WO2020129667A1

WO2020129667A1 - Acid-group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member

Info

Publication number: WO2020129667A1
Application number: PCT/JP2019/047584
Authority: WO
Inventors: 駿介山田; 康介桑田
Original assignee: Dic株式会社
Priority date: 2018-12-19
Filing date: 2019-12-05
Publication date: 2020-06-25
Also published as: KR102500020B1; KR20210076076A; CN113195574B; JP6780809B1; JPWO2020129667A1; TW202031703A; TWI797403B; CN113195574A

Abstract

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

Description

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

The present invention provides 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. , A solder resist resin material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.

In recent years, acid group-containing epoxy acrylate resins obtained by reacting an acid anhydride after acrylate conversion of epoxy resin with acrylic acid are widely used as resin materials for solder resists for printed wiring boards. There are various requirements for the resin material for a solder resist, such as curing with a small amount of exposure, excellent alkali developability, and excellent heat resistance in the cured product.

Conventionally known solder resist resin materials include active energy ray-curable products obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. Although a resin is known (for example, refer to Patent Document 1 below), although it has excellent heat resistance in a cured product, it does not satisfy the ever-increasing required properties and is sufficient for the recent market demands. Was not.

Therefore, there was a demand for a material that has excellent photosensitivity and alkali developability and that has even higher heat resistance in the cured product.

Japanese Patent Laid-Open No. 61-243869

The problem to be solved by the present invention is to provide 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, An object of the present invention is to provide an insulating material comprising a curable resin composition, a resin material for solder resist, 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 amide imide 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 An acid group-containing (meth)acrylate resin using an acid anhydride as an essential reaction raw material, wherein the amide imide 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 used as a raw material of an acid group-containing (meth)acrylate resin or a hydroxyl group-containing (meth)acrylate compound used as a raw material of an amideimide resin. One or both contain a (meth)acrylate compound having two hydroxyl groups, and/or a (meth)acrylate compound having three hydroxyl groups. The inventors have found that the above problems can be solved by using them, and completed the present invention.

That is, the present invention relates to an amide imide 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 An acid group-containing (meth)acrylate resin containing a carboxylic acid anhydride (D) as an essential reaction raw material, wherein the amideimide resin (A) is a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2). Or a reaction product (A-2) of the polyisocyanate compound (a1), the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3). Either or both of the containing (meth)acrylate compound (B) and the hydroxyl group-containing (meth)acrylate compound (a3) have (meth)acrylate compound having two hydroxyl groups, and/or have three hydroxyl groups (meth ) Acid group-containing (meth)acrylate resin containing an acrylate compound, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material, and a solder resist The present invention relates to a resin material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.

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, and thus can be suitably used for an insulating material, a resin material for solder resist and a resist member. ..

The acid group-containing (meth)acrylate resin of the present invention includes an amide imide 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 acid anhydride (D) are essential reaction raw materials.

In the present invention, the term “(meth)acrylate” means acrylate and/or methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

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

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

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)" Or [2] a reaction product (A-2) of a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2) and a hydroxyl group-containing (meth)acrylate compound (a3) (hereinafter referred to as an amide imide resin (A -2) is sometimes used).

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

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

Examples of the polyisocyanate compound (a1) include, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and other aliphatic diisocyanate compounds; norbornane diisocyanate, Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'- Aromatic diisocyanate compounds such as diisocyanato-3,3'-dimethylbiphenyl and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (1); modified isocyanurates thereof, biuret Examples include modified products and allophanate modified products. In addition, these polyisocyanate compounds may be used alone or in combination of two or more kinds. These polyisocyanate compounds (a1) have excellent photosensitivity and alkali developability, and are capable of forming an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance. Nurate modified products are preferred.

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

Among these, the alicyclic diisocyanate compound or its modified product is preferable, and the alicyclic diisocyanate is preferable, in terms of the acid group-containing (meth)acrylate resin having excellent solvent solubility. Further, the aliphatic diisocyanate compound or a modified product thereof is preferable in that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat sensitivity and excellent photosensitivity and alkali developability can be obtained. , Aliphatic diisocyanates are preferred. Furthermore, the ratio of the total mass of the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, It is more preferably 90 mass% or more. When the alicyclic diisocyanate compound or modified product thereof and the aliphatic diisocyanate compound or modified product thereof are used in combination, the mass ratio of both is preferably in the range of 20/80 to 80/20.

Examples of the polycarboxylic acid anhydride (a2) include aliphatic polycarboxylic acid anhydride, alicyclic polycarboxylic acid anhydride, aromatic polycarboxylic acid anhydride and the like.

Examples of the aliphatic polycarboxylic acid anhydrides 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 itacone. Examples thereof include acids, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. In the aliphatic polycarboxylic acid anhydride, the aliphatic hydrocarbon group may be linear or branched and may have an unsaturated bond in the structure.

As the alicyclic polycarboxylic acid anhydride, in the present invention, the acid anhydride group is bonded to the alicyclic structure as an alicyclic polycarboxylic acid anhydride, the aromatic ring of the other structural site It does not matter whether it is present or not. Examples of the alicyclic polycarboxylic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2, 3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acid.

Examples of the aromatic polycarboxylic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, Examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.

These polycarboxylic acid anhydrides (a2) can be used alone or in combination of two or more kinds. In addition, among these, since the 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, the alicyclic polycarboxylic acid An acid anhydride or the aromatic polycarboxylic acid anhydride is preferable. Further, since it is possible to obtain an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat sensitivity and excellent photosensitivity and alkali developability, it is possible to obtain a carboxyl group and an acid anhydride in the molecular structure. It is preferable to use a tricarboxylic acid anhydride having both a group and a cyclohexanetricarboxylic acid anhydride or a trimellitic acid anhydride. At this time, the content of the tricarboxylic acid anhydride in the polycarboxylic acid anhydride (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.

