KR20210076076A - Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for soldering resist and resist member - Google Patents

Abstract

The present invention relates to an amideimide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound, an epoxy group-containing (meth)acrylate compound, and an acid group-containing ( As the meth)acrylate resin, the amideimide resin is a reaction product of a polyisocyanate compound and a polycarboxylic acid anhydride, or a polyisocyanate compound, a polycarboxylic acid anhydride, and a hydroxyl group-containing (meth)acrylate compound. ) An acid group-containing (meth)acrylate resin is provided, wherein the acrylate compound contains a (meth)acrylate compound having two hydroxyl groups, and/or a (meth)acrylate compound having three hydroxyl groups. . This acid group-containing (meth)acrylate resin has excellent photosensitivity and alkali developability, and can form a cured product having excellent heat resistance.

Description

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

The present invention provides an acid group-containing (meth)acrylate resin excellent in photosensitivity and alkali developability and excellent heat resistance in a cured product, a curable resin composition containing the same, an insulating material comprising the curable resin composition, and a resin for soldering resist It relates to a material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.

In recent years, after acrylated an epoxy resin with acrylic acid as a resin material for soldering resists for printed wiring boards, the acidic radical containing epoxy acrylate resin obtained by making an acid anhydride react is used widely. Various things, such as a thing excellent in alkali developability, and the thing excellent in the heat resistance in hardened|cured material, are mentioned as for the performance requested|required with respect to the resin material for soldering resists hardening with a small exposure amount.

As a conventionally known resin material for soldering resists, active energy ray-curable resin 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 is known (for example, Patent Document 1 below reference), the heat resistance in the cured product is excellent, but it does not satisfy the required properties that will increase gradually in the future, and it is not sufficient for the current market demand.

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

Japanese Patent Laid-Open No. 61-243869

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

As a result of intensive studies to solve the above problems, the present inventors have found that an amideimide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound, an epoxy group-containing (meth)acrylate compound, and a polycarboxylic acid anhydride are essential As an acid group-containing (meth)acrylate resin used as a raw material for the reaction of, the amideimide resin is a reaction product of a polyisocyanate compound and a polycarboxylic acid anhydride, or a reaction product of a polyisocyanate compound, a polycarboxylic acid anhydride and a hydroxyl group-containing (meth)acrylate and either or both of the hydroxyl group-containing (meth)acrylate compound used as a raw material of the acid group-containing (meth)acrylate resin or the hydroxyl group-containing (meth)acrylate compound used as the raw material of the amideimide resin is a hydroxyl group By using an acid group-containing (meth)acrylate resin characterized in that it contains a (meth)acrylate compound having two, and/or a (meth)acrylate compound having three hydroxyl groups, the above problems can be solved found out, and completed the present invention.

That is, the present invention relates to an amideimide resin (A) having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), an epoxy group-containing (meth)acrylate compound (C), and a polycarboxylic acid An acid group-containing (meth)acrylate resin using an anhydride (D) as an essential reaction raw material, wherein the amideimide resin (A) is a reaction product (A-1) of a polyisocyanate compound (a1) and a polycarboxylic anhydride (a2) , or a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2), and a reaction product (A-2) of a hydroxyl group-containing (meth)acrylate compound (a3), the hydroxyl group-containing (meth)acrylate compound (B) or It is characterized in that either or both of the hydroxyl group-containing (meth)acrylate compound (a3) contains a (meth)acrylate compound having two hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups An acid group-containing (meth)acrylate resin, a curable resin composition containing the same, a cured product comprising the curable resin composition, an insulating material, a resin material for a solder resist, a resist member, and a method for producing an acid group-containing (meth)acrylate resin is about

The acid group-containing (meth)acrylate resin of the present invention is excellent in photosensitivity and alkali developability, and is excellent in heat resistance in a cured product, so that it is suitable for an insulating material, a resin material for soldering resists, and a resist member. Can be used.

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

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

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

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

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

As the amide-imide resin (A), [1] a reaction product (A-1) of a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2) (hereinafter referred to as “amide-imide resin (A-1)” in some cases) ), or [2] a reaction product (A-2) of a polyisocyanate compound (a1), a polycarboxylic anhydride (a2), and a hydroxyl group-containing (meth)acrylate compound (a3) (hereinafter referred to as amidimide resin (A-2) sometimes called) is used.

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

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

As said polyisocyanate compound (a1), For example, aliphatic diisocyanate, such as butane diisocyanate, hexamethylene diisocyanate, 2,2, 4- trimethyl hexamethylene diisocyanate, and 2,4, 4- trimethyl hexamethylene diisocyanate. compound; Alicyclic diisocyanate compounds, such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; Tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, o- aromatic diisocyanate compounds such as tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); These isocyanurate modified products, biuret modified products, allophanate modified products, and the like are mentioned. In addition, these polyisocyanate compounds may be used independently or may use 2 or more types together. These polyisocyanate compounds (a1) have excellent photosensitivity and alkali developability, and since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance is obtained, a non-isocyanurate modified product is obtained. desirable.

[In formula (1), R ¹ is each independently any one of a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is each independently any one of the bonding points connecting the C1-C4 alkyl group or the structural moiety represented by Structural Formula (1) and the methylene group to which the * mark is attached. l is 0 or an integer from 1 to 3, and m is an integer from 1 to 15]

Among these, the said alicyclic diisocyanate compound or its modified body is preferable at the point used as acidic radical containing (meth)acrylate resin which has the outstanding solvent solubility, and alicyclic diisocyanate is preferable. In addition, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance, the aliphatic diisocyanate compound or a modified product thereof is preferable, and an aliphatic diisocyanate is preferable. . In addition, the ratio of the total mass of the alicyclic diisocyanate compound or its modified product and the aliphatic diisocyanate compound or its modified product to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, and 90% by mass or more, It is more preferable that it is mass % or more. Moreover, when using together the said alicyclic diisocyanate compound or its modified body, and the said aliphatic diisocyanate compound or its modified body, it is preferable that the mass ratio of both is the range of 20/80-80/20.

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

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

As the alicyclic polycarboxylic acid anhydride, in the present invention, an alicyclic polycarboxylic acid anhydride in which an acid anhydride group is bonded to an alicyclic structure is defined as an alicyclic polycarboxylic acid anhydride, and the presence or absence of an aromatic ring in other structural sites is not questioned. 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, The acid anhydride of 2-dicarboxylic acid, etc. are mentioned.

Examples of the aromatic polycarboxylic anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetriccarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenone. The acid anhydride of tetracarboxylic acid, etc. are mentioned.

These polycarboxylic anhydrides (a2) may be used independently or may use 2 or more types together. In addition, among these, an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance is obtained, so that the alicyclic polycarboxylic acid anhydride or the aromatic polycarboxylic acid anhydride is desirable. In addition, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and excellent heat resistance, a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure is used. It is preferable to use cyclohexanetricarboxylic acid anhydride or trimellitic acid anhydride, and it is particularly preferable to use cyclohexanetricarboxylic acid anhydride. At this time, 70 mass % or more is preferable and, as for content of the said tricarboxylic acid anhydride in the said polycarboxylic acid anhydride (a2), 90 mass % or more is more preferable.

Moreover, as the said amideimide resin (A-1), you may use together other compound as a reaction raw material other than the said polyisocyanate compound (a1) and the said polycarboxylic anhydride (a2) as needed. When the other compounds are used in combination, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2) in the reaction raw material of the amideimide resin (A-1) are obtained from the viewpoint of sufficiently exhibiting the effects of the present invention. 80 mass % or more is preferable and, as for total content, 85 mass % is more preferable.

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

As the polycarboxylic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetriccarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like. Moreover, as said polycarboxylic acid, it is a copolymer of a conjugated diene type vinyl monomer and acrylonitrile, for example, and the polymer which has a carboxy group in the molecule|numerator can also be used. These polycarboxylic acids (a2) may be used independently or may use 2 or more types together.

As a copolymer of the conjugated diene-based vinyl monomer and acrylonitrile, the polymer having a carboxy group in its molecule, for example, has a carboxy group in the butadiene-acrylonitrile copolymer represented by the following structural formula (2-1) and 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. Moreover, although the position of a carboxy group may be located anywhere in the side chain or terminal of a molecule|numerator, the terminal is preferable.

