JP7707570B2 - Resin, curable resin composition, cured product, insulating material, and resist member - Google Patents

Description

The present invention relates to a resin that has high photosensitivity and excellent alkaline developability and has excellent dielectric properties in the cured product, a curable resin composition containing the resin, a cured product, and an insulating material and a resist member made of the cured product.

In recent years, curable resin compositions that can be cured by active energy rays such as ultraviolet rays have been widely used as resin materials for solder resists on printed wiring boards. The required properties of the resin materials for solder resists include being cured with a small amount of light exposure, having excellent alkaline developability, and having excellent heat resistance, strength, and dielectric properties in the cured product.

A conventional resin material for solder resist is a photosensitive resin composition containing an acid group-containing epoxy acrylate resin obtained by reacting an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride with tetrahydrophthalic anhydride (see, for example, Patent Document 1). However, this composition does not satisfy the increasingly high requirements for photosensitivity and alkaline developability, and its dielectric properties are also insufficient to meet current market demands.

Therefore, there was a demand for a material that has high photosensitivity, excellent alkaline developability, and excellent dielectric properties when cured.

Japanese Patent Application Publication No. 8-259663

The problem that the present invention aims to solve is to provide a resin that has high photosensitivity and excellent alkaline developability and has excellent dielectric properties in the cured product, a curable resin composition containing the resin, a cured product, and an insulating material and a resist member made of the cured product.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems can be solved by using a resin having at least one polymerizable unsaturated group, at least one acid group, and at least one specific structure in one molecule, and thus completed the present invention.

That is, the present invention relates to a resin characterized by having at least one polymerizable unsaturated group, at least one acid group, and at least one structure represented by the following general formula (1) in one molecule.

In formula (1), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring.

The resin of the present invention has high photosensitivity and excellent alkaline developability, and can form a cured product with excellent dielectric properties, so it can be suitably used for insulating materials, resin materials for solder resists, and resist members. In the present invention, "excellent dielectric properties" refers to a low dielectric constant and a low dielectric tangent.

The resin of the present invention is characterized by having at least one polymerizable unsaturated group, at least one acid group, and at least one structure represented by the following general formula (1) in one molecule.

In formula (1), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring.

Examples of the polymerizable unsaturated group include (meth)acryloyl, allyl, isopropenyl, 1-propenyl, styryl, styrylmethyl, maleimide, and vinyl ether groups. In the present invention, "(meth)acryloyl" means acryloyl and/or methacryloyl. "(meth)acrylate" means acrylate and/or methacrylate. "(meth)acrylic" means acrylic and/or methacrylic.

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

The polymerizable unsaturated group equivalent in the resin of the present invention is preferably in the range of 250 to 1200 g/equivalent, more preferably in the range of 300 to 1000 g/equivalent, and even more preferably in the range of 400 to 1000 g/equivalent, since the resin has high photosensitivity and excellent alkaline developability, and has excellent dielectric properties in the cured product.

The acid value of the resin of the present invention is preferably in the range of 40 to 140 gKOH/g, more preferably in the range of 50 to 130 mgKOH/g, and even more preferably in the range of 60 to 120 mgKOH/g, since the resin has high photosensitivity and excellent alkaline developability, and has excellent dielectric properties in the cured product.

Furthermore, the ester bond equivalent of the structure represented by the general formula (1) in the resin of the present invention is preferably in the range of 200 to 1000 g/equivalent, more preferably in the range of 250 to 800 g/equivalent, and even more preferably in the range of 250 to 600 g/equivalent, since a resin having high photosensitivity and excellent alkaline developability and having excellent dielectric properties in the cured product can be obtained.

Examples of the substituent that may be possessed by the Ar ¹ and Ar ² carbon atoms in the formula (1) include 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.

Examples of the resin of the present invention include resin (I) having as essential raw materials an aromatic compound (A) having a phenolic hydroxyl group, an aromatic compound having an acid group other than the aromatic compound (A), its acid halide and/or its ester (B), a (meth)acrylate compound (C) having an epoxy group, and a polybasic acid anhydride and/or its acid halide (D); resin (II) having as essential raw materials an aromatic compound (A) having a phenolic hydroxyl group, an aromatic compound having an acid group other than the aromatic compound (A), its acid halide and/or its ester (B), and an unsaturated monobasic acid, its acid halide and/or its ester (E).

