(Meth)acrylate compounds, resin compositions using the same, cured products thereof, and their uses

Abstract

The present invention aims to provide a resin composition that combines excellent insulation reliability and heat decomposition resistance while also exhibiting superior adhesion during alkaline development. [Solution] In order to solve the above problems, the present inventors conducted diligent studies and found that the above problems can be solved by providing a resin composition comprising a (meth)acrylate compound (A) obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, an alkali-soluble resin (B), and a photopolymerization initiator (C).

Description

Technical Field

[0001] The present invention relates to a resin composition comprising a (meth)acrylate compound (A) obtained by adding a 5-membered heterocyclic compound (b) containing one or more nitrogen atoms in one molecule to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, an alkali-soluble resin (B), and a photopolymerization initiator (C), a cured product thereof, and uses thereof.

[0002] The resin composition of the present invention is excellent in insulation reliability, thermal decomposition resistance, and adhesion during alkali development, and thus can be used as wiring protection and insulating materials for electronic materials, materials for display devices, and the like.

Background Art

[0003] Polyfunctional (meth)acrylate compounds are known to be cured by light or heat, and are widely used in coating materials, three-dimensional photofabrication materials, wiring protection materials, insulating materials and the like. In addition, compositions containing a polyfunctional (meth)acrylate compound, an alkali-soluble resin, and a photopolymerization initiator are used as alkali-developable materials for photolithography in the production of printed wiring boards, semiconductor packages, display devices and the like.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

[0005] In recent years, advancements in lithography technology have led to rapid miniaturization of patterns, making adhesion during development a challenge. While it is possible to improve development adhesion with additives, some types may negatively affect insulation reliability and thermal degradation resistance. Therefore, improving the adhesion of the curable resin itself is required. [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a resin composition that combines excellent insulation reliability and heat decomposition resistance while also exhibiting superior adhesion during alkaline development. [Means for solving the problem]

[0007] In order to solve the aforementioned problems, the present inventors conducted diligent research and found that a resin composition using an unsaturated group-containing compound having a specific structure solves the aforementioned problems, thus completing the present invention.

[0008] In other words, the present invention relates to the following: [1] A resin composition comprising a (meth)acrylate compound (A) obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, an alkali-soluble resin (B), and a photopolymerization initiator (C). [2] The resin composition according to [1], wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule has a benzene ring structure. [3] The resin composition according to [1] or [2], wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule contains two or more nitrogen atoms. [4] The resin composition according to any one of [1] to [3], wherein the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule is a polyfunctional (meth)acrylate compound having three or more (meth)acrylic groups in one molecule, and the (meth)acrylate compound (A) has one or more (meth)acrylic groups in one molecule. [5] The resin composition according to any one of [1] to [4], wherein the alkali-soluble resin (B) containing one or more carboxyl groups is a reactive polycarboxylic acid resin (B-1) obtained by reacting an epoxy resin (c) with a compound (d) having both polymerizable ethylenically unsaturated groups and carboxyl groups in one molecule, and then reacting the reaction product with a polybasic acid anhydride (e). [6] A resin composition according to any one of [1] to [5], containing solvent (D). [7] A resin composition according to any one of [1] to [6], containing a curing agent (E). [8] A resin composition according to any one of [1] to [7], containing a coloring agent (F). [9] The resin composition according to any one of [1] to [8], wherein the coloring agent (F) comprises a black pigment.

[10] A resin composition according to any one of [1] to [9], which is a material for a display device.

[11] A resin composition according to any one of [1] to

[10] , which is a material for forming a film for insulating purposes.

[12] A resin composition according to any one of [1] to

[11] for use in permanent resists.

[13] The resin composition according to any one of the following [1] to

[12] , wherein the solid content acid value of the alkali-soluble resin (B) is 40 to 140 mg·KOH / g. A cured product of the resin composition described in any one of the items in

[14] [1] to

[13] . [Effects of the Invention]

[0009] The resin composition of the present invention possesses excellent insulating reliability, heat decomposition resistance, and adhesion during alkaline development, making it suitable for use in materials requiring the above-mentioned physical properties. [Brief explanation of the drawing]

[0010] [Figure 1] 1H-NMR chart of the acrylate compound (A1) obtained in Synthesis Example 1 [Modes for carrying out the invention]

[0011] The (meth)acrylate compound (A) in the present invention is obtained by reacting a polyfunctional (meth)acrylate compound (a) having one or more (meth)acrylic groups in one molecule with a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule.

[0012] In the present invention, the polyfunctional (meth)acrylate compound (a) is preferably an acrylate compound having two (meth)acrylic groups in one molecule. Examples of polyfunctional acrylate compounds having two (meth)acrylic groups in one molecule include hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, and dicyclopentanyl di(meth)acrylate.

[0013] A polyfunctional acrylate compound having 2 or more, preferably 3 or more (meth)acrylic groups in one molecule is more preferred, and preferred examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ECH (epichlorohydrin)-modified glycerol tri(meth)acrylate, EO (ethylene oxide)-modified glycerol tri(meth)acrylate, PO (propylene oxide)-modified glycerol tri(meth)acrylate, EO-modified phosphate tri(meth)acrylate, and the like. These compounds may be used alone, or two or more thereof may be used in combination.

[0014] Examples of the 5-membered heterocyclic compound (b) containing one or more nitrogen atoms in one molecule in the present invention include oxazole, thiazole, pyrrole and the like.

[0015] Among the 5-membered heterocyclic compounds (b) containing one or more nitrogen atoms in one molecule, examples of those containing two or more nitrogen atoms in one molecule include 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, tetrazole, pentazole and the like.

