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

Abstract

To provide an acid group-containing (meth)acrylate resin which enables formation of a cured product that has high sensitivity and is excellent in base material adhesion and low elasticity.SOLUTION: An acid group-containing (meth)acrylate resin contains a copolymer (I) composed of a polymer containing a (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth)acrylate compound (A) as essential polymerization components, and a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) which has a functional group capable of reacting with a reactive functional group that the polymerizable unsaturated bond-containing compound (B) has, and a polybasic acid anhydride (D) as essential reaction raw materials. The (meth)acrylate compound (A) contains a specific phenol compound as a raw material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an acid group-containing (meth)acrylate resin that has high photosensitivity and is capable of forming a cured product that has excellent substrate adhesion and low elasticity, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material, a resin material for a solder resist, and a resist member. [Background technology]

[0002] In recent years, curable compositions, such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat, have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. In particular, for the coating agent applications, it is generally required that the composition be able to impart design features to the surfaces of various substrates, have excellent curability, and be able to form a coating film that can prevent deterioration of the substrate surface. Furthermore, when used as a curable composition for solder resists for printed wiring boards, it is also required that the composition be able to cure with a low exposure dose, have excellent adhesion to the substrate, and have low elasticity.

[0003] Known active energy ray-curable compositions that can be cured by active energy rays include curable compositions containing di(meth)acrylates represented by the following general formula (1) (see, for example, Patent Document 1).

[0004] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group.]

[0005] However, this curable composition does not satisfy the recently increasing demands for substrate adhesion and low elasticity.

[0006] Therefore, there has been a demand for a material that has high photosensitivity, and is capable of forming a cured product that has excellent substrate adhesion and low elasticity. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-314320 Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin that has high photosensitivity and is capable of forming a cured product that has excellent substrate adhesion and low elasticity; a curable resin composition containing the same; a cured product of the curable resin composition; an insulating material; a resin material for a solder resist; and a resist member. [Means for solving the problem]

[0009] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a copolymer (I) consisting of a polymer containing, as essential polymerization components, a specific (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth)acrylate compound (A); a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B), which has a functional group capable of reacting with the reactive functional group of the polymerizable unsaturated bond-containing compound (B); and a polybasic acid anhydride (D), thereby completing the present invention.

[0010] That is, the present invention provides an acid group-containing (meth)acrylate resin obtained by using, as essential reaction raw materials, a copolymer (I) consisting of a polymer containing, as essential polymerization components, a (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth)acrylate compound (A), a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) having a functional group capable of reacting with the reactive functional group of the polymerizable unsaturated bond-containing compound (B), and a polybasic acid anhydride (D), The present invention relates to an acid group-containing (meth)acrylate resin, characterized in that the meth)acrylate compound (A) contains, as essential reaction raw materials, a phenolic hydroxyl group-containing compound (a1), a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2), and an unsaturated monocarboxylic acid (a3), and the phenolic hydroxyl group-containing compound (a1) is a phenol compound having at least three hydroxyl groups as substituents on an aromatic ring; a curable resin composition containing the acid group-containing (meth)acrylate resin; a cured product of the curable resin composition; an insulating material; a resin material for solder resist; and a resist member. [Effects of the Invention]

[0011] The acid group-containing (meth)acrylate resin of the present invention has high photosensitivity and can form a cured product excellent in substrate adhesion and low elasticity. Therefore, a curable resin composition containing the (meth)acrylate compound and a photopolymerization initiator can be used as a coating agent or an adhesive, and as the coating agent, it is particularly suitable for use in solder resist applications. DETAILED DESCRIPTION OF THE INVENTION

[0012] The acid group-containing (meth)acrylate resin of the present invention is characterized in that it is produced using, as essential reaction raw materials, a copolymer (I) consisting of a polymer containing, as essential polymerization components, a (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) other than the (meth)acrylate compound (A) that has a reactive functional group (hereinafter abbreviated as "polymerizable unsaturated bond-containing compound (B)"), a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) that has a functional group reactive with the reactive functional group of the polymerizable unsaturated bond-containing compound (B) (hereinafter abbreviated as "polymerizable unsaturated bond-containing compound (C)"), and a polybasic acid anhydride (D).

[0013] In the present invention, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylic" means acrylic and / or methacrylic.

[0014] The copolymer (I) is a polymer containing the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) as essential polymerization components.

[0015] The (meth)acrylate compound (A) used contains, as essential reaction raw materials, a phenolic hydroxyl group-containing compound (a1), a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2), and an unsaturated monocarboxylic acid (a3).

[0016] The phenolic hydroxyl group-containing compound (a1) essentially contains a phenol compound having at least three hydroxyl groups as substituents on the aromatic ring.

[0017] The phenol compound having at least three hydroxyl groups as substituents on the aromatic ring is not particularly limited as long as it has three hydroxyl groups as substituents on the aromatic ring, and may have other substituents.

[0018] Examples of the phenol compound having at least three hydroxyl groups as substituents on the aromatic ring include compounds represented by the following structural formulas (1-1) to (1-3).

[0019] [ka]

[0020] In the above structural formulas (1-1) to (1-3), R 1 is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. Also, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 3 or more. Note that the position of the substituent on the aromatic ring in the above structural formula is arbitrary; for example, in the naphthalene ring of structural formula (1-2), the substituent may be on any ring, and in structural formula (1-3), the substituent may be on any ring of the benzene ring present in one molecule, and p and q indicate the number of substituents in one molecule.

