WO2019244868A1

WO2019244868A1 - Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product and resin material for solder resists

Info

Publication number: WO2019244868A1
Application number: PCT/JP2019/024034
Authority: WO
Inventors: 駿介山田; 亀山　裕史; 裕美子中村
Original assignee: Dic株式会社
Priority date: 2018-06-20
Filing date: 2019-06-18
Publication date: 2019-12-26
Also published as: JP6753552B2; TWI811384B; TW202006060A; JPWO2019244868A1

Abstract

The present invention provides: an acid group-containing (meth)acrylate resin composition which contains an acid group-containing (meth)acrylate resin (A) and an amine-modified epoxy resin (B), and which is characterized in that the content of the amine-modified epoxy resin (B) is from 0.5 part by mass to 40 parts by mass (inclusive) in terms of solid content relative to 100 parts by mass of the solid content of the acid group-containing (meth)acrylate resin (A); a curable resin composition which contains this acid group-containing (meth)acrylate resin composition; a cured product; an insulating material which is composed of the above-described photosensitive resin composition; a resin material for solder resists; and a resist member. This acid group-containing (meth)acrylate resin composition has excellent adhesion to a base material, high optical sensitivity and excellent alkali developability at the same time, and is able to form a cured product that exhibits excellent elongation.

Description

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

The present invention relates to an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability, and excellent in substrate adhesion and elongation in a cured product, and a curable resin composition containing the same. The present invention relates to a cured product, an insulating material comprising the curable resin composition, a resin material for a solder resist, and a resist member.

Recently, as a resin material for a solder resist for a printed wiring board, a curable resin composition curable by active energy rays such as ultraviolet rays has been widely used. The required properties for the solder resist resin material include: curing with a small exposure dose, excellent alkali developability, excellent substrate adhesion to copper foil and the like, and heat resistance and strength, Various things, such as being excellent in characteristics, are mentioned. Among these required properties, substrate adhesion is a fundamental and important performance, but the mechanism of performance development has not been sufficiently elucidated, and it has been one of the properties that are difficult to improve.

As a method for improving the substrate adhesion, a technique of adding phosphoric acid to an acid pendant type epoxy acrylate resin composition is known (for example, see Patent Document 1). It was not satisfying and not enough for today's market demands.

Therefore, there has been a demand for a material which is more excellent in the adhesion of the cured product to the substrate.

JP 2006-307020 A

The problem to be solved by the present invention is to provide an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability, and excellent in substrate adhesion and elongation in a cured product. The present invention provides a curable resin composition, a cured product, an insulating material composed of the photosensitive resin composition, a resin material for a solder resist, and a resist member.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an acid group-containing (meth) acrylate resin composition containing an acid group-containing (meth) acrylate resin and a specific amount of an amine-modified epoxy resin. It has been found that the above problem can be solved by using the present invention, and the present invention has been completed.

That is, the present invention provides an acid group-containing (meth) acrylate resin composition containing an acid group-containing (meth) acrylate resin (A) and an amine-modified epoxy resin (B), wherein the amine-modified epoxy resin ( The content of B) is 0.5 part by mass or more and 40 parts by mass or less in terms of solids based on 100 parts by mass of the solids of the acid group-containing (meth) acrylate resin (A). The present invention relates to an acid group-containing (meth) acrylate resin composition, a curable resin composition containing the same, a cured product, an insulating material composed of the curable resin composition, a resin material for a solder resist, and a resist member.

The acid group-containing (meth) acrylate resin composition of the present invention has high photosensitivity and excellent alkali developability, and has excellent substrate adhesion and elongation in a cured product. It can be suitably used for a material and a resist member made of the solder resist resin.

酸 The acid group-containing (meth) acrylate resin composition of the present invention is characterized by containing an acid group-containing (meth) acrylate resin (A) and an amine-modified epoxy resin (B).

In the present invention, “(meth) acrylate” means acrylate and / or methacrylate. Further, “(meth) acryloyl” means acryloyl and / or methacryloyl. Further, “(meth) acryl” means acryl and / or methacryl.

The acid group-containing (meth) acrylate resin (A) may have an acid group and a (meth) acryloyl group, and other specific structures and molecular weights are not particularly limited, and a wide variety of resins may be used. Can be.

酸 Examples of the acid group contained in the acid group-containing (meth) acrylate resin (A) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred because of exhibiting excellent alkali developability.

Examples of the acid group-containing (meth) acrylate resin (A) include [1] an epoxy resin (A-1) having an acid group and a (meth) acryloyl group, and [2] an acid group and a (meth) acryloyl group. An acrylamide resin (A-2) having [3] an amide imide resin (A-3) having an acid group and a (meth) acryloyl group, [4] an acryl resin having an acid group and a (meth) acryloyl group (A-4), [5] Urethane resin (A-5) having an acid group and a (meth) acryloyl group.

(1) The epoxy resin (A-1) having an acid group and a (meth) acryloyl group will be described.

Examples of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group include an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic anhydride ( a1-3) as an essential reaction raw material.

The specific structure of the epoxy resin (a1-1) is not particularly limited as long as the epoxy resin has a plurality of epoxy groups in the resin.

Examples of the epoxy resin (a1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, triphenyl Methane epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, phenol Aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, biphenyl aralkyl epoxy resin Carboxymethyl resins, fluorene type epoxy resin, a xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and oxazolidone type epoxy resins and the like.

The unsaturated monocarboxylic acid (a1-2) refers to a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, esters, acid halides, acid anhydrides and the like of the unsaturated monocarboxylic acids (a1-2) can also be used. These unsaturated monocarboxylic acids (a1-2) can be used alone or in combination of two or more.

As the esterified product of the unsaturated monocarboxylic acid (a1-2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( Alkyl (meth) acrylates such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Compounds: Hydroxy group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, (meth) acryl Nitrogen-containing (meth) acrylates such as diethylaminoethyl acrylate Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and other (meth) acrylates And the like.

酸 Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid chloride.

酸 Examples of the acid anhydride of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic anhydride.

As the polycarboxylic anhydride (a1-3), any acid anhydride of a compound having two or more carboxyl groups in one molecule can be used. Examples of the polycarboxylic anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, Glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, 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-tetrahydro Naphthalene-1,2-dicarboxylic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene Carboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid and acid anhydride of a dicarboxylic acid compound such as benzophenone tetracarboxylic acid.

The method for producing the epoxy resin (A-1) having an acid group and a (meth) acryloyl group comprises the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride. There is no particular limitation as long as the product (a1-3) is used as an essential reaction raw material, and it may be produced by any method. For example, it may be manufactured by a method of reacting all of the reaction materials at once, or by a method of sequentially reacting the reaction materials. Above all, since the reaction can be easily controlled, the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) are first reacted, and then the polycarboxylic anhydride (a1-3) Is preferred. In the reaction, for example, an epoxy resin (a1-1) is reacted with an unsaturated monocarboxylic acid (a1-2) in the presence of an esterification reaction catalyst at a temperature in the range of 100 to 150 ° C. The reaction can be carried out by, for example, adding a polycarboxylic anhydride (a1-3) to the mixture and reacting the mixture in a temperature range of 90 to 120 ° C.

The reaction ratio of the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) is such that the unsaturated monocarboxylic acid (a1-2) is added to 1 mole of the epoxy group in the epoxy resin (a1-1). Is preferably used in the range of 0.9 to 1.1 mol. The reaction ratio of the polycarboxylic acid anhydride (a1-3) is preferably in the range of 0.2 to 1.0 mol per 1 mol of the epoxy group in the epoxy resin (a1-1).

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

添加 The amount of the reaction catalyst to be added is preferably in the range of 0.001 to 5 parts by mass based on 100 parts by mass of the reaction raw materials in total.