[0016] Among 5-membered heterocyclic compounds (b) containing one or more nitrogen atoms in one molecule, examples of those having a benzene ring include indole, benzoxazole, benzimidazole, oxindole, benzimidazolinone, benzoxazolinone, benzothiazole, and benzothiazolone.

[0017] The benzene ring may have a substituent, and examples thereof include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carboxy group, and an aldehyde group. Specific examples include 1H-methylbenzotriazole, 1H-ethylbenzotriazole, 1H-methylimidazole, 1H-methylbenzimidazolinone, 1H-benzoxazolinone, and 1H-benzotriazole-carboxylic acid.

[0018] The amount of the 5-membered heterocyclic compound (b) containing one or more nitrogen atoms in one molecule is preferably in a range that satisfies an amount such that 1 mole of the amino group of (b) is 0.01 to 0.99 relative to 1 mole of the unsaturated bond of the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, and more preferably in a range that satisfies an amount of 0.02 to 0.9 from the viewpoints of curability and crosslinking density.

[0019] In the process of producing (meth)acrylate compound (a), dilution with an organic solvent may be used as needed. Examples of solvents that can be used include: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and propylene glycol methyl ether. Alkylene glycol monoalkyl ether acetates such as methyl acetate and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; and esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate. These solvents may be used individually or in mixtures of two or more.

[0020] Furthermore, catalysts can be used to accelerate the reaction as needed. Examples of catalysts include trimethylamine, triethylamine, tripropylamine, dimethylaniline, isoquinoline, trisdimethylaminophenol, lutidine, triethylenediamine, dimethylbenzylamine, dimethylpiperazine, cyclohexylamine, diisopropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, triphenylphosphine, tory-p-tolylphosphine, sodium hydroxide, potassium hydroxide, and the like.

[0021] Polymerization inhibitors may also be added during the reaction as needed. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine. The amount used is 0.01 to 1% by weight relative to the reaction mixture.

[0022] During the reaction, heating may be added as needed, preferably in the range of 60°C to 160°C, and particularly preferably in the range of 70°C to 150°C, and the reaction time is preferably 1 to 60 hours.

[0023] The (meth)acrylate compound (A) of the present invention is obtained as described above. Preferably, the (meth)acrylate compound (A) has one or more (meth)acrylic groups in one molecule.

[0024] The alkali-soluble resin (B) can be any resin that is soluble in an alkaline (water) solution and is not particularly limited, for example, a compound having a carboxyl group. Examples of alkaline (water) solutions include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium bicarbonate, tetramethylammonium hydroxide, diethanolamine, ethanolamine, etc., as well as mixtures of these with appropriate surfactants, organic amine solutions, etc.

[0025] The carboxyl group may be a salt such as a sodium salt or a potassium salt, and if the molecule contains two or more carboxyl groups, it may be an acid anhydride formed by the linkage of these groups.

[0026] Examples of alkali-soluble resins (B) include reactive polycarboxylic acid resins (B-1) (hereinafter simply referred to as "reactive polycarboxylic acid resins (B-1)") obtained by reacting an epoxy resin (c) with a compound (d) having both polymerizable ethylenically unsaturated groups and carboxyl groups in a single molecule, and then reacting that product with a polybasic acid anhydride (e).

[0027] Epoxy resin (c) is, The following general formula (2): [ka]

[0028] [In formula (2), R 6 R represents a hydrocarbon group containing an aromatic ring or an alicyclic skeleton with 1 to 40 carbon atoms, 7 These may be the same or different, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 40 carbon atoms. Examples include novolac-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, epoxy compounds containing a naphthyl skeleton, and epoxy compounds containing a fluorenyl skeleton.

[0029] Examples of novolac-type epoxy resins include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product names), DEN-431, DEN-439 (both manufactured by Dow Chemical Co., Ltd., product names), EOCN-120, EOCN-102S, EOCN-103S, and EOCN-104. S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (all manufactured by Nippon Kayaku Co., Ltd., trade names), EPN-1138, EPN-1235, EPN-1299 (all manufactured by BASF Japan Ltd., trade names), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (all manufactured by DIC Corporation, trade names), etc., are commercially available. Examples of commercially available bisphenol A type epoxy resins or bisphenol F type epoxy resins include Epicote 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, and 1009 (all manufactured by Mitsubishi Chemical Corporation, trade names), DER-330, DER-301, DER-361 (all manufactured by Dow Chemical Ltd., trade names), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade names). As biphenyl-type epoxy resins, commercially available products include NC3000, NC3000H, NC3000L, NC3100 (all manufactured by Nippon Kayaku Co., Ltd.), GK3207 (manufactured by Toto Kasei Co., Ltd.), YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.), and BPAE (manufactured by Nippon Steel Chemical Co., Ltd.). As dicyclopentadiene-type epoxy resins, commercially available products include HP7200, HP7200H, HP7200HH (all manufactured by DIC Corporation), XD-1000, XD-1000-L, and XD-10002L (all manufactured by Nippon Kayaku Co., Ltd.). Commercially available epoxy compounds containing a naphthyl skeleton include HP4032, 4700, 4770, 5000, 6000 (manufactured by DIC Corporation), NC-7000, 7300 (manufactured by Nippon Kayaku Co., Ltd.), ESN-175 (manufactured by Nippon Steel Chemical Co., Ltd.), and ESN-475V (manufactured by Toto Kasei Co., Ltd.).Epoxy compounds containing a fluorenyl skeleton include OGSOL PG-100 and OGSOL EG-200 (both manufactured by Osaka Gas Chemical Co., Ltd.), which are commercially available.

