a manufacturing method of the said amide imine resin (A-2), It can manufacture using any method. For example, it may be manufactured by a method of reacting all the reaction materials in a unified manner, or may be manufactured by a method of sequentially reacting the reaction materials. Among them, from the viewpoint of easy control of the reaction, it is preferable to react the aforementioned polycarboxylic anhydride (a2) with the aforementioned hydroxyl-containing (meth)acrylate compound (a3) (step A1), and to make the intermediate obtained in the aforementioned step A1 It is produced by the method of reacting the reaction product with the aforementioned polyisocyanate compound (a1) (step A2).

The aforementioned step A1 is a step of reacting the aforementioned polycarboxylic anhydride (a2) with the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) to obtain an intermediate reaction product. This reaction mainly involves the reaction between the acid anhydride group of the polycarboxylic anhydride (a2) and the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (a3). In the reaction ratio of the aforementioned reaction, the number of moles of the polycarboxylic acid anhydride (a2) is preferably in the range of 2-8 relative to 1 mole of the hydroxyl group of the hydroxyl-containing (meth)acrylate compound (a3). The reaction of Step A1 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst at a temperature of about 80 to 140°C. In addition, the reaction can also be carried out in an organic solvent as required.

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

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the aforementioned step A2, the intermediate reaction product obtained in the aforementioned step A1 is reacted with the aforementioned polyisocyanate compound (a1). This reaction is mainly to react the acid group and/or acid anhydride group of the intermediate reaction product obtained in the aforementioned step A1 with the isocyanate group of the aforementioned polyisocyanate compound (a1). The reaction of Step A2 can be carried out, for example, by heating and stirring in the presence of a suitable alkaline catalyst under a temperature condition of about 100 to 180°C. In addition, the reaction can also be carried out in an organic solvent as required. When step A1 and step A2 are continuously performed, the alkaline catalyst and organic solvent may not be added, or may be added appropriately.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the aforementioned hydroxyl-containing (meth)acrylate compound (B), the same as the aforementioned hydroxyl-containing (meth)acrylate compound (a3), and the aforementioned hydroxyl-containing (meth)acrylate compound (B) can be used It can be used individually or in combination of 2 or more types. In addition, as the aforementioned amide amide resin (A), when the aforementioned amide amide resin (A-1) is used, as the aforementioned hydroxyl group-containing (meth)acrylate compound (B), it is necessary to use 2 A (meth)acrylate compound having three hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups.

In addition, when the aforementioned amide amide resin (A) is used the aforementioned amide amide resin (A-2), the aforementioned hydroxyl group-containing (() as the raw material of the aforementioned amide amide resin (A-2) The meth)acrylate compound (a3) or either or both of the above-mentioned hydroxyl-containing (meth)acrylate compound (B), it is necessary to use a (meth)acrylate compound having two hydroxyl groups and/or (Meth)acrylate compound with 3 hydroxyl groups.

The molecular weight of the aforementioned hydroxyl-containing (meth)acrylate compound (B) can be obtained from an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product with excellent heat resistance From a viewpoint, it is preferably 1,000 or less. In addition, when the hydroxyl group-containing (meth)acrylate compound (B) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.

As the aforementioned epoxy-containing (meth)acrylate compound (C), as long as the molecular structure has a (meth)acryloyl group and an epoxy group, other specific structures are not particularly limited, and various formulas can be used Various compounds. As an example, for example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, etc. containing glycidyl Base (meth)acrylate monomer; dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, diphenol diglycidyl ether, bisphenol diglycidyl ether, etc. Mono(meth)acrylate ester products of glycidyl ether compounds, etc. These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more kinds. Among these, from the viewpoint of easy control of the reaction, a (meth)acrylate compound having one epoxy group is preferred, in order to obtain excellent sensitivity and alkali developability as well as excellent formation properties. From the viewpoint of the acid group-containing (meth)acrylate resin of the heat-resistant cured product, a glycidyl-containing (meth)acrylate monomer is preferable. In addition, the molecular weight of the glycidyl-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, relative to the total mass of the epoxy group-containing (meth)acrylate compound (C), the ratio of the glycidyl group-containing (meth)acrylate monomer is preferably 70% by mass or more, More preferably, it is 90% by mass or more.

As said polycarboxylic acid anhydride (D), the same thing as the said polycarboxylic acid anhydride (a3) can be used. In addition, in view of obtaining an acid group-containing (meth)acrylate resin having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, an aliphatic polycarboxylic anhydride or alicyclic The polycarboxylic acid anhydride is more preferably an aliphatic dicarboxylic acid anhydride or an alicyclic dicarboxylic acid anhydride. These polycarboxylic anhydrides (D) may be used alone or in combination of two or more kinds.

As the acid group-containing (meth)acrylate resin of the present invention, in accordance with the desired resin performance and the like, in addition to the aforementioned amide resin (A) and the aforementioned hydroxyl-containing (meth)acrylate compound (B) , In addition to the epoxy group-containing (meth)acrylate compound (C) and the polycarboxylic anhydride (D), other reaction raw materials may be used in combination. When the aforementioned other reaction materials are used in combination, from the viewpoint of fully exerting the effects achieved by the present invention, the total content of the aforementioned (A) to (D) components in the reaction materials of the acid group-containing (meth)acrylate resin is preferably 80% by mass or more, more preferably 85% by mass or more.

The manufacturing method of the acid group-containing (meth)acrylate resin of this invention is not specifically limited, It can manufacture by any method. For example, it may be manufactured by a method in which all reaction materials are reacted in a unified manner, or may be manufactured by a method in which reaction materials are sequentially reacted. Among them, from the viewpoint of ease of reaction control, it is preferable to manufacture by the following method: reacting the aforementioned amide imide resin (A) with the aforementioned hydroxyl-containing (meth)acrylate compound (B) (step 1), The product of step 1 is reacted with the aforementioned epoxy group-containing (meth)acrylate compound (C) (step 2), and the product of step 2 is reacted with the aforementioned polycarboxylic anhydride (D) (step 3).

As the aforementioned step 1, it is the reaction of the aforementioned amide imine resin (A) and the aforementioned hydroxyl group-containing (meth)acrylate compound (B). This reaction mainly reacts the acid group and/or acid anhydride group in the said amidoimine resin (A) with the hydroxyl group in the hydroxyl-containing (meth)acrylate compound (B). The aforementioned hydroxyl group-containing (meth)acrylate compound (B) is particularly excellent in the reactivity of an acid anhydride group. As described above, the aforementioned amide imine resin (A) preferably has an acid anhydride group. In addition, the content of the acid anhydride group in the aforementioned amide imine resin (A) can be determined by the difference between the measured value of the acid value in 2 above, that is, the difference between the acid value under the condition of ring-opening the acid anhydride group and the Calculate the difference in acid value under the condition of ring-opening the acid anhydride group.

The reaction ratio of the aforementioned amide imide resin (A) and the aforementioned hydroxyl-containing (meth)acrylate compound (B), when the aforementioned amide imide resin (A) has an acid group and an acid anhydride group, and when When the above-mentioned amide imide resin (A) has an acid anhydride group, 1 mol of the above-mentioned amide imide resin (A) has an acid anhydride group, and the above-mentioned hydroxyl group-containing (meth)acrylate compound (B ) It is preferred to use the molar number of the hydroxyl group in the range of 0.9 to 1.1. In addition, when the aforementioned amide imide resin (A) has an acid group, 1 mol of the acid group contained in the aforementioned amide imide resin (A) is used in the aforementioned hydroxyl-containing (meth)acrylate The molar number of the hydroxyl group which the compound (B) has is preferably used within the range of 0.1 to 0.5.

The reaction between the aforementioned amide imine resin (A) and the aforementioned hydroxyl-containing (meth)acrylate compound (B), for example, can be carried out in the presence of a suitable esterification catalyst at a temperature of about 80 to 140°C Under heating and stirring. As the aforementioned esterification catalyst, the same ones as the aforementioned esterification catalyst can be used. The aforementioned esterification catalyst may be used alone or in combination of two or more kinds. The addition amount of the aforementioned esterification catalyst is preferably used in the range of 0.001 to 5 parts by mass relative to 100 parts by mass of the total mass of the reaction raw materials.

The reaction can be carried out in an organic solvent as required, and an acidic catalyst can also be used as required.

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types. In addition, when the production of the above-mentioned amidoimide resin (A) and step 1 are continuously performed, the reaction may be continued directly in the organic solvent used in the production of the above-mentioned amidoimide resin (A).

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, and other Lewis Acid etc. These acidic catalysts may be used alone or in combination of two or more kinds.