[0021] Among the compounds represented by the above structural formulas (1-1) to (1-3), trihydroxybenzene in which p is 0 and q is 3 in structural formula (1-1) is preferred because it gives a (meth)acrylate resin that has high photosensitivity and can form a cured product that is excellent in substrate adhesion and low elasticity. More specifically, 1,2,3-trihydroxybenzene (hereinafter sometimes referred to as "pyrogallol") having hydroxyl groups at the 1-, 2-, and 3-positions, or 1,2,4-trihydroxybenzene having hydroxyl groups at the 1-, 2-, and 4-positions is more preferred.

[0022] Examples of the cyclic carbonate compound (a2-1) 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. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a (meth)acrylate resin that has high photosensitivity and can form a cured product with excellent substrate adhesion and low elasticity.

[0023] Examples of the cyclic ether compound (a2-2) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more. Among these, ethylene oxide and propylene oxide are preferred because they can produce a (meth)acrylate resin that has high photosensitivity and can form a cured product that has excellent substrate adhesion and low elasticity.

[0024] The molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)], or the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic ether compound (a2-2) [(a2-2) / (a1)], is preferably 3 or more, since this results in a (meth)acrylate resin that can form a cured product having high photosensitivity, excellent substrate adhesion, and low elasticity.

[0025] The unsaturated monocarboxylic acid (a3) ​​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. Furthermore, a compound represented by the following structural formula (2) can also be used as the unsaturated monocarboxylic acid (a3). Furthermore, esters, acid halides, acid anhydrides, etc. of the unsaturated monocarboxylic acid (a3) ​​can also be used. These unsaturated monocarboxylic acids (a3) ​​can be used alone or in combination of two or more.

[0026] [ka] [In the formula, X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in its structure. Y represents a hydrogen atom or a methyl group.]

[0027] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0028] An example of the (poly)ester chain is a (poly)ester chain represented by the following structural formula (3).

[0029] [ka] (In the formula, R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.)

[0030] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0031] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following structural formula (4).

[0032] [ka] (In the formula, R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.)

[0033] Examples of the esters of the unsaturated monocarboxylic acid (a3) ​​include (meth)acrylic acid alkyl ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acid ester compounds such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; nitrogen-containing (meth)acrylic acid ester compounds such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate; and other (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0034] Examples of the acid halide of the unsaturated monocarboxylic acid (a3) ​​include (meth)acrylic acid chloride.

[0035] Examples of the acid anhydrides of the unsaturated monocarboxylic acids (a3) ​​include (meth)acrylic anhydride.

[0036] The molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated monocarboxylic acid (a3) ​​[(a3) / (a2-1)], or the molar ratio of the cyclic ether compound (a2-2) to the unsaturated monocarboxylic acid (a3) ​​[(a3) / (a2-2)], is preferably 0.65 or more, and more preferably in the range of 0.65 to 1.05, in order to obtain an acid group-containing (meth)acrylate resin that can form a cured product having high photosensitivity, excellent substrate adhesion, and low elasticity.

[0037] The weight average molecular weight of the (meth)acrylate compound (A) is preferably 1,000 or less, since this allows for the production of an acid group-containing (meth)acrylate resin that has high photosensitivity and is capable of forming a cured product that has excellent substrate adhesion and low elasticity.

[0038] In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC).

[0039] The method for producing the (meth)acrylate compound (A) is not particularly limited, and the compound can be produced by any known method. For example, the compound can be produced by reacting all of the reactant materials at once, or by sequentially reacting the reactant materials. Among these, the reaction can be easily controlled by first reacting a phenolic hydroxyl group-containing compound (a1) with a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2) in the presence of a basic catalyst at a temperature of 60 to 200°C, followed by reacting an unsaturated monocarboxylic acid (a3) ​​or an ester thereof in the presence of an acidic catalyst at a temperature of 60 to 140°C. This reaction can be carried out under reduced pressure, normal pressure, or elevated pressure.

[0040] The polymerizable unsaturated bond-containing compound (B) used herein has a reactive functional group. In the present invention, the term "polymerizable unsaturated bond" refers to an unsaturated bond that can be radically polymerized.

[0041] Examples of the reactive functional group include a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, an acrylamide group, etc. These reactive functional groups may be present alone or in combination of two or more.

[0042] Examples of the polymerizable unsaturated bond-containing compound (B) include a hydroxyl group-containing (meth)acrylate compound, an epoxy group-containing (meth)acrylate compound, an isocyanate group-containing (meth)acrylate compound, a carboxyl group-containing compound, and a compound having an acrylamide group. These polymerizable unsaturated bond-containing compounds (B) can be used alone or in combination of two or more.

[0043] Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0044] Examples of the epoxy group-containing (meth)acrylate compound include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylate products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0045] Examples of the isocyanate group-containing (meth)acrylate compound include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc. These isocyanate group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0046] Examples of the carboxyl group-containing compound include (meth)acrylic acid, ω-carboxy-polycaprolactone monoacrylate, etc. These carboxyl group-containing compounds can be used alone or in combination of two or more.

[0047] Examples of the acrylamide group-containing compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The acrylamide group-containing compounds can be used alone or in combination of two or more.

[0048] The copolymer (I) may contain other polymerization components in addition to the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B), if necessary.

[0049] Examples of the other polymerization components include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; tetrahydrofuran compounds such as tetrahydrofuran, ... Heterocyclic mono(meth)acrylate compounds such as difurfuryl acrylate; aromatic mono(meth)acrylate compounds such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; and mono(meth)acrylate compounds such as the above-mentioned various mono(meth)acrylate monos. (Poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the monomer; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate aliphatic di(meth)acrylate compounds such as acrylate and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate;Polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; Examples of suitable poly(meth)acrylate compounds include lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of a tri(meth)acrylate compound; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound.