[0030] Compound (d) containing both polymerizable ethylenically unsaturated groups and carboxyl groups in a single molecule is reacted to impart reactivity to active energy rays. There are no restrictions as long as there is one or more ethylenically unsaturated groups and carboxyl groups in the molecule. Examples include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or reaction products of saturated or unsaturated dibasic acids with unsaturated group-containing monoglycidyl compounds. Examples of (meth)acrylic acids mentioned above include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimers, semi-esters which are equimolar reactions between saturated or unsaturated dibasic acid anhydrides and (meth)acrylate derivatives having one hydroxyl group per molecule, semi-esters which are equimolar reactions between saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives, and other monocarboxylic acid compounds containing one carboxyl group per molecule, as well as semi-esters which are equimolar reactions between saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives, and polycarboxylic acid compounds having multiple carboxyl groups per molecule.

[0031] Of these, the epoxy resin (c) and the compound (d) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule are preferably monocarboxylic acids, and even when monocarboxylic acids and polycarboxylic acids are used in combination, the value expressed as the molar amount of monocarboxylic acid / molar amount of polycarboxylic acid is preferably 15 or more. Most preferably, in terms of sensitivity to active energy rays when used as a resin composition, (meth)acrylic acid, the reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid are mentioned. As for the compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, it is preferable that the compound does not have a hydroxyl group.

[0032] As the polybasic acid anhydride (e), any compound having a cyclic acid anhydride structure in one molecule can be used, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hydrogenated trimellitic anhydride, trimellitic anhydride, or maleic anhydride are preferred due to their excellent alkaline aqueous solution developability, heat resistance, hydrolysis resistance, etc.

[0033] The reactive polycarboxylic acid resin (B-1) preferably has a solid content acid value (according to JIS K5601-2-1:1999) of 20 to 140 mg·KOH / g, more preferably 30 to 120 mg·KOH / g, and even more preferably 40 to 110 mg·KOH / g. When the solid content acid value is within this range, the resin composition of the present invention exhibits good alkaline aqueous solution developability. That is, it exhibits good patterning properties, a wide range of control over overdevelopment, and no excess acid anhydride remains.

[0034] To introduce hydroxyl groups into carboxylate compounds, a compound (f) (hereinafter also simply referred to as compound (f)) containing both a hydroxyl group and a carboxyl group in one molecule may be reacted as needed. These include compounds containing one hydroxyl group and one carboxyl group in one molecule, compounds containing two or more hydroxyl groups and one carboxyl group in one molecule, and compounds containing one or more hydroxyl groups and two or more carboxyl groups in one molecule. Examples of compounds containing one hydroxyl group and one carboxyl group in a single molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid. Examples of compounds containing two or more hydroxyl groups and one carboxyl group in a single molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of compounds containing one or more hydroxyl groups and two or more carboxyl groups in a single molecule include hydroxyphthalic acid. Of these, those containing two or more hydroxyl groups per molecule are preferable considering the effects of the present invention. Furthermore, those containing one carboxyl group per molecule are preferable considering the stability of the carboxylation reaction. Most preferably, those having two hydroxyl groups and one carboxyl group per molecule are preferable. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As a compound having one or more hydroxyl groups and one or more carboxyl groups in a single molecule, it is preferable that the compound does not contain polymerizable ethylenically unsaturated groups.

[0035] The ratio of epoxy resin (c), compound (d) containing both polymerizable ethylenically unsaturated and carboxyl groups in a single molecule, and compound (f) used as needed in this carboxylation reaction should be appropriately adjusted depending on the application. That is, if all epoxy groups are carboxylated, no unreacted epoxy groups remain, resulting in high storage stability as a reactive epoxy carboxylate resin. In this case, only the reactivity due to the introduced double bond is utilized.

[0036] The preferred molecular weight range for the reactive polycarboxylic acid resin (B-1) is a polystyrene-equivalent weight-average molecular weight in GPC (gel permeation chromatography) measurements of 500 to 50,000, more preferably 800 to 30,000, and particularly preferably 800 to 10,000. If the molecular weight is lower than this range, the toughness of the cured product will not be fully exhibited, and if it is too high, the viscosity will be high, making coating, developing, etc., difficult.

[0037] Other examples of alkali-soluble resins (B) include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as "carboxyl-group-containing unsaturated monomer") and other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as "other unsaturated monomers"). Such copolymers may be block copolymers or random copolymers. Examples of unsaturated monomers having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or their acid anhydrides; and unsaturated polycarboxylic acids with a carboxyl group of 3 or higher or their anhydrides. These unsaturated monomers having a carboxyl group can be used individually or in combination of two or more.

[0038] Other unsaturated monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and p-methoxystyrene; unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl acrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; and 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, and 3-aminopropyl methacrylate. Unsaturated aminoalkyl carboxylates such as; unsaturated glycidyl carboxylates such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; acrylamide, methacrylamide, Examples include unsaturated amides or imides such as α-chloroacrylamide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and macromonomers having monoacryloyl or monomethacryloyl groups at the ends of polymer molecular chains, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysilicone.These other unsaturated monomers may be used individually or in combination of two or more.

[0039] (Meth)acrylic acid is a preferred unsaturated monomer having a carboxyl group, and other unsaturated monomers include at least one monomer selected from the group consisting of methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

[0040] Preferably, the polymer having the carboxyl group is acrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid Acrylic acid copolymers such as methyl methacrylate / styrene copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, and acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer;Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / styrene Examples of methacrylic acid copolymers include copolymers such as methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymers, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymers, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymers, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymers, and methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers.