反応 The reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride (a1-3) can be performed in an organic solvent, 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 and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers , Glycol ether solvents such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, Chiruserosorubu, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, since the reaction efficiency becomes good.

The acid value of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group has a high photosensitivity and an excellent alkali developability, and forms a cured product having excellent substrate adhesion and elongation. From the viewpoint of obtaining a possible acid group-containing (meth) acrylate resin composition, the range is preferably 30 to 150 mgKOH / g, and more preferably 40 to 120 mgKOH / g. In the present invention, the acid value of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K 0070 (1992).

Next, [2] the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group will be described.

Examples of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group include a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2- 2b), an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic anhydride (a2-4) as essential reaction raw materials. And the like obtained.

The phenolic hydroxyl group-containing resin (a2-1) refers to a resin having two or more phenolic hydroxyl groups in a molecule, for example, an aromatic polyhydroxy compound or a compound having one phenolic hydroxyl group in a molecule. A novolak-type phenol resin using one or more kinds of reaction raw materials, a compound having one phenolic hydroxyl group and a compound represented by any of the following structural formulas (x-1) to (x-5) ( x) as an essential reaction raw material.

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

Examples of the aromatic polyhydroxy compound, for example, dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei and the like can be mentioned. Examples of the substituent on the aromatic nucleus include, for example, methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Aliphatic hydrocarbon group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nucleus thereof The aliphatic hydrocarbon group, the alkoxy group, an aryl group substituted with the halogen atom or the like; a phenyloxy group, a naphthyloxy group, and the aromatic hydrocarbon group, the alkoxy group, An aryloxy group substituted by a halogen atom or the like; a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and These aromatic nuclei wherein the aliphatic hydrocarbon group on the alkoxy group, the halogen atom and the like and aralkyl groups substituted. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, a compound containing no halogen is preferable since an acid group-containing (meth) acrylate resin having high insulation reliability can be obtained.

Examples of the novolak phenolic resin include those obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound under an acidic catalyst.

As the compound having one phenolic hydroxyl group in the molecule, any compound may be used as long as it is an aromatic compound having one hydroxyl group on an aromatic nucleus. A phenol compound having one or more substituents on an aromatic nucleus of naphthol or naphthol; anthracen having one or more substituents on an aromatic nucleus of anthracenol or anthracenol Senol compounds and the like can be mentioned. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group and the like, and specific examples thereof are as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, and hexyl aldehyde; salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and 2-hydroxy-4. Hydroxybenzaldehydes such as -methylbenzaldehyde, 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, -Ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde Having both a hydroxy group and an alkoxy group: alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like Hydroxynaphthaldehyde; halogenated benzaldehyde such as bromobenzaldehyde, and the like.

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, and boron acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And the like. These acidic catalysts can be used alone or in combination of two or more.

Examples of a reaction product using the compound having one phenolic hydroxyl group and the compound (x) as essential reaction raw materials include, for example, a compound having one phenolic hydroxyl group in the molecule and the compound (x). Can be obtained by heating and stirring under a temperature condition of about 80 to 200 ° C. under an acidic catalyst. The reaction ratio between the compound having one phenolic hydroxyl group in the molecule and the compound (x) is such that the compound having one phenolic hydroxyl group in the molecule is 0 per mole of the compound (x). It is preferable that the ratio be 0.5 to 5 mol.

Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds can be used alone or in combination of two or more. In addition, since an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent substrate adhesion and elongation can be obtained, ethylene carbonate, Or propylene carbonate is preferred.

Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more. Further, among these, an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation can be obtained. , Ethylene oxide or propylene oxide is preferred.

として As the unsaturated monocarboxylic acid (a2-3a), the same as the above-mentioned unsaturated monocarboxylic acid (a1-2) can be used.

Examples of the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxy Ethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like can be mentioned. Among them, an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation is obtained. -Methoxymethyl (meth) acrylamide is preferred. These N-alkoxyalkyl (meth) acrylamide compounds can be used alone or in combination of two or more.

ポリ As the polycarboxylic anhydride (a2-4), the same as the above-mentioned polycarboxylic anhydride (a1-3) can be used.

When the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is used, the equivalent ratio [(a2-3b) / (a2-4)) with the polycarboxylic anhydride (a2-4) is: Since an acid group-containing (meth) acrylate resin composition having excellent substrate adhesion, high photosensitivity, and excellent alkali developability and having excellent elongation in a cured product can be obtained, 0.2 to 0.2% 7 is preferable, and the range of 0.25 to 6.7 is more preferable.

The method for producing the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method. For example, it may be manufactured by a method of reacting all of the reaction materials at once, or by a method of sequentially reacting the reaction materials. Among them, since the reaction can be easily controlled, the phenolic hydroxyl group-containing resin (a2-1) is first reacted with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), After reacting the obtained reaction product 1 with an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), the obtained reaction product 2 A method of reacting a polycarboxylic anhydride (a2-4) is preferred. The reaction is carried out, for example, by reacting the phenolic hydroxyl group-containing resin (a2-1) with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst in the range of 50 to 200. After reacting in a temperature range of ° C., the resulting reaction product is reacted with an unsaturated polycarboxylic acid (b2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b) in the presence of an acidic catalyst. ) In a temperature range of 80 to 140 ° C., and then a polycarboxylic anhydride (a2-4) is added, and the reaction is carried out in a temperature range of 80 to 140 ° C.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonene- 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- ( 2-aminoethyl) aminopropyltri Amine compounds such as toxicoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; trimethylphosphine and tributylphosphine And phosphines such as triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium Phosphonium salts such as chloride; dibutyl Dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dinedecanoate, dibutyltin diacetate, tin octylate, 1,1,3,3-tetrabutyl-1,3-dodecanoyldista Organotin compounds such as noxane; organometallic compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. These basic catalysts can be used alone or in combination of two or more.

The phenolic hydroxyl group-containing resin (a2-1), the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxy The reaction of the alkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic anhydride (a2-4) can be performed in an organic solvent, if necessary.

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

使用 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass based on 100 parts by mass of the total amount of the reaction raw materials, since the reaction efficiency is improved.

The specific structure of the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group is not particularly limited, and a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic carbonate compound (a2-2a) may be used. An ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic anhydride (a2-4) As an essential reaction raw material, any resin having an acid group and a (meth) acryloyl group may be used as the essential acrylamide resin (B-2) having the acid group and the (meth) acryloyl group. A structural unit (I) represented by the following structural formula (a-1) and a structural unit (II) represented by the following structural formula (a-2) Having a resin structure as a repeating structural unit), comprising a structural part (III) represented by the following structural formula (a-3) and a structural part (IV) represented by the following structural formula (a-4) Those having a resin structure as a unit (for example, a repeating structural unit) are exemplified.

[In the formulas (a-1) and (a-2), R ² is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ³ is 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 ⁴ is each independently a methylene group or a structural site represented by any of the following structural formulas (x′-1) to (x′-5). R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Also, R ⁵ and R ⁶ may be linked to form a saturated or unsaturated ring. R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁸ is a hydrogen atom or a methyl group. x represents a structural site represented by R ³ or a structural site (I) represented by the structural formula (a-1) or a structural site (II) represented by the structural formula (a-2) , * Is the point of attachment linked through R ⁴ marked. ]

[In the formulas (a-3) and (a-4), R ² is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ³ is 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 ⁴ is each independently a methylene group or a structural site represented by any of the following structural formulas (x′-1) to (x′-5). R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Also, R ⁵ and R ⁶ may be linked to form a saturated or unsaturated ring. R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁸ is a hydrogen atom or a methyl group. x represents a structural site represented by R ³ or a structural site (III) represented by structural formula (a-3) or a structural site (IV) represented by structural formula (a-4) , * Is the point of attachment linked through R ⁴ marked. ]

[In the formula (x′-1), h is 0 or 1. In the formulas (x′-2) to (x′-5), R ⁹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and i is 0 or 1 It is an integer of ４4. In the formulas (x′-2), (x′-3) and (x′-5), R ¹⁰ is a hydrogen atom or a methyl group. In the formula (x′-4), W is the following structural formula (w-1) or (w-2). In the formula (x′-5), Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group, and j is an integer of 1 to 4. ]

[In the formulas (w-1) and (w-2), R ¹¹ is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. In the formula (w-1), R ¹² and R ¹³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² and R ¹³ are linked to each other to form a saturated or unsaturated A ring may be formed. In the formula (w-2), R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁵ is a hydrogen atom or a methyl group. ]

The acid value of the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group has a high photosensitivity and excellent alkali developability, and forms a cured product having excellent substrate adhesion and elongation. From the viewpoint of obtaining a possible acid group-containing (meth) acrylate resin composition, the range is preferably 30 to 150 mgKOH / g, and more preferably 40 to 120 mgKOH / g. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured based on a neutralization titration method according to JIS K 0070 (1992).