[In 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]

[In 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 amideimide resin (A-1) has excellent photosensitivity and alkali developability, and an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance is obtained under neutral conditions, that is, It is preferable that the measured value under conditions in which the acid anhydride group is not ring-opened is in the range of 60 to 350 mgKOH/g, and the measured value under the conditions in which the acid anhydride group is ring-opened, such as in the presence of water, is 61 to 360 mgKOH/g. range is preferred. In addition, in this invention, an acid value is a value measured by the neutralization titration method of JISK0070 (1992).

It does not specifically limit as a manufacturing method of the said amideimide resin (A-1), You may manufacture by any method. For example, it can manufacture by the method similar to general amideimide resin. Specifically, 0.8 to 3.5 mol of the polycarboxylic anhydride (a2) is used with respect to 1 mol of the isocyanate group of the polyisocyanate compound (a1), and stirred and mixed under temperature conditions of about 100 to 180° C. method can be found.

The said reaction may be performed in an organic solvent as needed, and a basic catalyst may be used as needed.

As said organic solvent, For example, Ketone solvents, such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone; Cyclic ether solvents, such as tetrahydrofuran and a dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; Methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. are mentioned. These organic solvents may be used independently or may use 2 or more types together. Moreover, it is preferable to use the usage-amount of the said organic solvent in the range of about 0.1-5 times with respect to the total mass of reaction raw materials from a point which reaction efficiency becomes favorable.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene -5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine , imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc. amine compounds; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; Tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, benzylphosph phosphonium salts such as phonium chloride; Dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,1,3,3 -organotin compounds, such as tetrabutyl-1, 3- dodecanoyl distanoxane; organometallic compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; Inorganic metal compounds etc. are mentioned. These basic catalysts may be used independently or may use 2 or more types together.

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

The amideimide 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 above-mentioned polyisocyanate compound (a1) can be used, The said polyisocyanate compound may be used independently or may use 2 or more types together.

As said polycarboxylic acid anhydride (a2), the thing similar to the above-mentioned polycarboxylic acid anhydride (a2) can be used.

The amount of the polycarboxylic acid anhydride (a2) to be used is that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and excellent heat resistance is obtained, so that the polyisocyanate compound (a1) is It is preferable to use in the range used as 0.8-3.5 mol with respect to 1 mol of isocyanate groups which have.

As said hydroxyl-containing (meth)acrylate compound (a3), if it is a compound which has a hydroxyl group and a (meth)acryloyl group in a molecular structure, another specific structure will not be specifically limited, A wide variety of compounds can be used. As an example thereof, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylol propane (meth) acrylate, trimethylol propane di (meth) acrylate, pentaerythritol (meth) ) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, di Trimethylolpropane tri(meth)acrylate etc. are mentioned. In addition, (poly)oxyalkylene chains such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. are introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds (poly) ) oxyalkylene modified products and lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl-containing (meth)acrylate compounds (a3) may be used independently or may use 2 or more types together.

Moreover, as said amideimide resin (A-2), as needed, other compounds other than the said polyisocyanate compound (a1), the said polycarboxylic anhydride (a2), and the said hydroxyl-containing (meth)acrylate compound (a3). can also be used together as a reaction raw material. When the other compounds are used together, the polyisocyanate compound (a1), the polycarboxylic anhydride (a2) and the polycarboxylic acid anhydride (a2) in the reaction raw material of the amideimide resin (A-2) are sufficiently exhibited. 80 mass % or more is preferable and, as for content of the sum total of the said hydroxyl-containing (meth)acrylate compound (a3), 85 mass % is more preferable.

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

As said polycarboxylic acid, the thing similar to the above-mentioned polycarboxylic acid can be used. The said polycarboxylic acid may be used independently and may use 2 or more types together.

The acid value of the amideimide resin (A-2) has excellent photosensitivity and alkali developability, and an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance is obtained under neutral conditions, that is, It is preferable that the measured value under conditions in which the acid anhydride group is not ring-opened is in the range of 60 to 350 mgKOH/g, and the measured value under the conditions in which the acid anhydride group is ring-opened, such as in the presence of water, is 61 to 360 mgKOH/g. range is preferred.

There is no restriction|limiting in particular as a manufacturing method of the said amideimide resin (A-2), You may manufacture by any method. For example, it may manufacture by the method of making all the reaction raw materials react collectively, and you may manufacture by the method of making the reaction raw materials react sequentially. Among them, from the viewpoint of easy control of the reaction, the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3) are reacted (step A1), and the intermediate reaction product obtained in the step A1 and the above It is preferable to manufacture by the method of making the polyisocyanate compound (a1) react (step A2).

The step A1 is a step of reacting the polycarboxylic anhydride (a2) with the hydroxyl group-containing (meth)acrylate compound (a3) to obtain an intermediate reaction product. The said reaction mainly makes the acid anhydride group of the said polycarboxylic acid anhydride (a2) react with the hydroxyl group of the said hydroxyl-containing (meth)acrylate compound (a3). As for the reaction ratio of the said reaction, the range of the mole number of the said polycarboxylic acid anhydride (a2) with respect to 1 mol of the hydroxyl groups which the said hydroxyl-containing (meth)acrylate compound (a3) has is preferable in the range of 2-8. The reaction of step A1 can be carried out, for example, by heating and stirring in the presence of a suitable esterification catalyst under temperature conditions of about 80 to 140°C. In addition, you may perform reaction in an organic solvent as needed.

Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, and 2-methylimidazole imidazole compounds such as , 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole; can These esterification catalysts may be used independently and may use 2 or more types together.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

The step A2 is a reaction between the intermediate reaction product obtained in the step A1 and the polyisocyanate compound (a1). This reaction mainly reacts the acid group and/or acid anhydride group which the intermediate reaction product obtained in the said process A1 has, and the isocyanate group of the said polyisocyanate compound (a1). The reaction of step A2 can be carried out, for example, by heating and stirring in the presence of a suitable basic catalyst under temperature conditions of about 100 to 180°C. In addition, you may perform reaction in an organic solvent as needed. When performing the process A1 and the process A2 continuously, it is not necessary to add a basic catalyst and an organic solvent, and you may add it suitably.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said organic solvent may be used independently or may use 2 or more types together.

As said hydroxyl-containing (meth)acrylate compound (B), the thing similar to the above-mentioned hydroxyl-containing (meth)acrylate compound (a3) can be used, The said hydroxyl-containing (meth)acrylate compound (B) is independent It may be used as or two or more types may be used in combination. Moreover, when the said amidimide resin (A-1) is used as said amidimide resin (A), as said hydroxyl-containing (meth)acrylate compound (B), the (meth)acrylate compound which has two hydroxyl groups; And/or the (meth)acrylate compound which has three hydroxyl groups is used as essential.

In addition, when the amideimide resin (A-2) is used as the amideimide resin (A), the hydroxyl group-containing (meth)acrylate compound (a3) as a raw material for the amideimide resin (A-2), or A (meth)acrylate compound having two hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups in either one or both of the hydroxyl group-containing (meth)acrylate compound (B) is essentially used. .

The molecular weight of the hydroxyl group-containing (meth)acrylate compound (B) is 1,000 or less from the viewpoint of obtaining an acidic group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and excellent heat resistance. desirable. Moreover, when the said hydroxyl-containing (meth)acrylate compound (B) is an oxyalkylene modified body or a lactone modified body, as for a weight average molecular weight (Mw), 1,000 or less are preferable.

As said epoxy-group containing (meth)acrylate compound (C), if it has a (meth)acryloyl group and an epoxy group in a molecular structure, another specific structure will not be specifically limited, A large variety of compounds can be used. As an example, glycidyl group containing (meth), such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, for example, acrylate monomers; Mono(meth)acrylated product of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether and bisphenol diglycidyl ether and the like. These epoxy group-containing (meth)acrylate compounds may be used independently or may use 2 or more types together. Among these, (meth)acrylate compounds having one epoxy group are preferable from the viewpoint of facilitating reaction control, and having excellent photosensitivity and alkali developability, and containing an acid group (meth) capable of forming a cured product having excellent heat resistance. A glycidyl group containing (meth)acrylate monomer is preferable at the point from which an acrylate resin is obtained. Moreover, it is preferable that the molecular weight of the said glycidyl group containing (meth)acrylate monomer is 500 or less. Further, the ratio of the glycidyl group-containing (meth)acrylate monomer to the total mass of the epoxy group-containing (meth)acrylate compound (C) is preferably 70% by mass or more, and more preferably 90% by mass or more.

As said polycarboxylic acid anhydride (D), the thing similar to the above-mentioned polycarboxylic acid anhydride (a3) can be used. In addition, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance, an aliphatic polycarboxylic acid anhydride or an alicyclic polycarboxylic acid anhydride is preferable, and an aliphatic dicarboxylic acid Anhydride or alicyclic dicarboxylic acid anhydride is more preferable. These polycarboxylic acid anhydrides (D) may be used independently or may use 2 or more types together.