As the aforementioned step 2, it is the reaction between the product of the aforementioned step 1 and the aforementioned epoxy group-containing (meth)acrylate compound (C). This reaction is mainly to react the acid group in the product obtained in the aforementioned step 1 with the aforementioned epoxy-containing (meth)acrylate compound. The reaction ratio is preferably based on the number of moles of epoxy groups contained in the epoxy group-containing (meth)acrylate compound (C) relative to the acid group 1 mole in the product obtained in step 1. Use it in the range of 0.7 to 1.2, and more preferably use it in the range of 0.9 to 1.1. The reaction of step 2 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst at a temperature of about 90 to 140°C. When step 1 and step 2 are continuously performed, the esterification catalyst may not be added, or may be added appropriately. In addition, the reaction can also be carried out in an organic solvent as required. In addition, the aforementioned esterification catalyst and organic solvent can be the same as the aforementioned esterification catalyst and organic solvent, and these can be used alone or in combination of two or more kinds.

As the aforementioned step 3, it is the reaction between the product of the aforementioned step 2 and the aforementioned polycarboxylic anhydride (D). This reaction is mainly to react the hydroxyl group in the product obtained in the aforementioned step 2 with the aforementioned polycarboxylic anhydride (D). In the product of the aforementioned step 2, for example, there are hydroxyl groups generated due to ring opening of the epoxy group in the aforementioned epoxy group-containing (meth)acrylate compound (C). The reaction ratio of the aforementioned polycarboxylic anhydride (D) is preferably adjusted so that the acid value of the acid group-containing (meth)acrylate resin as the product becomes about 60 to 120 mgKOH/g. The reaction of step 3 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst at a temperature of about 80 to 140°C. When step 2 and step 3 are continuously performed, the esterification catalyst may not be added, or may be added appropriately. In addition, the reaction can also be carried out in an organic solvent as required. In addition, the aforementioned esterification catalyst and organic solvent can be the same as the aforementioned esterification catalyst and organic solvent, and these can be used alone or in combination of two or more kinds.

According to the acid value of the acid group-containing (meth)acrylate resin of the present invention, it is possible to obtain an acid group-containing (meth)acrylate having excellent sensitivity and alkali developability and forming a cured product with excellent heat resistance In terms of resin, it is preferably in the range of 50 to 120 mgKOH/g, more preferably in the range of 60 to 110 mgKOH/g. In addition, the acid value of the acid group-containing (meth)acrylate resin in the present invention is a value measured by JIS K 0070 (1992) neutralization titration method.

In addition, the weight average molecular weight (Mw) of the 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) represents a value measured by a gel permeation chromatography (GPC) method.

The acid group-containing (meth)acrylate resin of the present invention can be formed as a curable resin by adding a photopolymerization initiator in view of the polymerizable (meth)acrylic acid group in the molecular structure物用。 For use.

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。此等分別可單獨使用，亦可併用2種類以上。The aforementioned photopolymerization initiator may be used by selecting an appropriate one according to the type of active energy rays to be irradiated and the like. In addition, photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds may be used in combination. As specific examples of the photopolymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-

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

Alkylphenone-based photopolymerization initiators such as (linyl) phenyl]-1-butanone; Phosphine oxide-based light such as 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide Polymerization initiator; Intramolecular hydrogen removal type photopolymerization initiators such as benzophenone compounds. These can be used alone or in combination of two or more types.

及9-氧硫

衍生物、2,2’-二甲氧基-1,2-二苯基乙-1-酮、二苯基(2,4,6-三甲氧基苄醯基)膦氧化物、2,4,6-三甲基苄醯基二苯基膦氧化物、雙(2,4,6-三甲基苄醯基)苯基膦氧化物、2-甲基-1-(4-甲基硫基苯基)-2-

啉基丙-1-酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-1-丁酮等。As the aforementioned photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl (Oxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 9-oxysulfur

And 9-oxysulfur

Derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxybenzyl) phosphine oxide, 2,4 ,6-Trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylsulfide Phenyl)-2-

Linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

(Alolinylphenyl)-1-butanone and the like.

Commercial products of the aforementioned other photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad- 379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100" , "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "kayacure-DETX", "kayacure-MBP", "kayacure-DMBI", "kayacure -EPA", "kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stauffer Chemical), "Trigonal P1" (manufactured by AKZO), "Sandoray 1000" "(Manufactured by SANDOZ), "Deap" (manufactured by APJOHN), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), "Runtecure-1104" (manufactured by Runtec) Wait. These photopolymerization initiators may be used alone or in combination of two or more kinds.

The addition amount of the aforementioned photopolymerization initiator, for example, 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 components other than the solvent of the curable resin composition range.

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

The resin (E) having an acid group and a polymerizable unsaturated bond may be any resin as long as the resin has an acid group and a polymerizable unsaturated bond. Examples include: an acid group and a polymerizable unsaturated bond. Epoxy resins, urethane resins with acid groups and polymerizable unsaturated bonds, acrylic resins with acid groups and polymerizable unsaturated bonds, amide imides with acid groups and polymerizable unsaturated bonds Resins, acrylamide resins having acid groups and polymerizable unsaturated bonds, etc.

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

As the aforementioned epoxy resin having an acid group and a polymerizable unsaturated bond, for example, an acid group-containing epoxy (meth)acrylic acid which uses epoxy resin, unsaturated monobasic acid, and polybasic acid anhydride as essential reaction materials Ester resin, epoxy resin, unsaturated monobasic acid, polybasic acid anhydride, polyisocyanate compound, and hydroxyl group-containing (meth)acrylate compound as reaction raw materials containing acid group and urethane group epoxy (former) Base) Acrylic resin etc.

As the aforementioned epoxy resin, for example, bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol- Cresol cocondensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl group Type epoxy resin, sulphur type epoxy resin, xanthene 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 kinds.

The aforementioned unsaturated monobasic acid refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. As said acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, for example. Examples of the unsaturated monobasic acid (D) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, and the like. In addition, esters, acid halides, acid anhydrides and the like of the aforementioned unsaturated monobasic acids can also be used. These unsaturated monobasic acids may be used alone or in combination of two or more kinds.

Examples of the aforementioned polybasic acid anhydride include: phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydrophthalic anhydride Acid anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride, etc. These polybasic acid anhydrides may be used alone or in combination of two or more kinds. Among these, tetrahydrophthalic anhydride is preferable, and succinic anhydride is more preferable in terms of obtaining a curable resin composition having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance. .

As said polyisocyanate compound, the thing similar to the said polyisocyanate compound (a1) can be used, and the said polyisocyanate compound may be used individually or in combination of 2 or more types.

As the aforementioned hydroxyl group-containing (meth)acrylate compound, the same as the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) can be used, and the aforementioned hydroxyl group-containing (meth)acrylate compound can be used alone or in combination. More than 2 kinds.

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

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said alkaline catalyst may be used individually or in combination of 2 or more types.

As the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond, for example, polyisocyanate compounds, hydroxyl-containing (meth)acrylate compounds, carboxyl-containing polyol compounds, and optionally polyvalent Polyol compounds other than acid anhydrides and polyol compounds other than the aforementioned carboxyl-containing polyol compounds, or polyol compounds other than polyisocyanate compounds, hydroxyl-containing (meth)acrylate compounds, polybasic acid anhydrides, and carboxyl-containing polyol compounds Those who received the reaction, etc.

As said polyisocyanate compound, the thing similar to the said polyisocyanate compound (a1) can be used, and the said polyisocyanate compound may be used individually or in combination of 2 or more types.

As the aforementioned hydroxyl group-containing (meth)acrylate compound, the same as the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) can be used, and the aforementioned hydroxyl group-containing (meth)acrylate compound can be used alone or in combination. More than 2 kinds.

Examples of the aforementioned carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like. The aforementioned carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.

As the said polybasic acid anhydride, the same thing as the said polybasic acid anhydride can be used, and the said polybasic acid anhydride may be used individually or in combination of 2 or more types.

Examples of polyol compounds other than the aforementioned carboxyl group-containing polyol compound include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, and neopentyl Aliphatic polyol compounds such as tetraol and dineopentylerythritol; aromatic polyol compounds such as biphenol and bisphenol; introducing (poly)oxyethylene chain and (poly) into the molecular structure of the aforementioned various polyol compounds (Poly)oxyalkylene modification products of (poly)oxyalkylene chains such as oxypropylene chain, (poly)oxytetramethylene chain, etc.; introduced (poly)into the molecular structure of the aforementioned various polyol compounds Lactone modification of ester structure, etc. The polyol compounds other than the aforementioned carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.