Further, as the amide-imide resin (A-1), if necessary, other compounds may be used in combination as a reaction raw material in addition to the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2). .. When the other compound is used in combination, the effects of the present invention are sufficiently exhibited, and therefore, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride in the reaction raw material of the amide imide resin (A-1) are used. The total content of (a2) is preferably 80% by mass or more, and more preferably 85% by mass.

Examples of the other compounds include polycarboxylic acid and the like.

As the polycarboxylic acid, any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. To be Further, as the polycarboxylic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polycarboxylic acids (a2) can be used alone or in combination of two or more kinds.

The copolymer of the conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, is, for example, a butadiene-acrylonitrile copolymer represented by the following structural formula (2-1). Half of a polymer having a carboxyl group in the polymer and a polymer having a hydroxyl group in the molecule of a butadiene-acrylonitrile copolymer represented by the following structural formula (2-2) and a polybasic acid anhydride such as maleic anhydride Examples thereof include esters. The position of the carboxyl group may be located on either the side chain or the terminal of the molecule, but the terminal is preferred.

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

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

Since the acid value of the amide-imide resin (A-1) has excellent photosensitivity and alkali developability, an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance can be obtained. It is preferable that the measured value under a neutral condition, that is, under the condition that the acid anhydride group is not ring-opened is in the range of 60 to 350 mgKOH/g, and the acid anhydride group was ring-opened in the presence of water. The measured value under the condition is preferably in the range of 61 to 360 mgKOH/g. In the present invention, the acid value is a value measured by the neutralization titration method of JIS K0070 (1992).

The method for producing the amide-imide resin (A-1) is not particularly limited and may be produced by any method. For example, it can be produced by a method similar to that of a general amide-imide resin. Specifically, 0.8 to 3.5 mol of the polycarboxylic acid anhydride (a2) is used with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1), and the temperature condition is about 100 to 180° C. The method of stirring and mixing under the reaction is mentioned.

The reaction may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more kinds. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency becomes good.

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-( Amine compounds such as 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate Primary ammonium salts; phosphines such as trimethylphosphine, tributylphosphine and triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dinedecanoate, dibutyltin diacetate, tin octylate, Organotin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; Inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more kinds.

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

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

As the polyisocyanate compound (a1), the same ones as the above polyisocyanate compound (a1) can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

As the polycarboxylic acid anhydride (a2), the same polycarboxylic acid anhydride (a2) as described above can be used.

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

As the hydroxyl group-containing (meth)acrylate compound (a3), other specific structures are not particularly limited as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in the molecular structure, and various compounds can be used. it can. Examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate. ) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta Examples thereof include (meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds ( It is also possible to use a modified poly)oxyalkylene, a modified lactone obtained by introducing a (poly)lactone structure into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds (a3) can be used alone or in combination of two or more kinds.

As the amide imide resin (A-2), if necessary, other than the polyisocyanate compound (a1), the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3), Other compounds can be used together as a reaction raw material. When the other compound is used in combination, the effect of the present invention is sufficiently exhibited, and therefore, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride in the reaction raw material of the amide imide resin (A-2) are used. The total content of (a2) and the hydroxyl group-containing (meth)acrylate compound (a3) is preferably 80% by mass or more, and more preferably 85% by mass.

Examples of the other compounds include polycarboxylic acid and the like.

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

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

The method for producing the amide-imide resin (A-2) is not particularly limited and may be produced by any method. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easily controlled, the polycarboxylic acid anhydride (a2) is reacted with the hydroxyl group-containing (meth)acrylate compound (a3) (step A1) to obtain the intermediate obtained in the step A1. It is preferable that the reaction product and the polyisocyanate compound (a1) are reacted (step A2).

The step A1 is a step of reacting the polycarboxylic acid anhydride (a2) with the hydroxyl group-containing (meth)acrylate compound (a3) to obtain an intermediate reaction product. The reaction is mainly to react the acid anhydride group of the polycarboxylic acid anhydride (a2) with the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (a3). The reaction ratio of the reaction is preferably such that the number of moles of the polycarboxylic acid anhydride (a2) is 1 to 8 with respect to 1 mole of the hydroxyl group contained in the hydroxyl group-containing (meth)acrylate compound (a3). The reaction of step A1 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C. Further, the reaction may be carried out in an organic solvent, if necessary.

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

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

The step A2 is a reaction between the intermediate reaction product obtained in the step A1 and the polyisocyanate compound (a1). The reaction is mainly to react the acid group and/or acid anhydride group of the intermediate reaction product obtained in step A1 with the isocyanate group of the polyisocyanate compound (a1). The reaction of step A2 can be carried out, for example, in the presence of a suitable basic catalyst, with heating and stirring under a temperature condition of about 100 to 180°C. Further, the reaction may be carried out in an organic solvent, if necessary. When step A1 and step A2 are continuously performed, the basic catalyst and the organic solvent may not be added, or may be appropriately added.

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

As the hydroxyl group-containing (meth)acrylate compound (B), the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3) can be used, and the hydroxyl group-containing (meth)acrylate compound (B) is independent. Can also be used in combination with two or more kinds. When the amide imide resin (A-1) is used as the amide imide resin (A), the hydroxyl group-containing (meth)acrylate compound (B) is a (meth)acrylate compound having two hydroxyl groups, and/or A (meth)acrylate compound having three hydroxyl groups is used as an essential component.

When the amide imide resin (A-2) is used as the amide imide resin (A), the hydroxyl group-containing (meth)acrylate compound (a3), which is a raw material of the amide imide resin (A-2), or the hydroxyl group containing A (meth)acrylate compound having two hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups is essentially used for either or both of the (meth)acrylate compound (B).

The molecular weight of the hydroxyl group-containing (meth)acrylate compound (B) 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. Therefore, 1,000 or less is preferable. Further, when the hydroxyl group-containing (meth)acrylate compound (B) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.