[0041] Furthermore, polymers in which an unsaturated double bond is introduced into the side chain of the polymer having the carboxyl group are also useful as binder polymers. Examples of such polymers include compounds obtained by reacting the acid anhydride portion of a copolymer of maleic anhydride and copolymerizable therewith, such as styrene, vinylphenol, acrylic acid, acrylic acid ester, and acrylamide, with an acrylate having an alcoholic hydroxyl group, such as hydroxyethyl acrylate, or an acrylate having an epoxy group, such as glycidyl methacrylate, to form a half-esterified compound, and compounds obtained by reacting the hydroxyl group of a copolymer of acrylic acid or acrylic acid ester with an acrylate having an alcoholic hydroxyl group, such as hydroxyethyl acrylate, with acrylic acid.

[0042] Other examples of alkali-soluble resins (B) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, and heterocompounds containing one or more carboxyl groups.

[0043] Aliphatic compounds containing one or more carboxyl groups include, for example, linear aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, linear aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may have a hydrogen atom and substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups in their molecules. Furthermore, if these compounds have two or more carboxyl groups in their molecules, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in their molecules, they may be acid anhydrides formed by the linkage of the carboxyalkyl group and the carboxyl group. If these compounds have two or more carboxyalkyl groups in their molecules, they may be acid anhydrides formed by the linkage of these groups.

[0044] Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy groups. Examples of aryloxy groups include phenoxy groups and p-tolyloxy groups. Examples of aryl groups include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthyl groups. Examples of aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl groups. Examples of carboxyalkyl groups include carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxybutyl group, carboxyhexyl group, and carboxynonyl group.

[0045] Examples of chain-like aliphatic monocarboxylic acids include saturated fatty acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid, as well as unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

[0046] Examples of alicyclic monocarboxylic acids include monocyclic carboxylic acids such as cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid, as well as polycyclic or bridged alicyclic carboxylic acids such as norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid, ethyladamantanecarboxylic acid, and butyladamantanecarboxylic acid.

[0047] Examples of linear aliphatic polycarboxylic acids include carboxylic acids in which one or more carboxyl groups are further added to a linear aliphatic monocarboxylic acid. Examples include propionidioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

[0048] Examples of alicyclic polycarboxylic acids include carboxylic acids in which one or more carboxyl groups are further added to an alicyclic monocarboxylic acid. Examples include monocyclic carboxylic acids such as cyclopropanedicarboxylic acid, cyclopropenedicarboxylic acid, cyclopropanetricarboxylic acid, cyclopropentricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutentricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopententricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexenetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexenetetracarboxylic acid, cyclohexenepentacarboxylic acid, cyclohexanehexacarboxylic acid, cyclohexenehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptenedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclooctenedicarboxylic acid, as well as polycyclic or bridged alicyclic dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid.

[0049] Examples of the parent skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenyleneacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, naphthalenetetracarboxylic acid, anthracenecarboxylic acid, anthracenedicarboxylic acid, anthracenetricarboxylic acid, anthracenetetracarboxylic acid, and anthracenepentacarboxylic acid. Aromatic compounds may have substituents on the aromatic ring of these parent skeletons, such as hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups. Furthermore, if these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by the linkage of the carboxyalkyl group and a carboxyl group. If these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by the linkage of these groups. For these substituents, please refer to the above.

[0050] Examples of heterocompounds containing one or more carboxyl groups include compounds with one or more carboxyl groups in a heterocycle, such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole. These heterocompounds may have substituents on their parent skeletons, such as hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups. Furthermore, if these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by the linkage of the carboxyalkyl group and the carboxyl group. These compounds may also be acid anhydrides formed by the linkage of two or more carboxyalkyl groups within the molecule. Refer to the above for details regarding these substituents.

[0051] The content range of the alkali-soluble resin (B) in the present invention is 90% to 5% by weight, more preferably 80% to 10% by weight, and even more preferably 70% to 20% by weight, relative to the total components.

[0052] When an N-methylpyrrolidone solution containing 1% by weight of alkali-soluble resin (B) is prepared and its transmittance is measured using an active energy ray including a wavelength of 365 nm (i-line), it is preferable that the transmittance is 5% or higher. Such alkali-soluble resin (B) exhibits excellent light transmittance. Furthermore, when an N-methylpyrrolidone solution containing 1% by weight of alkali-soluble resin (B) is measured using an active energy ray including a wavelength of 405 nm (h-line), it is preferable that the transmittance is 5% or higher, and in this case as well, it exhibits excellent light transmittance. When such alkali-soluble resin (B) is used, for example, when manufacturing printed circuit boards with high-density and high-definition wiring formation (patterns) using a direct lithography exposure method, the photoradical reaction occurs efficiently even when an active energy ray including a wavelength of 405 nm (h-line) is used. The transmittance at a wavelength of 365 nm (i-line) is preferably in the following order: 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in order, as this allows for obtaining a resin composition with superior photocurability. The transmittance at a wavelength of 405 nm (h-line) is preferably in the following order: 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in order, as this allows for obtaining a resin composition with superior photocurability. The upper limits for the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) are, for example, 99.9% or less, and may also be 100% or less.

[0053] Alkali-soluble resin (B) can be used alone or by mixing two or more types as appropriate.

[0054] The photopolymerization initiator (C) used in the resin composition of the present invention can be used without particular limitations, but specifically, for example, acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyldimethyl ketal, thioxatone, 2-chlorothioxatone, 2-methylthioxatone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethone [Xy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione=2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone Examples include 1-(O-acetyloxime) and 2,4-dimethylthioxanthone. These photopolymerization initiators may be used individually or in combination of two or more.

