KR102465156B1 - Acid group-containing (meth)acrylamide resin, curable resin composition, resin material for solder resist and resist member - Google Patents

Abstract

The present invention provides a phenolic hydroxyl group-containing resin (A), a cyclic carbonate compound (B1) or a cyclic ether compound (B2), an N-alkoxyalkyl (meth)acrylamide compound (C), and an acid anhydride (D) An acid group-containing (meth)acrylamide resin is provided as an essential reaction raw material. This acid group-containing (meth)acrylamide resin has high photosensitivity and excellent alkali developability, and can form a cured product excellent in insulation reliability.

Description

Acid group-containing (meth)acrylamide resin, curable resin composition, resin material for solder resist and resist member

The present invention relates to an acid group-containing (meth)acrylamide resin having high photosensitivity and excellent alkali developability and excellent insulation reliability in a cured product, a curable resin composition containing the same, a cured product, an insulating material, and a resin material for soldering resist and a resist member.

After acrylated epoxy resin with acrylic acid for the resin material for soldering resists for printed wiring boards, the acidic radical containing epoxy acrylate resin obtained by making an acid anhydride react is used widely. As for the performance requested|required with respect to the resin material for soldering resists, hardening with a small exposure amount, the thing excellent in alkali developability, etc. are mentioned.

As a conventionally known resin material for soldering resists, an acid group-containing epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac-type epoxy resin with acrylic acid and phthalic anhydride is known (for example, .

In addition, since the epoxy resin used as a raw material already contains a large amount of chlorine ions as for the said acid group-containing epoxy acrylate resin, chlorine ions are liberated with long-term use, and by ionizing the circuit, electromigration Insulation reliability was not sufficient, for example, in some cases causing dielectric breakdown.

Therefore, there has been a demand for a material having high insulation reliability in a cured product and excellent in photosensitivity and alkali developability.

Japanese Patent Laid-Open No. 8-259663

The problem to be solved by the present invention is an acid group-containing (meth)acrylamide resin having high photosensitivity and excellent alkali developability and excellent insulation reliability in a cured product, a curable resin composition containing the same, a cured product, an insulating material, A resin material for soldering resists and a resist member are provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors have phenolic hydroxyl group containing resin (A), a cyclic carbonate compound (B1) or a cyclic ether compound (B2), and N-alkoxyalkyl (meth)acrylamide By using the acid group-containing (meth)acrylamide resin using the compound (C) and the acid anhydride (D) as essential reaction raw materials, the chlorine ion content in the resin can be reduced and the above problems can be solved. and completed the present invention.

That is, the present invention relates to a phenolic hydroxyl group-containing resin (A), a cyclic carbonate compound (B1) or a cyclic ether compound (B2), an N-alkoxyalkyl (meth)acrylamide compound (C), and an acid anhydride (D) ) as an essential reaction raw material, an acid group-containing (meth)acrylamide resin, a curable resin composition containing the same, an insulating material comprising the curable resin composition, a resin material for soldering resists, and a resist member.

Since the acid group-containing (meth)acrylamide resin of the present invention has high photosensitivity and excellent alkali developability, and excellent insulation reliability in cured products, the acid group-containing (meth)acrylamide resin and a photopolymerization initiator Curable resin composition can be used suitably for the resist member which consists of an insulating material, the resin material for soldering resists, and the said resin for soldering resists.

The acid group-containing (meth)acrylamide resin of the present invention comprises a phenolic hydroxyl group-containing resin (A), a cyclic carbonate compound (B1) or a cyclic ether compound (B2), and an N-alkoxyalkyl (meth)acrylamide compound (C ) and an acid anhydride (D) as essential reaction raw materials.

In addition, in this invention, "(meth)acrylamide resin" means resin which has one or both of an acryloyl group and a methacryloyl group in a molecule|numerator. In addition, "(meth)acryloyl group" means one or both of acryloyl group and methacryloyl group, and "(meth)acrylamide" means one or both of acrylamide and methacrylamide.