Examples of the aromatic compound (A) include compounds represented by the following structural formulas (2-1) to (2-10). Among these, compounds having at least one hydroxyl group on an aromatic ring and at least one acid group in one molecule are preferred, since they have high photosensitivity and excellent alkaline developability, and can give resins with excellent dielectric properties in the cured product.

In the above structural formulas (2-1) to (2-10), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an acid group, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group. In addition, p is each independently an integer of 0 or 1 or more, and q is each independently an integer of 1 or more. n is an integer of 1 to 10, and m is an integer of 1 to 5. The positions of the substituent R ¹ and the hydroxyl group on the aromatic ring in the above structural formulas are arbitrary, and for example, in the naphthalene ring of structural formula (2-2), they may be substituted on any ring, and in structural formulas (2-3) and (2-4), they may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents on the benzene ring in one molecule is p+q.

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

The aromatic compound having an acid group, its acid halide and/or its ester (B) (hereinafter abbreviated as "aromatic compound (B)") is not particularly limited as long as it is a compound having an acid group in one molecule other than the aromatic compound (A), and examples thereof include compounds represented by the following structural formulas (3-1) to (3-5).

In the above structural formulas (3-1) to (3-5), R ³ is an acid group, R ⁴ is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and R ⁵ is each independently a hydrogen atom or a methyl group. In addition, r is an integer of 1 or more, and s is an integer of 0 or 1 or more. The positions of the substituents R ³ and R ⁴ on the aromatic ring in the above structural formulas are arbitrary, and for example, in the naphthalene ring of structural formula (3-2), they may be substituted on any ring, and in structural formulas (3-3) to (3-5), they may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents on the benzene ring in one molecule is r+s.

In addition, the aromatic compound (B) may have at least one acid group per molecule.

These aromatic compounds (B) can be used alone or in combination of two or more.

The amount of the aromatic compound (B) used is preferably such that the number of moles of functional groups capable of reacting with the phenolic hydroxyl groups of the aromatic compound (B) is in the range of 0.9 to 1.5, and more preferably 0.95 to 1.25, per mole of the phenolic hydroxyl groups of the aromatic compound (A), since this results in a resin with high photosensitivity, excellent alkaline developability, and excellent dielectric properties in the cured product.

Examples of the (meth)acrylate compound (C) having an epoxy group include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as mono(meth)acrylates of diglycidyl ether compounds such as hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds (C) having an epoxy group can be used alone or in combination of two or more.

Examples of the polybasic acid anhydride and/or its acid halide (D) (hereinafter abbreviated as "polybasic acid anhydride (D)") include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, acid halides of aromatic polybasic acid anhydrides, etc.

Examples of the aliphatic polybasic acid anhydrides include 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, and 1,2,3,4-butanetetracarboxylic acid. In addition, 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.

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 aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include anhydrides of 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.

Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic 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.

These polybasic acid anhydrides (D) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred because they have high photosensitivity and excellent alkaline developability, and can give resins with excellent dielectric properties in the cured product.

Examples of the unsaturated monobasic acid, its acid halide and/or its ester (E) (hereinafter abbreviated as "unsaturated monobasic acid (E)") include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, etc. In addition, acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (4) can also be used.

[In formula (4), 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.]

Examples of the polyoxyalkylene chain include polyoxyethylene chains and polyoxypropylene chains.

The (poly)ester chain may be, for example, a (poly)ester chain represented by the following structural formula (X-1).

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

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain. In addition, 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.

The (poly)carbonate chain may be, for example, a (poly)carbonate chain represented by the following structural formula (X-2).

[In formula (X-2), R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

The molecular weight of the compound represented by the general formula (1) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400.

These unsaturated monobasic acids can be used alone or in combination of two or more.

Examples of the resin (I) include resins having a structure represented by the following general formula (I) in one molecule.

[In formula (I), Ar ¹ represents a substituted or unsubstituted aromatic ring, Ar ² represents a substituted or unsubstituted aromatic ring, Z ¹ represents any one of the following formulae (z-1) to (z-27), and R ¹ represents a hydrogen atom or a methyl group.]

(In formulas (z-1) to (z-27), "*" indicates the point of attachment to the oxygen atom.)

Examples of the resin (II) include resins having a structure represented by the following general formula (I) in one molecule.

[In formula (II), Ar ¹ represents a substituted or unsubstituted aromatic ring, and Ar ² represents a substituted or unsubstituted aromatic ring. Like Z ¹ in formula (I), Z ² represents any of the groups represented by formulas (z-1) to (z-27), W represents any of the groups represented by formulas (w-1) to (w-10) below, and R ² represents a hydrogen atom or a methyl group. n and m each independently represent an integer of 1 or more, and n+m is in the range of 2 to 10.]