[0055] Among these, it is preferable to use one that efficiently generates radicals at exposure wavelengths of 310 nm to 436 nm (more preferably 365 nm), from the viewpoint that it can form fine patterns using a reduction projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm), which is standardly used in the manufacturing process of semiconductor protective films, etc. Preferred photopolymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione=2-(O-benzoyl oxime) (BASF Japan, "IRGACURE OXE-01"), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime) (BASF Japan, "IRGACURE OXE-02"), 2,4-dimethylthioxanthone (Nippon Kayaku Co., Ltd., "DETX-S"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IGM Resins BV, "Omirad 907"). The amount of photopolymerization initiator used is preferably 0.1% to 20% by weight, more preferably 1% to 5% by weight, relative to 100% by weight of the compound represented by formula (1).

[0056] A sensitizer may be used in combination with the photopolymerization initiator. The sensitizer that can be used in combination is not particularly limited as long as it is conventionally known, but examples include 4,4'-bis(diethylamino)benzophenone. The amount of sensitizer used is preferably 2% by weight or less, and more preferably 0.05% to 0.5% by weight, relative to 100% by weight of the compound represented by formula (2). By using a sensitizer in combination, the sensitivity to light during self-polymerization can be increased.

[0057] The resin composition of this embodiment may optionally contain solvent (D). Using an organic solvent allows for adjustment of the viscosity during the preparation of the resin composition. The type of organic solvent is not particularly limited, as long as it can dissolve part or all of the resin in the resin composition. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, and γ-butyrolactone; polar solvents such as amides such as dimethylacetamide and dimethylformamide; and nonpolar solvents such as aromatic hydrocarbons such as toluene, xylene, and anisole. These organic solvents can be used individually or in appropriate mixtures of two or more. There are no particular restrictions on the content of the organic solvent in the composition of the present invention, but typically the solvent content in the composition is 95% by weight or less, preferably 20% to 90% by weight.

[0058] The resin composition of the present invention may contain a curing agent (E) as appropriate depending on the application. The curing agent is used particularly in materials intended for electrical insulation, to obtain a strong cured film through reaction with the contained acidic groups.

[0059] Examples of the curing agent (E) include epoxy compounds, and among them, epoxy compounds containing two or more epoxy groups in one molecule are preferred. This is because a stronger cured product can be obtained compared to using monofunctional epoxy compounds. Furthermore, the epoxy equivalent of these epoxy compounds is preferably in the range of 150 to 450 g / eq, and more preferably in the range of 180 to 350 g / eq. If the epoxy equivalent is smaller than this, the resulting cured product tends to be brittle, and if it is larger, the resulting cured product tends to be soft because the number of crosslinking sites decreases.

[0060] The epoxy compound can be arbitrarily selected depending on the intended use and required properties of the cured product, and any commonly known epoxy compound can be used.

[0061] Examples of monofunctional epoxy compounds include phenylglycidyl ether and glycidyl (meth)acrylate.

[0062] Examples of epoxy compounds having two or more epoxy groups in their molecules include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadienephenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, glyoxal type epoxy resins, and heterocyclic epoxy resins.

[0063] Examples of phenol novolac type epoxy resins include Epiclon N-770 (manufactured by DIC Corporation), DEN438 (manufactured by Dow Chemical Company), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201, and RE-306 (all manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolac type epoxy resin include Epiclon N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

[0064] Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), and jER E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the dicyclopentadienephenol type epoxy resin include Epiclon EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by Dow Chemical Company).

[0065] Examples of bisphenol-type epoxy resins include bisphenol-A type epoxy resins such as jER828, jER1001 (both manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by Union Carbide), DER-331 (manufactured by Dow Chemical), YD-8125 (manufactured by Toto Kasei Co., Ltd.), NER-1202, NER-1302 (both manufactured by Nippon Kayaku Co., Ltd.), and bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.), NER-7403, NER-7604 (both manufactured by Nippon Kayaku Co., Ltd.).

[0066] Examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), bixylenol-type epoxy resin such as YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.), and YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include Epiclon N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

[0067] Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation). Examples of the glyoxal-type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of alicyclic epoxy resins include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

[0068] When the epoxy compound is included, a suitable amount is approximately 5 to 80% by weight, more preferably 10 to 70% by weight, of the solid content of the active energy ray curable resin composition of the present invention. If the amount is less than this, the resulting cured product tends to be soft, and if it is too much, it may adversely affect the curability due to balance issues with the epoxy curing agent described below.

[0069] The resin composition of the present invention may further contain a thermosetting catalyst, for example, imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacate dihydrazide; and phosphorus compounds such as triphenylphosphine.

[0070] Furthermore, commercially available examples include 2MZ-A, 2MZOK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names for imidazole compounds) from Shikoku Chemicals, Inc., and U-CAT(registered trademark) 3503N and U-CAT3502T (both trade names for dimethylamine blocked isocyanate compounds), DBU, DBN, UCATSA102, and U-CAT5002 (all bicyclic amidine compounds and their salts) from Sunapro Co., Ltd. In particular, it is not limited to these, and any thermosetting catalyst for epoxy compounds or oxetane compounds, or a catalyst that promotes the reaction between epoxy groups and / or oxetanyl groups and carboxyl groups, may be used individually or in combination of two or more.

[0071] Furthermore, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct can also be used, and preferably these compounds that also function as adhesion imparters are used in combination with a thermosetting catalyst.