As an acidic radical which the said acidic radical containing (meth)acrylamide resin contains, a carboxy group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, for example. Among these, since excellent alkali developability is expressed, a carboxyl group is preferable.

The phenolic hydroxyl group-containing resin (A) refers to a resin having two or more phenolic hydroxyl groups in a molecule, for example, an aromatic polyhydroxy compound or a compound (a1) having one phenolic hydroxyl group in the molecule. Or a novolak-type phenol resin using two or more as a reaction raw material, the compound (a1) having a phenolic hydroxyl group, and a compound (x) represented by any one of the following structural formulas (x-1) to (x-5) Reaction products used as essential reaction raw materials, etc. are mentioned.

[In the formula, h is 0 or 1. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and i is 0 or an integer of 1-4. Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. Y is any one of a C1-C4 alkylene group, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer from 1 to 4]

Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxy In addition to anthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and the like, a compound having one or more substituents on their aromatic nucleus can be mentioned. Moreover, as a substituent on an aromatic nucleus, For example, aliphatic hydrocarbon groups, such as a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group; Alkoxy groups, such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; a phenyl group, a naphthyl group, an anthryl group, and an aryl group in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, etc. are substituted on their aromatic nucleus; a phenyloxy group, a naphthyloxy group, and an aryloxy group in which the aliphatic hydrocarbon group, the alkoxy group, and the halogen atom are substituted on their aromatic nucleus; A phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and the aralkyl group etc. which the said aliphatic hydrocarbon group, the said alkoxy group, the said halogen atom etc. substituted on these aromatic nucleus are mentioned. These aromatic polyhydroxy compounds may be used independently and may use 2 or more types together. Among these, since the acidic radical containing (meth)acrylamide resin which can form the hardened|cured material which has high insulation reliability is obtained, the compound which does not contain a halogen is preferable.

The compound (a1) having one phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having one hydroxyl group on the aromatic nucleus, for example, phenol or phenol having one or more substituents on the aromatic nucleus and phenolic compounds, naphthol or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracenol or anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol, and the like. Moreover, as a substituent on an aromatic nucleus, an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group etc. are mentioned, for example, Each specific example is as above-mentioned. The compound (a1) which has one of these phenolic hydroxyl groups may be used independently and may use 2 or more types together. Among these, an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained, and therefore a phenolic compound is preferable, and the above substituents on phenol or its aromatic nucleus A compound having one or both of is preferred. As a substituent on an aromatic nucleus, a C1-C6 aliphatic hydrocarbon group or an aralkyl group is preferable.

The reaction between the compound (a1) having one phenolic hydroxyl group in the molecule and the compound (x) can be carried out by a method of heating and stirring under an acid catalyst condition and a temperature condition of about 80 to 200°C. The reaction ratio between the compound (a1) having one phenolic hydroxyl group in the molecule and the compound (x) is 0.5 to 1 mole of the compound (x) in the compound (a1) having a phenolic hydroxyl group in the molecule It is preferable that it is a ratio used as -5 mol.

Examples of the cyclic carbonate compound (B1) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used independently and may use 2 or more types together. Among these, ethylene carbonate or propylene carbonate is preferable because an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained.

As said cyclic ether compound (B2), ethylene oxide, a propylene oxide, tetrahydrofuran, etc. are mentioned, for example. These cyclic ether compounds may be used independently and may use 2 or more types together. Among these, ethylene oxide or propylene oxide is preferable because an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained.

Examples of the N-alkoxyalkyl (meth)acrylamide compound (C) 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, etc. are mentioned. These N-alkoxyalkyl (meth)acrylamide compounds may be used independently and may use 2 or more types together. Among these, N-methoxymethyl (meth)acrylamide is preferable because an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained.

Examples of the acid anhydride (D) include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydro and phthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, and tetrapropenyl succinic anhydride. These acid anhydrides may be used independently and may use 2 or more types together. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable because an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained.