[0050] The method for producing the copolymer (I) is not particularly limited, and any method may be used, such as a method of polymerizing all of the polymerization components containing the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) at a time at 50 to 200°C.

[0051] In the polymerization, a polymerization initiator can be used as needed.

[0052] Examples of the polymerization initiator include radical polymerization initiators such as persulfates, organic peroxides, and hydrogen peroxide, and azo initiators such as 4,4'-azobis(4-cyanovaleric acid) and 2,2'-azobis(2-amidinopropane) dihydrochloride. The radical polymerization initiator may also be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

[0053] Examples of the persulfate include potassium persulfate, sodium persulfate, ammonium persulfate, etc. These persulfates can be used alone or in combination of two or more.

[0054] Examples of the organic peroxides include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, peroxy esters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, and t-butylperoxybenzoate, and hydroperoxides such as cumene hydroperoxide, paramenthane hydroperoxide, and t-butyl hydroperoxide. These organic peroxides can be used alone or in combination of two or more.

[0055] The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, and is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total of the polymerization components containing the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B).

[0056] The polymerizable unsaturated bond-containing compound (C) has a functional group that can react with the reactive functional group of the polymerizable unsaturated bond-containing compound (B).

[0057] Examples of the polymerizable unsaturated bond-containing compound (C) include the same compounds as those exemplified above as the polymerizable unsaturated bond-containing compound (B). When a hydroxyl group-containing (meth)acrylate compound is used as the polymerizable unsaturated bond-containing compound (B), it is preferable to use an isocyanate group-containing (meth)acrylate compound and / or an acrylamide group-containing compound as the polymerizable unsaturated bond-containing compound (C). When an epoxy group-containing (meth)acrylate compound is used as the polymerizable unsaturated bond-containing compound (B), it is preferable to use a carboxyl group-containing compound as the polymerizable unsaturated bond-containing compound (C). Preferably, when an isocyanate group-containing (meth)acrylate compound is used as the polymerizable unsaturated bond-containing compound (B), a hydroxyl group-containing (meth)acrylate is preferably used as the polymerizable unsaturated bond-containing compound (C). When a carboxyl group-containing compound is used as the polymerizable unsaturated bond-containing compound (B), an epoxy group-containing (meth)acrylate is preferably used as the polymerizable unsaturated bond-containing compound (C). When an acrylamide group-containing compound is used as the polymerizable unsaturated bond-containing compound (B), a hydroxyl group-containing (meth)acrylate is preferably used as the polymerizable unsaturated bond-containing compound (C). These polymerizable unsaturated bond-containing compounds (C) can be used alone or in combination of two or more.

[0058] Examples of the polybasic acid anhydride (D) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0059] Examples of the aliphatic polybasic acid anhydrides include acid anhydrides of 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, etc. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

[0060] In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0061] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0062] These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0063] The method for producing the acid group-containing (meth)acrylate resin of the present invention is not particularly limited, and any method may be used for production. For example, the acid group-containing (meth)acrylate resin may be produced by a method (Method 1) in which all of the reaction raw materials containing the copolymer (I), the polymerizable unsaturated bond-containing compound (C), and the polybasic acid anhydride (D) are reacted at once, or by a method (Method 2) in which the reaction raw materials are reacted sequentially.

[0064] An example of the method 1 is a method in which reaction raw materials including the copolymer (I), the polymerizable unsaturated bond-containing compound (C), and the polybasic acid anhydride (D) are reacted at 50 to 150°C in the presence of a basic catalyst or an acidic catalyst.

[0065] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri Examples of suitable basic catalysts include quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; 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.

[0066] Examples of the acid 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 Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These acid catalysts can be used alone or in combination of two or more.

[0067] Examples of the method 2 include a method in which the copolymer (I) and the polymerizable unsaturated bond-containing compound (C) are first reacted at 70 to 140°C in the presence of a basic catalyst or an acid catalyst to obtain a reaction product (II), and then the reaction product (II) is reacted with the polybasic acid anhydride (D) in the presence of a basic catalyst at 70 to 140°C.

[0068] The basic catalyst may be the same as those exemplified above. These basic catalysts may be used alone or in combination of two or more.

[0069] The acid catalyst may be the same as those exemplified above. These acid catalysts may be used alone or in combination of two or more.

[0070] When the acid group-containing (meth)acrylate resin of the present invention is produced by the method 2, an acid group-containing (meth)acrylate resin having high photosensitivity and capable of forming a cured product excellent in substrate adhesion and low elasticity can be obtained. Therefore, it is preferable that the reaction product (II) has a hydroxyl group, and the number of moles of the polybasic acid anhydride (D) per mole of the hydroxyl group is in the range of 0.05 to 1 mole, and more preferably in the range of 0.1 to 0.95.

[0071] In the production of the (meth)acrylate resin having an acid group of the present invention, a polymerization inhibitor, an antioxidant, etc. may also be used, if necessary.

[0072] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,3-diphenyl-4-phenylenediamine), and methyl-p-benzoquinone.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination.

[0073] As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0074] Commercially available examples of the polymerization inhibitor and antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0075] The acid group-containing (meth)acrylate resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

[0076] Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0077] Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); and "Vicure 10" and "Vicure 55" (manufactured by Stoffa Examples of photopolymerization initiators include "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop), and "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

[0078] The amount of the photopolymerization initiator added is preferably within a range of, for example, 1 to 20% by mass in the curable resin composition.