Next, the [3] amide imide resin (A-3) having an acid group and a (meth) acryloyl group will be described.

Examples of the amide imide resin (A-3) having an acid group and a (meth) acryloyl group include an amide imide resin (a3-1) having an acid group or an acid anhydride group and a hydroxyl group-containing (meth) acrylate compound (a3). And -2) as an essential reaction raw material.

The amide imide resin (a3-1) may have only one of an acid group and an acid anhydride group, or may have both. From the viewpoint of the reactivity with the hydroxyl group-containing (meth) acrylate compound (a3-2) and the control of the reaction, the compound preferably has an acid anhydride group, and has both an acid group and an acid anhydride group. Is more preferable. The acid value of the amide imide resin (a3-1) is preferably in the range of 60 to 350 mgKOH / g as measured under neutral conditions, that is, without opening the acid anhydride group. On the other hand, it is preferable that the measured value under conditions in which the acid anhydride group is opened, such as in the presence of water, is in the range of 61 to 360 mgKOH / g.

具体 The specific structure and production method of the amide imide resin (a3-1) are not particularly limited, and general amide imide resins and the like can be widely used. For example, a compound obtained by using a polyisocyanate compound and a polycarboxylic acid or an acid anhydride thereof as reaction raw materials can be used.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, and the like. Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenyl methane diisocyanate, 1,5-naphthalenedi isocyanate, 4,4'-diisocyanato-3 Aromatic diisocyanates such as 3,3'-dimethylbiphenyl and o-tolidine diisocyanate Cyanate compound; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate modified product, a biuret modified product, and the like allophanate modified product. These polyisocyanate compounds can be used alone or in combination of two or more.

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

In addition, since an acid group-containing (meth) acrylate resin composition having high solvent solubility can be obtained as the polyisocyanate compound, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof may be used. Preferred are alicyclic diisocyanates or modified isocyanurates thereof, and aliphatic diisocyanates or modified isocyanurates thereof.

Further, in the total mass of the polyisocyanate compound, the ratio of the total mass of the alicyclic diisocyanate compound or the modified product thereof and the aliphatic diisocyanate compound or the modified product thereof is preferably 70% by mass or more, and 90% by mass or more. % Is preferable.

In the case where an alicyclic diisocyanate compound or a modified product thereof is used in combination with an aliphatic diisocyanate compound or a modified product thereof, the mass ratio of the two is preferably in the range of 30/70 to 70/30.

The specific structure of the polycarboxylic acid or its acid anhydride is not particularly limited as long as it is a compound having a plurality of carboxyl groups in its molecular structure or its acid anhydride, and various kinds of compounds can be used. In order for the amide imide resin (a3-1) to have both an amide group and an imide group, both the carboxyl group and the acid anhydride group need to be present in the system. Alternatively, a compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

Examples of the polycarboxylic acid or an acid anhydride thereof include, for example, an aliphatic polycarboxylic acid compound or an acid anhydride thereof, an alicyclic polycarboxylic acid compound or an acid anhydride thereof, an aromatic polycarboxylic acid compound or an acid anhydride thereof. And the like.

として As the aliphatic polycarboxylic acid compound or an acid anhydride thereof, the aliphatic hydrocarbon group may be any of a linear type and a branched type, and may have an unsaturated bond in the structure.

Examples of the aliphatic polycarboxylic acid compound or an acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Examples thereof include citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.

As the alicyclic polycarboxylic acid compound or an acid anhydride thereof, in the present invention, a compound in which a carboxyl group or an acid anhydride group is bonded to an alicyclic structure is an alicyclic polycarboxylic acid compound or an acid anhydride thereof. The presence or absence of an aromatic ring in other structural sites is not considered. Examples of the alicyclic polycarboxylic acid compound or an acid anhydride thereof include, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1]. Heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.

Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include, for example, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyl Examples include tetracarboxylic acid and benzophenonetetracarboxylic acid.

Among these, an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation is obtained. The alicyclic polycarboxylic acid compound or an acid anhydride thereof, or the aromatic polycarboxylic acid compound or an acid anhydride thereof is preferable. Further, from the viewpoint that the amide imide resin (a3-1) can be efficiently produced, it is preferable to use a tricarboxylic anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and it is preferable to use cyclohexanetricarboxylic anhydride or It is particularly preferable to use trimellitic anhydride. Furthermore, the ratio of the total amount of the alicyclic tricarboxylic anhydride and the aromatic tricarboxylic anhydride to the total mass of the polycarboxylic acid or the acid anhydride thereof is preferably 70% by mass or more, and more preferably 90% by mass or more. Is more preferable.

When the amide imide resin (a3-1) uses the polyisocyanate compound and the polycarboxylic acid or its acid anhydride as reaction raw materials, other reaction raw materials may be used depending on desired resin performance and the like. May be used in combination. In this case, since the effect of the present invention is sufficiently exhibited, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or the acid anhydride thereof to the total mass of the reaction raw materials of the amide imide resin (a3-1) Is preferably 90% by mass or more, and more preferably 95% by mass or more.

When the amide imide resin (a3-1) uses a polyisocyanate compound and a polycarboxylic acid or an acid anhydride as a reaction raw material, it is not particularly limited, and may be produced by any method. For example, it can be produced by a method similar to a general amide imide resin. Specifically, 0.5 to 5.0 moles of a polycarboxylic acid or an acid anhydride thereof is used under stirring at a temperature of about 120 to 180 ° C. with respect to 1 mole of an isocyanate group contained in the polyisocyanate compound. Reaction.

反応 The reaction between the polyisocyanate compound and the polycarboxylic acid or an acid anhydride thereof can be carried out in the presence of a basic catalyst, if necessary. Further, the reaction can be carried out in an organic solvent, if necessary.

As the basic catalyst, those similar to the above-described basic catalysts can be used, and the basic catalysts can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound (a3-2), other specific structures are not particularly limited as long as the compound has a hydroxyl group and a (meth) acryloyl group in a molecular structure, and various kinds of compounds are used. be able to. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate Hydroxy (meth) acrylate compounds such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, and the like in the molecular structures of the various hydroxy (meth) acrylate compounds. (Poly) oxyalkylene modified products having an alkylene chain introduced; lactone modified products obtained by introducing a (poly) lactone structure into the molecular structure of the above various hydroxy (meth) acrylate compounds. Among these, an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation is obtained, and thus has a molecular weight of Is preferably 1,000 or less. When the hydroxyl group-containing (meth) acrylate compound (a3-2) is a modified oxyalkylene or a modified lactone, the weight average molecular weight (Mw) is preferably 1,000 or less. These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.