The equivalent ratio [(C)/(D)] of the N-alkoxyalkyl (meth)acrylamide compound (C) and the acid anhydride (D) is an acid group-containing (meth)acryl group having high photosensitivity and excellent alkali developability. Since an amide resin is obtained, the range of 0.2-7 is preferable, and the range of 0.25-6.7 is more preferable.

The manufacturing method of the acidic radical containing (meth)acrylamide resin of this invention is not specifically limited, You may manufacture by any method. For example, you may manufacture by the method of making all the reaction raw materials react collectively, and you may manufacture by the method of making the reaction raw materials react sequentially. Among them, since control of the reaction is easy, first, the phenolic hydroxyl group-containing resin (A) and the cyclic carbonate compound (B1) or the cyclic ether compound (B2) are reacted, and then the N-alkoxyalkyl ( The method in which the said acid anhydride (D) is made to react after making a meth)acrylamide compound (C) react is preferable. In the reaction, for example, the phenolic hydroxyl group-containing resin (A) and the cyclic carbonate compound (B1) or the cyclic ether compound (B2) are reacted in the presence of a basic catalyst in a temperature range of 100 to 200°C. Then, in the presence of an acid catalyst, the N-alkoxyalkyl (meth)acrylamide compound (C) is reacted at a temperature range of 80 to 140° C., then the acid anhydride (D) is added, and 80 to 140° C. It can be carried out by a method of reacting in a temperature range of

As said basic catalyst, For example, alkaline-earth metal hydroxides, such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; and amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. These basic catalysts may be used independently and may use 2 or more types together.

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

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

The specific structure of the acid group-containing (meth)acrylamide resin of the present invention is not particularly limited, and the phenolic hydroxyl group-containing resin (A), the cyclic carbonate compound (B1) or the cyclic ether compound (B2), and N-alkoxyalkyl ( A meth)acrylamide compound (C) and an acid anhydride (D) are used as essential reaction raw materials, and what is necessary is just to have an acidic radical and a (meth)acryloyl group in resin. As said acidic radical-containing (meth)acrylamide resin obtained, Examples include those having a resin structure in which the structural moiety (I) represented by the following structural formula (1) and the structural moiety (II) represented by the following structural formula (2) are repeating structural units.

[In the formula, R ³ is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ⁴ is each independently any one of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and n is each independently 1 or 2. R ⁵ is each independently a methylene group or a structural moiety represented by any one of the following structural formulas (x'-1) to (x'-5). R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Moreover, R<^6> and R< ⁷ > may connect and may form a saturated or unsaturated ring. R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁹ is a hydrogen atom or a methyl group. x is the structural moiety represented by R ⁴ , or structural moiety (I) represented by Structural Formula (1) or structural moiety (II) represented by Structural Formula (2), via R ⁵ to which the * symbol is attached. It is a junction that connects

[In the formula, h is 0 or 1. R ¹⁰ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group, and i is 0 or an integer of 1-4. R ¹¹ is a hydrogen atom or a methyl group. W is the following structural formula (w-1) or (w-2). Y is any one of a C1-C4 alkylene group, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4]

[In the formula, R ¹² is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ¹³ and R ¹⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Moreover, ^R13 and ^R14 may connect and may form a saturated or unsaturated ring. R ¹⁵ is a hydrocarbon group having 1 to 12 carbon atoms. R ¹⁶ is a hydrogen atom or a methyl group]

The acid value of the acid group-containing (meth)acrylamide resin is 30 to 150 mgKOH/g because an acid group-containing (meth)acrylamide resin capable of forming a cured product having high photosensitivity and excellent alkali developability and excellent insulation reliability is obtained. It is preferable, and the range of 40-100 mgKOH/g is more preferable. In addition, in this invention, the acid value of the said acidic radical containing (meth)acrylamide resin is a value measured based on the neutralization titration method of JISK0070 (1992).

In addition, the polymerizable unsaturated bond group equivalent in the acid group-containing (meth)acrylamide resin has high photosensitivity and excellent alkali developability, and an acid group-containing (meth)acrylamide resin capable of forming a cured product having excellent insulation reliability is obtained, 250-1600 g/eq is preferable and the range of 260-1000 g/eq is more preferable.