[0079] The curable resin composition of the present invention may contain other resin components in addition to the acid group-containing (meth)acrylate resin described above. Examples of the other resin components include a resin (E) having an acid group and a polymerizable unsaturated bond, various (meth)acrylate monomers, etc.

[0080] The resin (E) having an acid group and a polymerizable unsaturated bond may be any resin as long as it has an acid group and a polymerizable unsaturated bond in the resin, and examples thereof include an epoxy resin having an acid group and a polymerizable unsaturated bond, a urethane resin having an acid group and a polymerizable unsaturated bond, an acrylic resin having an acid group and a polymerizable unsaturated bond, an amide-imide resin having an acid group and a polymerizable unsaturated bond, and an acrylamide resin having an acid group and a polymerizable unsaturated bond.

[0081] Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0082] Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include an acid group-containing epoxy (meth)acrylate resin which uses an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials, and an acid group- and urethane group-containing epoxy (meth)acrylate resin which uses an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound as reaction raw materials.

[0083] Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0084] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0085] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0086] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0087] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0088] 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. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (5) can also be used.

[0089] [ka] [In formula (5), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

[0090] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0091] An example of the (poly)ester chain is a (poly)ester chain represented by the following structural formula (X-1).

[0092] [ka] [In formula (X-1), R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0093] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0094] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0095] 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; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating unit represented by the following structural formula (6); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these. These polyisocyanate compounds can be used alone or in combination of two or more.

[0096] [ka] [In the formula, R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently either an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by structural formula (6) via a methylene group marked with an *. 1 is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0097] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as the hydroxyl group-containing (meth)acrylate compound can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0098] The method for producing the epoxy resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the epoxy resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0099] 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; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, as this improves reaction efficiency.

[0100] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0101] Examples of the urethane resin having an acid group and a polymerizable unsaturated bond include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and, if necessary, a polybasic acid anhydride with a polyol compound other than the carboxyl group-containing polyol compound, and those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride with a polyol compound other than the carboxyl group-containing polyol compound.

[0102] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0103] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as the hydroxyl group-containing (meth)acrylate compound can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0104] Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0105] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0106] Examples of polyol compounds other than the carboxyl group-containing polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various polyol compounds; and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0107] The method for producing the urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0108] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0109] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0110] Examples of the acrylic resin having an acid group and a polymerizable unsaturated bond include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

[0111] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0112] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred 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 preferred 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), it is preferred to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compounds (β) can be used alone or in combination of two or more.

[0113] The polybasic acid anhydride can be the same as those exemplified above as the polybasic acid anhydride (D), and the polybasic acid anhydrides can be used alone or in combination of two or more.

[0114] The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0115] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0116] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0117] Examples of the amide-imide resin having an acid group and a polymerizable unsaturated bond include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a hydroxyl group-containing (meth)acrylate compound and / or an epoxy group-containing (meth)acrylate compound, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group.

[0118] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with hydroxyl group-containing (meth)acrylate compounds and (meth)acryloyl group-containing epoxy compounds, it is preferable for it to have an acid anhydride group, and it is more preferable for it to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0119] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0120] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0121] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0122] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0123] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of suitable polybasic acids include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0124] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as the hydroxyl group-containing (meth)acrylate compound can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0125] As the epoxy group-containing (meth)acrylate compound, the same compounds as those exemplified as the epoxy group-containing (meth)acrylate compounds described above can be used, and the epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0126] The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the amide-imide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0127] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0128] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0129] Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include those obtained by reacting a phenolic hydroxyl group-containing compound, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, a polybasic acid anhydride, and, if necessary, an unsaturated monobasic acid.

[0130] The phenolic hydroxyl group-containing compound refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (7-1) to (7-4).

[0131] [ka]

[0132] In the above structural formulas (7-1) to (7-4), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (7-2), the substituent may be on any ring; in structural formula (7-3), the substituent may be on any ring of the benzene ring present in one molecule; and in structural formula (7-4), the substituent may be on any ring of the benzene ring present in one molecule; and the numbers of substituents in one molecule are p and q.

[0133] The compound having a phenolic hydroxyl group may also be, for example, a reaction product obtained by using, as essential reaction raw materials, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5). Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule.

[0134] [ka]

[0135] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group. In formula (x-5), Y represents 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.

[0136] These phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more.

[0137] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition that has high photosensitivity and can form a cured product that has excellent substrate adhesion and low elasticity. The alkylene oxides can be used alone or in combination of two or more.

[0138] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a curable resin composition that has high photosensitivity and can form a cured product that has excellent substrate adhesion and low elasticity. The alkylene carbonates can be used alone or in combination of two or more.

[0139] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0140] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (D) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0141] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0142] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0143] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0144] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0145] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0146] The amount of the resin (E) having an acid group and a polymerizable unsaturated bond used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the acid group-containing (meth)acrylate resin of the present invention.

[0147] Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono(meth)acrylate compounds such as the aromatic mono(meth)acrylate compounds of the above: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

[0148] In addition to those mentioned above, the other (meth)acrylate monomers that can be used include phenol compounds other than the phenol compounds having at least three hydroxyl groups as substituents on the aromatic ring (hereinafter sometimes referred to as "other phenol compounds"), and (meth)acrylate monomers that have as essential reaction raw materials a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid.

[0149] Examples of the other phenol compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and cyclo ring structure-containing phenol resin.

[0150] As the cyclic carbonate compound and the cyclic ether compound, the same compounds as the above-mentioned cyclic carbonate compound (a2-1) and the above-mentioned cyclic ether compound (a2-2) can be used.

[0151] As the unsaturated monocarboxylic acid, the same unsaturated monocarboxylic acid as the unsaturated monocarboxylic acid (a3) ​​can be used.