The manufacturing method of the urethane resin which has the said acid group and a polymerizable unsaturated bond is not specifically limited, It can manufacture by any method. In the manufacture of the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond, it can be carried out in an organic solvent as required, and a basic catalyst can also be used as required.

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said alkaline catalyst may be used individually or in combination of 2 or more types.

As the aforementioned acrylic resin having an acid group and a polymerizable unsaturated bond, for example, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group is essential And polymerize the resulting acrylic resin intermediate, and further react with the (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups to introduce (meth)acrylic acid The reaction product obtained thereby, or a reaction product obtained by reacting the hydroxyl group in the aforementioned reaction product with a polybasic acid anhydride, etc.

In addition to the aforementioned (meth)acrylate compound (α), the aforementioned acrylic resin intermediate can also copolymerize compounds containing other polymerizable unsaturated groups as required. The aforementioned compounds containing other polymerizable unsaturated groups, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as 2-ethylhexyl; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate and other alicyclic structures ( Meth) acrylate; (meth) acrylates containing aromatic rings such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl acrylate, etc.; 3-methacryloxypropyl Silicon-containing (meth)acrylates such as trimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can be used individually or in combination of 2 or more types.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but from the viewpoint of reactivity, it is more Preferably the following combination. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl-containing (meth)acrylate as the (meth)acrylate compound ( β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β) . When using a glycidyl-containing (meth)acrylate as the aforementioned (meth)acrylate compound (α), it is preferable to use a carboxyl-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 kinds.

The polybasic acid anhydride may be the same as the polybasic acid anhydride, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and it can be produced by any method. The production of the aforementioned acrylic resin having acid groups and polymerizable unsaturated bonds can be carried out in organic solvents as required, and alkaline catalysts can also be used as required.

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said alkaline catalyst may be used individually or in combination of 2 or more types.

Examples of the amide resin having an acid group and a polymerizable unsaturated bond include: an amide resin having an acid group and/or an acid anhydride group, and a hydroxyl group-containing (meth)acrylate compound And/or epoxy-containing (meth)acrylate compounds, optionally having one or more reactive functional groups selected from the group consisting of hydroxyl, carboxyl, isocyanate, glycidyl and anhydride groups Compound reaction. In addition, the compound having the aforementioned reactive functional group may or may not have a (meth)acryloyl group.

As said amide imine resin, it may have only either an acid group or an acid anhydride group, and may have both. From the viewpoint of reactivity with hydroxyl-containing (meth)acrylate compounds or (meth)acrylic acid group-containing epoxides and reaction control, it is preferred to have an acid anhydride group, more preferably an acid group and Both acid anhydride groups. The acid value of the aforementioned amide imine resin is preferably in the range of 60 to 350 mgKOH/g as measured under neutral conditions, that is, without ring-opening the acid anhydride group. On the other hand, in the presence of water, etc., the measured value under the condition of ring-opening the acid anhydride group is preferably in the range of 61 to 360 mgKOH/g.

Examples of the above-mentioned amidoimine resin include those obtained by using polyisocyanate compounds and polybasic acid anhydrides as reaction raw materials.

As the aforementioned polyisocyanate compound, the same as the aforementioned polyisocyanate compound (a1) can be used.

As the said polybasic acid anhydride, the same thing as the said polybasic acid anhydride can be used, and the said polybasic acid anhydride may be used individually or in combination of 2 or more types.

In addition, if necessary, in addition to the aforementioned polyisocyanate compound and polybasic acid anhydride, a polybasic acid may be used in combination with a polybasic acid as a reaction raw material for the aforementioned amidoimine resin.

As the aforementioned polybasic acid, any one can be used as long as it is a compound having two or more carboxyl groups in one molecule. Examples 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, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butane tetracarboxylic acid Acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid 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 polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, that is, a polymer having a carboxyl group in its molecule can also be used. These polybasic acids may be used alone or in combination of two or more kinds.

As the aforementioned hydroxyl group-containing (meth)acrylate compound, the same as the aforementioned hydroxyl group-containing (meth)acrylate compound (a3) can be used, and the aforementioned hydroxyl group-containing (meth)acrylate compound can be used alone or in combination. More than 2 kinds.

As the aforementioned epoxy group-containing (meth)acrylate compound, the same as the aforementioned epoxy group-containing (meth)acrylate compound (C) can be used. The aforementioned epoxy group-containing (meth)acrylate compound It can be used individually or in combination of 2 or more types.

The method for producing the above-mentioned amide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and it can be produced by any method. In the production of the aforementioned amide resin having an acid group and a polymerizable unsaturated bond, it can be carried out in an organic solvent as required, and a basic catalyst can also be used as required.

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said alkaline catalyst may be used individually or in combination of 2 or more types.

Examples of acrylamide resins having acid groups and polymerizable unsaturated bonds include: phenolic hydroxyl-containing compounds, alkylene oxides or alkylene carbonates, and N-alkoxyalkyl (meth) propylene It is obtained by reaction of amide compound, polybasic acid anhydride, and optionally unsaturated monobasic acid.

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

In the above structural formulas (3-1) to (3-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, R ^{2 is} each independently a hydrogen atom or a methyl group. 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 still more preferably 0. q is an integer of 2 or more, preferably 2 or 3. In addition, the position of the substituent on the aromatic ring in the above structural formula is arbitrary, which means that, for example, the naphthalene ring of the structural formula (3-2) can be substituted on any ring, as shown in the structural formula (3-3) Substitution can be made on any ring of the benzene ring existing in one molecule. In the structural formula (3-4), it can be substituted on any ring of the benzene ring existing in one molecule, and the substitution in one molecule is shown The number of bases is p and q.

In addition, as the aforementioned phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) can also be used A reaction product as an essential reaction material, and a compound having at least two phenolic hydroxyl groups in the molecule and a compound represented by any of the following structural formulas (x-1)~(x-5) as the essential reaction material The reaction products and so on. In addition, a novolak-type phenol resin using one or two or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or two compounds having at least two phenolic hydroxyl groups in the molecule can also be used. More than one kind of novolak-type phenol resin etc. as reaction raw materials.

[式(x-1)中，h為0或1。式(x-2)~(x-5)中，R³ 為碳原子數1~20的烷基、碳原子數1~20的烷氧基、芳基、鹵素原子的任一者，i為0或1~4的整數。式(x-2)、(x-3)及(x-5)中，Z為乙烯基、鹵甲基、羥基甲基、烷氧基甲基的任一者。式(x-5)中，Y為碳原子數1~4的伸烷基、氧原子、硫原子、羰基的任一者，j為1~4的整數]。

[In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer from 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is any one of vinyl, halomethyl, hydroxymethyl, and alkoxymethyl. In the 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 compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).

In the above structural formulas (4-1) to (4-4), R ⁴ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, R ^{5 is} each 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 still more 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, the naphthalene ring of the structural formula (4-2) can be substituted on any ring, in the structural formula (4-3) Substitution is performed on any ring of the benzene ring present in one molecule, and in the structural formula (4-4), substitution is performed 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-mentioned structural formulae (3-1) to (3-4) can be used.

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

As said alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, pentane oxide, etc. are mentioned, for example. Among these, in view of obtaining a curable resin composition having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, ethylene oxide or propylene oxide is preferred. The said alkylene oxide may be used individually or in combination of 2 or more types.

As said alkylene carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. are mentioned, for example. Among these, in terms of obtaining a curable resin composition having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, ethylene carbonate or propylene carbonate is preferred. The aforementioned alkylene carbonate may be used alone or in combination of two or more kinds.

As the aforementioned N-alkoxyalkyl(meth)acrylamide compound, for example, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide Amine, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butyl Oxyethyl (meth)acrylamide and the like. The aforementioned N-alkoxyalkyl(meth)acrylamide compounds may be used alone or in combination of two or more kinds.

As the said polybasic acid anhydride, the same thing as the said polybasic acid anhydride can be used, and the said polybasic acid anhydride may be used individually or in combination of 2 or more types.

As the said unsaturated monobasic acid, the same thing as the said unsaturated monobasic acid can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

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

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

As the said alkaline catalyst, the same thing as the said alkaline catalyst can be used, and the said alkaline catalyst may be used individually or in combination of 2 or more types.

As the said acidic catalyst, the same thing as the said acidic catalyst can be used, and the said acidic catalyst may be used individually or in combination of 2 or more types.