As the epoxy group-containing (meth)acrylate compound (C), other specific structures are not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and various compounds are used. be able to. Examples thereof include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether and dihydroxy. Examples thereof include mono(meth)acrylate compounds of diglycidyl ether compounds such as naphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more kinds. Among these, a (meth)acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and it forms a cured product having excellent photosensitivity and alkali developability and excellent heat resistance. Glycidyl group-containing (meth)acrylate monomers are preferred because they give possible acid group-containing (meth)acrylate resins. The molecular weight of the glycidyl group-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, the ratio of the glycidyl group-containing (meth)acrylate monomer to the total mass of the epoxy group-containing (meth)acrylate compound (C) is preferably 70% by mass or more, and more preferably 90% by mass or more. ..

As the polycarboxylic acid anhydride (D), the same polycarboxylic acid anhydride (a3) as described above can be used. In addition, since an acid group-containing (meth)acrylate resin having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance can be obtained, an aliphatic polycarboxylic acid anhydride or an alicyclic resin can be obtained. Formula polycarboxylic acid anhydrides are preferred, and aliphatic dicarboxylic acid anhydrides or alicyclic dicarboxylic acid anhydrides are more preferred. These polycarboxylic acid anhydrides (D) can be used alone or in combination of two or more kinds.

Examples of the acid group-containing (meth)acrylate resin of the present invention include the amideimide resin (A), the hydroxyl group-containing (meth)acrylate compound (B), and the epoxy group-containing (meth)acrylate depending on desired resin performance and the like. In addition to the compound (C) and the polycarboxylic acid anhydride (D), other reaction raw materials can be used in combination. When the above-mentioned other reaction raw materials are used in combination, the effect of the present invention is sufficiently exhibited. Therefore, the total content of the above components (A) to (D) in the reaction raw materials of the acid group-containing (meth)acrylate resin is included. The amount is preferably 80% by mass or more, more preferably 85% by mass or more.

The method for producing the acid group-containing (meth)acrylate resin of the present invention is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction can be easily controlled, the amide-imide resin (A) is reacted with the hydroxyl group-containing (meth)acrylate compound (B) (step 1), and the product of step 1 and the epoxy group-containing ( It is preferably produced by a method of reacting a (meth)acrylate compound (C) (step 2) and reacting the product of step 2 with the polycarboxylic acid anhydride (D) (step 3).

The step 1 is a reaction between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B). The reaction mainly reacts the acid group and/or acid anhydride group in the amide-imide resin (A) with the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (B). Since the hydroxyl group-containing (meth)acrylate compound (B) is particularly excellent in reactivity with the acid anhydride group, it is preferable that the amide imide resin (A) has an acid anhydride group as described above. The content of the acid anhydride group in the amide imide resin (A) is the difference between the above-mentioned two measured values of the acid value, that is, the acid value under the condition where the acid anhydride group is ring-opened, It can be calculated from the difference from the acid value under the condition that the acid anhydride group is not opened.

The reaction ratio between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is such that when the amide imide resin (A) has an acid group and an acid anhydride group, and the amide imide resin (A) is When it has an acid anhydride group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0.9 to 1.1 with respect to 1 mole of the acid anhydride group of the amide imide resin (A). It is preferable to use it within the range. When the amide imide resin (A) has an acid group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0. 1 mole of the acid group of the amide imide resin (A). It is preferably used in the range of 1 to 0.5.

The reaction between the amide-imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is carried out, for example, by heating and stirring under a temperature condition of about 80 to 140° C. in the presence of a suitable esterification catalyst. You can As the esterification catalyst, the same esterification catalyst as described above can be used. The esterification catalysts may be used alone or in combination of two or more. The esterification catalyst is preferably added in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.

The reaction may be carried out in an organic solvent if necessary, and an acidic catalyst may be used if necessary.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds. When the production of the amide imide resin (A) and step 1 are carried out continuously, 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 acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, boron trifluoride, anhydrous aluminum chloride, Lewis acids such as zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more kinds.

The step 2 is a reaction between the product of the step 1 and the epoxy group-containing (meth)acrylate compound (C). The reaction is mainly to react the acid group in the product obtained in the step 1 with the epoxy group-containing (meth)acrylate compound. The reaction ratio is such that the number of moles of the epoxy group contained in the epoxy group-containing (meth)acrylate compound (C) is 0.7 to 1.2 with respect to 1 mole of the acid group in the product obtained in step 1. It is preferable to use the above range, more preferably to the range of 0.9 to 1.1. The reaction of step 2 can be carried out, for example, in the presence of a suitable esterification catalyst with heating and stirring under temperature conditions of about 90 to 140°C. When step 1 and step 2 are carried out continuously, the esterification catalyst may not be added, or may be added appropriately. Further, the reaction may be carried out in an organic solvent, if necessary. The esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.

The step 3 is a reaction between the product of the step 2 and the polycarboxylic acid anhydride (D). The reaction is mainly to react the hydroxyl group in the product obtained in the step 2 with the 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) is present. The reaction ratio of the polycarboxylic acid anhydride (D) is preferably adjusted so that the acid value of the product (meth)acrylate resin containing an acid group is about 60 to 120 mgKOH/g. The reaction of step 3 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C. When step 2 and step 3 are carried out continuously, the esterification catalyst may not be added, or may be added appropriately. Further, the reaction may be carried out in an organic solvent, if necessary. The esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.

The acid value of the acid group-containing (meth)acrylate resin of the present invention 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. Therefore, the range of 50 to 120 mgKOH/g is preferable, and the range of 60 to 110 mgKOH/g is more preferable. The acid value of the acid group-containing (meth)acrylate resin in the present invention is a value measured by the neutralization titration method of JIS K0070 (1992).

The weight average molecular weight (Mw) of the acid group-containing (meth)acrylate resin is preferably in the range of 1,000 to 20,000. In addition, in this invention, a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.

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

The photopolymerization initiator may be appropriately selected and used depending on the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino). Alkylphenone-based photopolymerization initiator such as 2-[[4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

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

Examples of commercial products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100" and "Omnirad-2100". Omnirad-754, "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA". , "Kayakyu-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" ( Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop), "Runtecure-1104" (Runtec) Manufactured by the company) and the like. These photopolymerization initiators can be used alone or in combination of two or more kinds.