The amide imide resin (A-3) having an acid group and a (meth) acryloyl group may be, if necessary, the amide imide resin (a3-1) and a hydroxyl group-containing (meth) acrylate compound (b3-2). Alternatively, a (meth) acryloyl group-containing epoxy compound (a3-3) may be used in combination as a reaction raw material. The amide imide resin (A-3) having an acid group and a (meth) acryloyl group may be, if necessary, an amide imide resin (a3-1) and a hydroxyl group-containing (meth) acrylate compound (a3-2). In addition, a (meth) acryloyl group-containing epoxy compound (a3-3) and a polycarboxylic anhydride (a3-4) can be used in combination as a reaction raw material.

The specific structure of the (meth) acryloyl group-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure. Can be used. For example, glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether; Mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether are exemplified. Among these, glycidyl is an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product having excellent substrate adhesion and elongation. Group-containing (meth) acrylate monomers are preferred. Further, the molecular weight is preferably 500 or less. Further, the ratio of the glycidyl group-containing (meth) acrylate monomer to the total mass of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 70% by mass or more, and more preferably 90% by mass or more. Is more preferred.

As the polycarboxylic anhydride (a3-4), those exemplified above as the polycarboxylic anhydride (b1-3) can be used, and the polycarboxylic acid (a3-4) is used alone. It is also possible to use two or more kinds in combination.

The amide imide resin (A-3) having an acid group and a (meth) acryloyl group may be selected from the group consisting of the amide imide resin (a3-1) having an acid group or an acid anhydride group and the hydroxyl group-containing resin according to desired resin performance and the like. In addition to the (meth) acrylate compound (a3-2), the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic anhydride (a3-4), other reaction raw materials can be used in combination. In this case, the ratio of the total mass of the components (a3-1) to (a3-4) to the total mass of the reaction raw materials of the acid group-containing (meth) acrylate resin (A-3) is 80% by mass or more. More preferably, it is 90% by mass or more.

The method for producing the amide imide resin (A-3) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method. For example, it may be manufactured by a method in which all of the reaction raw materials containing the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) are reacted at once, or the reaction raw materials are sequentially reacted. It may be manufactured by a method for causing the above.

The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is mainly caused by the reaction between the acid group and / or acid anhydride group in the amide imide resin (a3-1). It reacts with the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2). Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is particularly excellent in reactivity with an acid anhydride group, the amide imide resin (a3-1) has an acid anhydride group as described above. Is preferred. The content of the acid anhydride group in the amide imide resin (a3-1) is the difference between the two measured values of the acid value, that is, the acid value under the condition that the acid anhydride group is opened. And the acid value under the condition that the acid anhydride group is not ring-opened.

The reaction ratio between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is determined when the amide imide resin (a3-1) has an acid group and an acid anhydride group, and When the amide imide resin (a3-1) has an acid anhydride group, the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a3-2) is based on 1 mol of the acid anhydride group of the amide imide resin (a3-1). Is preferably used in the range of 0.9 to 1.1. When the amide imide resin (a3-1) has an acid group, the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a3-2) is based on 1 mol of the acid group of the amide imide resin (a3-1). It is preferable that the number of moles is in the range of 0.01 to 1.0.

The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) may use a basic catalyst or an acidic catalyst, if necessary. Among them, when the amide imide resin (a3-1) has an acid group and an acid anhydride group, and when the amide imide resin (a3-1) has an acid anhydride group, it is preferable to use a basic catalyst. When the amide imide resin (a3-1) has an acid group, it is preferable to use an acidic catalyst.

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

酸性 As the acidic catalyst, those exemplified above as the acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.

The amount of the basic catalyst or the acidic catalyst is preferably in the range of 0.001 to 5 parts by mass based on 100 parts by mass of the total mass of the reaction raw materials.

The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is carried out by heating and stirring at a temperature of about 80 to 140 ° C. in the presence of a suitable catalyst. It can be carried out.

The reaction may be carried out in an organic solvent if necessary.As the organic solvent, the same organic solvents as described above can be used, and the organic solvent may be used alone or in combination of two or more. They can be used together. When the reaction is performed continuously with the production of the amide imide resin (a3-1), the reaction may be continued in the organic solvent used in the production of the amide imide resin (a3-1).

The amide imide resin (A-3) having an acid group and a (meth) acryloyl group is a reaction raw material other than the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), When the (meth) acryloyl group-containing epoxy compound (a3-3) is used, the amide imide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2), and the (meth) acryloyl group-containing epoxy compound The reaction raw materials containing (a3-3) may be manufactured by a method of reacting all at once, or may be manufactured by a method of sequentially reacting the reaction raw materials. Above all, a product obtained by reacting the amide imide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2) (hereinafter referred to as “product Product (1) ") with the (meth) acryloyl group-containing epoxy compound (a3-3).

The reaction between the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) is mainly based on the acid group in the product (1) and the (meth) acryloyl group-containing epoxy compound ( a3-3). The reaction ratio is such that the number of moles of the epoxy group of the (meth) acryloyl group-containing epoxy compound (a3-3) per mole of the acid group of the product (1) is 0.05 to 1.1. It is preferable to use it in a certain range. The reaction can be carried out, for example, by heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of a suitable basic catalyst. When the reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is performed continuously, a basic catalyst may not be added, or may be added as appropriate. . Further, the reaction may be performed in an organic solvent, if necessary. The basic catalyst and the organic solvent can be the same as the basic catalyst and the organic solvent described above, and they can be used alone or in combination of two or more.

The amide imide resin (A-3) having an acid group and a (meth) acryloyl group is a reaction raw material other than the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), When the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic anhydride (a3-4) are used, the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) , The reaction raw material containing the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic anhydride (a3-4) may be produced by a method of reacting all at once. You may manufacture by the method of making it react sequentially. Above all, since the control of the reaction is easy, the product (1) obtained by reacting the amide imide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2) includes: The (meth) acryloyl group-containing epoxy compound (a3-3) is reacted, and the obtained product (hereinafter sometimes referred to as “product (2)”) is added to the polycarboxylic anhydride (a3). It is preferable to produce it by a method of reacting -4).

反応 The reaction between the product (2) and the polycarboxylic acid anhydride (a3-4) is mainly for reacting the hydroxyl group in the product (2) with the polybasic acid anhydride. At this time, in the product (2), the reaction ratio between the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) is 1 mole of the acid group in the product (1). The number of moles of the epoxy group in the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 0.1 to 1.2, more preferably 0.2 to 1.1. Is more preferred. Here, in the product (2), for example, a hydroxyl group or the like generated by ring opening of the epoxy group in the (meth) acryloyl group-containing epoxy compound (a3-3) is present. The reaction rate of the polycarboxylic anhydride (a3-4) is adjusted so that the acid value of the amideimide resin (A-3) having an acid group and a (meth) acryloyl group to be produced is about 50 to 120 mgKOH / g. Preferably. The reaction can be carried out, for example, by heating and stirring at a temperature of about 80 to 140 ° C. in the presence of a suitable basic catalyst. When the reaction between the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) is performed continuously, a basic catalyst may not be added, or may be added as appropriate. Further, the reaction may be performed in an organic solvent, if necessary. The basic catalyst and the organic solvent can be the same as the basic catalyst and the organic solvent described above, and they can be used alone or in combination of two or more.

The acid value of the amide imide resin (A-3) having an acid group and a (meth) acryloyl group has a high photosensitivity and excellent alkali developability, and forms a cured product excellent in substrate adhesion and elongation. From the viewpoint of obtaining a possible acid group-containing (meth) acrylate resin composition, the range is preferably 30 to 150 mgKOH / g, and more preferably 40 to 120 mgKOH / g. In the present invention, the acid value of the amide imide resin (A-3) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K 0070 (1992).

(4) Next, the acrylic resin (A-4) having an acid group and a (meth) acryloyl group will be described.