As the acid group-containing (meth)acrylate resin of the present invention, the amideimide resin (A), the hydroxyl group-containing (meth)acrylate compound (B), and the epoxy group-containing (meth)acrylate compound ( In addition to C) and the said polycarboxylic acid anhydride (D), you may use together other reaction raw materials. When using together the said other reaction raw materials, since the effect shown by this invention is fully exhibited, content of the total of the said (A)-(D) components in the reaction raw material of an acidic radical containing (meth)acrylate resin is 80 Mass % or more is preferable, and 85 mass % or more is more preferable.

It does not specifically limit as a manufacturing method of the acidic radical containing (meth)acrylate resin of this invention, You may manufacture by any method. For example, it may manufacture by the method of making all the reaction raw materials react collectively, and you may manufacture by the method of making the reaction raw materials react sequentially. Among them, from the viewpoint of easy reaction control, the amideimide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) are reacted (Step 1), and the product of Step 1 and the epoxy group-containing (meth) ) The acrylate compound (C) is reacted (Step 2), and the product of Step 2 and the polycarboxylic anhydride (D) are reacted (Step 3).

As said process 1, it is reaction of the said amideimide resin (A) and the said hydroxyl-containing (meth)acrylate compound (B). This reaction is mainly to react the acid group and/or acid anhydride group in the amideimide resin (A) and the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (B). Since the said hydroxyl-containing (meth)acrylate compound (B) is especially excellent in the reactivity with an acid-anhydride group, as mentioned above, it is preferable that the said amidimide resin (A) has an acid-anhydride group. In addition, the content of the acid anhydride group in the amideimide resin (A) is determined by the difference between the measured values of the two types of acid values, i.e., the acid value under the condition in which the acid anhydride group is ring-opened, and the acid value in the condition in which the acid anhydride group is not ring-opened. It can be calculated from the difference between the acid values of

The reaction ratio between the amideimide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is, when the amideimide resin (A) has an acid group and an acid anhydride group, and the amideimide resin (A) has an acid anhydride group, the number of moles of hydroxyl groups in the hydroxyl group-containing (meth)acrylate compound (B) relative to 1 mole of acid anhydride groups in the amide-imide resin (A) is 0.9 to 1.1. It is preferable to use Further, when the amideimide resin (A) has an acid group, the number of moles of hydroxyl groups in the hydroxyl group-containing (meth)acrylate compound (B) relative to 1 mole of the acid groups in the amidimide resin (A) is 0.1 It is preferable to use it in the range used as -0.5.

The reaction between the amideimide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is, for example, carried out by heating and stirring in the presence of a suitable esterification catalyst under a temperature condition of about 80 to 140°C. can As said esterification catalyst, the thing similar to the above-mentioned esterification catalyst can be used. The said esterification catalyst may be used independently and may use 2 or more types together. It is preferable to use the addition amount of the said esterification catalyst in the range of 0.001-5 mass parts with respect to 100 mass parts of total mass of reaction raw materials.

The said reaction may be performed in an organic solvent as needed, and an acidic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together. In the case where the production of the amide-imide resin (A) and the step 1 are continuously performed, the reaction may be continued as it is in the organic solvent used in the production of the amide-imide resin (A).

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, para-toluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. have. These acidic catalysts may be used independently or may use 2 or more types together.

As the said process 2, it is reaction of the product of the said process 1, and the said epoxy-group containing (meth)acrylate compound (C). The said reaction mainly makes the acidic radical in the product obtained in the said process 1 react the said epoxy-group containing (meth)acrylate compound. The reaction ratio is preferably used in a range where the number of moles of the epoxy groups of the epoxy group-containing (meth)acrylate compound (C) with respect to 1 mole of acid groups in the product obtained in step 1 is 0.7 to 1.2, and 0.9 It is more preferable to use in the range used as -1.1. The reaction in step 2 can be carried out, for example, in the presence of a suitable esterification catalyst by heating and stirring under temperature conditions of about 90 to 140°C. When performing the process 1 and the process 2 continuously, it is not necessary to add an esterification catalyst, and you may add it suitably. In addition, you may perform reaction in an organic solvent as needed. Moreover, as for the said esterification catalyst and organic solvent, the thing similar to the above-mentioned esterification catalyst and organic solvent can be used, They may be used independently or may use 2 or more types together.

The step 3 is a reaction between the product of step 2 and the polycarboxylic anhydride (D). The said reaction is mainly to make the hydroxyl group in the product obtained in the said process 2 react the said polycarboxylic acid anhydride (D). In the product of the step 2, for example, a hydroxyl group generated by ring-opening of the epoxy group in the epoxy group-containing (meth)acrylate compound (C) exists. The reaction ratio of the polycarboxylic anhydride (D) is preferably adjusted so that the acid value of the acid group-containing (meth)acrylate resin as a product is about 60 to 120 mgKOH/g. The reaction in step 3 can be performed, for example, in the presence of a suitable esterification catalyst by heating and stirring under temperature conditions of about 80 to 140°C. When performing the process 2 and the process 3 continuously, it is not necessary to add an esterification catalyst, and you may add it suitably. In addition, you may perform reaction in an organic solvent as needed. Moreover, as for the said esterification catalyst and organic solvent, the thing similar to the above-mentioned esterification catalyst and organic solvent can be used, They may be used independently or may use 2 or more types together.

The acid value of the acid group-containing (meth)acrylate resin of the present invention is 50 to 120 mg, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance. The range of KOH/g is preferable, and the range of 60-110 mgKOH/g is more preferable. In addition, in this invention, the acid value of acidic radical containing (meth)acrylate resin is a value measured by the neutralization titration method of JISK0070 (1992).

Moreover, it is preferable that the range of the weight average molecular weight (Mw) of the said acidic radical containing (meth)acrylate resin is 1,000-20,000. In addition, in this invention, the weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.

Since the acidic radical containing (meth)acrylate resin of this invention has a polymerizable (meth)acryloyl group in molecular structure, it can use as curable resin composition by adding a photoinitiator, for example.

What is necessary is just to use the said photoinitiator by selecting an appropriate thing according to the kind etc. of the active energy ray irradiated. Moreover, you may use together with photosensitizers, such as an amine compound, a urea compound, a sulfur compound, a phosphorus compound, a chlorine-containing compound, and a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-( alkylphenone photoinitiators such as dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photoinitiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Intramolecular hydrogen extraction type photoinitiators, such as a benzophenone compound, etc. are mentioned. These may be used independently, respectively, and may use 2 or more types together.

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

As a commercial item of the said other photoinitiator, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", " “Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO”, “Omnirad-819”, “Omnirad-2022”, “Omnirad-2100”, “Omnirad- 754”, “Omnirad-784”, “Omnirad-500”, “Omnirad-81” (manufactured by IGM), “Gaya Cure-DETX”, “Gaya Cure-MBP”, “Gaya Cure-DMBI”, “Gaya Cure- EPA", "Gayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stawoofer Chemicals), "Trigonal P1" (manufactured by Arc Isa) , "Sandorei 1000" (Sandoz, Inc.), "Deep" (Upzon), "Quanta Cure-PDO", "Quanta Cure-ITX", "Quanta Cure-EPD" (Ward Brenkin Soap), "Runtecure- 1104" (manufactured by Runtec) and the like. These photoinitiators may be used independently and may use 2 or more types together.

It is preferable that it is the range of 0.05-15 mass % with respect to the total of components other than the solvent of curable resin composition, for example, and, as for the addition amount of the said photoinitiator, it is more preferable that it is the range of 0.1-10 mass %.

The curable resin composition of this invention may contain other resin components other than the acidic radical containing (meth)acrylate resin mentioned above. As said other resin component, resin (E) which has an acidic radical 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 having an acid group and a polymerizable unsaturated bond, for example, an epoxy resin having an acid group and a polymerizable unsaturated bond, an acid group, and a polymerizable unsaturated bond. and a urethane resin having a bond, an acrylic resin having an acid group and a polymerizable unsaturated bond, an amideimide resin having an acid group and a polymerizable unsaturated bond, and an acrylamide resin having an acid group and a polymerizable unsaturated bond.

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

Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include an acid group-containing epoxy (meth) acrylate resin using an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials, an epoxy resin, an unsaturated and epoxy (meth)acrylate resins containing an acid group and a urethane group using a monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound as a reaction raw material.