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

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

The resin (E) having an acid group and a polymerizable unsaturated bond may be any resin having an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond Epoxy resin having, urethane resin having acid group and polymerizable unsaturated bond, acrylic resin having acid group and polymerizable unsaturated bond, amide imide resin having acid group and polymerizable unsaturated bond, acid group and polymerizable unsaturated Examples thereof include an acrylamide resin having a bond.

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

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid means a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like. 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. Further, esterified products of unsaturated monobasic acids, acid halides, acid anhydrides and the like can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more kinds.

Examples of the polybasic acid anhydrides include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, and hexahydro. Examples thereof include phthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride and tetrapropenyl succinic anhydride. These polybasic acid anhydrides can be used alone or in combination of two or more kinds. Further, among these, since a curable resin composition having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance is obtained, tetrahydrophthalic anhydride and succinic anhydride are preferable.

The same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

The hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3), and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.

The method for producing the epoxy resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the epoxy resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

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

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 carboxyl group-containing polyol compound, and optionally a polybasic acid anhydride, the carboxyl group Those obtained by reacting with a polyol compound other than the containing polyol compound, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound And the like.

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

As the polybasic acid anhydride, the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.

Examples of the polyol compound 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)oxyethylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds Modified (poly)oxyalkylene modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structures of the various polyol compounds are included. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.

The method for producing the urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

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

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compound. Examples of the other polymerizable unsaturated group-containing compound include (meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate and 2-ethylhexyl(meth)acrylate. Acrylic acid alkyl ester; alicyclic structure-containing (meth)acrylate such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples thereof include aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

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

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

Examples of the amide imide resin having an acid group and a polymerizable unsaturated bond include an amide imide 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. Examples thereof include those obtained by reacting a compound with 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. To be The compound having a reactive functional group may or may not have a (meth)acryloyl group.

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

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

The same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound.

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

As the polybasic acid, any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. To be As the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

The same epoxy group-containing (meth)acrylate compound as the above-mentioned epoxy group-containing (meth)acrylate compound (C) can be used, and the epoxy group-containing (meth)acrylate compound can be used alone. It is also possible to use two or more kinds in combination.

The method for producing the amide-imide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method. The amide-imide resin having an acid group and a polymerizable unsaturated bond may be produced in an organic solvent, if necessary, and a basic catalyst may be used, if necessary.

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. Examples thereof include those obtained by reacting with an unsaturated monobasic acid, if necessary.

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

In the above structural formulas (3-1) to (3-4), R ¹ is any 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 are each independently a hydrogen atom or a methyl group. Further, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0. q is an integer of 2 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and In 3-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (3-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be substituted, and the number of substituents in one molecule is p and q.

As the phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) are essential. An essential reaction between the reaction product used as the reaction raw material, the compound having at least two phenolic hydroxyl groups in the molecule, and the compound represented by any of the following structural formulas (x-1) to (x-5) A reaction product as a raw material can also be used. In addition, a novolac type phenol resin using one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule It is also possible to use a novolac-type phenol resin as a reaction raw material.

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

Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).

In the above structural formulas (4-1) to (4-4), R ⁴ is any 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 are each independently a hydrogen atom or a methyl group. Further, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (4-2), the substituent may be substituted on any ring. In 4-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (4-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be replaced.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above structural formulas (3-1) to (3-4) can be used.

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

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

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

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

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

The method for producing the acrylamide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method. The production of the acrylamide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and a basic catalyst and an acidic catalyst may be used, if necessary.

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

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

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2 -Aliphatic mono(meth)acrylate compounds such as ethylhexyl(meth)acrylate and octyl(meth)acrylate; cycloaliphatic (meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate and other alicyclic mono(meth)acrylates Acrylate compounds; Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. (Meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxy in the molecular structure of the various mono(meth)acrylate monomers A (poly)oxyalkylene-modified mono(meth)acrylate compound having a polyoxyalkylene chain such as a tetramethylene chain introduced therein; a lactone-modified mono compound having a (poly)lactone structure introduced into the molecular structure of each of the various mono(meth)acrylate compounds (Meth)acrylate compound; aliphatic such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Di(meth)acrylate compound; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane di Alicyclic di(meth)acrylate compounds such as methanol di(meth)acrylate; biphenol di(meth)acrylate, bisphenol Aromatic di(meth)acrylate compounds such as enol di(meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene in the molecular structures of the various di(meth)acrylate compounds. A polyoxyalkylene-modified di(meth)acrylate compound having a (poly)oxyalkylene chain introduced therein such as a chain; a lactone-modified di(meth) having a (poly)lactone structure introduced into the molecular structure of each of the above-mentioned various di(meth)acrylate compounds ) Acrylate compound; Aliphatic tri(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyethylene chain in the molecular structure of the aliphatic tri(meth)acrylate compound. A (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a (poly)oxypropylene chain or a (poly)oxytetramethylene chain; a molecule of the aliphatic tri(meth)acrylate compound A lactone-modified tri(meth)acrylate compound having a (poly)lactone structure introduced into the structure; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, or the like in the molecular structure of the aliphatic poly(meth)acrylate compound A tetra- or higher functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced; a tetra-functional or higher functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples include modified poly(meth)acrylate compounds. The various (meth)acrylate monomers may be used alone or in combination of two or more.

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

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxy group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds. Further, among these, since a curable resin composition having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance is obtained, a phenol novolac type epoxy resin, a cresol novolac type is obtained. Novolak type epoxy resins such as epoxy resin, bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin are preferable, and the softening point is 20 to 120°C. The range of is particularly preferable.

The curing accelerator is for promoting a curing reaction of the curing agent, 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, Examples thereof include amine complex salts. These curing accelerators can be used alone or in combination of two or more kinds. Further, the addition amount of the curing accelerator is preferably, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.

⑦ As a source of ultraviolet rays, ultraviolet lamps are generally used from the viewpoint of practicality and economy. Specific examples thereof include 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, and an LED.