In addition, the chlorine ion content in the acid group-containing (meth)acrylamide resin is preferably less than 100 ppm, since an acid group-containing (meth)acrylamide resin capable of forming a cured product having excellent insulation reliability is obtained, and the resin contains chlorine ions. It is more preferable not to do it. Moreover, when chlorine ion content is 100 ppm or more, when the said acidic radical containing (meth)acrylamide resin is used as a resin material for soldering resists, with long-term use, chlorine ions are advantageous, and electromigration by ionizing a circuit There is a possibility of causing insulation breakdown by

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

The photoinitiator is, for example, 1-hydroxycyclohexylphenylketone, 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

As a commercial item of the said photoinitiator, "Irgacure 184", "Irgacure 149", "Irgacure 261", "Irgacure 369", "Irgacure 500", "Irgacure", for example, 651", "Irgacure 754", "Irgacure 784", "Irgacure 819", "Irgacure 907", "Irgacure 1116", "Irgacure 1664", "Irgacure 1700" ', "Irgacure 1800", "Irgacure 1850", "Irgacure 2959", "Irgacure 4043", "Darocure 1173" (manufactured by BASF Japan), "Lucirin TPO" ( BASF Corporation), “Kaya Cure DETX”, “Kaya Cure MBP”, “Kaya Cure DMBI”, “Kaya Cure EPA”, “Kaya Cure OA” (manufactured by Nihon Kayaku Co., Ltd.), “Vicure 10”, “Vicure 55” (Stopper Chemicals), “Trigonal P1” (Arc Jojo), “Sandorei 1000” (Sandoz), “Dip” (Upzon), “Quanta Cure PDO”, “Quanta” Cure ITX", "Quanta Cure EPD" (manufactured by Ward Plekin Soap), and the like.

It is preferable to use the addition amount of the said photoinitiator in the range of 1-20 mass parts with respect to 100 mass parts of said curable resin compositions, for example.

The curable resin composition of this invention may contain other resin components other than the said acidic radical containing (meth)acrylamide resin. As said other resin component, for example, (meth)acrylic acid, dicarboxylic acid anhydride, unsaturated monocarboxylic acid anhydride etc. are made to react with epoxy resins, such as a bisphenol-type epoxy resin and a novolak-type epoxy resin, as needed. Resin obtained by making Resin which has a carboxy group and a (meth)acryloyl group, various (meth)acrylate monomers, etc. are mentioned in it.

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

The curable resin composition of this invention may contain the organic solvent for the objective, such as coating viscosity adjustment, and the kind and addition amount are suitably selected and adjusted according to desired performance.

As said organic solvent, For example, Ketone solvents, such as methyl ethyl ketone, acetone, isobutyl ketone; Cyclic ether solvents, such as tetrahydrofuran and a dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Glycol ether solvents, such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate, etc. are mentioned. These organic solvents may be used independently and may use 2 or more types together.

In addition, the curable resin composition of the present invention may contain various additives such as inorganic fine particles, polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers as needed.

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

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

Moreover, since the hardened|cured material obtained by hardening the curable resin composition of this invention has high insulation reliability and is excellent in photosensitivity and alkali developability, for example, a soldering resist in a semiconductor device use, an interlayer insulating material, a package It can be suitably used as a package adhesive layer, such as a material, an underfill material, and a circuit element, and the adhesive layer of an integrated circuit element and a circuit board. Moreover, it can use suitably for the thin-film transistor protective film in the thin display use represented by LCD and OELD, a liquid-crystal color filter protective film, the pigment resist for color filters, the resist for black matrices, a spacer, etc.