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

As the aforementioned various (meth)acrylate monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Aliphatic mono(meth)acrylate compounds such as pentyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; (meth)acrylic acid Alicyclic mono(meth)acrylate compounds such as cyclohexyl ester, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate; glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate Heterocyclic mono(meth)acrylate compounds; benzyl (meth)acrylate, phenyl(meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy(meth)acrylate, (meth)acrylate Base) phenoxyethyl acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate , Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as benzyl benzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc.: In the aforementioned various mono(methyl) ) Introducing (poly)oxyethylene chain, (poly)oxyethylene chain, (poly)oxytetramethylene chain and other polyoxyethylene chain (poly)oxyethylene chain into the molecular structure of acrylate monomer Alkyl-modified mono(meth)acrylate compound; Lactone-modified mono(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the aforementioned various mono(meth)acrylate compounds; B Glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth) Aliphatic di(meth)acrylate compounds such as acrylates; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol bis(meth) Yl) acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other alicyclic di(meth)acrylate compounds; biphenol bis(meth) Aromatic di(meth)acrylate compounds such as acrylates and bisphenol di(meth)acrylates; the molecular structure of the aforementioned various di(meth)acrylate compounds introduces (poly)oxyethylene chain, ( (Poly)oxyalkylene chain, (poly)oxytetramethylene chain and other (poly)oxyalkylene chain polyoxyalkylene modified di(meth)acrylate compound; in the aforementioned various di(methyl) ) Lactone modified di(meth)acrylate compound with (poly)lactone structure introduced into the molecular structure of acrylate compound; trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate Aliphatic tri(meth)acrylate compounds; in the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound, (poly)oxyethylene chain, (poly)oxyethylene chain, (poly) (Poly)oxyalkylene modified tris(meth)acrylate compound of (poly)oxyalkylene chain such as oxytetramethylene chain; in the aforementioned aliphatic tri(meth)acrylate compound Introducing the (poly)lactone structure into the molecular structure of the lactone to modify the tri(meth)acrylate compound; neopenteritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylic acid Aliphatic poly(meth)acrylate compounds with more than four functions, such as esters and dineopentaerythritol hexa(meth)acrylate; introducing (poly) into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound (Poly) oxyalkylene chain modified poly(methyl) oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene chain Yl)acrylate compound; a poly(meth)acrylate compound modified by a lactone having a (poly)lactone structure introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound, etc. The aforementioned various (meth)acrylate monomers may be used alone or in combination of two or more kinds.

In addition, the curable resin composition of the present invention may optionally contain a curing agent, a curing accelerator, an organic solvent, inorganic particles or polymer particles, pigments, defoamers, viscosity regulators, leveling agents, and flame retardants. , Storage stabilizers and other additives.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth)acrylate resin, and examples include epoxy resins. As the aforementioned epoxy resin, for example, bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol- Cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl group Type epoxy resin, pyrene 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 kinds. In addition, among these, in terms of obtaining a curable resin composition having excellent sensitivity and alkali developability and forming a cured product having excellent heat resistance, phenol novolak type epoxy resin and cresol are preferred. Novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensation novolak type epoxy resin, naphthol-cresol co-condensation novolak type epoxy Novolac type epoxy resins such as resins are particularly preferably those with a softening point in the range of 20 to 120°C.

The curing accelerator is one that promotes the curing reaction of the curing agent. When epoxy resin is used as the curing agent, examples include phosphorus-based compounds, amine-based compounds, imidazoles, metal salts of organic acids, Lewis acids, and amine salts. Wait. These hardening accelerators may be used alone or in combination of two or more kinds. Moreover, the addition amount of the said hardening accelerator is, for example, it is preferable to use it in the range of 1-10 mass parts with respect to 100 mass parts of said hardening agents.

As the said organic solvent, what is the same as the said organic solvent can be used, and the said organic solvent may be used individually or in combination of 2 or more types.

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

As a source of ultraviolet light, in terms of practicality and economy, an ultraviolet lamp is generally used. Specifically, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, and the like.

Although the cumulative light quantity of the aforementioned active energy rays is not particularly limited, it is preferably 10 to 5,000 mJ/cm ² , and more preferably 50 to 1,000 mJ/cm ² . If the accumulated light amount is in the above range, the generation of unhardened portions can be prevented or suppressed, which is preferable.

In addition, the aforementioned active energy ray irradiation may be performed in one stage, or may be performed in two or more stages.

In addition, because the cured product of the present invention has excellent heat resistance, for example, it can be ideally used as a solder resist, interlayer insulating material, packaging material, underfill material, circuit element, etc. packaging adhesive layer or integrated circuit in semiconductor device applications. Adhesive layer of component and circuit board. In addition, for thin display related applications represented by LCD and OELD, it can be ideally used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, and black matrix resists. Etching agent, spacer layer, etc. Among these, it can be particularly ideally used for solder resist applications.

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

The solder resist member of the present invention can be obtained, for example, by coating the aforementioned resin material for solder resist on a substrate, and after volatilizing and drying an organic solvent in a temperature range of about 60 to 100°C, the desired result is formed by forming The patterned photomask is exposed with active energy rays, unexposed areas are developed with an aqueous alkali solution, and then heated and cured in a temperature range of about 140 to 200°C.

As said base material, metal foils, such as copper foil and aluminum foil, etc. are mentioned, for example. [Example]

Examples and comparative examples are given below to explain the present invention in more detail.

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

The molecular weight of the acid group-containing (meth)acrylate resin in the examples of this case was measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by TOSOH Co., Ltd., String: Protection string "HXL-L" manufactured by TOSOH Co., Ltd. +TOSOH Corporation "TSK-GEL G2000HXL" +TOSOH Corporation "TSK-GEL G2000HXL" +TOSOH Corporation "TSK-GEL G3000HXL" +TOSOH Corporation "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℃ Developing 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 is the following known monodisperse polystyrene. (Use polystyrene) TOSOH Corporation "A-500" TOSOH Corporation "A-1000" TOSOH Corporation "A-2500" "A-5000" manufactured by TOSOH Corporation TOSOH Corporation "F-1" TOSOH Corporation "F-2" TOSOH Corporation "F-4" TOSOH Corporation "F-10" TOSOH Corporation "F-20" TOSOH Corporation "F-40" TOSOH Corporation "F-80" TOSOH Corporation "F-128" Sample: obtained by filtering 1.0% by mass tetrahydrofuran solution with a microfilter in conversion of resin solid content (50μl)

The liquid chromatogram in this example was measured under the following conditions. [Measurement conditions] Installation: "LCMS-2010EV" manufactured by Shimadzu Corporation Data processing: "LCMS Solution" manufactured by Shimadzu Corporation Column: TOSOH Co., Ltd. "ODS-100V" (2.0mmID×150mm, 3μm) at 40°C Eluent: water/acetonitrile, 0.4mL/min Detector: PDA, MS Sample adjustment: 1. Dissolve 50mg of sample in 10ml of acetonitrile (for LC) 2. Stir with vortex for 30 seconds 3. Let stand for 30 minutes 4. Pass a 0.2μm filter as a measurement sample Calculation of area ratio: Calculate with UV wavelength 210nm

(Synthesis example 1: Production of neopentylerythritol polyacrylate (A1)) 201.6 parts by mass of acrylic acid, 136 parts by mass of neopentylerythritol, 10.6 parts by mass of sulfuric acid, 1.1 parts by mass of copper dichloride, and 153 parts by mass of toluene were added to a flask equipped with a thermometer, a stirrer, and a condenser. The temperature was raised to 105°C while stirring, and it was allowed to react at the same temperature for 12 hours while refluxing in the system. 287 parts by mass of toluene was added to the reaction mixture, and washed with 123 parts by mass of distilled water. Furthermore, a 20% by mass aqueous sodium hydroxide solution was added to neutralize the reaction mixture and wash with 62 parts by mass of distilled water. After adding 500 ppm of hydroquinone monomethyl ether with respect to the resin solid content, toluene was distilled off to obtain neopenteritol polyacrylate (A1). The hydroxyl value of this neopentyl erythritol polyacrylate (A1) is 290 mgKOH/g, and the content of neopenteritol tetraacrylate (a1) calculated from the area ratio of the liquid chromatogram is 16% by mass. The content of alcohol triacrylate (a2) is 50% by mass, the content of neopentaerythritol diacrylate (a3) is 29% by mass, the content of neopentaerythritol monoacrylate (a4) is 3% by mass, others are high The content of the molecular weight component (a') is 2% by mass.