The cumulative light amount of the active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , and more preferably 50 to 1,000 mJ/cm ² . When the integrated light amount is within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.

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

Further, since the cured product of the present invention has excellent heat resistance, for example, in a semiconductor device application, a solder resist, an interlayer insulating material, a package material, an underfill material, a package adhesive layer such as a circuit element, or an integrated circuit. It can be suitably used as an adhesive layer between an element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer and the like in a thin display application represented by LCD and OELD. Among them, it can be particularly preferably used for solder resist applications.

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

The resist member of the present invention is, for example, a photomask on which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100°C. Through exposure with an active energy ray, the unexposed area is developed with an alkaline aqueous solution, and then heat-cured in a temperature range of about 140 to 200° C.

Examples of the base material include metal foils such as copper foil and aluminum foil.

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

In the examples of the present application, the acid value of the acid group-containing (meth)acrylate resin was measured by the neutralization titration method of JIS K0070 (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: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 Model II Version 4.10”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation “A-1000”
Tosoh Corporation "A-2500"
Tosoh Corporation “A-5000”
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation “F-20”
Tosoh Corporation “F-40”
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

In this example, the liquid chromatography chart was measured under the following conditions.
[Measurement condition]
Equipment: Shimadzu Corporation “LCMS-2010EV”
Data processing: Shimadzu Corporation “LCMS Solution”
Column: "ODS-100V" manufactured by Tosoh Corporation (2.0 mm ID x 150 mm, 3 µm) 40°C
Eluent: water/acetonitrile, 0.4 mL/min Detector: PDA, MS
Sample preparation: 1. Dissolve 50 mg of the material in 10 ml of acetonitrile (for LC) 2. Stir with vortex for 30 seconds 3. Let stand for 30 minutes 4. Pass through a 0.2 μm filtration filter and use as a measurement sample Calculation of area ratio: UV wavelength calculated at 210 nm

(Synthesis Example 1: Production of pentaerythritol polyacrylate (A1))
A flask equipped with a thermometer, a stirrer, and a condenser was charged with 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. I prepared it. The temperature was raised to 105° C. with stirring, and the reaction was carried out at the same temperature for 12 hours while refluxing the system. To the reaction mixture, 287 parts by mass of toluene was added and washed with 123 parts by mass of distilled water. Furthermore, a 20 mass% sodium hydroxide aqueous solution was added to neutralize the reaction mixture, and the mixture was washed with 62 parts by mass of distilled water. After adding 500 ppm of hydroquinone monomethyl ether to the resin solid content, toluene was distilled off to obtain pentaerythritol polyacrylate (A1). The hydroxyl value of this pentaerythritol polyacrylate (A1) is 290 mgKOH/g, the content of pentaerythritol tetraacrylate (a1) calculated from the area ratio of the liquid chromatography chart is 16% by mass, and the pentaerythritol triacrylate (a2) content The content 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 the content of the other high molecular weight component (a') is 2%. It was mass %.

(Synthesis Example 2: Production of pentaerythritol diacrylate (A2))
A flask equipped with a thermometer, a stirrer, and a condenser was charged with 136 parts by mass of pentaerythritol and 600 parts by mass of N,N-dimethylformamide, and 3.7 parts by mass of paratoluenesulfonic acid was added as a catalyst. The temperature was raised to 80° C. with stirring to dissolve pentaerythritol in N,N-dimethylformamide, and 78 parts by mass of cyclohexanone was added. While maintaining the reaction temperature at 80° C., the pressure in the reaction system was reduced to 140 mmHg, and the reaction was continued while distilling off the produced water. When generation of water could not be confirmed, the mixture was refluxed for another hour. While continuing stirring, the mixture was cooled to room temperature and returned to normal pressure, and unreacted pentaerythritol was removed by vacuum filtration. N,N-dimethylformamide was removed from the obtained filtrate under reduced pressure, ethyl acetate was added, and the precipitated pentaerythritol was removed by filtration again. The obtained filtrate was washed with a saturated aqueous solution of sodium hydrogen carbonate and then with a saturated aqueous solution of sodium chloride, and the organic layer was dehydrated with magnesium sulfate. The reaction product after dehydration was concentrated to obtain a ketal compound (x1).

Then, 21.6 parts by mass of the ketal compound (x1) obtained above, 120 parts by mass of dichloromethane, and 46.5 parts by mass of triethylamine were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and cooled to -5°C. did. What melt|dissolved 29 mass parts of 3-chloropropionyl chloride in 40 mass parts of dichloromethane was dripped little by little, keeping the reaction system inside at 0 degreeC or less. After the dropping was completed, the temperature was gradually raised to room temperature and the reaction was continued for 4 hours. After confirming disappearance of the ketal compound (x1) as a raw material by gas chromatography, triethylamine hydrochloride was removed by vacuum filtration. The obtained filtrate was washed with a saturated aqueous solution of sodium hydrogen carbonate, further washed with a saturated aqueous solution of sodium chloride, and dehydrated with anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of an acrylate compound (x2).

Next, 6.5 parts by mass of the acrylate compound (x2) obtained above and 30 parts by mass of acetone were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and cooled to 0° C. with stirring. 10 parts by mass of a 10% aqueous solution of sulfuric acid was dropped little by little so that the temperature in the reaction system would not exceed 10° C., and after the entire amount was added, the reaction was carried out at room temperature for 16 hours. After confirming the disappearance of the raw material acrylate compound (x2) by gas chromatography, 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 solution of sodium hydrogen carbonate 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: Production of dipentaerythritol polyacrylate (A3))
A flask equipped with a thermometer, a stirrer, and a condenser was charged with 220 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105° C. with stirring, and the reaction was carried out at the same temperature for 13 hours while refluxing the system. The amount of water produced was 61 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, a 20% aqueous sodium hydroxide solution was added to neutralize the reaction mixture, and the mixture was washed with 100 parts by mass of distilled water. After adding 500 ppm of hydroquinone monomethyl ether to the resin solid content, toluene was distilled off to obtain dipentaerythritol acrylate (A3). The hydroxyl value of this dipentaerythritol acrylate (A3) was 140 mgKOH/g. Further, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 28% by mass, the content of dipentaerythritol pentaacrylate (b2) is 42% by mass, dipentaerythritol hexaacrylate. The content of (b3) was 22% by mass, and the content of the high molecular weight component (b') was 8% by mass.