The resin material for soldering resists of the present invention is, if necessary, in the curable resin composition containing the acid group-containing (meth)acrylamide resin and the photoinitiator, for example, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles, Various additives such as polymer particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers can be used.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth)acrylamide resin, and examples thereof include an epoxy resin. Examples of the epoxy resin include a bisphenol-type epoxy resin, a phenylene ether-type epoxy resin, a naphthylene ether-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, a phenol novolac-type epoxy resin, and cresolno. Volak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin , a dicyclopentadiene-phenol addition reaction type epoxy resin, and the like. These epoxy resins may be used independently and may use 2 or more types together. Moreover, among these, since it is excellent in the heat resistance in hardened|cured material, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a bisphenol novolak-type epoxy resin, a naphthol novolak-type epoxy resin, a naphthol-phenol coaxial novolak-type epoxy resin Novolac-type epoxy resins, such as an epoxy resin and a naphthol-cresol coaxial novolak-type epoxy resin, are preferable, and it is especially preferable that the softening point is the range of 50-120 degreeC.

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

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth)acrylamide resin and curing agent, and examples thereof include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; Cyclic ether solvents, such as tetrahydrofuran and a dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Glycol ether solvents, such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate, etc. are mentioned. These organic solvents may be used independently and may use 2 or more types together.

In the resist member of the present invention, for example, the resin material for soldering resist is applied on a substrate, the organic solvent is evaporated to dryness in a temperature range of about 60 to 100° C., and then activated through a photomask in which a desired pattern is formed. It can be obtained by exposing it to an energy ray, developing an unexposed part with aqueous alkali solution, and also making it heat-harden in the temperature range of about 140-180 degreeC.

(Example)

Hereinafter, an Example and a comparative example demonstrate this invention concretely.

(Synthesis Example 1: Synthesis of hydroxyl group-containing resin (1))

70.3 parts by mass of diethylene glycol monomethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and a cresol novolac type phenol resin (DIC Corporation "PHENOLITE") as a phenolic hydroxyl group-containing resin (A-1) KA-1165", hydroxyl equivalent; 119 g/eq, softening point; 125 degreeC) 120 mass parts was dissolved. Next, 88 mass parts of ethylene carbonate and 0.6 mass parts of triphenylphosphine were added, in nitrogen atmosphere, it reacted at 160 degreeC for 8 hours, and hydroxyl-containing resin (1) was obtained.

(Synthesis Example 2: Synthesis of hydroxyl group-containing resin (2))

63.9 parts by mass of diethylene glycol monomethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and a phenol novolac type phenol resin (DIC Corporation "PHENOLITE") as a phenolic hydroxyl group-containing resin (A-2) TD-2093", hydroxyl equivalent; 104 g/eq, softening point; 100 degreeC) 105 mass parts was dissolved. Next, 88 mass parts of ethylene carbonate and 0.5 mass parts of triphenylphosphine were added, in nitrogen atmosphere, it reacted at 160 degreeC for 8 hours, and hydroxyl-containing resin (2) was obtained.

(Synthesis Example 3: Synthesis of phenolic hydroxyl group-containing resin (A-3))

To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 parts by mass of o-dihydroxybenzene, 1.1 parts by mass of oxalic acid and 41.5 mass % aqueous formaldehyde solution were added, and the temperature was raised to 105° C. in a nitrogen atmosphere. Next, 50.4 mass parts of 41.5 mass % formaldehyde aqueous solution was dripped at 105 degreeC over 3 hours, and it hold|maintained for 1 hour. Next, after heating up to 130 degreeC and holding for 1 hour, it heated up to 180 degreeC, and held for 1 hour. After cooling to 150 degreeC, it pressure-reduced, the unreacted material was removed, and phenolic hydroxyl-containing resin (A-3) was obtained.