Examples of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group include 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. An acrylic resin intermediate obtained by polymerization as an essential component is further reacted with a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups to introduce a (meth) acryloyl group. And a reaction product obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be obtained by copolymerizing another polymerizable unsaturated group-containing compound as required in addition to the (meth) acrylate compound (α). Examples of the other compound having a polymerizable unsaturated group 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 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; That. These can 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 of the (meth) acrylate compound (α). From the viewpoint of reactivity, the following combination is used. Is preferred. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate compound (β). When a carboxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use a glycidyl 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) may be used alone or in combination of two or more.

Examples of the polybasic anhydride include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydroanhydride. Examples include phthalic acid, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like. These polybasic acid anhydrides can be used alone or in combination of two or more.

製造 The method for producing the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is not particularly limited, and it may be produced by any method. The production of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group may be performed in an organic solvent, if necessary, or a basic catalyst may be used, if necessary. .

The acid value of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group has a high photosensitivity and excellent alkali developability, and forms a cured product having excellent substrate adhesion and elongation. From the viewpoint of obtaining a possible acid group-containing (meth) acrylate resin composition, the range is preferably 30 to 150 mgKOH / g, and more preferably 40 to 120 mgKOH / g. In the present invention, the acid value of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K 0070 (1992).

Next, [5] the urethane resin (A-5) having an acid group and a (meth) acryloyl group will be described.

Examples of the urethane resin (A-5) having an acid group and a (meth) acryloyl group include a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride. , A product obtained by reacting a polyol compound other than the carboxyl group-containing polyol compound, a polyol other than a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a polybasic acid anhydride, and a carboxyl group-containing polyol compound And those obtained by reacting with epoxy compounds, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and hydroxyl group-containing (meth) acrylate compounds. No.

同様 As the polyisocyanate compound, those similar to the above-described polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, those similar to the above-mentioned hydroxyl group-containing (meth) acrylate compound (a3-2) can be used, and the hydroxyl group-containing (meth) acrylate compound can be used alone. Two or more can be used in combination.

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

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

Examples of polyol compounds other than the carboxyl group-containing polyol compound include, for example, aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenol and bisphenol; (Poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are included in the molecular structures of the various polyol compounds. Introduced (poly) oxyalkylene modified products; lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the above-mentioned various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more.

As the epoxy resin, those exemplified as the epoxy resin (a1-1) described above can be used, and the epoxy resin can be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Further, esters, acid halides, acid anhydrides and the like of the above-mentioned unsaturated monobasic acids can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more.

The method for producing the urethane resin (A-5) having an acid group and a (meth) acryloyl group is not particularly limited, and may be 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, or a basic catalyst may be used, if necessary.

The amine-modified epoxy resin (B) is obtained by reacting the epoxy resin (b1) with the amine compound (b2).

エポキシ As the epoxy resin (b1), the same one as exemplified above as the epoxy resin (a1-1) can be used. Above all, bisphenol-based resins having an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation can be obtained. Epoxy resins are preferred. The epoxy resin (b1) may be used alone or in combination of two or more.

Examples of the amine compound (b2) include monoalkanolamines such as ethylethanolamine, ethanolamine, 4-amino-1-butanol and propanolamine; dialkanolamines such as diethanolamine, dipropanolamine and dibutanolamine. No. These amine compounds (b2) can be used alone or in combination of two or more. Among them, monoalkanolamine and dialkanolamine are preferably used in combination because the reaction with the epoxy resin (b1) can be easily controlled.

When the monoalkanolamine and the dialkanolamine are used in combination, the ratio of the number of moles of the monoalkanolamine to the number of moles of the dialkanolamine is easy to control the reaction with the epoxy resin (b1). [(Mol number of monoalkanolamine) / (mol number of dialkanolamine)] is preferably in the range of 0.5 to 10.

The method for producing the amine-modified epoxy resin (B) is not particularly limited as long as the epoxy resin (b1) and the amine compound (b2) are used as essential reaction raw materials. May be. For example, the reaction raw material containing the epoxy resin (b1) and the amine compound (b2) may be manufactured by a method of reacting all at once, or may be manufactured by a method of sequentially reacting the reaction raw materials. Among them, a method in which the epoxy resin (b1) is produced and then the amine compound (b2) is reacted is preferable because the reaction can be easily controlled. The reaction can be performed, for example, by a method in which the epoxy resin (b1) and the amine compound (b2) are reacted in a temperature range of 50 to 150 ° C.

In the production of the amine-modified epoxy resin (B), the production may be carried out in an organic solvent, if necessary, or a basic catalyst may be used, if necessary.

Since the reaction between the epoxy resin (b1) and the amine compound (b2) is easy to control, the amine compound (b2) has the mole ratio of the epoxy group of the epoxy resin (b1) with respect to the number of moles. The ratio of the number of moles of active hydrogen [(number of moles of active hydrogen) / (number of moles of epoxy group)] is preferably in the range of 0.9 to 1.1, and more preferably in the range of 0.95 to 1.03. More preferably,

The weight-average molecular weight (Mw) of the amine-modified epoxy resin (B) is preferably 5,000 or more, because an acid group-containing (meth) acrylate resin composition having excellent substrate adhesion can be obtained. The range is more preferably from 000 to 50,000, and even more preferably from 15,000 to 30,000.

In the present invention, the weight average molecular weight (Mw) is a value measured by a gel permeation chromatography (GPC) method.

The amine-modified epoxy resin (B) has high photosensitivity and excellent alkali developability, and is an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent substrate adhesion and elongation. Because it is obtained, it may have an acid group and / or a substituent containing a polymerizable unsaturated bond.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred because of exhibiting excellent alkali developability.

The above-mentioned substituent having a polymerizable unsaturated bond means a substituent having at least one polymerizable unsaturated bond, and specific examples thereof include a vinyl group, an allyl group, and a (meth) acryloyl group. Among these, a (meth) acryloyl group is preferred because of exhibiting high photosensitivity.

The content of the amine-modified epoxy resin (B) is 0.5 to 40 parts by mass in terms of solids based on 100 parts by mass of the solids of the acid group-containing (meth) acrylate resin (A). 1 part by mass, since an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation is obtained. Or more, more preferably 1.5 parts by mass or more. Further, since an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation is obtained, 30 parts by mass is obtained. The following is preferred.

酸 The acid group-containing (meth) acrylate resin composition of the present invention may contain other resin components other than the acid group-containing (meth) acrylate resin (A) and the amine-modified epoxy resin (B). As the other resin component, for example, bisphenol type epoxy resin, epoxy resin such as novolak type epoxy resin, (meth) acrylic acid, if necessary, obtained by reacting an unsaturated monocarboxylic anhydride and the like, Examples of the resin include a resin having a (meth) acryloyl group in the resin and various (meth) acrylate monomers.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl. Aliphatic mono (meth) acrylate compounds such as (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate A heterocyclic mono (meth) acrylate compound such as glycidyl (meth) acrylate or tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylben (Meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl ( Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as meth) acrylate and phenylphenoxyethyl (meth) acrylate: (poly) oxyethylene chains in the molecular structure of the various mono (meth) acrylate monomers (Poly) oxyalkylene-modified mono (meth) acrylate compounds into which polyoxyalkylene chains such as (poly) oxypropylene chains and (poly) oxytetramethylene chains have been introduced; Lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the compound; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol Aliphatic di (meth) acrylate compounds such as di (meth) acrylate and neopentyl glycol di (meth) acrylate; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di ( Alicyclic di (meth) acrylate compounds such as meth) acrylate, dicyclopentanyl di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate; biphenol di (meth) acrylate, bisphenol Aromatic di (meth) acrylate compounds such as rudi (meth) acrylate; (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene in the molecular structure of the above various di (meth) acrylate compounds Polyoxyalkylene-modified di (meth) acrylate compound into which a (poly) oxyalkylene chain such as a chain has been introduced; lactone-modified di (meth) acrylate having a (poly) lactone structure introduced into the molecular structure of the above-mentioned various di (meth) acrylate compounds A) an acrylate compound; an aliphatic tri (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; and a (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound. , (Poly) oxypropylene chains, (poly) oxyte (Poly) oxyalkylene-modified tri (meth) acrylate compounds having a (poly) oxyalkylene chain such as a ramethylene chain; lactone modified by introducing a (poly) lactone structure into the molecular structure of the aliphatic tri (meth) acrylate compound Tri (meth) acrylate compounds; tetra- or higher-functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 4- or more-functional (poly) in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, and a (poly) oxytetramethylene chain is introduced into the molecular structure of the poly (meth) acrylate compound. Oxyalkylene-modified poly Meth) acrylate compound; and the aliphatic poly (meth) acrylate compound in the molecular structure of (poly) lactone 4 or more functional introducing the lactone structure-modified poly (meth) acrylate compounds.