Examples of the epoxy resin include a bisphenol-type epoxy resin, a phenylene ether-type epoxy resin, a naphthylene ether-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, a phenol novolac-type epoxy resin, and cresolno. Volak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin , dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, etc. have. These epoxy resins may be used independently or may use 2 or more types together.

The unsaturated monobasic acid refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. Examples of the unsaturated monobasic acid (D) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. In addition, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride, or the like can also be used. These unsaturated monobasic acids may be used independently or may use 2 or more types together.

Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride, etc. are mentioned. These polybasic acid anhydrides may be used independently or may use 2 or more types together. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable from the viewpoint of obtaining a curable resin composition capable of forming a cured product having excellent photosensitivity and alkali developability and excellent heat resistance.

As said polyisocyanate compound, the thing similar to the above-mentioned polyisocyanate compound (a1) can be used, The said polyisocyanate compound may be used independently or may use 2 or more types together.

As said hydroxyl-containing (meth)acrylate compound, the thing similar to the above-mentioned hydroxyl-containing (meth)acrylate compound (a3) can be used, The said hydroxyl-containing (meth)acrylate compound can be used independently, or 2 or more types may be used in combination.

It does not specifically limit as a manufacturing method of the epoxy resin which has the said acidic radical and a polymerizable unsaturated bond, You may manufacture by any method. In manufacture of the epoxy resin which has the said acidic radical and a polymerizable unsaturated bond, you may carry out in an organic solvent as needed, and a basic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said basic catalyst may be used independently or may use 2 or more types together.

As the urethane resin having an acid group and a polymerizable unsaturated bond, for example, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxy group-containing polyol compound, and optionally a polybasic acid anhydride, a polyol other than the carboxyl group-containing polyol compound What was obtained by making a compound react, the thing obtained by making polyol compounds other than a polyisocyanate compound, a hydroxyl-containing (meth)acrylate compound, a polybasic acid anhydride, and a carboxy-group containing polyol compound react are mentioned.

As said polyisocyanate compound, the thing similar to the above-mentioned polyisocyanate compound (a1) can be used, The said polyisocyanate compound may be used independently or may use 2 or more types together.

As said hydroxyl-containing (meth)acrylate compound, the thing similar to the above-mentioned hydroxyl-containing (meth)acrylate compound (a3) can be used, The said hydroxyl-containing (meth)acrylate compound can be used independently, or 2 or more types may be used in combination.

Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The said carboxyl group containing polyol compound may be used individually or may use 2 or more types together.

As said polybasic acid anhydride, the thing similar to the above-mentioned polybasic acid anhydride can be used, The said polybasic acid anhydride may be used independently or may use 2 or more types together.

Examples of polyol compounds other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. ; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified body in which (poly)oxyalkylene chain, such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, was introduce|transduced into the molecular structure of the said various polyol compound; and lactone-modified substances in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds described above. Polyol compounds other than the said carboxyl group containing polyol compound may be used independently or may use 2 or more types together.

It does not specifically limit as a manufacturing method of the urethane resin which has the said acidic radical and a polymerizable unsaturated bond, You may manufacture by any method. In manufacture of the urethane resin which has the said acidic radical and a polymerizable unsaturated bond, you may carry out in an organic solvent as needed, and a basic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said basic catalyst may be used independently or may use 2 or more types together.

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

The said acrylic resin intermediate|middle may copolymerize other polymerizable unsaturated-group containing compounds other than the said (meth)acrylate compound ((alpha)) as needed. The other polymerizable unsaturated group-containing compound is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (meth)acrylic acid alkyl esters such as acrylates; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isoboronyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; Styrene derivatives, such as styrene, (alpha)-methylstyrene, and chlorostyrene, etc. are mentioned. These may be used independently or may use 2 or more types together.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferable. That is, when hydroxyl group containing (meth)acrylate is used as said (meth)acrylate compound ((alpha)), it is preferable to use isocyanate group containing (meth)acrylate as (meth)acrylate compound ((beta)). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When the isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (?), it is preferable to use the hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (?), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The said (meth)acrylate compound ((beta)) may be used independently or may use 2 or more types together.

As the said polybasic acid anhydride, the thing similar to the above-mentioned polybasic acid anhydride can be used, The said polybasic acid anhydride may be used independently or may use 2 or more types together.

It does not specifically limit as a manufacturing method of the acrylic resin which has the said acidic radical and a polymerizable unsaturated bond, You may manufacture by any method. In manufacture of the acrylic resin which has the said acidic radical and a polymerizable unsaturated bond, you may carry out in an organic solvent as needed, and a basic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said basic catalyst may be used independently or may use 2 or more types together.

As the amideimide resin having an acid group and a polymerizable unsaturated bond, for example, an amideimide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound and/or an epoxy group-containing (meth)acrylate compound and, if necessary, a compound obtained by reacting a compound having at least one reactive functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. Moreover, the compound which has the said reactive functional group may have a (meth)acryloyl group, and does not need to have it.

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

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

As said polyisocyanate compound, the thing similar to the above-mentioned polyisocyanate compound (a1) can be used.

As said polybasic acid anhydride, the thing similar to the above-mentioned polybasic acid anhydride can be used, The said polybasic acid anhydride may be used independently or may use 2 or more types together.

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

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2 ,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetra Hydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetriccarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. can be heard Moreover, as said polybasic acid, it is a copolymer of a conjugated diene type vinyl monomer and acrylonitrile, for example, and the polymer which has a carboxy group in the molecule|numerator can also be used. These polybasic acids may be used independently or may use 2 or more types together.

As said hydroxyl-containing (meth)acrylate compound, the thing similar to the above-mentioned hydroxyl-containing (meth)acrylate compound (a3) can be used, The said hydroxyl-containing (meth)acrylate compound can be used independently, or 2 or more types may be used in combination.

As said epoxy group-containing (meth)acrylate compound, the thing similar to the above-mentioned epoxy group-containing (meth)acrylate compound (C) can be used, The said epoxy group-containing (meth)acrylate compound can be used independently, and 2 or more types may be used in combination.

It does not specifically limit as a manufacturing method of the amide-imide resin which has the said acidic radical and a polymerizable unsaturated bond, You may manufacture by any method. In manufacture of the amideimide resin which has the said acidic radical and a polymerizable unsaturated bond, you may carry out in an organic solvent as needed, and a basic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said basic catalyst may be used independently or may use 2 or more types together.

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include a phenolic hydroxyl group-containing compound, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and a polybasic acid anhydride; What was obtained by making an unsaturated monobasic acid react as needed is mentioned.

As said phenolic hydroxyl group containing compound, the compound which has at least two phenolic hydroxyl groups in a molecule|numerator is said. Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).

In the structural formulas (3-1) to (3-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, R ² is each independently a hydrogen atom or a methyl group. Moreover, p is 0 or an integer of 1 or more, Preferably it is 0 or an integer of 1-3, More preferably, it is 0 or 1, More preferably, it is 0. q is an integer of 2 or more, Preferably, it is 2 or 3. In addition, the position of the substituent on the aromatic ring in the said structural formula is arbitrary, for example, in the naphthalene ring of Structural formula (3-2), you may substitute on any ring, and in Structural formula (3-3), , which may be substituted on any ring of the benzene ring present in one molecule, and in Structural Formula (3-4), indicates that it may be substituted with any ring of the benzene ring present in one molecule, It shows that the number of substituents is p and q.

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

[In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, i is, It is 0 or an integer of 1-4. In formulas (x-2), (x-3) and (x-5), Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. 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, or a carbonyl group, and j is an integer of 1 to 4]

As a compound which has one phenolic hydroxyl group in the said molecule|numerator, the compound etc. which are represented by following structural formula (2-1) - (2-4) are mentioned, for example.

In the 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. Moreover, p is 0 or an integer of 1 or more, Preferably it is 0 or an integer of 1-3, More preferably, it is 0 or 1, More preferably, it is 0. Moreover, about the position of the substituent on the aromatic ring in the said structural formula, it is arbitrary, for example, in the naphthalene ring of structural formula (4-2), you may substitute on any ring, and in structural formula (4-3), , which may be substituted on any ring of the benzene ring present in one molecule, and in Structural Formula (4-4), indicates that it may be substituted with any ring of the benzene ring present in one molecule.

As a compound which has at least two phenolic hydroxyl groups in the said molecule|numerator, the compound represented by the above-mentioned structural formula (3-1) - (3-4) can be used.

These phenolic hydroxyl group containing compounds may be used independently or may use 2 or more types together.