[0152] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0153] Furthermore, the curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as needed.

[0154] Examples of the curing agent include polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

[0155] Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo[2.2.1]heptacarboxylic acid. Examples of suitable polybasic acids include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0156] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0157] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more.

[0158] Examples of the amide compounds include dicyandiamide, polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more.

[0159] Examples of the azo compounds include azobisisobutyronitrile.

[0160] Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, alkyl peroxycarbonate, etc. These organic peroxides can be used alone or in combination of two or more.

[0161] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. Examples of suitable polyols include polyester polyols obtained by co-condensation of the above polyol monomers with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

[0162] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0163] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0164] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0165] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0166] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0167] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0168] The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. 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 inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0169] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0170] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0171] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0172] Furthermore, since the cured product of the present invention has high photosensitivity, excellent substrate adhesion, and low elasticity, it can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, etc., or adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCD and OELD as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. Among these, it can be particularly suitably used in solder resist applications.

[0173] The resin material for a solder resist of the present invention comprises the above-mentioned curable resin composition.

[0174] The resist member of the present invention can be obtained, for example, by applying the solder resist resin material to a substrate, evaporating and drying the organic solvent at a temperature in the range of about 60 to 100°C, exposing the material to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the material at a temperature in the range of about 140 to 200°C.

[0175] Examples of the substrate include a metal-clad laminate made of copper, aluminum, or the like. [Example]

[0176] The present invention will be specifically described below with reference to examples and comparative examples.

[0177] In the examples, the weight average molecular weight (Mw) is a value measured using a gel permeation chromatograph (GPC) under the following conditions.

[0178] Measuring device: Tosoh Corporation HLC-8220 Column: Guard column H manufactured by Tosoh Corporation XL -H + Tosoh TSKgel G5000HXL + Tosoh TSKgel G4000HXL + Tosoh TSKgel G3000HXL + Tosoh TSKgel G2000HXL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40℃ Solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: Polystyrene Sample: 100 μl of tetrahydrofuran solution containing 0.4% by mass of resin solids filtered through a microfilter

[0179] (Synthesis Example 1: Production of (meth)acrylate compound (A-1)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 126 parts by weight of pyrogallol, 277 parts by weight of ethylene carbonate, and 0.7 parts by weight of 50% aqueous potassium hydroxide solution, and the mixture was reacted at 170°C for 20 hours under a nitrogen atmosphere. The resulting reaction mixture was then dissolved in 333 parts by weight of toluene, followed by 228 parts by weight of acrylic acid, 5.0 parts by weight of paratoluenesulfonic acid, and 0.2 parts by weight of methylhydroquinone. The mixture was then reacted at 100°C for 10 hours while blowing air into it and stirring. The mixture was then cooled to 50°C, and the resulting reaction solution was washed with water. The toluene was removed to obtain (meth)acrylate compound (A-1). The weight-average molecular weight (Mw) of this (meth)acrylate compound (A-1) was 620, and its viscosity at 25°C was 330 mPa·s. The viscosity was measured at 25°C using an E-type rotational viscometer (RE80U, manufactured by Toki Sangyo Co., Ltd.). The molar ratio of pyrogallol to ethylene carbonate [(moles of ethylene carbonate) / (moles of pyrogallol)] corresponding to the molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)] was 3.15, and the molar ratio of ethylene carbonate to acrylic acid [(moles of acrylic acid) / (moles of ethylene carbonate)] corresponding to the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-1)] was 1.004.

[0180] (Synthesis Example 2: Production of (meth)acrylate compound (A-2)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 126 parts by weight of pyrogallol, 337 parts by weight of propylene carbonate, and 0.7 parts by weight of 50% aqueous potassium hydroxide solution, and the mixture was reacted at 170°C for 30 hours under a nitrogen atmosphere. The resulting reaction mixture was then dissolved in 379 parts by weight of toluene, followed by 237 parts by weight of acrylic acid, 5.7 parts by weight of paratoluenesulfonic acid, and 0.2 parts by weight of methylhydroquinone. The mixture was then reacted at 100°C for 20 hours while blowing in air and stirring. The mixture was then cooled to 50°C, and the resulting reaction solution was washed with water. The toluene was removed to obtain (meth)acrylate compound (A-2). The weight-average molecular weight (Mw) of this (meth)acrylate compound (A-2) was 780, and its viscosity at 25°C was 500 mPa·s. Furthermore, the molar ratio of pyrogallol to propylene carbonate [(moles of propylene carbonate) / (moles of pyrogallol)] corresponding to the molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)] was 3.30, and the molar ratio of propylene carbonate to acrylic acid [(moles of acrylic acid) / (moles of propylene carbonate)] corresponding to the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-1)] was 0.994.

[0181] (Synthesis Example 3: Production of (meth)acrylate compound (A-3)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 126 parts by weight of pyrogallol, 277 parts by weight of ethylene carbonate, and 0.7 parts by weight of 50% aqueous potassium hydroxide solution, and the mixture was reacted at 170°C for 20 hours under a nitrogen atmosphere. The resulting reaction mixture was then dissolved in 282 parts by weight of toluene, and 152 parts by weight of acrylic acid, 4.2 parts by weight of paratoluenesulfonic acid, and 0.1 parts by weight of methylhydroquinone were added. The mixture was then reacted at 100°C for 10 hours while blowing in air and stirring. The mixture was then cooled to 50°C, and the resulting reaction solution was washed with water. The toluene was removed to obtain (meth)acrylate compound (A-3). The weight-average molecular weight (Mw) of this (meth)acrylate compound (A-3) was 580, and its viscosity at 25°C was 520 mPa·s. Furthermore, the molar ratio of pyrogallol to ethylene carbonate [(number of moles of ethylene carbonate) / (number of moles of pyrogallol)] corresponding to the molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)] was 3.15, and the molar ratio of ethylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of ethylene carbonate)] corresponding to the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-1)] was 0.669.