酸 The acid group-containing (meth) acrylate resin composition of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl 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-morpho Nofeniru) -1-butanone, and the like.

Commercial products of the other photopolymerization initiators include, for example, “Omnirad-1173”, “Omnirad-184”, “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, “Omnirad-379” "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100", "Omnirad-2100", "Omnirad-2100" Omnirad-754, Omnirad-784, Omnirad-500, Omnirad-81 (manufactured by IGM), Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacure -EPA, "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Bicure-55" (manufactured by Stouffa Chemical), "Trigonal P1" (manufactured by Akzo), "Sandrey 1000 ("Sands"), "Deep" ("Apjohn"), "Quantum Cure-PDO", "Quantum Cure-ITX", "Quantum Cure-EPD" (Made by Word Brenkin Sop), "Runtecure-1104" (Manufactured by Runtec) and the like.

添加 The amount of the photopolymerization initiator to be added is preferably, for example, in the range of 1 to 20% by mass in the curable resin composition.

硬化 The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity and the like, and the type and amount of the organic solvent are appropriately selected and adjusted according to the desired performance.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and 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; alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers and dialkylene glycols Glycol ether solvents such as monoalkyl ether acetate; These organic solvents can be used alone or in combination of two or more.

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

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin. As the epoxy resin, for example, bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resin, biphenyl aralkyl epoxy resin, fluorene epoxy resin, xanthene epoxy resin, dihydric Kishibenzen type epoxy resin, trihydroxybenzene type epoxy resin, and oxazolidone type epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more. Further, among these, an acid group-containing (meth) acrylate resin composition having high photosensitivity and excellent alkali developability and capable of forming a cured product excellent in substrate adhesion and elongation can be obtained. Novolak epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, and naphthol-cresol co-condensed novolak epoxy resin Those having a softening point in the range of 20 to 120 ° C. are particularly preferred.

The curing accelerator promotes a curing reaction of the curing agent. When an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, imidazole, an organic acid metal salt, a Lewis acid, Amine complex salts and the like. These curing accelerators can be used alone or in combination of two or more. 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.

硬化 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 beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform a curing reaction by the ultraviolet rays.

紫外線 Ultraviolet lamps are generally used as a source of ultraviolet light in terms of practicality and economy. Specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.

The integrated light amount of the active energy ray is not particularly limited, but is preferably 50 to 5,000 mJ / cm ² , and more preferably 300 to 1,000 mJ / cm ² . It is preferable that the integrated light amount is within the above range, since the occurrence of uncured portions can be prevented or suppressed.

The irradiation with the active energy ray may be performed in one stage, or may be performed in two or more stages.

Further, the cured product obtained by curing the curable resin composition of the present invention has excellent substrate adhesion, and also has excellent elongation, for example, in semiconductor device applications, It can be suitably used as a package adhesive layer for a solder resist, an interlayer insulating material, a package material, an underfill material, a circuit element, or the like, or an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer, etc. in a thin display application represented by LCD and OELD.

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

The resist member of the present invention is, for example, a photomask in which a desired pattern is formed after applying the resin material for a solder resist on a substrate, evaporating and drying an organic solvent in a temperature range of about 60 to 100 ° C. Through exposure to active energy rays, developing the unexposed portions with an aqueous alkali solution, and further heating and curing at a temperature in the range of about 140 to 180 ° C.

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In this example, the weight average molecular weight (Mw) is a value measured using a gel permission chromatograph (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; polystyrene sample; tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 μl)

(Synthesis Example 1: Production of acid group-containing (meth) acrylate resin (A-1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monoethyl ether acetate, and an ortho-cresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214 g / 428 parts by weight), 4 parts by weight of dibutylhydroxytoluene as an antioxidant, and 0.4 parts by weight of methoquinone as a thermal polymerization inhibitor, and then 144 parts by weight of acrylic acid and 1.6 parts by weight of triphenylphosphine. The mixture was added, and the esterification reaction was performed at 120 ° C. for 10 hours while blowing air. Thereafter, 311 parts by weight of diethylene glycol monoethyl ether acetate and 160 parts by weight of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (A-1) having a nonvolatile content of 64%. Obtained. The acid value of the solid content of the acid group-containing (meth) acrylate resin (A-1) was 85 mgKOH / g, and the weight average molecular weight was 8,540. The acid value is a value measured based on the neutralization titration method of JIS K0070 (1992).

(Synthesis Example 2: Production of acid group-containing (meth) acrylate resin (A-2))
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 isophorone diisocyanate (“VESTANAT T-1890 / 100” manufactured by EVONIK, has an isocyanate group content of 17.) 244 parts by mass, 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene 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. The acid value of the solid content measured under the condition that the acid anhydride group was not ring-opened was 160 mgKOH / g. Methoquinone 0.3 parts by mass, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content about 67%, hydroxyl value 159.7 mg KOH / g) (hereinafter, "M-306") 172 parts by mass and 3.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Next, 163 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added, and reacted at 110 ° C. for 5 hours. The amide imide resin (A) having a non-volatile content of 62.1% by mass and having an acid group and a polymerizable unsaturated group (A -2) was obtained. The acid value of the solid content of this amide imide resin (A-2) was 79 mgKOH / g, and the weight average molecular weight was 3790.

(Synthesis Example 3: Production of amine-modified epoxy resin (B-1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 1117 parts by mass of diethylene glycol monoethyl ether acetate was put, and a bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 187 g / equivalent) 374 parts by mass, 215 parts by mass of bisphenol A, and 0.6 parts by mass of tetramethylammonium chloride were added, and the mixture was reacted at 145 ° C. for 8 hours while blowing in nitrogen. Thereafter, 12 parts by mass of diethanolamine was added and reacted at 140 ° C. for 4 hours to obtain an amine-modified epoxy resin (B-1). The nonvolatile content of this amine-modified epoxy resin (B-1) was 35%, and the weight average molecular weight (Mw) was 23,000. Further, the ratio of the number of moles of active hydrogen of diethanolamine to the number of moles of epoxy group of the bisphenol A type epoxy resin [(number of moles of active hydrogen) / (number of moles of epoxy group)] is 1.00. .

(Synthesis Example 4: Production of amine-modified epoxy resin (B-2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 1117 parts by mass of diethylene glycol monoethyl ether acetate was put, and a bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 187 g / equivalent) 374 parts by mass, 215 parts by mass of bisphenol A, and 0.6 parts by mass of tetramethylammonium chloride were added, and the mixture was reacted at 145 ° C. for 8 hours while blowing in nitrogen. Thereafter, 12 parts by mass of diethanolamine was added and reacted at 140 ° C. for 4 hours to obtain an amine-modified epoxy resin. Next, 97 parts by mass of succinic anhydride and 2.1 parts by mass of triphenylphosphine were added and reacted at 110 ° C. for 3 hours under a nitrogen atmosphere to obtain an amine-modified epoxy resin (B-2) having an acid group. . The nonvolatile content of this amine-modified epoxy resin (B-2) was 38.4%, the acid value of the solid content was 80 mgKOH / g, and the weight average molecular weight (Mw) was 25,500. Further, the ratio of the number of moles of active hydrogen of diethanolamine to the number of moles of epoxy group of the bisphenol A type epoxy resin [(number of moles of active hydrogen) / (number of moles of epoxy group)] is 1.00. .