(Synthesis Example 2: Production of Neopentylerythritol Diacrylate (A2)) In a flask equipped with a thermometer, a stirrer, and a condenser, 136 parts by mass of neopentylerythritol and 600 parts by mass of N,N-dimethylformamide were added, and 3.7 parts by mass of p-toluenesulfonic acid was added as a catalyst. The temperature was raised to 80°C while stirring to dissolve neopentylerythritol in N,N-dimethylformamide, and 78 parts by mass of cyclohexanone was added. While maintaining the reaction temperature at 80°C, while reducing the pressure in the reaction system to 140 mmHg, the reaction was continued while distilling off the generated water. When the generation of water could not be confirmed, it was further refluxed for 1 hour. While continuing to stir, cool to room temperature, return to normal pressure, and remove unreacted neopentylerythritol by filtration under reduced pressure. After removing N,N-dimethylformamide from the resulting filtrate under reduced pressure, ethyl acetate was added, and the precipitated neopentylerythritol was removed by filtration again. The obtained filtrate was washed with a saturated aqueous solution of sodium bicarbonate, and then washed with a saturated aqueous solution of sodium chloride, and the organic layer was dehydrated with magnesium sulfate. The reaction product after dehydration was concentrated to obtain a ketal compound (x1).

Next, 21.6 parts by mass of the previously obtained ketal compound (x1), 120 parts by mass of dichloromethane, and 46.5 parts by mass of triethylamine were added to a flask equipped with a thermometer, stirrer, and condenser, and cooled to -5°C . It is obtained by dissolving 29 parts by mass of 3-chloropropanoyl chloride in 40 parts by mass of dichloromethane while keeping the inside of the reaction system at 0°C or lower. After the dripping was completed, the temperature was gradually raised to room temperature, and the reaction was continued for 4 hours. After confirming the disappearance of the ketal compound (x1) as a raw material with a gas chromatograph, the triethylamine hydrochloride was removed by filtration under reduced pressure. After washing the obtained filtrate with saturated sodium bicarbonate aqueous solution, it is washed with saturated sodium chloride aqueous solution and dehydrated with anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of acrylate compound (x2).

Next, 6.5 parts by mass of the acrylate compound (x2) obtained previously and 30 parts by mass of acetone were added to a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was cooled to 0°C while stirring. In order to avoid the method of exceeding 10°C in the reaction system, 10 parts by mass of 10% sulfuric acid aqueous solution were dropped successively in small amounts, and after the total amount was added, it was allowed to react at room temperature for 16 hours. After confirming the disappearance of the acrylate compound (x2) as a raw material by a gas chromatograph, 10 parts by mass of water was added, and acetone was removed under reduced pressure. The obtained aqueous layer was extracted with ethyl acetate, and washed with a saturated aqueous sodium hydrogen carbonate solution until the pH reached 7. After the organic layer was dehydrated with magnesium sulfate, it was concentrated under reduced pressure at room temperature to obtain neopentylerythritol diacrylate (A2).

(Synthesis Example 3: Production of Dineopentaerythritol Polyacrylate (A3)) A flask equipped with a thermometer, a stirrer, and a condenser was charged with 220 parts by mass of acrylic acid, 180 parts by mass of dineopentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of copper dichloride, and 300 parts by mass of toluene. The temperature was raised to 105°C while stirring, and the system was refluxed while being allowed to react at the same temperature for 13 hours. The water produced was 61 parts by mass. To the reaction mixture was added 425 parts by mass of toluene, and washed with 200 parts by mass of distilled water. Furthermore, a 20% sodium hydroxide aqueous solution was added to neutralize the reaction mixture, and it was washed with 100 parts by mass of distilled water. After adding 500 ppm of hydroquinone monomethyl ether with respect to the resin solid content, the toluene was distilled off to obtain dineopentaerythritol acrylate (A3). The hydroxy value of this dineopentaerythritol acrylate (A3) was 140 mgKOH/g. In addition, the content of dineopentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatogram is 28% by mass, the content of dineopentaerythritol pentaacrylate (b2) is 42% by mass, and The content of neopentylerythritol hexaacrylate (b3) is 22% by mass, and the content of the high molecular weight component (b′) is 8% by mass.

(Example 1: Production of acid group-containing (meth)acrylate resin (1)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentyleneerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoxyphenol, 0.7 parts by mass of triphenylphosphine, and blowing in air at 120°C It reacted for 6 hours. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 72 parts by mass of a mixture of neopentyl erythritol polyacrylate ("ARONIX M-306" manufactured by Toagosei Co., Ltd., with a neopentyl erythritol triacrylate content of approximately 67%, and a hydroxyl value of 159.7 mgKOH/g) was added. It was allowed to react at 110°C for 3 hours. 148 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 151 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (1). The solid acid value of the acid group-containing (meth)acrylate resin (1) was 87 mgKOH/g, and the weight average molecular weight was 2,390.

(Example 2: Production of acid group-containing (meth)acrylate resin (2)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentyleneerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.7 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 72 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 148 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 99 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (2). The solid acid value of the acid group-containing (meth)acrylate resin (2) was 94 mgKOH/g, and the weight average molecular weight was 2,300.

(Example 3: Production of acid group-containing (meth)acrylate resin (3)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentyleneerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.7 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 72 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. Add 216 parts by mass of 3,4-epoxycyclohexyl methyl methacrylate ("CYCLOMER M100" manufactured by DAICEL Co., Ltd., epoxy equivalent 207g/equivalent), 2.2 parts by mass of triphenylphosphine, and make it at 110°C It reacted for 5 hours. Furthermore, 99 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (3). The solid acid value of the acid group-containing (meth)acrylate resin (3) was 85 mgKOH/g, and the weight average molecular weight was 2,540.

(Example 4: Production of acid group-containing (meth)acrylate resin (4)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, and 44 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentyleneerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.6 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate (“Desmodur W” manufactured by Sumika Covestro Urethane Co., Ltd.) was added and reacted at 120° C. for 8 hours to confirm that the isocyanate group content was 0.1% by mass or less. Next, 52 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 111 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 75 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (4). The solid acid value of the acid group-containing (meth)acrylate resin (4) was 85 mgKOH/g, and the weight average molecular weight was 2,440.

(Example 5: Production of acid group-containing (meth)acrylate resin (5)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, and 44 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.6 parts by mass of triphenylphosphine, reacted at 120°C while blowing in air 6 hour. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 52 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 162 parts by mass of "CYCLOMER M100" and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 75 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (5). The solid acid value of the acid group-containing (meth)acrylate resin (5) was 78 mgKOH/g, and the weight average molecular weight was 2610.

(Example 6: Production of acid group-containing (meth)acrylate resin (6)) Add 374 parts by mass of diethylene glycol monomethyl ether acetate and 173 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3 in a flask equipped with a thermometer, a stirrer, and a reflux cooler. 4-acid anhydride, 53 parts by mass of neopentyl erythritol polyacrylate (A1) obtained in Synthesis Example 1, 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.7 parts by mass of three The phenylphosphine was reacted at 120°C for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 74 parts by mass of "ARONIX M-306" was added, and the reaction was carried out at 110°C for 3 hours. 220 parts by mass of "CYCLOMER M100" and 2.3 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 154 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (6). The solid acid value of the acid group-containing (meth)acrylate resin (6) was 80 mgKOH/g, and the weight average molecular weight was 2,370.

(Example 7: Production of acid group-containing (meth)acrylate resin (7)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 341 parts by mass of diethylene glycol monomethyl ether acetate and 149 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3 were added, 4-acid anhydride, 44 parts by mass of neopentyl erythritol polyacrylate (A1) obtained in Synthesis Example 1, 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.6 parts by mass of three The phenylphosphine was reacted at 120°C for 6 hours while blowing air. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 53 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 165 parts by mass of "CYCLOMER M100" and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 76 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (7). The solid acid value of the acid group-containing (meth)acrylate resin (7) was 78 mgKOH/g, and the weight average molecular weight was 2580.

(Example 8: Production of acid group-containing (meth)acrylate resin (8)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler were added 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, 0.5 parts by mass of dibutylhydroxytoluene was dissolved. In a nitrogen atmosphere, it was made to react at 160 degreeC for 8 hours, and it confirmed that the isocyanate group content became 0.1 mass% or less. Next, 0.2 parts by mass of p-methoxyphenol, 22 parts by mass of neopentyl erythritol polyacrylate (A1) obtained in Synthesis Example 1 and 1.6 parts by mass of triphenylphosphine were added, and the air was blown at 110°C. Let it react for 5 hours. Next, 85 parts by mass of glycidyl methacrylate was added and reacted at 110°C for 5 hours. Furthermore, 57 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (8). The solid acid value of the acid group-containing (meth)acrylate resin (8) was 89 mgKOH/g, and the weight average molecular weight was 1,850.