As said alkylene oxide, ethylene oxide, a propylene oxide, a butylene oxide, pentylene oxide etc. are mentioned, for example. Among these, ethylene oxide or propylene oxide is preferable from the viewpoint of obtaining a curable resin composition capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance. The said alkylene oxide may be used independently or may use 2 or more types together.

As said alkylene carbonate, ethylene carbonate, a propylene carbonate, a butylene carbonate, pentylene carbonate etc. are mentioned, for example. Among these, ethylene carbonate or propylene carbonate is preferable from the viewpoint of obtaining a curable resin composition capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance. The said alkylene carbonate may be used independently or may use 2 or more types together.

As said N-alkoxyalkyl (meth)acrylamide compound, For example, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide, etc. are mentioned. The said N-alkoxyalkyl (meth)acrylamide compound may be used individually or may use 2 or more types together.

As said polybasic acid anhydride, the thing similar to the above-mentioned polybasic acid anhydride can be used, The said polybasic acid anhydride may be used independently or may use 2 or more types together.

As said unsaturated monobasic acid, the thing similar to the above-mentioned unsaturated monobasic acid can be used, The said organic solvent may be used independently or may use 2 or more types together.

It does not specifically limit as a manufacturing method of the acrylamide resin which has the said acidic radical and a polymerizable unsaturated bond, You may manufacture by any method. In manufacture of the acrylamide resin which has the said acidic radical and a polymerizable unsaturated bond, you may carry out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may be used as needed.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

As said basic catalyst, the thing similar to the above-mentioned basic catalyst can be used, The said basic catalyst may be used independently or may use 2 or more types together.

As said acidic catalyst, the thing similar to the above-mentioned acidic catalyst can be used, The said acidic catalyst may be used independently or may use 2 or more types together.

As for the usage-amount of resin (E) which has the said acidic radical and a polymerizable unsaturated bond, the range of 10-900 mass parts is preferable with respect to 100 mass parts of acidic radical containing (meth)acrylate resin of this invention.

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl. Aliphatic mono(meth)acrylate compounds, such as (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; Heterocyclic mono(meth)acrylate compounds, such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; Benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, Aromatic mono(meth)acrylics such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate Mono(meth)acrylate compounds such as rate compounds: Polyoxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. in the molecular structure of the various mono(meth)acrylate monomers (poly)oxyalkylene-modified mono(meth)acrylate compound into which an alkylene chain is introduced; a lactone-modified mono(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the various mono(meth)acrylate compounds; Aliphatic di(meth), such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate ) acrylate compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornanedi(meth)acrylate, norbornanedimethanoldi(meth)acrylate, dicyclofentanyldi(meth)acrylate, tricyclodecanedimethanol alicyclic di(meth)acrylate compounds such as di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; Polyoxyalkylene-modified polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various di(meth)acrylate compounds. di(meth)acrylate compound; a lactone-modified di(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkyl in which (poly)oxyalkylene chains such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. are introduced into the molecular structure of the aliphatic tri(meth)acrylate compound Lene-modified tri(meth)acrylate compound; a lactone-modified tri(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; In the molecular structure of the aliphatic poly(meth)acrylate compound, a tetrafunctional or higher (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, and a (poly)oxytetramethylene chain is introduced. ) oxyalkylene-modified poly (meth) acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound. The said various (meth)acrylate monomers may be used independently or may use 2 or more types together.

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

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin include a bisphenol-type epoxy resin, a phenylene ether-type epoxy resin, a naphthylene ether-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, a phenol novolac-type epoxy resin, and cresolno. Volak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin , dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, etc. have. These epoxy resins may be used independently or may use 2 or more types together. Moreover, among these, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, and a bisphenol novolak-type epoxy resin have excellent photosensitivity and alkali developability, and the curable resin composition which can form the hardened|cured material which has excellent heat resistance is obtained. Resins, naphthol novolak type epoxy resins, naphthol-phenol coaxial novolak type epoxy resins, and novolak type epoxy resins such as naphthol-cresol coaxial novolak type epoxy resins are preferred, and those having a softening point in the range of 20 to 120 ° C. desirable.

As the curing accelerator, the curing reaction of the curing agent is accelerated, and when an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, an amine complex salt, etc. are mentioned. These hardening accelerators may be used independently or may use 2 or more types together. Moreover, it is preferable to use the addition amount of the said hardening accelerator in the range of 1-10 mass parts with respect to 100 mass parts of said hardening|curing agents, for example.

As said organic solvent, the thing similar to the above-mentioned organic solvent can be used, The said organic solvent can be used independently or can also use 2 or more types together.

The hardened|cured material of this invention can be obtained by irradiating an active energy ray to the said curable resin composition. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. In addition, when using an ultraviolet-ray as said active energy ray, in performing hardening reaction by an ultraviolet-ray efficiently, you may irradiate in inert gas atmosphere, such as nitrogen gas, and may irradiate in an air atmosphere.

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

Although the amount of accumulated light in particular of the said active energy ray is not restrict|limited, It is preferable that it is 10-5,000 mJ/cm<2>, and it is more preferable that it is 50-1,000 mJ/cm<2>. It is preferable at the point which can prevent or suppress generation|occurrence|production of an uncured part as the amount of integrated light is the said range.

Moreover, irradiation of the said active energy ray may be performed in one step, and may be divided and performed in two or more steps.

Moreover, since the hardened|cured material of this invention has the outstanding heat resistance, for example, package adhesive layers, such as a soldering resist in a semiconductor device use, an interlayer insulating material, a package material, an underfill material, a circuit element, and an integrated circuit It can be used suitably as an adhesive layer of an element and a circuit board. Moreover, it can use suitably for the thin-film transistor protective film in the thin display use represented by LCD and OELD, a liquid-crystal color filter protective film, the pigment resist for color filters, the resist for black matrices, a spacer, etc. Among these, it can use especially suitably for a soldering resist use.

The resin material for soldering resists of this invention consists of the said curable resin composition.

In the resist member of the present invention, for example, the above-mentioned resin material for soldering resist is applied on a substrate, the organic solvent is evaporated and dried in a temperature range of about 60 to 100° C., and then activated through a photomask in which a desired pattern is formed. It can be obtained by exposing it to an energy ray, developing an unexposed part with aqueous alkali solution, and also making it heat-harden in the temperature range of about 140-200 degreeC.

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

[Example]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples.

In the examples of the present application, the acid value of the (meth)acrylate resin containing an acid group was measured by the neutralization titration method of JIS K 0070 (1992).

In the Examples of the present application, the molecular weight of the acid group-containing (meth)acrylate resin was measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: Guard column "HXL-L" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" made by Tosoh Corporation

+ "TSK-GEL G2000HXL" made by Tosoh Corporation

+ "TSK-GEL G3000HXL" made by Tosoh Corporation

+ "TSK-GEL G4000HXL" made by Tosoh Corporation

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 model II version 4.10" made by Tosoh Corporation

Measurement conditions: Column temperature 40℃

developing solvent tetrahydrofuran

flow rate 1.0ml/min

Standard: In accordance with the measurement manual of "GPC-8020 Model II Version 4.10", the following monodisperse polystyrene having a known molecular weight was used.

(Use polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

"F-40" made by Tosoh Corporation

"F-80" made by Tosoh Corporation

"F-128" made by Tosoh Corporation

Sample: A 1.0 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a microfilter (50 μl)

In this example, the liquid chromatography chart was measured under the following conditions.

[Measuring conditions]

Device: "LCMS-2010EV" manufactured by Shimadzu Corporation, Ltd.

Data processing: "LCMS Solution" manufactured by Shimadzu Corporation, Ltd.