[0182] (Synthesis Example 4: Production of (meth)acrylate compound (A-4)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 126 parts by weight of pyrogallol, 277 parts by weight of ethylene carbonate, and 0.7 parts by weight of 50% aqueous potassium hydroxide solution, and the mixture was reacted at 170°C for 20 hours under a nitrogen atmosphere. The resulting reaction mixture was then dissolved in 277 parts by weight of toluene, and 144 parts by weight of acrylic acid, 4.2 parts by weight of paratoluenesulfonic acid, and 0.1 parts by weight of methylhydroquinone were added. The mixture was then reacted at 100°C for 10 hours while blowing in air and stirring. The mixture was then cooled to 50°C, and the resulting reaction solution was washed with water. The toluene was removed to obtain (meth)acrylate compound (A-4). The weight-average molecular weight (Mw) of this (meth)acrylate compound (A-4) was 560, and its viscosity at 25°C was 600 mPa·s. Furthermore, the molar ratio of pyrogallol to ethylene carbonate [(number of moles of ethylene carbonate) / (number of moles of pyrogallol)] corresponding to the molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)] was 3.15, and the molar ratio of ethylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of ethylene carbonate)] corresponding to the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-1)] was 0.636.

[0183] (Example 1: Production of Acid Group-Containing (Meth)acrylate Resin (1)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (1). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (1) was 103 mgKOH / g, and the weight average molecular weight (Mw) was 18,890.

[0184] (Example 2: Production of Acid Group-Containing (Meth)acrylate Resin (2)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-2) obtained in Synthesis Example 2, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (2). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (2) was 102 mgKOH / g, and the weight average molecular weight (Mw) was 19,030.

[0185] (Example 3: Production of Acid Group-Containing (Meth)acrylate Resin (3)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-3) obtained in Synthesis Example 3, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (3). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (3) was 104 mgKOH / g, and the weight average molecular weight (Mw) was 17,880.

[0186] (Example 4: Production of acid group-containing (meth)acrylate resin (4)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-4) obtained in Synthesis Example 4, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (4). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (4) was 103 mgKOH / g, and the weight average molecular weight (Mw) was 17,230.

[0187] (Example 5: Production of Acid Group-Containing (Meth)acrylate Resin (5)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 18 parts by weight of methyl methacrylate, 10 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of tetrahydrophthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (5). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (5) was 102 mgKOH / g, and the weight average molecular weight (Mw) was 20,170.

[0188] (Example 6: Production of acid group-containing (meth)acrylate resin (6)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 37 parts by mass of tetrahydrophthalic anhydride and 32 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (6). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (6) was 81 mgKOH / g, and the weight average molecular weight (Mw) was 17,980.

[0189] (Example 7: Production of acid group-containing (meth)acrylate resin (7)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 26 parts by mass of tetrahydrophthalic anhydride and 22 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (7). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (7) was 61 mgKOH / g, and the weight average molecular weight (Mw) was 16,240.

[0190] (Example 8: Production of acid group-containing (meth)acrylate resin (8)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of glycidyl methacrylate, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were charged, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by mass of hexahydroxyphthalic anhydride and 44 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the target acid group-containing (meth)acrylate resin (8). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (8) was 101 mgKOH / g, and the weight average molecular weight (Mw) was 18,610.

[0191] (Example 9: Production of acid group-containing (meth)acrylate resin (9)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 54 parts by weight of cyclohexanone and heated to 120°C under a nitrogen atmosphere. Next, 69 parts by weight of methacrylic acid, 26 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of cyclohexanone, and 5 parts by weight of perbutyl 0 were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 114 parts by weight of cyclohexanone, 0.3 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 112 parts by weight of glycidyl methacrylate, and 0.8 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110°C for 20 hours while blowing in air and stirring. Next, 55 parts by weight of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110°C for 5 hours to obtain the desired acid group-containing (meth)acrylate resin (9). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (9) was 103 mgKOH / g, and the weight average molecular weight (Mw) was 22,380.

[0192] (Example 10: Production of acid group-containing (meth)acrylate resin (10)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 54 parts by weight of cyclohexanone and heated to 120°C under a nitrogen atmosphere. Next, 78 parts by weight of methacrylic acid, 17 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of cyclohexanone, and 5 parts by weight of perbutyl 0 were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 55 parts by weight of cyclohexanone, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 90 parts by weight of glycidyl methacrylate, and 0.8 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110°C for 15 hours while blowing in air and stirring. Next, 10 parts by weight of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110°C for 3 hours to obtain the desired acid group-containing (meth)acrylate resin (10). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (10) was 102 mg KOH / g.

[0193] (Example 11: Production of acid group-containing (meth)acrylate resin (11)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 54 parts by weight of cyclohexanone and heated to 120°C under a nitrogen atmosphere. Next, 72 parts by weight of methacrylic acid, 23 parts by weight of methyl methacrylate, 5 parts by weight of the (meth)acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by weight of cyclohexanone, and 5 parts by weight of perbutyl O were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 62 parts by weight of cyclohexanone, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 90 parts by weight of glycidyl methacrylate, and 0.8 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110°C for 15 hours while blowing in air and stirring. Next, 9 parts by weight of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110°C for 3 hours to obtain the desired acid group-containing (meth)acrylate resin (11). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (11) was 81 mgKOH / g, and the weight average molecular weight (Mw) was 18,770.