(Synthesis Example 5: Production of amine-modified epoxy resin (B-3))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 1117 parts by mass of diethylene glycol monoethyl ether acetate, and a bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 187 g / equivalent 374 parts by mass, 215 parts by mass of bisphenol A, and 0.6 parts by mass of tetramethylammonium chloride were added, and the mixture was reacted at 145 ° C. for 8 hours while blowing in nitrogen. Thereafter, 12 parts by mass of diethanolamine was added and reacted at 140 ° C. for 4 hours to obtain an amine-modified epoxy resin. Next, 135 parts by mass of succinic anhydride and 3.9 parts by mass of triphenylphosphine were added, and reacted at 110 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, 38 parts by mass of glycidyl methacrylate and 0.4 part by mass of methoquinone were added, and the mixture was reacted at 120 ° C. for 5 hours while blowing in air to obtain an amine-modified epoxy resin having an acid group and a substituent having a polymerizable unsaturated bond (B- 3) was obtained. The nonvolatile content of this amine-modified epoxy resin (B-3) was 40.9%, the acid value of the solid component was 80 mgKOH / g, and the weight average molecular weight (Mw) was 26,900. Further, the ratio of the number of moles of active hydrogen of diethanolamine to the number of moles of epoxy group of the bisphenol A type epoxy resin [(number of moles of active hydrogen) / (number of moles of epoxy group)] is 1.00. .

(Synthesis Example 6: Production of amine-modified epoxy resin (B-4))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 836 parts by mass of diethylene glycol monoethyl ether acetate, and a bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 187 g / equivalent After adding 374 parts by mass, 150 parts by mass of bisphenol A and 0.3 parts by mass of tetramethylammonium chloride, the mixture was reacted at 145 ° C. for 4 hours while blowing nitrogen. Thereafter, 16.7 parts by mass of ethanolamine and 14.2 parts by mass of diethanolamine were added and reacted at 110 ° C. for 6 hours to obtain an amine-modified epoxy resin (B-4). The nonvolatile content of this amine-modified epoxy resin (B-4) was 40%, and the weight average molecular weight (Mw) was 15,400. The ratio of the number of moles of the ethanolamine to the number of moles of the diethanolamine [(number of moles of ethanolamine) / (number of moles of diethanolamine)] is 2.03, and the epoxy group of the bisphenol A type epoxy resin is The ratio [(moles of active hydrogen) / (moles of epoxy group)] of the total number of active hydrogens of ethanolamine and diethanolamine to the number of moles of 0.999 is 0.999.

(Synthesis Example 7: Production of amine-modified epoxy resin (B-5))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 200 parts by mass of the amine-modified epoxy resin (B-4) obtained in Synthesis Example 6, 13 parts by mass of succinic anhydride, and 0.1% of triphenylphosphine. 3 parts by mass were added and reacted at 110 ° C. for 3 hours under a nitrogen atmosphere to obtain an amine-modified epoxy resin (B-5) having an acid group. The nonvolatile content of this amine-modified epoxy resin (B-5) was 43.6%, the acid value of the solid content was 80 mgKOH / g, and the weight average molecular weight (Mw) was 16,100.

(Synthesis Example 8: Production of amine-modified epoxy resin (B-6))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 1122 parts by mass of diethylene glycol monoethyl ether acetate, and a bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 187 g / equivalent 374 parts by mass, 215 parts by mass of bisphenol A, and 0.6 parts by mass of tetramethylammonium chloride were added, and the mixture was reacted at 145 ° C. for 8 hours while blowing in nitrogen. Thereafter, 15.2 parts by mass of diisopropanolamine was added and reacted at 140 ° C. for 4 hours to obtain an amine-modified epoxy resin (B-6). The nonvolatile content of this amine-modified epoxy resin (B-6) was 35%, and the weight average molecular weight (Mw) was 23,600. The ratio of the number of moles of active hydrogen of diisopropanolamine to the number of moles of epoxy group of the bisphenol A type epoxy resin [(mol of active hydrogen) / (mol of epoxy group)] is 1.00. It is.

(Example 1: Preparation of curable resin composition (1))
156.3 parts by mass (100 parts by mass of solid content) of the acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and the amine-modified epoxy resin (B-1) 31.1 obtained in Synthesis Example 3 By mass (solid content: 10.9 parts by mass) to obtain an acid group-containing (meth) acrylate resin composition (1). Next, 187.4 parts by mass (solid content: 110.9 parts by mass) of the obtained acid group-containing (meth) acrylate resin composition (1) and an ortho-cresol novolak-type epoxy resin ("EPICLON" manufactured by DIC Corporation) as a curing agent. N-680 "), 38.9 parts by mass, diethylene glycol monoethyl ether acetate (20.9 parts by mass), and a photopolymerization initiator (IGN Corp.," Omnirad 907 "), 5.6 parts by mass, were mixed by a roll mill. This was cured to obtain a curable resin composition (1).

(Examples 2 to 11: Preparation of curable resin compositions (2) to (11))
A curable resin composition was prepared in the same manner as in Example 1, except that the acid group-containing (meth) acrylate resin (A-1) and the amine-modified epoxy resin were changed to the compositions and the amounts shown in Table 1. (2) to (11) were obtained.

(Comparative Example 1: Preparation of curable resin composition (C1))
156.3 parts by mass (solids content: 100 parts by mass) of an acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and an ortho-cresol novolac type epoxy resin (“EPICLON N- manufactured by DIC Corporation”) as a curing agent. 680 "), 38.9 parts by mass, diethylene glycol monoethyl ether acetate 20.9 parts by mass, and 5.6 parts by mass of a photopolymerization initiator (" Omnirad 907 "manufactured by IGM) are kneaded by a roll mill. Thus, a curable resin composition (C1) was obtained.

(Comparative Example 2: Preparation of curable resin composition (C2))
156.3 parts by mass (solid content: 100 parts by mass) of the acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and 142.9 parts of the amine-modified epoxy resin (B-1) obtained in Synthesis Example 3 And an acid group-containing (meth) acrylate resin composition (C2). Next, 299.2 parts by mass (solid content: 150 parts by mass) of the obtained acid group-containing (meth) acrylate resin composition (C2) and an ortho-cresol novolak-type epoxy resin ("EPICLON N-" manufactured by DIC Corporation) as a curing agent. 680 "), 38.9 parts by mass, diethylene glycol monoethyl ether acetate 20.9 parts by mass, and 5.6 parts by mass of a photopolymerization initiator (" Omnirad 907 "manufactured by IGM) are kneaded by a roll mill. Thus, a curable resin composition (C2) was obtained.

下記 The following evaluation was performed using the curable resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 and 2.

[Preparation of test piece]
The curable resin composition obtained in each of Examples and Comparative Examples was coated on a copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) base material with a thickness of 50 μm using an applicator. And dried at 80 ° C. for 30 minutes. Ultraviolet rays of 1,000 mJ / cm ² were irradiated using a metal halide lamp, and further heat-cured at 160 ° C. for 1 hour to obtain a test piece.

[Evaluation method of substrate adhesion]
The evaluation of the substrate adhesion was performed by measuring the peel strength.

<Method of measuring peel strength>
The test piece was cut into a size of 1 cm in width and 12 cm in length, and 90 ° peel strength was measured using a peeling tester (“A & D Tensilon” manufactured by A & D Co., Ltd., peeling speed: 50 mm / min).

[Method of measuring elongation]
The elongation was measured by a tensile test.