(Example 9: Production of acid group-containing (meth)acrylate resin (9)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler were added 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, 0.5 parts by mass of dibutylhydroxytoluene was dissolved. In a nitrogen atmosphere, it was made to react at 160 degreeC for 8 hours, and it confirmed that the isocyanate group content became 0.1 mass% or less. Next, 0.2 parts by mass of p-methoxyphenol, 14 parts by mass of neopentylerythritol diacrylate (A2) obtained in Synthesis Example 2 and 1.6 parts by mass of triphenylphosphine were added, and air was blown in at 110°C. It reacted for 5 hours. Next, 86 parts by mass of glycidyl methacrylate was added and reacted at 110°C for 5 hours. Furthermore, 58 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (9). The solid acid value of the acid group-containing (meth)acrylate resin (9) was 91 mgKOH/g, and the weight average molecular weight was 2,120.

(Example 10: Production of acid group-containing (meth)acrylate resin (10)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 34 parts by mass of the new compound obtained in Synthesis Example 2 were added Pentaerythritol diacrylate (A2), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.6 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 68 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 130 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then, 87 parts by mass of succinic anhydride and 71 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (10 ). The solid acid value of the acid group-containing (meth)acrylate resin (10) was 92 mgKOH/g, and the weight average molecular weight was 2,590.

(Example 11: Production of acid group-containing (meth)acrylate resin (11)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentyleneerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.7 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 25 parts by mass of the neopentylerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110°C for 3 hours. 150 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then 100 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (11 ). The solid acid value of the acid group-containing (meth)acrylate resin (11) was 103 mgKOH/g, and the weight average molecular weight was 2710.

(Example 12: Production of acid group-containing (meth)acrylate resin (12)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 34 parts by mass of the new compound obtained in Synthesis Example 2 were added Pentaerythritol diacrylate (A2), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.6 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 23 parts by mass of the neopentylerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110°C for 3 hours. 144 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then 96 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (12 ). The solid acid value of the acid group-containing (meth)acrylate resin (12) was 105 mgKOH/g, and the weight average molecular weight was 2,990.

(Example 13: Production of acid group-containing (meth)acrylate resin (13)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 34 parts by mass of the new compound obtained in Synthesis Example 2 were added Pentaerythritol diacrylate (A2), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.6 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 37 parts by mass of neopentylerythritol polyacrylate (A1) obtained in Synthesis Example 1 was added, and the reaction was carried out at 110°C for 3 hours. 140 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 94 parts by mass of succinic anhydride and 62 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (13 ). The solid acid value of the acid group-containing (meth)acrylate resin (13) was 101 mgKOH/g, and the weight average molecular weight was 2,590.

(Example 14: Production of acid group-containing (meth)acrylate resin (14)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 332 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 97 parts by mass of "ARONIX M-306", 0.8 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.8 parts by mass of triphenylphosphine were reacted at 120°C for 6 hours while blowing in air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 46 parts by mass of the neopentylerythritol polyacrylate (A1) obtained in Synthesis Example 1 was added and reacted at 110°C for 3 hours. 153 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 102 parts by mass of succinic anhydride and 56 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (14 ). The solid acid value of the acid group-containing (meth)acrylate resin (14) was 94 mgKOH/g, and the weight average molecular weight was 2,330.

(Example 15: Production of acid group-containing (meth)acrylate resin (15)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 332 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 97 parts by mass of "ARONIX M-306", 0.8 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.8 parts by mass of triphenylphosphine were reacted at 120°C for 6 hours while blowing in air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 29 parts by mass of the neopentylerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110°C for 3 hours. 153 parts by mass of glycidyl methacrylate and 1.8 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 102 parts by mass of succinic anhydride and 46 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (15 ). The solid acid value of the acid group-containing (meth)acrylate resin (15) was 96 mgKOH/g, and the weight average molecular weight was 2490.

(Example 16: Production of acid group-containing (meth)acrylate resin (16)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 392 parts by mass of diethylene glycol monomethyl ether acetate and 244 parts by mass of isophorone diisocyanate were added to the cyanuric acid modification product (EVONIK "VESTANAT T-1890/100" manufactured by the company, isocyanate group content 17.2% by mass), 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene were dissolved. In a nitrogen atmosphere, the reaction was performed at 160°C for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-methoxyphenol, 81 parts by mass of neopentyl erythritol polyacrylate (A1) obtained in Synthesis Example 1 and 1.4 parts by mass of triphenylphosphine, and blow in the air at 110°C. React for 5 hours. Next, 165 parts by mass of glycidyl methacrylate and 1.8 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then 110 parts by mass of tetrahydrophthalic anhydride and 67 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (16). The solid acid value of the acid group-containing (meth)acrylate resin (16) was 86 mgKOH/g, and the weight average molecular weight was 7,450.

(Example 17: Production of acid group-containing (meth)acrylate resin (17)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 418 parts by mass of diethylene glycol monomethyl ether acetate, 192 parts by mass of trimellitic anhydride, and 26 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentaerythritol polyacrylate (A1), 1.0 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.7 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 244 parts by mass of "VESTANAT T-1890/100" was added and reacted at 120°C for 10 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 79 parts by mass of "ARONIX M-306" was added, and the reaction was carried out at 110°C for 3 hours. 167 parts by mass of glycidyl methacrylate and 2.7 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. 112 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (17 ). The solid acid value of the acid group-containing (meth)acrylate resin (17) was 84 mgKOH/g, and the weight average molecular weight was 7,390.

(Example 18: Production of acid group-containing (meth)acrylate resin (18)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler were added 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, 0.5 parts by mass of dibutylhydroxytoluene was dissolved. In a nitrogen atmosphere, it was made to react at 160 degreeC for 8 hours, and it confirmed that the isocyanate group content became 0.1 mass% or less. Then add 0.2 parts by mass of p-methoxyphenol, 22 parts by mass of the dineopentyl erythritol polyacrylate (A3) obtained in Synthesis Example 3, and 1.6 parts by mass of triphenylphosphine, while blowing in air at 110°C Let it react for 5 hours. Next, 85 parts by mass of glycidyl methacrylate was added and reacted at 110°C for 5 hours. Furthermore, 57 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (18). The solid acid value of this acid group-containing (meth)acrylate resin (18) was 83 mgKOH/g, and the weight average molecular weight was 1,910.

(Example 19: Production of acid group-containing (meth)acrylate resin (19)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 345 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 110 parts by mass of synthesis example 3 were added. Neopentyl erythritol polyacrylate (A3), 0.9 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, 0.8 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hours. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 87 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 148 parts by mass of glycidyl methacrylate and 2.1 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 99 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (19). The solid acid value of the acid group-containing (meth)acrylate resin (19) was 85 mgKOH/g, and the weight average molecular weight was 2,480.

(Example 20: Production of acid group-containing (meth)acrylate resin (20)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 258 parts by mass of diethylene glycol monomethyl ether acetate, 139 parts by mass of trimellitic anhydride, and 52 parts by mass of the new compound obtained in Synthesis Example 2 were added Pentaerythritol diacrylate (A2), 0.6 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, and 0.6 parts by mass of triphenylphosphine, reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate were added and reacted at 120° C. for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 65 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 111 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 74 parts by mass of succinic anhydride and 53 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (20 ). The solid acid value of the acid group-containing (meth)acrylate resin (20) was 85 mgKOH/g, and the weight average molecular weight was 2,340.

(Example 21: Production of acid group-containing (meth)acrylate resin (21)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 279 parts by mass of diethylene glycol monomethyl ether acetate, 197 parts by mass of trimellitic anhydride, and 15 parts by mass of the new compound obtained in Synthesis Example 2 were added Pentaerythritol diacrylate (A2), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.6 parts by mass of triphenylphosphine, reacted at 120°C while blowing in air 6 hour. 111 parts by mass of isophorone diisocyanate were added and reacted at 120° C. for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 70 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 160 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then, 88 parts by mass of succinic anhydride and 86 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (21 ). The solid acid value of the acid group-containing (meth)acrylate resin (21) was 100 mgKOH/g, and the weight average molecular weight was 2,750.

(Example 22: Production of acid group-containing (meth)acrylate resin (22)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 254 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the new compound obtained in Synthesis Example 1 were added Pentaerythritol polyacrylate (A1), 0.6 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, 0.7 parts by mass of triphenylphosphine, and reacted at 120°C while blowing in air 6 hour. 77 parts by mass of 1,5-pentamethylene diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 64 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 131 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Then, 88 parts by mass of succinic anhydride and 75 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (22 ). The solid acid value of the acid group-containing (meth)acrylate resin (22) was 95 mgKOH/g, and the weight average molecular weight was 2050.