(Synthesis Example 4: Synthesis of hydroxyl group-containing resin (3))

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 54.2 parts by mass of diethylene glycol monomethyl ether acetate was put, and 120 parts by mass of the phenolic hydroxyl group-containing resin (A-3) obtained in Synthesis Example 3 was dissolved. Next, 184.8 mass parts of ethylene carbonate and 0.6 mass parts of triphenylphosphine were added, and reaction was performed at 170 degreeC in nitrogen atmosphere for 6 hours. Next, 88 mass parts of ethylene carbonate and 0.6 mass parts of triphenylphosphine were added, in nitrogen atmosphere, it reacted at 160 degreeC for 8 hours, and hydroxyl-containing resin (3) was obtained.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 31 parts by mass of diethylene glycol monomethyl ether acetate was put, 234 parts by mass of the hydroxyl group-containing resin (1) obtained in Synthesis Example 1 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.5 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of N-methoxymethylacrylamide and 1.1 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 10 hours. . Then, 47 mass parts of diethylene glycol monomethyl ether acetate and 59 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (1) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (1) was 80 mgKOH/g.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 36 parts by mass of diethylene glycol monomethyl ether acetate was put, 234 parts by mass of the hydroxyl group-containing resin (1) obtained in Synthesis Example 1 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.6 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 85 parts by mass of N-methoxymethylacrylamide and 1.2 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 10 hours. . Then, 38 mass parts of diethylene glycol monomethyl ether acetate and 43 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (2) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (2) was 60 mgKOH/g.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 33 parts by mass of diethylene glycol monomethyl ether acetate was put, and 234 parts by mass of the hydroxyl group-containing resin (1) obtained in Synthesis Example 1 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.5 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 76 parts by mass of N-methoxymethylacrylamide and 1.1 parts by mass of oxalic acid were added, and the reaction was performed for 10 hours at 100° C. under reduced pressure of 150 Torr while blowing air. . Then, 34 mass parts of diethylene glycol monomethyl ether acetate and 36 mass parts of succinic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (3) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (3) was 80 mgKOH/g.

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

37 parts by mass of diethylene glycol monomethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 234 parts by mass of the hydroxyl group-containing resin (1) obtained in Synthesis Example 1 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.6 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 86 parts by mass of N-methoxymethylacrylamide and 1.2 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 10 hours. . Then, 29 mass parts of diethylene glycol monomethyl ether acetate and 27 mass parts of succinic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (4) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (4) was 60 mgKOH/g.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 33 parts by mass of diethylene glycol monomethyl ether acetate was put, 213 parts by mass of the hydroxyl group-containing resin (2) obtained in Synthesis Example 2 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.6 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 77 parts by mass of N-methoxymethylacrylamide and 1.2 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 10 hours. . Then, 43 mass parts of diethylene glycol monomethyl ether acetate and 56 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (5) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (5) was 80 mgKOH/g.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 38 parts by mass of diethylene glycol monomethyl ether acetate was put, and 213 parts by mass of the hydroxyl group-containing resin (2) obtained in Synthesis Example 2 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.6 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 89 parts by mass of N-methoxymethylacrylamide and 1.2 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 10 hours. . Then, 35 mass parts of diethylene glycol monomethyl ether acetate and 41 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 5 hours, and acidic radical containing (meth)acrylamide resin (6) was obtained. The solid content acid value of this acidic radical containing (meth)acrylamide resin (6) was 60 mgKOH/g.

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

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 83 parts by mass of diethylene glycol monomethyl ether acetate was put, 200 parts by mass of the hydroxyl group-containing resin (3) obtained in Synthesis Example 4 was dissolved, and dibutylhydroxytoluene as an antioxidant After adding 0.6 parts by mass and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 103 parts by mass of N-methoxymethylacrylamide and 1.1 parts by mass of oxalic acid were added, and the reaction was performed at 100° C. and under reduced pressure of 150 Torr while blowing air for 30 hours. . Thereafter, 8 parts by mass of diethylene glycol monomethyl ether acetate, 42 parts by mass of tetrahydrophthalic anhydride, and 0.8 parts by mass of triphenylphosphine were added, reacted at 110° C. for 6 hours, and acid group-containing (meth)acrylamide resin (7) was obtained. got it The solid content acid value of this acidic radical containing (meth)acrylamide resin (7) was 60 mgKOH/g.