(Example 1: Production of acid group-containing (meth)acrylate resin (1))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 72 parts by mass of a pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content: about 67%, hydroxyl value: 159.7 mgKOH/g) is added, and the mixture is added at 110° C. for 3 hours It was made to react. 148 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 151 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (1). The acid value of the solid content of the acid group-containing (meth)acrylate resin (1) was 87 mgKOH/g, and the weight average molecular weight was 2,390.

(Example 2: Production of acid group-containing (meth)acrylate resin (2))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 72 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 148 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 99 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (2). The acid value of the solid content of this acid group-containing (meth)acrylate resin (2) was 94 mgKOH/g, and the weight average molecular weight was 2,300.

(Example 3: Production of acid group-containing (meth)acrylate resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 72 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 216 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate (“Cyclomer M100” manufactured by Daicel Co., Ltd., epoxy group equivalent 207 g/equivalent) and 2.2 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Let Further, 99 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (3). The acid value of the solid content of the acid group-containing (meth)acrylate resin (3) was 85 mgKOH/g, and the weight average molecular weight was 2,540.

(Example 4: Production of acid group-containing (meth)acrylate resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate (“Desmodur W” manufactured by Sumika Covestrourethane Co., Ltd.) was added and reacted at 120° C. for 8 hours to give an isocyanate group content of 0.1% by mass or less. I confirmed that. Next, 52 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 111 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 75 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (4). The acid value of the solid content of the acid group-containing (meth)acrylate resin (4) was 85 mgKOH/g, and the weight average molecular weight was 2,440.

(Example 5: Production of acid group-containing (meth)acrylate resin (5))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 52 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 162 parts by mass of “Cyclomer M100” and 1.9 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Furthermore, 75 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (5). The acid value of the solid content of the acid group-containing (meth)acrylate resin (5) was 78 mgKOH/g, and the weight average molecular weight was 2610.

(Example 6: Production of acid group-containing (meth)acrylate resin (6))
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 53 parts by mass of pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. Let 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 74 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 220 parts by mass of “Cyclomer M100” and 2.3 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 154 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (6). The acid value of the solid content of the acid group-containing (meth)acrylate resin (6) was 80 mgKOH/g, and the weight average molecular weight was 2,370.

(Example 7: Production of acid group-containing (meth)acrylate resin (7))
In a flask equipped with a thermometer, a stirrer, and a reflux 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 44 parts by mass of pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 0.6 parts by mass of triphenylphosphine were added and reacted at 120° C. for 6 hours while blowing air. Let 131 parts by mass of dicyclohexylmethane 4,4-diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 53 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 165 parts by mass of "Cyclomer M100" and 1.9 parts by mass of triphenylphosphine were added and reacted at 110°C for 5 hours. Further, 76 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (7). The acid value of the solid content of the acid group-containing (meth)acrylate resin (7) was 78 mgKOH/g, and the weight average molecular weight was 2,580.

(Example 8: Production 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 were added and dissolved. Let The reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 0.2 parts by weight of methquinone, 22 parts by weight of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1 and 1.6 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. .. Then, 85 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 57 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (8). The acid value of the solid content of this acid group-containing (meth)acrylate resin (8) was 89 mgKOH/g, and the weight average molecular weight was 1850.

(Example 9: Production 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 were added and dissolved. Let The reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 0.2 parts by weight of methoquinone, 14 parts by weight of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2 and 1.6 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. .. Then, 86 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 58 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (9). The acid value of the solid content of the acid group-containing (meth)acrylate resin (9) was 91 mgKOH/g, and the weight average molecular weight was 2,120.

(Example 10: Production of acid group-containing (meth)acrylate resin (10))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 68 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. Glycidyl methacrylate (130 parts by mass) and triphenylphosphine (1.7 parts by mass) were added and reacted at 110° C. for 5 hours. Further, 87 parts by mass of succinic anhydride and 71 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (10). The acid value of the solid content of the acid group-containing (meth)acrylate resin (10) was 92 mgKOH/g, and the weight average molecular weight was 2,590.

(Example 11: Production of acid group-containing (meth)acrylate resin (11))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 25 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110° C. for 3 hours. 150 parts by mass of glycidyl methacrylate and 1.7 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 100 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (11). The acid value of the solid content of the acid group-containing (meth)acrylate resin (11) was 103 mgKOH/g, and the weight average molecular weight was 2710.

(Example 12: Production of acid group-containing (meth)acrylate resin (12))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 23 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110° C. for 3 hours. 144 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Furthermore, 96 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (12). The acid value of the solid content of the acid group-containing (meth)acrylate resin (12) was 105 mgKOH/g, and the weight average molecular weight was 2990.

(Example 13: Production 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, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 37 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1 was added, and the mixture was reacted at 110° C. for 3 hours. Glycidyl methacrylate (140 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110° C. for 5 hours. Further, 94 parts by mass of succinic anhydride and 62 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (13). The acid value of the solid content of the acid group-containing (meth)acrylate resin (13) was 101 mgKOH/g, and the weight average molecular weight was 2,590.

(Example 14: Production of acid group-containing (meth)acrylate resin (14))
In a flask equipped with a thermometer, a stirrer, and a reflux 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 part by mass of dibutylhydroxytoluene. Then, 0.3 parts by mass of methoquinone and 0.8 part of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 46 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1 was added, and the mixture was reacted at 110° C. for 3 hours. 153 parts by mass of glycidyl methacrylate and 1.9 parts of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 102 parts by mass of succinic anhydride and 56 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (14). The acid value of the solid content of the acid group-containing (meth)acrylate resin (14) was 94 mgKOH/g, and the weight average molecular weight was 2330.