[0072] The amount of these thermosetting catalysts blended is preferably 0.1 to 20% by weight, more preferably 0.5 to 15.0% by weight, based on 100 parts by weight of the curing agent (E) component.

[0073] The resin composition of the present invention may contain a coloring agent (F), such as a dye or a coloring pigment. The coloring pigment is used to color the resin composition of the present invention, and it is presumed that the hydroxyl groups of the alkali-soluble resin (B) used in the resin composition of the present invention exhibit particularly excellent affinity to the pigment, i.e., dispersibility. As a result of good dispersibility, the pigment concentration can be increased. Furthermore, in compositions that require development, dispersibility is even more preferable, resulting in good patterning characteristics and less development residue in the development dissolution area. In other words, the alkali-soluble resin (B) used in the resin composition of the present invention has a high affinity for coloring pigments such as carbon black, and can exhibit good developability even at high pigment concentrations. It can be suitably used as a resist material for color resists and color filters, especially as a black matrix material and a black column spacer.

[0074] Examples of coloring pigments include organic pigments such as phthalocyanine, azo, and quinacridone, and inorganic pigments such as carbon black and titanium dioxide. Among these, carbon black It is desirable because it has high diversification.

[0075] The content of the colorant (F) in the resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 35% by mass or more, and also preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. Setting it above the lower limit tends to ensure light shielding while suppressing the loss of ultraviolet light necessary for curing, and setting it below the upper limit tends to improve patternability.

[0076] The resin composition of the present invention may further contain a crosslinking agent, such as radical-reactive acrylates, cationic-reactive epoxy compounds, and vinyl compounds sensitive to both.

[0077] Examples of radical-reactive acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0078] Examples of these monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0079] Examples of these polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, and bisphenol di(meth)acrylate. Examples include acrylates, di(meth)acrylates of ε-caprolactone adducts of neopentyl glycol hydroxyvivariate, poly(meth)acrylates of reaction products of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, etc.

[0080] The cationic epoxy compounds are not particularly limited as long as they are compounds having an epoxy group, including epoxy compound (i). Examples include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., Union Carbide's "Cyracure UVR-6110"), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., Union Carbide's "ELR-4206"), and limonene dioxide. Examples include oxides (such as "Celoxide 3000" manufactured by Daicel Chemical Industries), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate (such as "Cyracure UVR-6128" manufactured by Union Carbide), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, and bis(3,4-epoxycyclohexyl) diethylsiloxane.

[0081] Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethyll isocyanurate.

[0082] The crosslinking agent may be used alone or in a mixture of two or more types. The content ratio of these crosslinking agents in the photosensitive resin composition is usually 2 to 40% by weight, preferably 3 to 30% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

[0083] The resin composition of this embodiment may further contain fillers to improve various properties such as film-forming properties and heat resistance. Preferably, the filler has insulating properties and does not hinder transmission to a wavelength of 405 nm (h-ray). The fillers are not particularly limited, but examples include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass (e.g., E glass, T glass, D glass, etc.)), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers can be used individually or in appropriate mixtures of two or more types.

[0084] Among these, it is preferable that one or more are selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers may be surface-treated with a silane coupling agent or the like.

[0085] From the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of this embodiment and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include SFP-130MC from Denka Co., Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA from Admatex Co., Ltd.

[0086] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, and preferably 0.01 to 50 μm.

[0087] In the resin composition of this embodiment, the content of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferably 1000% by weight or less, more preferably 500% by weight or less, and most preferably 300% by weight or less, relative to 100% by weight of the resin solids in the resin composition. When a filler is included, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is usually 1% by weight relative to 100% by weight of the resin solids in the resin composition.

[0088] Other additives that may be contained in the resin composition of the present invention include, for example, thixotropy agents such as Aerosil, silicone-based or fluorine-based leveling agents and defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, adhesion aids, surfactants, tackifiers, plasticizers, ultraviolet absorbers, antioxidants, and flame retardants for providing flame retardancy. In particular, when used as a film-forming material for electrical insulation, it is preferable to use it in combination with a flame retardant. Preferred flame retardants include commonly known ones, such as halogenated flame retardants like brominated epoxy resins and bromodiphenyl ethers, phosphate ester resins like phosphazene resins and triphenyl phosphates, organophosphorus flame retardants like dihydro-9-oxa-phosphaphenanthrene-10-oxide derivatives, metal hydroxide flame retardants like magnesium hydroxide, and inorganic flame retardants like red phosphorus and antimony trioxide.

[0089] Furthermore, the composition may contain resins that do not react to active energy rays. Examples of such resins include epoxy resins other than the epoxy resin used as a curing agent, phenolic resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified versions thereof, which may be included in the active energy ray-curable resin composition of the present invention. It is preferable to use these in amounts up to 40% by weight in the resin composition.

[0090] The resin composition of the present invention is easily cured by active energy rays. Examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and laser rays, and particle beams such as alpha rays, beta rays, and electron beams. Considering the preferred applications of the present invention, ultraviolet rays, laser rays, visible light, or electron beams are preferred among these.

[0091] To obtain the resin composition of the present invention, the above-mentioned components can be mixed, and the order and method of mixing are not particularly limited.

[0092] The present invention also includes using the resin composition as a film-forming material for coating the surface of a substrate. Specifically, this includes, for example, ink materials such as gravure inks, flexographic inks, silkscreen inks, and offset inks; coating materials such as hard coats, top coats, overprint varnishes, and clear coats; adhesive materials such as adhesives and tacks for lamination and optical discs; and resist materials such as solder resists, etching resists, and micromachine resists. Furthermore, so-called dry films, which are made by temporarily coating a film-forming material onto a releaseable substrate to form a film, and then laminating it onto the intended substrate to form a film, also fall under the category of film-forming materials.