Column: Tosoh Corporation "ODS-100V" (2.0 mm ID × 150 mm, 3 µm) 40°C

Eluent: water/acetonitrile, 0.4 mL/min

Detector: PDA, MS

Sample adjustment: 1. Dissolve 50 mg of sample in 10 ml of acetonitrile (for LC)

2. Stir with vortex for 30 seconds

3. 30 minutes of politics

4. Pass through a 0.2㎛ filtration filter and use as a measurement sample

Calculation of area ratio: Calculated with UV wavelength 210 nm

(Synthesis Example 1: Preparation of pentaerythritol polyacrylate (A1))

To a flask equipped with a thermometer, a stirrer, and a condenser, 201.6 parts by mass of acrylic acid, 136 parts by mass of pentaerythritol, 10.6 parts by mass of sulfuric acid, 1.1 parts by mass of cupric chloride, and 153 parts by mass of toluene were charged. The temperature was raised to 105°C while stirring, and the reaction was carried out at the same temperature for 12 hours while the system was refluxed. 287 mass parts of toluene was added to the reaction mixture, and it wash|cleaned with 123 mass parts of distilled water. Furthermore, the reaction mixture was neutralized by adding 20 mass % sodium hydroxide aqueous solution, and it wash|cleaned with 62 mass parts of distilled water. After adding 500 ppm amount of hydroquinone monomethyl ether with respect to resin solid content, toluene was distilled off and the pentaerythritol polyacrylate (A1) was obtained. The hydroxyl value of this pentaerythritol polyacrylate (A1) is 290 mgKOH/g, and the content of pentaerythritol tetraacrylate (a1) calculated from the area ratio of the liquid chromatography chart is 16% by mass, pentaerythritol triacrylic The content of the rate (a2) is 50% by mass, the content of pentaerythritol diacrylate (a3) is 29% by mass, the content of pentaerythritol monoacrylate (a4) is 3% by mass, and other high molecular weight components (a ') content was 2 mass %.

(Synthesis Example 2: Preparation of pentaerythritol diacrylate (A2))

To a flask equipped with a thermometer, a stirrer, and a condenser, 136 parts by mass of pentaerythritol and 600 parts by mass of N,N-dimethylformamide were charged, and 3.7 parts by mass of paratoluenesulfonic acid was added as a catalyst. After heating up to 80 degreeC and dissolving pentaerythritol in N,N- dimethylformamide, stirring, 78 mass parts of cyclohexanone was added. The inside of the reaction system was pressure-reduced to 140 mmHg, maintaining the reaction temperature at 80 degreeC, and reaction was continued, distilling the produced|generated water. At a point in time when the production of water could not be confirmed, it was refluxed for an additional 1 hour. It cooled to room temperature, returning to normal pressure, continuing stirring, and unreacted pentaerythritol was removed by reduced pressure filtration. After depressurizingly removing N,N-dimethylformamide from the obtained filtrate, ethyl acetate was added, and the pentaerythritol which precipitated was removed by filtration again. The resulting filtrate was washed with a saturated aqueous sodium hydrogencarbonate solution, then further washed with a saturated aqueous sodium chloride solution, 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 mass parts of ketal compound (x1) obtained previously, 120 mass parts of dichloromethane, and 46.5 mass parts of triethylamines were thrown into the flask provided with the thermometer, a stirrer, and a condenser, and it cooled to -5 degreeC. What dissolved 29 mass parts of 3-chloropropionyl chloride in 40 mass parts of dichloromethane was dripped little by little, maintaining the inside of a reaction system at 0 degreeC or less. After completion of the dropwise addition, the temperature was gradually raised to room temperature, and the reaction was further conducted for 4 hours. After confirming disappearance of the ketal compound (x1) as a raw material by a gas chromatograph, the triethylamine hydrochloride was removed by filtration under reduced pressure. The resulting filtrate was washed with a saturated aqueous sodium hydrogencarbonate solution, further washed with a saturated aqueous sodium chloride solution, and dehydrated over anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of an acrylate compound (x2).

Next, 6.5 mass parts of acrylate compounds (x2) obtained previously and 30 mass parts of acetone were thrown into the flask provided with the thermometer, a stirrer, and a condenser, and it cooled to 0 degreeC, stirring. 10 mass parts of 10% sulfuric acid aqueous solution was dripped little by little so that the inside of a reaction system might not exceed 10 degreeC, and after addition of the whole quantity, it was made to react at room temperature for 16 hours. After confirming disappearance of the acrylate compound (x2) as a raw material with 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 hydrogencarbonate solution until the pH reached 7. The organic layer was dehydrated with magnesium sulfate and then concentrated under reduced pressure at room temperature to obtain pentaerythritol diacrylate (A2).

(Synthesis Example 3: Preparation of dipentaerythritol polyacrylate (A3))

220 mass parts of acrylic acid, 180 mass parts of dipentaerythritol, 15 mass parts of sulfuric acid, 1.5 mass parts of cupric chloride, and 300 mass parts of toluene were thrown into the flask provided with a thermometer, a stirrer, and a condenser. The temperature was raised to 105°C while stirring, and the reaction was carried out at the same temperature for 13 hours while the system was refluxed. The produced|generated water was 61 mass parts. 425 mass parts of toluene was added to the reaction mixture, and it wash|cleaned with 200 mass parts of distilled water. Furthermore, the reaction mixture was neutralized by adding 20% sodium hydroxide aqueous solution, and it wash|cleaned with 100 mass parts of distilled water. After adding 500 ppm amount of hydroquinone monomethyl ether with respect to resin solid content, toluene was distilled off and dipentaerythritol acrylate (A3) was obtained. The hydroxyl value of this dipentaerythritol acrylate (A3) was 140 mgKOH/g. In addition, content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of a liquid chromatography chart is 28 mass %, content of dipentaerythritol pentaacrylate (b2) is 42 mass %, dipentaerythritol hexa Content of the acrylate (b3) was 22 mass %, and content of the high molecular weight component (b') was 8 mass %.

(Example 1: Preparation of acid group-containing (meth)acrylate resin (1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 72 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mgKOH/g) is added, The reaction was carried out at 110°C for 3 hours. 148 mass parts of glycidyl methacrylate and 1.9 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 151 mass parts of tetrahydrophthalic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (1) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (1) was 87 mgKOH/g, and the weight average molecular weight was 2390.

(Example 2: Preparation of acid group-containing (meth)acrylate resin (2))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 72 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 148 mass parts of glycidyl methacrylate and 1.9 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 99 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (2) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (2) was 94 mgKOH/g, and the weight average molecular weight was 2300.

(Example 3: Preparation of acid group-containing (meth)acrylate resin (3))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 72 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 216 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate ("Cychromer M100" manufactured by Daiser Co., Ltd., 207 g/equivalent of epoxy group) and 2.2 parts by mass of triphenylphosphine are added, and reacted at 110°C for 5 hours did it Furthermore, 99 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (3) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (3) was 85 mgKOH/g, and the weight average molecular weight was 2540.

(Example 4: Preparation of acid group-containing (meth)acrylate resin (4))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, 44 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.2 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate ("Desmodul W" manufactured by Sumika Covestro Urethane Co., Ltd.) was added, and it was made to react at 120 degreeC for 8 hours, and isocyanate group content became 0.1 mass % or less, confirmed that there is Next, 52 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 111 mass parts of glycidyl methacrylate and 1.7 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 75 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (4) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (4) was 85 mgKOH/g, and the weight average molecular weight was 2440.

(Example 5: Preparation of acid group-containing (meth)acrylate resin (5))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, 44 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 131 mass parts of dicyclohexylmethane 4, 4- diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 52 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 162 mass parts of "Cychromer M100" and 1.9 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 75 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (5) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (5) was 78 mgKOH/g, and the weight average molecular weight was 2610.

(Example 6: Preparation of acid group-containing (meth)acrylate resin (6))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 374 parts by mass of diethylene glycol monomethyl ether acetate, 173 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, obtained in Synthesis Example 1 It was made to react at 120 degreeC for 6 hours, adding 53 mass parts of pentaerythritol polyacrylate (A1), 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 74 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 220 mass parts of "Cychromer M100" and 2.3 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 154 mass parts of tetrahydrophthalic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (6) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (6) was 80 mgKOH/g, and the weight average molecular weight was 2370.

(Example 7: Preparation of acid group-containing (meth)acrylate resin (7))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 341 parts by mass of diethylene glycol monomethyl ether acetate, 149 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, obtained in Synthesis Example 1 It was made to react at 120 degreeC for 6 hours, adding 44 mass parts of pentaerythritol polyacrylates (A1), 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 131 mass parts of dicyclohexylmethane 4, 4- diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 53 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 165 mass parts of "Cychromer M100" and 1.9 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 76 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (7) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (7) was 78 mgKOH/g, and the weight average molecular weight was 2580.

(Example 8: Preparation of acid group-containing (meth)acrylate resin (8))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene are added and dissolved. did it It was made to react at 160 degreeC in nitrogen atmosphere for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 0.2 mass parts of metoquinone, 22 mass parts of pentaerythritol polyacrylate (A1) obtained by the synthesis example 1, and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours, blowing in air. Next, 85 mass parts of glycidyl methacrylate was added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 57 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (8) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (8) was 89 mgKOH/g, and the weight average molecular weight was 1850.