[0194] (Comparative Example 1: Production of Acid Group-Containing (Meth)acrylate Resin (12)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 54 parts by weight of diethylene glycol monomethyl ether acetate and heated to 120°C under a nitrogen atmosphere. Next, 30 parts by weight of glycidyl methacrylate, 70 parts by weight of methyl methacrylate, 68 parts by weight of diethylene glycol monomethyl ether acetate, and 5 parts by weight of perbutyl ether were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 37 parts by weight of acrylic acid, and 0.7 parts by weight of triphenylphosphine were added, and the mixture was reacted at 120°C for 10 hours while blowing in air and stirring. Next, 51 parts by weight of tetrahydrophthalic anhydride and 44 parts by weight of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110°C for 5 hours to obtain the desired acid group-containing (meth)acrylate resin (12). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (12) was 102 mgKOH / g.

[0195] (Comparative Example 2: Production of Acid Group-Containing (Meth)acrylate Resin (13)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 54 parts by weight of cyclohexanone and heated to 120°C under a nitrogen atmosphere. Next, 78 parts by weight of methacrylic acid, 22 parts by weight of methyl methacrylate, 68 parts by weight of cyclohexanone, and 5 parts by weight of perbutyl ether were premixed and added dropwise over 3 hours. After holding at 120°C for 4 hours, 0.2 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of methylhydroquinone, 62 parts by weight of cyclohexanone, 90 parts by weight of glycidyl methacrylate, and 0.8 parts by weight of triphenylphosphine were added, and the mixture was reacted at 110°C for 15 hours while blowing in air and stirring. Next, 9 parts by weight of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110°C for 3 hours to obtain the desired acid group-containing (meth)acrylate resin (13). The acid value of the solid content of the obtained acid group-containing (meth)acrylate resin (13) was 82 mgKOH / g.

[0196] (Example 12: Preparation of curable resin composition (1)) 100 parts by mass of the acid group-containing (meth)acrylate resin (1) having a nonvolatile content of 53% by mass obtained in Example 1, 2.7 parts by mass of a photopolymerization initiator ("Omnirad907" manufactured by IGM), 22 parts by mass of a bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent), 5.3 parts by mass of dipentaerythritol hexaacrylate, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.6 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (1).

[0197] (Examples 13 to 22: Preparation of curable resin compositions (2) to (11)) Curable resin compositions (2) to (11) were obtained in the same manner as in Example 12, except that the acid group-containing (meth)acrylate resins (2) to (11) obtained in Examples 2 to 11 were used in the amounts shown in Table 1 instead of the acid group-containing (meth)acrylate resin (1) used in Example 12.

[0198] (Comparative Example 3: Preparation of curable resin composition (C1)) A curable resin composition (C1) was obtained by mixing 100 parts by mass of the acid group-containing (meth)acrylate resin (12) having a nonvolatile content of 53% by mass obtained in Comparative Example 1, 2.7 parts by mass of a photopolymerization initiator ("Omnirad907" manufactured by IGM), 21.7 parts by mass of a bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent), 5.3 parts by mass of dipentaerythritol hexaacrylate, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.6 parts by mass of phthalocyanine green.

[0199] (Comparative Example 4: Preparation of curable resin composition (C2)) A curable resin composition (C2) was obtained in the same manner as in Comparative Example 3, except that the acid group-containing (meth)acrylate resin (13) obtained in Comparative Example 2 was used in the blending amount shown in Table 1 instead of the acid group-containing (meth)acrylate resin (12) used in Comparative Example 3.

[0200] The curable resin compositions (1) to (11), (C1) and (C2) obtained in the above Examples and Comparative Examples were evaluated as follows.

[0201] [Photosensitivity evaluation method] The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Then, the composition was irradiated with 1000 mJ / cm 2 of a metal halide lamp through a Kodak Step Tablet No. 2. 2 This was developed for 180 seconds in a 1% by mass aqueous solution of sodium carbonate, and the number of remaining steps was used for evaluation. The greater the number of remaining steps, the higher the photosensitivity.

[0202] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (11) prepared in Examples 12 to 22 and the curable resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2.

[0203] [Table 1]

[0204] (Example 23: Preparation of curable resin composition (12)) 100 parts by mass of the acid group-containing (meth)acrylate resin (1) having a nonvolatile content of 53% by mass obtained in Example 1, 22 parts by mass of a bisphenol A-type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent), and 2.7 parts by mass of a photopolymerization initiator ("Omnirad907" manufactured by IGM) were mixed to obtain a curable resin composition (12).

[0205] (Examples 24 to 33: Preparation of curable resin compositions (12) to (22)) Curable resin compositions (12) to (22) were obtained in the same manner as in Example 23, except that the acid group-containing (meth)acrylate resins (2) to (11) obtained in Examples 2 to 11 were used in the amounts shown in Table 2 instead of the acid group-containing (meth)acrylate resin (1) used in Example 23.

[0206] (Comparative Example 5: Preparation of curable resin composition (C3)) A curable resin composition (C3) was obtained by mixing 100 parts by mass of the acid group-containing (meth)acrylate resin (12) having a nonvolatile content of 53% by mass obtained in Comparative Example 2, 21.7 parts by mass of a bisphenol A-type epoxy resin (EPICLON 850S manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent), and 2.7 parts by mass of a photopolymerization initiator (Omnirad907 manufactured by IGM).