[0093] The present invention also includes the use of the resin composition as a film-forming material for the purpose of electrical insulation. Specifically, this includes materials that require electrical insulation, such as solder resist materials for circuit boards, insulating molding materials, interlayer insulating materials, semiconductor protective film materials, and wiring coating materials.

[0094] The present invention also includes the resin composition used for permanent resists. A permanent resist is a resist material that is not intended to be peeled off after drawing, but rather maintains its purpose and function without peeling off until the actual use of the substrate it is used on.

[0095] The active energy ray curable resin composition for resists of the present invention is applicable to various materials requiring patterning, and is particularly useful as a solder resist material and an interlayer insulating material for build-up methods. Furthermore, it can be used as an optical waveguide in electrical, electronic, and optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates.

[0096] Particularly suitable applications include a wide range of applications requiring resin compositions, such as photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins, taking advantage of its excellent heat resistance and developability. In particular, it is preferred for use as a resin composition for the insulating layer of multilayer printed wiring boards (multilayer printed wiring boards with a cured photosensitive resin composition as the insulating layer), a resin composition for the interlayer insulating layer (multilayer printed wiring boards with a cured photosensitive resin composition as the interlayer insulating layer), and a resin composition for plating formation (multilayer printed wiring boards with plating formed on a cured photosensitive resin composition).

[0097] In this invention, the display device material is a material used in display elements such as liquid crystal displays, organic EL displays, and electronic paper. Specific applications include color resists, resist materials for color filters, and especially black matrix materials for display devices, such as material spacers, protective films, planarization films, interlayer insulating films, and partitioning materials.

[0098] There are no particular restrictions on the method of film formation, but various coating methods such as gravure printing (intaglio printing), flexographic printing (relief printing), screen printing (stencil printing), offset printing (planographic printing), roll coaters, knife coaters, die coaters, curtain coaters, and spin coaters can be arbitrarily adopted.

[0099] The present invention also includes a cured product obtained by irradiating the resin composition with active energy rays and curing it. [Examples]

[0100] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited in any way by the following examples. Also, unless otherwise specified in the examples, % indicates weight %.

[0101] <Synthesis of (meth)acrylate compound (A)> [Synthesis Example 1] In a 300 mL flask equipped with a stirrer and reflux tubing, 76 g of KAYARAD DPHA (dipentaerythritol penta / hexaacrylate mixture, Nippon Kayaku Co., Ltd.), 34 g of benzotriazole, 0.3 g of triethylamine, and 0.05 g of dibutyl tertiary cresol were added. The mixture was stirred and mixed at 60°C for 1 hour, and then reacted at 110°C for 8 hours. After cooling to room temperature, acrylate compound (A1) was obtained. 1 Identified by 1H-NMR.

[0102] [Synthesis Example 2] In a 300 mL flask equipped with a stirrer and reflux tubing, 88 g of KAYARAD T-1420 (ditrimethylolpropanetetraacrylate, Nippon Kayaku Co., Ltd.), 34 g of benzotriazole, 0.5 g of diisopropylethylamine, and 0.05 g of dibutyl tert-cresol were added. The mixture was stirred at 60°C for 1 hour and then reacted at 110°C for 8 hours. After cooling to room temperature, acrylate compound (A2) was obtained. 1 Identified by 1H-NMR.

[0103] <Evaluation of resin compositions> The resin compositions of Examples 1-4 and Comparative Examples 1-2 were evaluated as follows. The compositions and evaluation results are shown in Tables 1 and 2.

[0104] (Examples 1, 2 and Comparative Example 1): Evaluation of development adhesion The resin compositions for Examples 1 and 2 and Comparative Example 1 were prepared by mixing the materials in the amounts (weight %) shown in Table 1. The prepared resin compositions were spin-coated onto a glass substrate and heated at 80°C for 10 minutes to form a coating with a thickness of 3 to 5 μm. The resulting coating was then exposed to ultraviolet light at a rate of 100 mJ / cm² using an ultraviolet irradiator (USHIO ultra-high pressure mercury lamp) through a line-and-space pattern mask with a width of 20 to 200 μm. 2 The substrate was irradiated with ultraviolet light using the specified energy. Afterward, it was developed for 30 seconds with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution), and then rinsed with pure water. The developed pattern was observed, and the degree to which the coating peeled from the glass substrate (presence or absence of pattern peeling) was evaluated based on the following evaluation criteria. [Evaluation Criteria] ◎: No peeling across the entire pattern ○: Less than 30% of the pattern has peeled off. ×: More than 90% of the pattern has peeled off.

[0105] [Table 1]

[0106] KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.): Dipentaerythritol hexaacrylate KAYARAD ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.): Biphenyl aralkyl type acid-modified epoxy acrylate (Solid content acid value: 60 mg·KOH / g) IRGACURE OXE-02 (manufactured by BASF Japan Ltd.): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) PGMEA: Propylene glycol monomethyl ether acetate

[0107] (Examples 3, 4 and Comparative Example 2): Evaluation of insulation reliability and thermal decomposition resistance The resin compositions for Examples 3, 4, and Comparative Example 2 were prepared by blending the materials in the amounts (weight %) shown in Table 2.