(Example 9: Preparation of acid group-containing (meth)acrylate resin (9))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene are added and dissolved. did it It was made to react at 160 degreeC in nitrogen atmosphere for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 0.2 mass parts of metoquinone, 14 mass parts of pentaerythritol diacrylate (A2) obtained by the synthesis example 2, and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours, blowing in air. Next, 86 mass parts of glycidyl methacrylates were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 58 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (9) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (9) was 91 mgKOH/g, and the weight average molecular weight was 2120.

(Example 10: Preparation of acid group-containing (meth)acrylate resin (10))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.2 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 68 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 130 mass parts of glycidyl methacrylate and 1.7 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 87 mass parts of succinic anhydride and 71 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (10) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (10) was 92 mgKOH/g, and the weight average molecular weight was 2590.

(Example 11: Preparation of acid group-containing (meth)acrylate resin (11))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.2 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 25 mass parts of pentaerythritol diacrylate (A2) obtained by the synthesis example 2 was added, and it was made to react at 110 degreeC for 3 hours. 150 mass parts of glycidyl methacrylate and 1.7 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 100 mass parts of succinic anhydride and 57 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (11) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (11) was 103 mgKOH/g, and the weight average molecular weight was 2710.

(Example 12: Preparation of acid group-containing (meth)acrylate resin (12))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.2 mass parts of metoquinone, and 0.6 parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 23 mass parts of pentaerythritol diacrylate (A2) obtained by the synthesis example 2 was added, and it was made to react at 110 degreeC for 3 hours. 144 mass parts of glycidyl methacrylate and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 96 mass parts of succinic anhydride and 57 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (12) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (12) was 105 mgKOH/g, and the weight average molecular weight was 2990.

(Example 13: Preparation of acid group-containing (meth)acrylate resin (13))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.2 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 37 mass parts of pentaerythritol polyacrylate (A1) obtained by the synthesis example 1 was added, and it was made to react at 110 degreeC for 3 hours. 140 mass parts of glycidyl methacrylate and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 94 mass parts of succinic anhydride and 62 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (13) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (13) was 101 mgKOH/g, and the weight average molecular weight was 2590.

(Example 14: Preparation of acid group-containing (meth)acrylate resin (14))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 mass of dibutylhydroxytoluene It was made to react at 120 degreeC for 6 hours, adding part, 0.3 mass parts of metoquinone, and 0.8 part of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 46 mass parts of pentaerythritol polyacrylate (A1) obtained by the synthesis example 1 was added, and it was made to react at 110 degreeC for 3 hours. 153 mass parts of glycidyl methacrylate and 1.9 parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 102 mass parts of succinic anhydride and 56 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (14) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (14) was 94 mgKOH/g, and the weight average molecular weight was 2330.

(Example 15: Preparation of acid group-containing (meth)acrylate resin (15))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 mass of dibutylhydroxytoluene It was made to react at 120 degreeC for 6 hours, adding part, 0.3 mass parts of metoquinone, and 0.8 part of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 29 mass parts of pentaerythritol diacrylate (A2) obtained by the synthesis example 2 was added, and it was made to react at 110 degreeC for 3 hours. 153 mass parts of glycidyl methacrylate and 1.8 parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 102 mass parts of succinic anhydride and 46 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (15) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (15) was 96 mgKOH/g, and the weight average molecular weight was 2490.

(Example 16: Preparation of acid group-containing (meth)acrylate resin (16))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 392 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate modified product of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, content of isocyanate groups) 17.2 mass %) 244 mass parts, 192 mass parts of trimellitic anhydride, and 1.0 mass parts of dibutylhydroxytoluene were added and dissolved. It was made to react at 160 degreeC in nitrogen atmosphere for 5 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. 0.3 mass parts of metoquinone, 81 mass parts of pentaerythritol polyacrylate (A1) obtained by the synthesis example 1, and 1.4 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours, blowing in air. Next, 165 mass parts of glycidyl methacrylate and 1.8 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 110 mass parts of tetrahydrophthalic anhydride and 67 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (16) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (16) was 86 mgKOH/g, and the weight average molecular weight was 7450.

(Example 17: Preparation of acid group-containing (meth)acrylate resin (17))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 418 parts by mass of diethylene glycol monomethyl ether acetate, 192 parts by mass of trimellitic anhydride, 26 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 1.0 mass part of dibutylhydroxytoluene, 0.3 mass part of metoquinone, and 0.7 mass part of triphenylphosphine, and blowing in air. 244 mass parts of "VESTANAT T-1890/100" was added, it was made to react at 120 degreeC for 10 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 79 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 167 mass parts of glycidyl methacrylate and 2.7 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 112 mass parts of succinic anhydride and 57 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (17) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (17) was 84 mgKOH/g, and the weight average molecular weight was 7390.

(Example 18: Preparation of acid group-containing (meth)acrylate resin (18))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene are added and dissolved. did it It was made to react at 160 degreeC in nitrogen atmosphere for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 0.2 mass parts of metoquinone, 22 mass parts of dipentaerythritol polyacrylate (A3) obtained by the synthesis example 3, and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours, blowing in air. Next, 85 mass parts of glycidyl methacrylate was added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 57 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (18) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (18) was 83 mgKOH/g, and the weight average molecular weight was 1910.

(Example 19: Preparation of acid group-containing (meth)acrylate resin (19))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 345 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, and 110 parts by mass of dipentaerythritol polyacrylate (A3) obtained in Synthesis Example 3 and adding 0.9 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.8 mass parts of triphenylphosphine, and blowing in air, it was made to react at 120 degreeC for 6 hours. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 87 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 148 mass parts of glycidyl methacrylate and 2.1 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 99 mass parts of succinic anhydride was added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (19) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (19) was 85 mgKOH/g, and the weight average molecular weight was 2480.

(Example 20: Preparation of acid group-containing (meth)acrylate resin (20))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 258 parts by mass of diethylene glycol monomethyl ether acetate, 139 parts by mass of trimellitic anhydride, 52 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, It was made to react at 120 degreeC for 6 hours, adding 0.6 mass part of dibutylhydroxytoluene, 0.2 mass part of metoquinone, and 0.6 mass part of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 12 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 65 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 111 mass parts of glycidyl methacrylate and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 74 mass parts of succinic anhydride and 53 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (20) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (20) was 85 mgKOH/g, and the weight average molecular weight was 2340.

(Example 21: Preparation of acid group-containing (meth)acrylate resin (21))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 279 parts by mass of diethylene glycol monomethyl ether acetate, 197 parts by mass of trimellitic anhydride, 15 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of dibutylhydroxytoluene, 0.3 mass parts of metoquinone, and 0.6 mass parts of triphenylphosphine, and blowing in air. 111 mass parts of isophorone diisocyanate was added, it was made to react at 120 degreeC for 12 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 70 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 160 mass parts of glycidyl methacrylate and 1.9 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 88 mass parts of succinic anhydride and 86 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (21) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (21) was 100 mgKOH/g, and the weight average molecular weight was 2750.

(Example 22: Preparation of acid group-containing (meth)acrylate resin (22))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 254 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, It was made to react at 120 degreeC for 6 hours, adding 0.6 mass part of dibutylhydroxytoluene, 0.2 mass part of metoquinone, and 0.7 mass part of triphenylphosphine, and blowing in air. 77 mass parts of 1, 5- pentamethylene diisocyanate was added, it was made to react at 120 degreeC for 8 hours, and it confirmed that isocyanate group content had become 0.1 mass % or less. Next, 64 parts by mass of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 131 mass parts of glycidyl methacrylate and 1.6 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 88 mass parts of succinic anhydride and 75 mass parts of diethylene glycol monomethyl ether acetate were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (22) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (22) was 95 mgKOH/g, and the weight average molecular weight was 2050.

(Example 23: Preparation of acid group-containing (meth)acrylate resin (23))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 271 parts by mass of dimethylacetamide, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutylhydroxy It was made to react at 120 degreeC for 6 hours, adding 0.7 mass parts of toluene, 0.2 mass parts of metoquinone, and 0.7 mass parts of triphenylphosphine, and blowing in air. 94 parts by mass of 1,3-bis(isocyanatomethyl)benzene ("Takenate 500" manufactured by Mitsui Chemicals Co., Ltd.) was added, and it was made to react at 120 degreeC for 6 hours, and isocyanate group content became 0.1 mass % or less, confirmed that there is Next, 68 mass parts of "Aronix M-306" was added, and it was made to react at 110 degreeC for 3 hours. 140 mass parts of glycidyl methacrylate and 1.7 mass parts of triphenylphosphine were added, and it was made to react at 110 degreeC for 5 hours. Furthermore, 93 mass parts of succinic anhydride and 80 mass parts of dimethylacetamide were added, it was made to react at 110 degreeC for 5 hours, and the target acidic radical containing (meth)acrylate resin (23) was obtained. The solid content acid value of this acidic radical containing (meth)acrylate resin (23) was 94 mgKOH/g, and the weight average molecular weight was 2450.