[0207] (Comparative Example 6: Preparation of curable resin composition (C4)) A curable resin composition (C4) was obtained in the same manner as in Comparative Example 5, except that the acid group-containing (meth)acrylate resin (13) obtained in Comparative Example 2 was used in the blending amount shown in Table 2 instead of the acid group-containing (meth)acrylate resin (12) used in Comparative Example 5.

[0208] The curable resin compositions obtained in the above Examples and Comparative Examples were evaluated as follows.

[0209] [Method for evaluating adhesion to substrate] The adhesion to the substrate was evaluated by measuring the peel strength.

[0210] <Preparation of test piece 1> The curable resin compositions obtained in the examples and comparative examples were applied to copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then exposed to 1000 mJ / cm 2 using a metal halide lamp. 2 After irradiating with ultraviolet light, the specimen was heated at 160°C for 1 hour to obtain a test piece 1.

[0211] <Method for measuring peel strength> The test piece 1 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength was measured using a peel tester ("A&D Tensilon" manufactured by A&D Co., Ltd., peel speed 50 mm / min).

[0212] [Elasticity evaluation method] The elasticity was evaluated by measuring the elastic modulus through a tensile test.

[0213] <Preparation of test piece 2> The curable resin compositions obtained in the examples and comparative examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied curable resin compositions to the copper foil to a thickness of 50 μm. 2 After irradiating with ultraviolet light, the cured product was heated at 160° C. for 1 hour, and the cured product was peeled off from the copper foil to obtain Test Piece 2.

[0214] <Tensile test> The test piece 2 was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece under the following measurement conditions using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

[0215] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm / min

[0216] The compositions and evaluation results of the curable resin compositions (12) to (22) obtained in Examples 23 to 33 and the curable resin compositions (C3) and (C4) obtained in Comparative Examples 5 and 6 are shown in Table 2.

[0217] [Table 2]

[0218] In Tables 1 and 2, the parts by mass of the acid group-containing (meth)acrylate resin are solid content values.

[0219] Examples 12 to 22 shown in Table 1 are examples in which the acid group-containing (meth)acrylate resin of the present invention was used. It was confirmed that the cured product of the curable resin composition containing the acid group-containing (meth)acrylate resin of the present invention had high photosensitivity, and the obtained cured product had excellent substrate adhesion and low elasticity.

[0220] On the other hand, Comparative Examples 3 to 6 are examples in which the (meth)acrylate compound (A) defined in the present invention is not used. These curable resin compositions had low peel strength and high elastic modulus, and it was confirmed that they were insufficient in terms of substrate adhesion and low elasticity.

Claims

1. a copolymer (I) consisting of a polymer containing, as essential polymerization components, a (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth)acrylate compound (A); a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B), which has a functional group capable of reacting with a reactive functional group possessed by the polymerizable unsaturated bond-containing compound (B); a polybasic acid anhydride (D), A method for producing an acid group-containing (meth)acrylate resin as an essential reaction raw material, comprising: the (meth)acrylate compound (A) is a compound obtained by reacting a phenolic hydroxyl group-containing compound (a1), a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2), and an unsaturated monocarboxylic acid (a3) ​​as essential reaction raw materials; the phenolic hydroxyl group-containing compound (a1) is a phenol compound having at least three hydroxyl groups as substituents on an aromatic ring, the phenol compound having at least three hydroxyl groups as substituents on an aromatic ring is 1,2,3-trihydroxybenzene or 1,2,4-trihydroxybenzene; a molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)], or a molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic ether compound (a2-2) [(a2-2) / (a1)], is 3 or more; the cyclic carbonate compound (a2-1) is ethylene carbonate and / or propylene carbonate, the cyclic ether compound (a2-2) is ethylene oxide and / or propylene oxide, the unsaturated monocarboxylic acid (a3) ​​is acrylic acid and / or methacrylic acid; the polymerizable unsaturated bond-containing compound (B) is an epoxy group- or carboxyl group-containing (meth)acrylate compound, the polymerizable unsaturated bond-containing compound (C) is a (meth)acrylate compound containing a carboxyl group or an epoxy group, The polybasic acid anhydride (D) is tetrahydrophthalic acid and / or hexahydrophthalic acid, a polymerizable unsaturated bond-containing compound (C) is reacted with the copolymer (I) to obtain a reaction product (II), and the reaction product (II) is reacted with the polybasic acid anhydride (D), A method for producing an acid group-containing (meth)acrylate resin.

2. 2. The method for producing an acid group-containing (meth)acrylate resin according to claim 1, wherein the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-1)], or the molar ratio of the cyclic ether compound (a2-2) to the unsaturated carboxylic acid (a3) ​​[(a3) / (a2-2)], is 0.65 or more.

3. 2. The method for producing an acid group-containing (meth)acrylate resin according to claim 1, wherein the reaction product (II) has a hydroxyl group, and the number of moles of the polybasic acid anhydride (D) per mole of the hydroxyl group is in the range of 0.05 to 1 mole.

4. A method for producing a curable resin composition, comprising the acid group-containing (meth)acrylate resin according to any one of claims 1 to 3 and a photopolymerization initiator.

5. The method for producing a curable resin composition according to claim 4, wherein the curable resin composition further contains a resin (E) having an acid group and a polymerizable unsaturated bond.

6. The method for producing a curable resin composition according to claim 4, wherein the curable resin composition further contains a curing agent and / or an organic solvent.

7. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 4 to 6.

8. A method for producing an insulating material comprising the curable resin composition according to any one of claims 4 to 6.

9. A method for producing a resin material for a solder resist, comprising the curable resin composition according to any one of claims 4 to 6.

10. A method for producing a resist member comprising the solder resist resin material according to claim 9.

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