(Example 23: Production of acid group-containing (meth)acrylate resin (23)) In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 271 parts by mass of dimethylacetamide, 168 parts by mass of trimellitic anhydride, and 53 parts by mass of the neopentylerythritol obtained in Synthesis Example 1 were added Acrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol, and 0.7 parts by mass of triphenylphosphine were reacted at 120°C for 6 hours while blowing in air. Add 94 parts by mass of 1,3-bis(isocyanatomethyl)benzene ("TAKENATE 500" manufactured by Mitsui Chemicals Co., Ltd.), and react at 120°C for 6 hours to confirm that the isocyanate group content is 0.1% by mass or less . Next, 68 parts by mass of "ARONIX M-306" was added and reacted at 110°C for 3 hours. 140 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Furthermore, 93 parts by mass of succinic anhydride and 80 parts by mass of dimethylacetamide were added and reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (23). The solid acid value of the acid group-containing (meth)acrylate resin (23) was 94 mgKOH/g, and the weight average molecular weight was 2,450.

(Comparative example 1: Production of acid group-containing acrylic resin (C1)) Add 101 parts by mass of diethylene glycol monomethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux cooler, and dissolve 428 parts by mass of o-cresol novolac epoxy resin (manufactured by DIC Co., Ltd.) "EPICLON N-680", epoxy equivalent: 214), 4 parts by mass of dibutylhydroxytoluene as an antioxidant, 0.4 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, and 144 parts by mass of acrylic acid , 1.6 parts by mass of triphenylphosphine, the esterification reaction was carried out at 120°C for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 2.5 hours to obtain the target acid group-containing acrylate resin (C1). The solid acid value of the acid group-containing acrylate resin (C1) was 85 mgKOH/g.

(Example 24: Preparation of curable resin composition (1)) The acid group-containing (meth)acrylate resin (1) obtained in Example 1 and ortho-cresol novolac type epoxy resin (manufactured by DIC Co., Ltd.) as a hardener were blended in the parts by mass shown in Table 1. "EPICLON N-680"), dineopentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, photopolymerization initiator ("Omnirad 907" made by IGM), 2-ethyl-4-methyl Glyimidazole and phthalocyanine green are kneaded by a roll mill to obtain a curable resin composition (1).

(Examples 25 to 46: Preparation of curable resin compositions (2) to (23)) The acid group-containing (meth)acrylate resins (2) to (23) obtained in Examples 2-23 were used instead of the acid group-containing (meth)acrylate resin (1) used in Example 24, Except for this, curable resin compositions (2) to (23) were obtained in the same manner as in Example 24.

(Comparative example 2: Preparation of curable resin composition (C2)) Except that the acid group-containing acrylate resin (C1) obtained in Comparative Example 1 was used instead of the acid group-containing acrylate resin (1) used in Example 24, a curable resin was obtained in the same manner as in Example 24 Composition (C2).

Using the curable resin compositions (1) to (23) and (C2) obtained in the above-mentioned examples and comparative examples, the following evaluations were performed.

[Method of Evaluation of Sensitivity] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator so that the film thickness became 50 μm, and then dried at 80° C. for 30 minutes. Next, the metal halide lamp was used to irradiate ultraviolet rays of 1000 mJ/cm ² through STEPTABLET No. 2 manufactured by KODAK. This was developed with a 1% by mass sodium carbonate aqueous solution for 180 seconds, and the evaluation was made with the number of remaining stages. In addition, the more the remaining segments, the higher the sensitivity.

[Evaluation method of alkali developability] After coating the curable resin composition obtained in each of the Examples and Comparative Examples on a glass substrate using a coater to make the film thickness 50μm, it was dried at 80°C for 30 minutes, 40 minutes, 50 minutes, 60 minutes to make samples with different drying times. This was developed with a 1% sodium carbonate aqueous solution at 30°C for 180 seconds, and the drying time at 80°C for the sample with no residue remaining on the substrate was evaluated as the drying management range. In addition, the longer the drying management range, the better the alkali developability.

The composition and evaluation results of the curable resin composition (1) to (23) produced in Examples 24 to 46 and the curable resin composition (C2) produced in Comparative Example 2 are shown in Tables 1 and 2.

Table 1 Table 1 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Curable resin composition (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (Meth)acrylate resin containing acid groups (1) Composition (parts by mass) 100 (Meth)acrylate resin containing acid groups (2) 100 (Meth)acrylate resin containing acid groups (3) 100 (Meth)acrylate resin containing acid groups (4) 100 (Meth)acrylate resin containing acid groups (5) 100 (Meth)acrylate resin containing acid groups (6) 100 (Meth) acrylate resin containing acid groups (7) 100 (Meth) acrylate resin containing acid groups (8) 100 (Meth) acrylate resin containing acid groups (9) 100 (Meth) acrylate resin containing acid groups (10) 100 (Meth) acrylate resin containing acid groups (11) 100 (Meth)acrylate resin containing acid groups (12) 100 hardener 27.6 29.1 27.2 25.2 22.4 25.1 23.0 26.0 26.4 26.0 29.1 29.7 Organic solvents 14.9 15.7 14.6 13.6 12.1 13.5 12.4 14.0 14.2 14.0 15.7 16.0 Photopolymerization initiator 3.5 3.4 3.5 3.2 3.1 3.4 3.2 3.2 3.2 3.1 3.1 3.1 Dineopentaerythritol hexaacrylate 6.9 6.8 7.0 6.5 6.3 6.9 6.5 6.4 6.3 6.2 6.2 6.2 2-ethyl-4-methylimidazole 0.6 0.6 0.5 0.5 0.4 0.5 0.5 0.5 0.5 0.5 0.6 0.6 Phthalocyanine Green 0.7 0.7 0.7 0.7 0.6 0.7 0.6 0.7 0.7 0.7 0.7 0.7 Sensitivity (segment) 10 9 8 9 8 9 8 7 8 9 8 9 Alkali developability [Drying management range (points)] 80 90 80 80 70 80 70 80 80 80 70 60

Table 2 Table 2 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Example 45 Example 46 Comparative example 2 Curable resin composition (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (C2) (Meth) acrylate resin containing acid groups (13) 100 (Meth)acrylate resin containing acid groups (14) 100 (Meth) acrylate resin containing acid groups (15) 100 (Meth) acrylate resin containing acid groups (16) 100 (Meth) acrylate resin containing acid groups (17) 100 (Meth) acrylate resin containing acid groups (18) 100 (Meth)acrylate resin containing acid groups (19) 100 (Meth) acrylate resin containing acid groups (20) 100 (Meth)acrylate resin containing acid groups (21) 100 (Meth)acrylate resin containing acid groups (22) 100 (Meth)acrylate resin containing acid groups (23) 100 Acid group-containing (meth)acrylate resin (C1) 100 hardener 28.6 26.6 27.2 24.3 23.7 24.7 24.4 24.0 24.0 26.9 26.6 21.9 Organic solvents 15.4 14.3 14.6 13.1 12.8 13.3 13.1 12.9 12.9 14.5 14.3 11.8 Photopolymerization initiator 3.1 3.1 3.1 3.1 3.1 3.3 3.1 3.1 3.1 3.1 3.1 3.2 Dineopentaerythritol hexaacrylate 6.2 6.2 6.2 6.2 6.2 6.5 6.3 6.2 6.2 6.2 6.2 6.4 2-ethyl-4-methylimidazole 0.6 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.4 Phthalocyanine Green 0.7 0.7 0.7 0.6 0.6 0.7 0.7 0.6 0.6 0.7 0.7 0.6 Sensitivity (segment) 9 10 10 9 9 8 8 10 7 8 12 6 Alkali developability [Drying management range (points)] 70 60 60 40 40 70 80 70 70 100 50 40

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)。(Example 47: Preparation of curable resin composition (24)) The acid group-containing (meth)acrylate resin (1) obtained in Example 1 was blended with the mass parts shown in Table 1 as a hardener O-cresol novolac epoxy resin ("EPICLON N-680" made by DIC Co., Ltd.), 2-methyl-1-(4-methylthiophenyl)-2 as a photopolymerization initiator -

Linylpropan-1-one ("Omnirad-907" manufactured by IGM Corporation) and diethylene glycol monomethyl ether acetate as an organic solvent gave curable resin composition (24).

(Examples 48 to 69: Preparation of curable resin compositions (25) to (46)) The acid group-containing (meth)acrylate resins (2) to (23) obtained in Examples 2-23 were used instead of the acid group-containing (meth)acrylate resin (1) used in Example 47, Except for this, curable resin compositions (25) to (46) were obtained in the same manner as in Example 47.