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

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was put, and an orthocresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy group equivalent; 214 g/ eq) 428 parts by mass was dissolved, 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of metoquinone as a thermal polymerization inhibitor were added, then 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and air was blown. The esterification reaction was performed at 120 degreeC for 10 hours while putting. Then, 311 mass parts of diethylene glycol monomethyl ether acetate and 160 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and acidic radical containing epoxy acrylate resin was obtained. The solid content acid value of this acid group containing epoxy acrylate resin was 85 mgKOH/g.

(Example 8: Preparation of curable resin composition (1))

100 parts by mass of the acid group-containing (meth)acrylamide resin (1) obtained in Example 1, 24 parts by mass of an orthocresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, dipentaerythritol 10 parts by mass of hexaacrylate, 5 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (“Irgacure 907” manufactured by BASF Japan Co., Ltd.) as a photoinitiator Part, 0.5 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator, 13 parts by mass of diethylene glycol monomethyl ether acetate as an organic solvent, and 0.65 parts by mass of phthalocyanine green as a pigment were blended and kneaded by a roll mill. ) to obtain a curable resin composition (1).

(Examples 9 to 14: Preparation of curable resin compositions (2) to (7))

Example except that the acid group-containing (meth)acrylamide resins (2) to (7) obtained in Examples 2 to 7 were respectively used instead of the acid group-containing (meth)acrylamide resin (1) used in Example 8. It carried out similarly to 8, and obtained curable resin composition (2)-(7).

(Comparative Example 2: Preparation of curable resin composition (C1))

Curable resin composition (C1) was obtained in the same manner as in Example 8 except that the acid group-containing epoxy acrylate resin obtained in Comparative Example 1 was used instead of the acid group-containing (meth)acrylamide resin (1) used in Example 8. .

The following evaluation was performed using the curable resin composition obtained by the said Example and the comparative example.

[Method for evaluating photosensitivity]

The curable resin composition obtained by each Example and the comparative example was apply|coated so that it might become a film thickness of 50 micrometers on a glass substrate using an applicator, and it was made to dry at 80 degreeC for 30 minutes. Next, "Step Tablet No. 2" made by Kodak Corporation was placed on the dried coating film, and a 500 mJ/cm 2 ultraviolet ray was irradiated using a metal halide lamp. This was developed with 1% sodium carbonate aqueous solution at 30 degreeC for 180 second, and the number of residual plates of a step tablet was evaluated based on the step tablet method. Moreover, it shows that a photosensitivity is so high that there are many remaining stages.

[Evaluation method of alkali developability]

After applying the curable resin composition obtained in each Example and Comparative Example to a film thickness of 50 µm on a glass substrate using an applicator, at 80° C. for 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, respectively, It was made to dry for 80 minutes, 90 minutes, and 100 minutes, and the sample with different drying times was created. These were developed with 1% sodium carbonate aqueous solution at 30 degreeC for 180 second, and the drying time at 80 degreeC of the sample which did not leave a residue on the board|substrate was evaluated as a drying control range. In addition, it shows that the alkali developability is excellent, so that the drying management range is long.

[Method for evaluating insulation reliability]

Curable resin composition obtained by each Example and the comparative example was produced on the comb-tooth-shaped electrode substrate (line and space is 100 micrometers / 100 micrometers) on condition of the following, and hardened|cured material. Curable resin composition was apply|coated, and it dried at 80 degreeC for 30 minutes. Using a metal halide lamp, 1000 mJ/cm<2> of ultraviolet-ray was irradiated, it hardened|cured after 1 hour at 160 degreeC, and the cured film was produced. The said cured film was put in the thermo-hygrostat set at the temperature of 120 degreeC, and the humidity of 85%, the bias voltage of DC 100V was applied, and the following evaluation criteria evaluated the presence or absence of migration after 240 hours visually.