(Comparative Example 1: Preparation of acid group-containing acrylate resin (C1))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was put, and an orthocresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214) Dissolving 428 parts by mass, adding 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of metoquinone as a thermal polymerization inhibitor, adding 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine while blowing air The esterification reaction was performed at 120 degreeC for 10 hours. Then, 311 mass parts of diethylene glycol monomethyl ether acetate and 160 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and the target acidic radical containing acrylate resin (C1) was obtained. The solid content acid value of this 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, an orthocresol novolak-type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, dipentaerythritol hexaacrylate, Diethylene glycol monoethyl ether acetate, photoinitiator ("Omnirad 907" manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green were blended in parts by mass shown in Table 1, and kneaded with a roll mill. Thus, curable resin composition (1) was obtained.

(Examples 25 to 46: Preparation of curable resin compositions (2) to (23))

Example 24 except that 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, respectively. Curable resin compositions (2) to (23) were obtained in the same manner as described above.

(Comparative Example 2: Preparation of curable resin composition (C2))

A curable resin composition (C2) was obtained in the same manner as in Example 24 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.

The following evaluation was performed using the curable resin compositions (1)-(23) and (C2) obtained by the said Example and the comparative example.

[Method for evaluating photosensitivity]

After apply|coating the curable resin composition obtained by each Example and the comparative example so that it might become a film thickness of 50 micrometers on a glass substrate using an applicator, it was dried at 80 degreeC for 30 minutes, respectively. Next, 1000 mJ/cm<2> of ultraviolet-ray was irradiated using the metal halide lamp through step tablet No. 2 made by Kodak. This was developed for 180 seconds in a 1 mass % sodium carbonate aqueous solution, and the number of remaining plates was evaluated. Moreover, the photosensitivity is so high that there are many remaining stages.

[Evaluation method of alkali developability]

The curable resin composition obtained in each Example and Comparative Example was applied to a film thickness of 50 µm on a glass substrate using an applicator, then dried at 80° C. for 30 minutes, 40 minutes, 50 minutes, and 60 minutes, respectively, and dried Time to write different samples. These were developed in 1% sodium carbonate aqueous solution at 30 degreeC for 180 second, and the drying time at 80 degreeC of the sample which did not leave a residue on the board|substrate was evaluated as drying control width. In addition, it shows that the alkali developability is excellent, so that the drying management range is long.

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

[Table 1]

[Table 2]

(Example 47: Preparation of curable resin composition 24)

Acid group-containing (meth)acrylate resin (1) obtained in Example 1, orthocresol novolak type epoxy resin as a curing agent (“EPICLON N-680” manufactured by DIC Corporation), 2-methyl-1-( 4-Methylthiophenyl)-2-morpholinopropan-1-one ("Omnirad-907" manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent were mix|blended in the mass part shown in Table 1, and curable resin composition (24) was obtained.

(Examples 48 to 69: Preparation of curable resin compositions (25) to (46))

Example 47 except that 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, respectively. Curable resin compositions (25) to (46) were obtained in the same manner as described above.

(Comparative Example 3: Preparation of curable resin composition (C3))

Curable resin composition ( C3) was obtained.

The following evaluation was performed using the curable resin compositions (24)-(46) and (C3) obtained by the said Example and the comparative example.

[Method for evaluating heat resistance]

<Preparation of test piece>

The curable resin composition obtained in Examples and Comparative Examples was applied on a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 µm) with a 50 µm applicator, and dried at 80°C for 30 minutes. After irradiating an ultraviolet-ray of 1000 mJ/cm<2> using a metal halide lamp, it heated at 160 degreeC for 1 hour. The hardened|cured material was peeled from copper foil, and the test piece (hardened|cured material) was obtained.

The test piece was cut into a size of 6 mm x 40 mm, and the elastic modulus was changed using a viscoelasticity measuring device (DMA: Rheometric, solid viscoelasticity measuring device “RSAII”, tensile method: frequency 1 Hz, temperature increase rate 3° C./min). The temperature at which α is maximum (the rate of change of tan δ is greatest) 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 4]

In addition, the mass part of "acidic radical containing (meth)acrylate resin" in Tables 1-4 is a solution value.

"Curing agent" in Tables 1-4 shows an orthocresol novolak-type epoxy resin (DIC Corporation "EPICLON N-680", epoxy equivalent: 214).

"Organic solvent" in Tables 1-4 shows diethylene glycol monomethyl ether acetate.

"Photoinitiator" in Tables 1-4 shows "Omnirad-907" by IGM.

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

In addition, Comparative Examples 2 and 3 are examples of curable resin compositions which do not use the acidic radical containing (meth)acrylate resin of this invention. It has confirmed that this curable resin composition is remarkably insufficient in photosensitivity and also remarkably insufficient in the heat resistance in hardened|cured material.

Claims (13)

Amideimide resin (A) having an acid group and/or acid anhydride group, hydroxyl group-containing (meth)acrylate compound (B), epoxy group-containing (meth)acrylate compound (C), and polycarboxylic acid anhydride (D) are essential As an acid group-containing (meth)acrylate resin used as a reaction raw material of
The amideimide resin (A) is a reaction product (A-1) of a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2), or a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2) and a hydroxyl group-containing (meta) ) is the reactant (A-2) of the acrylate compound (a3),
Either one or both of the hydroxyl group-containing (meth)acrylate compound (B) or the hydroxyl group-containing (meth)acrylate compound (a3) has two hydroxyl groups, and/or 3 hydroxyl groups Acidic group-containing (meth)acrylate resin, characterized in that it contains a (meth)acrylate compound having a dog. According to claim 1,
The acid group-containing (meth)acrylate resin wherein the polyisocyanate compound (a1) is an aliphatic diisocyanate or an alicyclic diisocyanate. According to claim 1,
Acid group-containing (meth)acrylate in which the said (meth)acrylate compound which has two hydroxyl groups contains pentaerythritol di(meth)acrylate and/or a dipentaerythritol tetra(meth)acrylate compound Suzy. According to claim 1,
Acid group containing (meth)acrylate resin in which the said (meth)acrylate compound which has three hydroxyl groups contains pentaerythritol mono(meth)acrylate and/or dipentaerythritol tri(meth)acrylate . According to claim 1,
The reactant (A-2) is an intermediate reaction product of the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3), and the polyisocyanate compound (a1) is a reaction product,
Acidic radical containing (meth)acrylate resin whose mole number of the said polycarboxylic anhydride (a2) with respect to 1 mol of the hydroxyl groups which the said hydroxyl-containing (meth)acrylate compound (a3) has is the range of 2-8. Curable resin composition containing the acidic radical containing (meth)acrylate resin in any one of Claims 1-5, and a photoinitiator. 7. The method of claim 6,
Furthermore, the curable resin composition which contains an organic solvent and a hardening|curing agent. 7. The method of claim 6,
Furthermore, curable resin composition containing resin (E) which has acidic radicals other than acidic radical containing (meth)acrylate resin in any one of Claims 1-5, and a polymerizable unsaturated bond. A cured product, which is a curing reaction product of the curable resin composition according to any one of claims 6 to 8. An insulating material comprising the curable resin composition according to any one of claims 6 to 8. It consists of curable resin composition in any one of Claims 6-8, The resin material for soldering resists characterized by the above-mentioned. The resist member which consists of the resin material for soldering resists of Claim 11 characterized by the above-mentioned. An amideimide resin (A) having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), an epoxy group-containing (meth)acrylate compound (C), and a polycarboxylic acid anhydride (D) are reacted As a method for producing an acid group-containing (meth)acrylate resin obtained by
The amideimide resin (A) is a reaction product (A-1) obtained by reacting a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2), or a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2) and a hydroxyl group It is a reactant (A-2) obtained by reacting a containing (meth)acrylate compound (a3),
Either one or both of the hydroxyl group-containing (meth)acrylate compound (B) or the hydroxyl group-containing (meth)acrylate compound (a3) has two hydroxyl groups, and/or 3 hydroxyl groups A method for producing an acid group-containing (meth)acrylate resin, characterized in that it contains a (meth)acrylate compound having a dog.