(Example 15: Production of acid group-containing (meth)acrylate resin (15))
In 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 part by mass of dibutylhydroxytoluene. Then, 0.3 parts by mass of methoquinone and 0.8 part of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 29 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2 was added and reacted at 110° C. for 3 hours. 153 parts by mass of glycidyl methacrylate and 1.8 parts of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 102 parts by mass of succinic anhydride and 46 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (15). The acid value of the solid content of the acid group-containing (meth)acrylate resin (15) was 96 mgKOH/g, and the weight average molecular weight was 2,490.

(Example 16: Production of acid group-containing (meth)acrylate resin (16))
In 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, isocyanate group content 17. (2 mass %) 244 mass parts, trimellitic anhydride 192 mass parts, and dibutyl hydroxytoluene 1.0 mass part were added and dissolved. The reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. 0.3 parts by weight of methoquinone, 81 parts by weight of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1 and 1.4 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 165 parts by mass of glycidyl methacrylate and 1.8 parts by mass of triphenylphosphine were added, and the reaction was carried out at 110° C. for 5 hours. Further, 110 parts by mass of tetrahydrophthalic anhydride and 67 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (16). The acid value of the solid content of the acid group-containing (meth)acrylate resin (16) was 86 mgKOH/g, and the weight average molecular weight was 7,450.

(Example 17: Production of acid group-containing (meth)acrylate resin (17))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. 1.0 parts by mass of hydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. After adding 244 parts by mass of "VESTANAT T-1890/100" and reacting at 120°C for 10 hours, it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 79 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 167 parts by mass of glycidyl methacrylate and 2.7 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 57 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (17). The acid value of the solid content of the acid group-containing (meth)acrylate resin (17) was 84 mgKOH/g, and the weight average molecular weight was 7,390.

(Example 18: Production of acid group-containing (meth)acrylate resin (18))
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 were added and dissolved. Let The reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 0.2 parts by weight of methquinone, 22 parts by weight of dipentaerythritol polyacrylate (A3) obtained in Synthesis Example 3 and 1.6 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. It was Then, 85 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 57 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (18). The acid value of the solid content of this acid group-containing (meth)acrylate resin (18) was 83 mgKOH/g, and the weight average molecular weight was 1910.

(Example 19: Production of acid group-containing (meth)acrylate resin (19))
In 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, 110 parts by mass of dipentaerythritol polyacrylate (A3) obtained in Synthesis Example 3, 0.9 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of metoquinone, and 0.8 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 87 parts by mass of “Aronix M-306” was added and reacted at 110° C. for 3 hours. 148 parts by mass of glycidyl methacrylate and 2.1 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 99 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (19). The acid value of the solid content of the acid group-containing (meth)acrylate resin (19) was 85 mgKOH/g, and the weight average molecular weight was 2,480.

(Example 20: Production of acid group-containing (meth)acrylate resin (20))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutyl. Hydroxytoluene (0.6 parts by mass), methoquinone (0.2 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 65 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 111 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 74 parts by mass of succinic anhydride and 53 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (20). The acid value of the solid content of the acid group-containing (meth)acrylate resin (20) was 85 mgKOH/g, and the weight average molecular weight was 2340.

(Example 21: Production 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, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Then, 70 parts by mass of "Aronix M-306" was added and reacted at 110°C for 3 hours. 160 parts by mass of glycidyl methacrylate and 1.9 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 88 parts by mass of succinic anhydride and 86 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (21). The acid value of the solid content of the acid group-containing (meth)acrylate resin (21) was 100 mgKOH/g, and the weight average molecular weight was 2750.

(Example 22: Production 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, dibutyl. Hydroxytoluene (0.6 parts by mass), methoquinone (0.2 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 77 parts by mass of 1,5-pentamethylene diisocyanate was added and reacted at 120° C. for 8 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 64 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. 131 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours. Further, 88 parts by mass of succinic anhydride and 75 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (22). The acid value of the solid content of the acid group-containing (meth)acrylate resin (22) was 95 mgKOH/g, and the weight average molecular weight was 2050.

(Example 23: Production of acid group-containing (meth)acrylate resin (23))
In a flask equipped with a thermometer, a stirrer, and a reflux 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, dibutylhydroxytoluene. 0.7 parts by mass, 0.2 parts by mass of metoquinone, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air. 94 parts by mass of 1,3-bis(isocyanatomethyl)benzene (“Takenate 500” manufactured by Mitsui Chemicals, Inc.) was added, and the mixture was reacted at 120° C. for 6 hours to give an isocyanate group content of 0.1% by mass or less. I confirmed that. Next, 68 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours. Glycidyl methacrylate (140 parts by mass) and triphenylphosphine (1.7 parts by mass) were added and reacted at 110° C. for 5 hours. Further, 93 parts by mass of succinic anhydride and 80 parts by mass of dimethylacetamide were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (23). The acid value of the solid content of the acid group-containing (meth)acrylate resin (23) was 94 mgKOH/g, and the weight average molecular weight was 2,450.

(Comparative Example 1: Production of acid group-containing acrylate resin (C1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monomethyl ether acetate, and orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214) 428 After dissolving 4 parts by weight of dibutylhydroxytoluene as an antioxidant and 0.4 parts by weight of methquinone as a thermal polymerization inhibitor, 144 parts by weight of acrylic acid and 1.6 parts by weight of triphenylphosphine were added, The esterification reaction was carried out at 120° C. for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 2.5 hours to obtain a target acid group-containing acrylate resin (C1). The acid value of the solid content of the acid group-containing acrylate resin (C1) was 85 mgKOH/g.

(Example 24: Preparation of curable resin composition (1))
The acid group-containing (meth)acrylate resin (1) obtained in Example 1, an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, dipentaerythritol hexaacrylate, and diethylene glycol mono Ethyl ether acetate, a photopolymerization initiator (“OMNIRAD 907” manufactured by IGM Co., Ltd.), 2-ethyl-4-methylimidazole, and phthalocyanine green were mixed in a mass part shown in Table 1 and kneaded by a roll mill. Curable resin composition (1) was obtained.