[0108] [Evaluation of insulation reliability] The prepared resin composition was coated to a thickness of 90 μm onto a comb-shaped electrode (material: copper, pattern pitch: 18 μm, L / S = 100 μm / 100 μm) formed on a substrate (polyimide film), pre-baked at 80°C for 30 minutes, and then subjected to a 500 mJ / cm² test. 2 Test specimens were obtained by exposure and heat curing at 150°C for 1 hour. After heating, the test specimens were placed in a chamber (ETACPLAMOUBTHASTCHAMBERPM220, Kusumoto Kasei Co., Ltd.) at 130°C and 85% humidity, and a DC voltage of 100V was applied between the electrodes using a migration tester (ETACSIR-13mini, Kusumoto Kasei Co., Ltd.) to measure the resistance between the electrodes. Insulation reliability was judged according to the following criteria. If the criteria for ○ are met, the insulation reliability is judged to be acceptable, and it has sufficient insulation retention for practical use and excellent insulation reliability. [Judgment criteria] ○: Resistance of 1 × 10⁹ Ω or higher lasts for more than 100 hours, and insulation is very good. ×: Resistance drops to less than 1 × 10⁸ Ω in less than 100 hours, considered an insulation failure.

[0109] [Evaluation of heat decomposition resistance at 230°C] The prepared resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 50 μm using an applicator. The coating was dried in a hot air dryer at 80°C for 30 minutes, and then treated with an ultraviolet irradiator (GS YUASA: CS 30L-1) at a rate of 500 mJ / cm². 2 The copper foil was then irradiated with ultraviolet light. Subsequently, the copper foil was removed with iron(III) chloride 45° Baume (manufactured by Junsei Chemical Co., Ltd.) to obtain a cured product. The weight change of the cured material prepared as described above was measured using a differential thermogravimetric thermometer (Seiko Instruments TG / DTA6200) while the temperature was increased from 50°C to 230°C under conditions of 10°C / min in a nitrogen atmosphere. The weight loss rate before and after the temperature increase was calculated, and a value of less than 3% was marked with ○, and a value of 3% or more was marked with ×. *Weight reduction rate (%) = 1-weight after heating / initial weight

[0110] [Table 2]

[0111] KAYARAD ZXR-1810H (manufactured by Nippon Kayaku Co., Ltd.): Dicyclopentadienephenol-type acid-modified epoxy acrylate (Solid content acid value: 60 mg·KOH / g) IRGACURE 907 (manufactured by BASF Japan Ltd.): 2-methyl-1-[(4-methylthio)phenyl]-2-morpholinopropan-1-one KAYACUREDETX-S (manufactured by Nippon Kayaku Co., Ltd.): 2,4-diethylthioxanthone YD-134 (manufactured by Nippon Steel Chemical & Material Co., Ltd.): Bisphenol A type epoxy resin TPP (manufactured by Hokko Chemical Industry Co., Ltd.): Triphenylphosphine

[0112] The results in Table 2 demonstrate that the composition of this embodiment exhibits excellent insulation reliability and thermal decomposition resistance.

[0113] (Examples 5-10): Evaluation of developability of resin compositions containing a colorant (F) The resin compositions for Examples 5-10 were prepared by mixing the resins in the amounts (weight %) shown in Table 3. The prepared resin compositions were spin-coated onto glass substrates and heated at 80°C for 10 minutes to form a coating film. Subsequently, dip development (shaking speed 50 rpm) was performed in a petri dish containing a 1% sodium carbonate aqueous solution for 60 seconds. The developability was evaluated by observing the condition of the substrate after development and checking for the presence or absence of residue. [Evaluation Criteria] ○: No residue after 60 seconds of development. ×: Residue present after 60 seconds of development.

[0114] [Table 3]

[0115] KAYARAD ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd.): Biphenyl aralkyl type acid-modified epoxy acrylate (Solid content acid value: 98 mg·KOH / g)

[0116] The results in Table 3 demonstrate that even embodiments containing a coloring agent exhibit excellent developability. [Industrial applicability]

[0117] The resin composition of the present invention possesses excellent insulating reliability and thermal decomposition resistance, while also exhibiting superior adhesion during alkaline development. Therefore, the resin composition of the present invention can be suitably used as a wiring protection and insulating material for electronic materials, as well as a material for display devices, and the like.

Claims

1. A (meth)acrylate compound (A) is obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, Alkali-soluble resin (B), A resin composition containing a photopolymerization initiator (C).

2. The resin composition according to claim 1, wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule has a benzene ring structure.

3. The resin composition according to claim 1, wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule contains two or more nitrogen atoms.

4. The resin composition according to claim 1, wherein the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule is a polyfunctional (meth)acrylate compound having three or more (meth)acrylic groups in one molecule, and the (meth)acrylate compound (A) has one or more (meth)acrylic groups in one molecule.

5. The resin composition according to claim 1, wherein the alkali-soluble resin (B) containing one or more carboxyl groups is a reactive polycarboxylic acid resin (B-1) obtained by reacting an epoxy resin (c) with a compound (d) having both polymerizable ethylenically unsaturated groups and carboxyl groups in one molecule, and then reacting that product with a polybasic acid anhydride (e).

6. The resin composition according to claim 1, comprising solvent (D).

7. The resin composition according to claim 1, comprising a curing agent (E).

8. The resin composition according to claim 1, comprising a coloring agent (F).

9. The resin composition according to claim 1, wherein the coloring agent (F) includes a black pigment.

10. The resin composition according to claim 1, which is a material for a display device.

11. The resin composition according to claim 1, which is a material for forming a film for insulating applications.

12. The resin composition according to claim 1 for use in a permanent resist.

13. The resin composition according to claim 1, wherein the solid content acid value of the alkali-soluble resin (B) is 40 to 140 mg / g.

14. A cured product of the resin composition according to any one of claims 1 to 13.

Images