<Tensile test>
The test piece was cut into a size of 10 mm × 80 mm, and a tensile test was performed on the test piece under the following measurement conditions using an automatic universal tester “AG-IS” manufactured by Shimadzu Corporation. The elongation (%) until the test piece was broken was measured.

Measurement conditions: temperature 23 ° C, humidity 50%, distance between marked lines 20mm, distance between supports 20mm, tensile speed 10mm / min

Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (11) prepared in Examples 1 to 11 and the curable resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2. Shown in

「" Curing agent "in Table 1 indicates an orthocresol novolak type epoxy resin (" EPICLON @ N-680 "manufactured by DIC Corporation).

ＥＤ "EDGAC" in Table 1 indicates diethylene glycol monoethyl ether acetate.

括弧 In parentheses in the description of parts by mass in Table 1, the solid content is shown.

(Example 12: Preparation of curable resin composition (12))
156.3 parts by mass (100 parts by mass of solid content) of the acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and the amine-modified epoxy resin (B-1) 31.1 obtained in Synthesis Example 3 And an acid group-containing (meth) acrylate resin composition (12). Subsequently, 187.4 parts by mass (solid content: 110.9 parts by mass) of the obtained acid group-containing (meth) acrylate resin composition (8) and an ortho-cresol novolak type epoxy resin ("EPICLON" manufactured by DIC Corporation) as a curing agent. N-680 ") 38.9 parts by mass, dipentaerythritol hexaacrylate 11 parts by mass, diethylene glycol monoethyl ether acetate 20.9 parts by mass, and a photopolymerization initiator (IGN's" Omnirad 907 ") 5.6. Parts by mass and 1 part by mass of phthalocyanine green were blended and kneaded by a roll mill to obtain a curable resin composition (12).

(Examples 13 to 22: Preparation of curable resin compositions (13) to (22))
A curable resin composition was prepared in the same manner as in Example 12, except that the acid group-containing (meth) acrylate resin (A-1) and the amine-modified epoxy resin were changed to the composition and the amount shown in Table 2. (13) to (22) were obtained.

(Comparative Example 3: Preparation of curable resin composition (C3))
156.3 parts by mass (solids content: 100 parts by mass) of an acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and an ortho-cresol novolac type epoxy resin (“EPICLON N- manufactured by DIC Corporation”) as a curing agent. 680 ") 38.9 parts by mass, dipentaerythritol hexaacrylate 11 parts by mass, diethylene glycol monoethyl ether acetate 20.9 parts by mass, and a photopolymerization initiator (IGN's" Omnirad 907 ") 5.6 parts by mass. And 1 part by mass of phthalocyanine green were mixed and kneaded by a roll mill to obtain a curable resin composition (C3).

(Comparative Example 4: Preparation of curable resin composition (C4))
156.3 parts by mass (solid content: 100 parts by mass) of the acid group (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and 142.9 parts of the amine-modified epoxy resin (B-1) obtained in Synthesis Example 3 By mass (solid content: 50 parts by mass) to obtain an acid group-containing (meth) acrylate resin composition (C4). Next, 299.2 parts by mass (solids content: 150 parts by mass) of the obtained acid group-containing (meth) acrylate resin composition (C4) and an ortho-cresol novolak type epoxy resin ("EPICLON N-" manufactured by DIC Corporation) as a curing agent. 680 ") 38.9 parts by mass, dipentaerythritol hexaacrylate 11 parts by mass, diethylene glycol monoethyl ether acetate 20.9 parts by mass, and a photopolymerization initiator (IGM" Omnirad 907 ") 5.6 parts by mass. And 1 part by mass of phthalocyanine green were mixed and kneaded by a roll mill to obtain a curable resin composition (C4).

下記 The following evaluation was performed using the acid group-containing (meth) acrylate resin compositions obtained in Examples 12 to 22 and Comparative Examples 3 and 4.

[Light sensitivity evaluation method]
The curable resin compositions obtained in each of the examples and comparative examples were applied on a glass substrate using an applicator so as to have a thickness of 50 μm, and dried at 80 ° C. for 30 minutes. Next, “Step Tablet No. 2” manufactured by Kodak Co., Ltd. was placed on the dried coating film, and ultraviolet rays of 1,000 mJ / cm ² were irradiated using a metal halide lamp. This was developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 180 seconds, and evaluated based on the number of remaining step tablets based on the step tablet method. It should be noted that the greater the number of remaining stages, the higher the light sensitivity.

[Evaluation method for alkali developability]
The curable resin composition obtained in each of the Examples and Comparative Examples was applied on a glass substrate using an applicator so as to have a 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 and 70 minutes to prepare samples having different drying times. These were developed with a 1% aqueous solution of sodium carbonate at 30 ° C. for 180 seconds, and the drying time at 80 ° C. of the sample having no residue on the substrate was evaluated as a drying control width. In addition, it shows that alkali developing property is so excellent that drying control width | variety is long.

Table 2 shows the compositions and evaluation results of the curable resin compositions (12) to (22) prepared in Examples 12 to 22, and the curable resin compositions (C3) and (C4) prepared in Comparative Examples 3 and 4. Shown in

「" Curing agent "in Table 2 indicates an orthocresol novolak type epoxy resin (" EPICLON @ N-680 "manufactured by DIC Corporation).

「" DPHA "in Table 2 indicates dipentaerythritol hexaacrylate.

「" EDGAC "in Table 2 indicates diethylene glycol monoethyl ether acetate.

括弧 In parentheses in the description of parts by mass in Table 2, the solid content is shown.

「"-"In Table 2 indicates that development is not possible.

Examples 1 to 22 shown in Tables 1 and 2 are examples using the acid group-containing (meth) acrylate resin composition of the present invention. A curable resin composition containing the acid group-containing (meth) acrylate resin composition of the present invention has both excellent substrate adhesion, high photosensitivity, and excellent alkali developability. It was confirmed that the cured product of the curable resin composition containing the acid group-containing (meth) acrylate resin composition had excellent elongation.

On the other hand, Comparative Examples 1 and 3 are examples of acid group-containing (meth) acrylate resin compositions without using an amine-modified epoxy resin. It was confirmed that the curable resin composition containing the acid group-containing (meth) acrylate resin composition was excellent in photosensitivity and alkali developability, but was extremely poor in substrate adhesion. Further, it was confirmed that the cured product of the curable resin composition obtained in Comparative Example 1 was insufficient in elongation.

Comparative Examples 2 and 4 are examples in which the compounding amount of the amine-modified epoxy resin is 50 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the acid group-containing (meth) acrylate resin. The curable resin composition containing the acid group-containing (meth) acrylate resin composition is excellent in substrate adhesion and elongation of the cured product, but is extremely insufficient in photosensitivity and alkali developability. Was confirmed.

Claims

An acid group-containing (meth) acrylate resin composition containing an acid group-containing (meth) acrylate resin (A) and an amine-modified epoxy resin (B),
When the content of the amine-modified epoxy resin (B) is 0.5 parts by mass or more and 40 parts by mass or less in terms of solids with respect to 100 parts by mass of the solids of the acid group-containing (meth) acrylate resin (A). An acid group-containing (meth) acrylate resin composition, characterized in that:
The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the weight average molecular weight of the amine-modified epoxy resin (B) is 5,000 or more.
The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the amine-modified epoxy resin (B) has an acid group.
The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the amine-modified epoxy resin (B) has a polymerizable unsaturated bond-containing substituent.
A curable resin composition comprising the acid group-containing (meth) acrylate resin composition according to any one of claims 1 to 4 and a photopolymerization initiator.
(6) The curable resin composition according to (5), further comprising an organic solvent and a curing agent.
A cured product, which is a cured reaction product of the curable resin composition according to claim 5 or 6.
An insulating material comprising the curable resin composition according to claim 5.
A resin material for a solder resist, comprising the curable resin composition according to claim 5 or 6.
A resist member comprising the solder resist resin material according to claim 9.