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

(Comparative Example 2: Preparation of curable resin composition (C2))
Curable resin composition 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. (C2) was obtained.

The following evaluations were carried out using the curable resin compositions (1) to (23) and (C2) obtained in the above Examples and Comparative Examples.

[Evaluation method of light sensitivity]
The curable resin compositions obtained in Examples and Comparative Examples were applied on a glass substrate with an applicator so as to have a film thickness of 50 μm, and then dried at 80° C. for 30 minutes each. Then, a step tablet No. manufactured by Kodak Co. Ultraviolet rays of 1000 mJ/cm ² were radiated through the No. ² using a metal halide lamp. This was developed with a 1 mass% sodium carbonate aqueous solution for 180 seconds, and the number of remaining steps was evaluated. The higher the number of remaining steps, the higher the photosensitivity.

[Evaluation method of alkali developability]
The curable resin composition obtained in each Example and Comparative Example was applied on a glass substrate using an applicator so as to have a film thickness of 50 μm, and then at 80° C. for 30 minutes, 40 minutes, and 50 minutes, respectively. The sample was dried for 60 minutes to prepare samples having different drying times. These were developed with a 1% aqueous sodium carbonate solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample in which no residue remained on the substrate was evaluated as the drying control width. It should be noted that the longer the dry control width, the better the alkali developability.

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

(Example 47: Preparation of curable resin composition (24))
The acid group-containing (meth)acrylate resin (1) obtained in Example 1, an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1 as a photopolymerization initiator. -(4-Methylthiophenyl)-2-morpholinopropan-1-one (“OMNIRAD-907” manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in a mass ratio shown in Table 1 to prepare a curable resin. A composition (24) was obtained.

(Examples 48 to 69: Preparation of curable resin compositions (25) to (46))
The acid group-containing (meth)acrylate resins (2) to (23) obtained in Examples 2 to 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 in Example 47.

(Comparative Example 3: Preparation of curable resin composition (C3))
The same procedure as in Example 47 was repeated except that the acid group-containing (meth)acrylate resin (C1) obtained in Comparative Example 1 was used instead of the acid group-containing (meth)acrylate resin (1) used in Example 47. Thus, a curable resin composition (C3) was obtained.

The following evaluations were carried out using the curable resin compositions (24) to (46) and (C3) obtained in the above Examples and Comparative Examples.

[Heat resistance evaluation method]
<Creation of test pieces>
The curable resin compositions obtained in Examples and Comparative Examples were applied on a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) with an applicator of 50 μm and dried at 80° C. for 30 minutes. It was After irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece (cured product).

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

Tables 3 and 4 show 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.

The parts by mass of the “acid group-containing (meth)acrylate resin” in Tables 1 to 4 are solution values.

“Curing agent” in Tables 1 to 4 indicates an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214).

“Organic solvent” in Tables 1 to 4 indicates diethylene glycol monomethyl ether acetate.

"Photoinitiator" in Tables 1 to 4 indicates "Omnirad-907" manufactured by IGM.

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

On the other hand, Comparative Examples 2 and 3 are examples of curable resin compositions that do not use the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition had remarkably insufficient photosensitivity and remarkably insufficient heat resistance in the cured product.

Claims

Amidoimide 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). ) And an acid group-containing (meth)acrylate resin, which are essential reaction raw materials,
The amide-imide 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 reaction product (A-2) of a hydroxyl group-containing (meth)acrylate compound (a3),
Either or both of the hydroxyl group-containing (meth)acrylate compound (B) and the hydroxyl group-containing (meth)acrylate compound (a3) have (meth)acrylate compound having two hydroxyl groups, and/or have three hydroxyl groups. An acid group-containing (meth)acrylate resin containing a (meth)acrylate compound.
The acid group-containing (meth)acrylate resin according to claim 1, wherein the polyisocyanate compound (a1) is an aliphatic diisocyanate or an alicyclic diisocyanate.
The acid group-containing (meth)acrylate resin according to claim 1, wherein the (meth)acrylate compound having two hydroxyl groups contains a pentaerythritol di(meth)acrylate and/or a dipentaerythritol tetra(meth)acrylate compound.
The acid group-containing (meth)acrylate resin according to claim 1, wherein the (meth)acrylate compound having three hydroxyl groups contains pentaerythritol mono(meth)acrylate and/or dipentaerythritol tri(meth)acrylate.
The reaction product (A-2) is a reaction product of the intermediate reaction product of the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3) with the polyisocyanate compound (a1). Yes,
The acid group-containing (meth)acrylate according to claim 1, wherein the number of moles of the polycarboxylic acid anhydride (a2) per mole of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (a3) is in the range of 2 to 8. resin.
A curable resin composition comprising the acid group-containing (meth)acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator.
The curable resin composition according to claim 6, further comprising an organic solvent and a curing agent.
7. The curing according to claim 6, further comprising a resin (E) having an acid group and a polymerizable unsaturated bond other than the acid group-containing (meth)acrylate resin according to any one of claims 1 to 5. Resin composition.
A cured product, which is a cured 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.
A resin material for solder resist, comprising the curable resin composition according to any one of claims 6 to 8.
A resist member comprising the resin material for solder resist according to claim 11.
Amidoimide 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). ) And a method for producing an acid group-containing (meth)acrylate resin obtained by reacting
The reaction product (A-1) obtained by reacting the amide-imide resin (A) with the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2), or the polyisocyanate compound (a1) and the polycarboxylic acid anhydride. A reaction product (A-2) obtained by reacting the compound (a2) with a hydroxyl group-containing (meth)acrylate compound (a3),
Either or both of the hydroxyl group-containing (meth)acrylate compound (B) and the hydroxyl group-containing (meth)acrylate compound (a3) have (meth)acrylate compound having two hydroxyl groups, and/or have three hydroxyl groups. A method for producing an acid group-containing (meth)acrylate resin, which comprises a (meth)acrylate compound.