(Comparative example 3: Preparation of curable resin composition (C3)) The acid group-containing (meth)acrylate resin (C1) obtained in Comparative Example 1 was used instead of the acid group-containing (meth)acrylate resin (1) used in Example 47. In addition, the same In the same manner as in Example 47, a curable resin composition (C3) was obtained.

Using the curable resin compositions (24) to (46) and (C3) obtained in the above-mentioned Examples and Comparative Examples, the following evaluations were performed.

[Evaluation method of heat resistance]> Preparation of test piece> The curable resin composition obtained in the examples and comparative examples was applied to copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2- WS (18μm) on top, and let it dry at 80°C for 30 minutes. After irradiating 1000mJ/cm ² of ultraviolet rays with a metal halide lamp, it was heated at 160°C for 1 hour. The cured product was peeled from the copper foil to obtain a test piece (cured product).

The aforementioned test piece was cut into a size of 6mm×40mm, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Co., Ltd., stretching method: frequency 1Hz, heating rate 3°C/min) was used to adjust the elasticity The temperature at which the coefficient change reached the maximum (the maximum tanδ change rate) was evaluated as the glass transition temperature (Tg).

The compositions and evaluation results of the curable resin compositions (24) to (46) produced in Examples 47 to 69 and the curable resin composition (C3) produced in Comparative Example 3 are shown in Tables 3 and 4.

table 3 table 3 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 Example 57 Example 58 Curable resin composition (twenty four) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (Meth)acrylate resin containing acid groups (1) Composition (parts by mass) 100 (Meth)acrylate resin containing acid groups (2) 100 (Meth)acrylate resin containing acid groups (3) 100 (Meth)acrylate resin containing acid groups (4) 100 (Meth)acrylate resin containing acid groups (5) 100 (Meth)acrylate resin containing acid groups (6) 100 (Meth) acrylate resin containing acid groups (7) 100 (Meth) acrylate resin containing acid groups (8) 100 (Meth) acrylate resin containing acid groups (9) 100 (Meth) acrylate resin containing acid groups (10) 100 (Meth) acrylate resin containing acid groups (11) 100 (Meth)acrylate resin containing acid groups (12) 100 hardener 27.6 29.1 27.2 25.2 22.4 25.1 23.0 26.0 26.4 26.0 29.1 29.7 Organic solvents 14.9 15.7 14.6 13.6 12.1 13.5 12.4 14.0 14.2 14.0 15.7 16.0 Photopolymerization initiator 3.5 3.4 3.5 3.2 3.1 3.4 3.2 3.2 3.2 3.1 3.1 3.1 Heat resistance [Tg(℃)] 196 197 221 189 209 205 181 189 182 195 192 184

Table 4

Table 4 Example 59 Example 60 Example 61 Example 62 Example 63 Example 64 Example 65 Example 66 Example 67 Example 68 Example 69 Comparative example 3 Curable resin composition (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (C3) (Meth) acrylate resin containing acid groups (13) 100 (Meth)acrylate resin containing acid groups (14) 100 (Meth) acrylate resin containing acid groups (15) 100 (Meth) acrylate resin containing acid groups (16) 100 (Meth) acrylate resin containing acid groups (17) 100 (Meth) acrylate resin containing acid groups (18) 100 (Meth)acrylate resin containing acid groups (19) 100 (Meth) acrylate resin containing acid groups (20) 100 (Meth)acrylate resin containing acid groups (21) 100 (Meth)acrylate resin containing acid groups (22) 100 (Meth)acrylate resin containing acid groups (23) 100 Acid group-containing (meth)acrylate resin (C1) 100 hardener 28.6 26.6 27.2 24.3 23.7 24.7 24.4 24.0 24.0 26.9 26.6 21.9 Organic solvents 15.4 14.3 14.6 13.1 12.8 13.3 13.1 12.9 12.9 14.5 14.3 11.8 Photopolymerization initiator 3.1 3.1 3.1 3.1 3.1 3.3 3.1 3.1 3.1 3.1 3.1 3.2 Heat resistance [Tg(℃)] 188 204 199 238 233 181 189 171 190 165 204 134

In addition, the mass parts of the "acid group-containing (meth)acrylate resin" in Tables 1 to 4 are the solution values.

The "hardener" in Tables 1 to 4 means ortho-cresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Co., Ltd., epoxy equivalent: 214).

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

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

Examples 22 to 63 shown in Tables 1 to 4 are examples of curable resin compositions using the acid group-containing (meth)acrylate resin of the present invention. It can be confirmed that the aforementioned curable resin composition has excellent sensitivity and alkali developability, and has excellent heat resistance in the cured product.

On the other hand, Comparative Examples 2 and 3 are examples of curable resin compositions in which the acid group-containing (meth)acrylate resin of the present invention is not used. It can be confirmed that the aforementioned curable resin composition has a markedly insufficient sensitivity, and the heat resistance of the cured product is also markedly insufficient.

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Claims (13)

An acid group-containing (meth)acrylate resin, which is composed of an acid group and/or acid anhydride group-containing amide resin (A), a hydroxyl group-containing (meth)acrylate compound (B), The epoxy (meth)acrylate compound (C) and the polycarboxylic anhydride (D) are the necessary reaction materials, and the acid group-containing (meth)acrylate resin is characterized by: The aforementioned amide imine resin (A) is a reactant (A-1) of polyisocyanate compound (a1) and polycarboxylic anhydride (a2), or polyisocyanate compound (a1), polycarboxylic anhydride (a2) and containing The reactant (A-2) of the hydroxyl (meth)acrylate compound (a3); Either or both of the aforementioned hydroxyl-containing (meth)acrylate compound (B) or the aforementioned hydroxyl-containing (meth)acrylate compound (a3), including a (meth)acrylate compound having two hydroxyl groups, and /Or (meth)acrylate compounds having 3 hydroxyl groups. The acid group-containing (meth)acrylate resin according to claim 1, wherein the aforementioned polyisocyanate compound (a1) is an aliphatic diisocyanate or an alicyclic diisocyanate. The acid group-containing (meth)acrylate resin of claim 1, wherein the (meth)acrylate compound having two hydroxyl groups includes neopentylerythritol di(meth)acrylate and/or dineopentyl Tetraol tetra(meth)acrylate compound. The acid group-containing (meth)acrylate resin of claim 1, wherein the (meth)acrylate compound having 3 hydroxyl groups includes neopentylerythritol mono(meth)acrylate and/or dineopentyl Tetraol tri(meth)acrylate. The acid group-containing (meth)acrylate resin of claim 1, wherein the aforementioned reactant (A-2) is the aforementioned polycarboxylic anhydride (a2) and the aforementioned hydroxyl-containing (meth)acrylate compound (a3) The intermediate reaction product and the reactant of the aforementioned polyisocyanate compound (a1); The number of moles of the polycarboxylic anhydride (a2) is in the range of 2-8 relative to 1 mole of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (a3). A curable resin composition characterized by comprising the acid group-containing (meth)acrylate resin as defined in any one of claims 1 to 5, and a photopolymerization initiator. The curable resin composition of claim 6, which further contains an organic solvent and a curing agent. The curable resin composition according to claim 6, which further contains resins having acid groups and polymerizable unsaturated bonds other than the acid group-containing (meth)acrylate resin of any one of claims 1 to 5 ( E). A hardened product characterized by being a hardening reactant of a hardening resin composition according to any one of claims 6 to 8. An insulating material characterized by containing the curable resin composition according to any one of claims 6 to 8. A resin material for solder resist, which is characterized by containing the curable resin composition according to any one of claims 6 to 8. A solder resist component characterized by containing the resin material for solder resist as in Claim 11. A method for producing an acid group-containing (meth)acrylate resin, which uses an acid group and/or acid anhydride group-containing amide resin (A) and a hydroxyl group-containing (meth)acrylate compound (B) ), a method for producing an acid group-containing (meth)acrylate resin obtained by reacting an epoxy group-containing (meth)acrylate compound (C) and a polycarboxylic anhydride (D), characterized by: The aforementioned amide imine resin (A) is a reactant (A-1) obtained by reacting a polyisocyanate compound (a1) and a polycarboxylic anhydride (a2), or a polyisocyanate compound (a1), a polycarboxylic anhydride ( a2) Reactant (A-2) obtained by reacting with hydroxyl-containing (meth)acrylate compound (a3); Either or both of the aforementioned hydroxyl-containing (meth)acrylate compound (B) or the aforementioned hydroxyl-containing (meth)acrylate compound (a3), including a (meth)acrylate compound having two hydroxyl groups, and /Or (meth)acrylate compounds having 3 hydroxyl groups.