○: No change at all

× : Migration occurred

[Method for measuring chlorine content]

0.3 g of the curable resin composition obtained by each Example and the comparative example was precisely weighed in a 200 ml Erlenmeyer flask with a revolution, 20 ml of 1-butanol was added, and it reflux-dissolved in a 120 degreeC oil bath. Furthermore, 1 g of metallic sodium was added, and it refluxed in an oil bath for 1 hour. After cooling, 5 ml of pure water and 5 ml of nitric acid were added, and the solution was determined by titration of NaCl produced with a potentiometric titrator (“AT-310J” manufactured by Kyoto Denko Kogyo Co., Ltd.) with an aqueous solution of 0.01 mol/liter of silver nitrate.

Table 1 shows the evaluation results of the curable resin compositions (1) to (7) produced in Examples 8 to 14 and the curable resin composition (C1) produced in Comparative Example 2.

[Table 1]

"ND" in Table 1 shows non-detection.

Examples 8 to 14 shown in Table 1 are examples of curable resin compositions using the acid group-containing (meth)acrylamide resin of the present invention. It was confirmed that it has insulation reliability and is extremely excellent in photosensitivity and alkali developability.

On the other hand, Comparative Example 2 is an example of a curable resin composition using an acid group-containing epoxy acrylate, but the cured product obtained using this curable resin composition has excellent photosensitivity, but is remarkably insufficient in alkali developability and insulation reliability. could check

Claims (9)

A reaction product of a phenolic hydroxyl group-containing resin (A) and a cyclic carbonate compound (B1) or a cyclic ether compound (B2) is reacted with an N-alkoxyalkyl (meth)acrylamide compound (C) and an acid anhydride (D) It is an acid group-containing (meth)acrylamide resin obtained by making
The acidic radical containing (meth)acrylamide resin whose polymerizable unsaturated bond group equivalent in the said acidic radical containing (meth)acrylamide resin is the range of 250-1000 g/eq. The method of claim 1,
The acid value of the said acid group containing (meth)acrylamide resin is the range of 30-150 mgKOH/g acidic radical containing (meth)acrylamide resin. 3. The method of claim 1 or 2,
The acid-group containing (meth)acrylamide resin whose equivalent ratio [(C)/(D)] of the said N-alkoxyalkyl (meth)acrylamide compound (C) and the acid anhydride (D) is the range of 0.2-7. 3. The method of claim 1 or 2,
The acid group-containing (meth)acrylamide resin has a resin structure in which the structural moiety (I) represented by the following structural formula (1) and the structural moiety (II) represented by the following structural formula (2) are repeating structural units Containing (meth)acrylamide resin.

[In the formula, R ³ is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ⁴ is each independently any one of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and n is each independently 1 or 2. R ⁵ is each independently a methylene group or a structural moiety represented by any one of the following structural formulas (x'-1) to (x'-5). R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Moreover, ^R6 and ^R7 may connect and may form a saturated or unsaturated ring. R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁹ is a hydrogen atom or a methyl group. x is the structural moiety represented by R ⁴ , or structural moiety (I) represented by Structural Formula (1) or structural moiety (II) represented by Structural Formula (2), via R ⁵ to which the * symbol is attached. It is a junction that connects

[In the formula, h is 0 or 1. R ¹⁰ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group, and i is 0 or an integer of 1-4. R ¹¹ is a hydrogen atom or a methyl group. W is the following structural formula (w-1) or (w-2). Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4]

[In the formula, R ¹² is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ¹³ and R ¹⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Moreover, ^R13 and ^R14 may connect and may form a saturated or unsaturated ring. R ¹⁵ is a hydrocarbon group having 1 to 12 carbon atoms. R ¹⁶ is a hydrogen atom or a methyl group] Curable resin composition containing the acidic radical containing (meth)acrylamide resin of Claim 1 or 2, and a photoinitiator, The curable resin composition characterized by the above-mentioned. A cured product, which is a curing reaction product of the curable resin composition according to claim 5. An insulating material comprising the curable resin composition according to claim 5. It consists of curable resin composition of Claim 5, The resin material for soldering resists characterized by the above-mentioned. The resist member which consists of the resin material for soldering resists of Claim 8, The resist member characterized by the above-mentioned.