[In formulas (w-1) to (w-10), R ³ is independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an acid group, or a halogen atom, and R ⁴ is independently a hydrogen atom or a methyl group. Each p is independently an integer of 0 or 1 or more. n is an integer of 1 to 10, and m is an integer of 1 to 5. The positions of the substituent R ³ and the hydroxyl group on the aromatic ring in the above structural formula are arbitrary. For example, in the naphthalene ring of structural formula (w-2), they may be substituted on any ring, and in structural formulas (w-3) and (w-4), they may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents on the benzene ring in one molecule is p+q. In addition, "*" indicates the point of attachment to the oxygen atom, s and r are each independently an integer of 1 or more, and s+r is in the range of 2 to 20.]

The method for producing the resin (I) is not particularly limited, and any method may be used. For example, the resin (I) may be produced by reacting all of the reaction raw materials containing the aromatic compound (A), the aromatic compound (B), the (meth)acrylate compound (C) having an epoxy group, and the polybasic acid anhydride (D) at once, or by reacting the reaction raw materials sequentially. Examples of the method of reacting the reaction raw materials in sequence include a method of first reacting an aromatic compound (A) with a (meth)acrylate compound (C) having an epoxy group in the presence of a basic catalyst at 60 to 140° C. to obtain a reaction product (I), then reacting the reaction product (I) with a polybasic acid anhydride (D) in the presence of a basic catalyst at 60 to 140° C. to obtain a reaction product (II), and then reacting the reaction product (II) with an aromatic compound (B) under basic conditions at 20 to 140° C. (Method 1); a method of first reacting an aromatic compound (A) with a (meth)acrylate compound (C) having an epoxy group in the presence of a basic catalyst at 60 to 140° C. to obtain a reaction product (I), then reacting the reaction product (I) with a polybasic acid anhydride (D) in the presence of a basic catalyst at 60 to 140° C. to obtain a reaction product (II), and then reacting the reaction product (II) with an aromatic compound (B) under basic conditions at 20 to 140° C. (Method 2); and a water (D) in the presence of a basic catalyst at 60 to 140°C to obtain a reaction product (II), and then reacting the reaction product (II) with the aromatic compound (A) and the aromatic compound (B) under basic conditions at 20 to 140°C to produce the resin (Method 2); first, the aromatic compound (A) and the aromatic compound (B) are reacted in the presence of a basic catalyst at 60 to 140°C to obtain a reaction product (III), then the reaction product (III) is reacted with a (meth)acrylate compound (C) having an epoxy group under basic conditions at 20 to 140°C to obtain a reaction product (IV), and then the reaction product (IV) is reacted with a polybasic acid anhydride (D) in the presence of a basic catalyst at 60 to 140°C to produce the resin (Method 3). Among these, Method 1 or Method 2 is preferred, and Method 2 is more preferred, since a resin having high photosensitivity and excellent alkaline developability and excellent dielectric properties in the cured product can be obtained.

Examples of the basic catalyst include amine compounds such as 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 tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri Examples of the quaternary ammonium salts include 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 octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. In particular, alkali metal hydroxides are preferred because they have excellent catalytic activity in the epoxy resin synthesis reaction, and for example, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts can be used alone or in combination of two or more types.

In the reaction of the aromatic compound (A) with the (meth)acrylate compound (C) having an epoxy group in the method 1, the number of moles of epoxy groups in the (meth)acrylate compound (C) having an epoxy group per mole of phenolic hydroxyl groups in the aromatic compound (A) is preferably 0.4 or more, more preferably in the range of 0.5 to 2.5.

In the reaction of the reaction product (I) with the polybasic acid anhydride (D) in the method 1, the number of moles of the polybasic acid anhydride (D) per mole of hydroxyl groups in the reaction product (I) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

In the reaction of the reaction product (II) with the aromatic compound (B) in the method 1, the number of moles of functional groups capable of reacting with the phenolic hydroxyl groups of the aromatic compound (B) per mole of the phenolic hydroxyl groups of the reaction product (II) is preferably in the range of 0.8 to 1.3, and more preferably 0.95 to 1.25.

In the reaction of the aromatic compound (A) with the (meth)acrylate compound (C) having an epoxy group in the method 2, the number of moles of the epoxy group in the (meth)acrylate compound (C) having an epoxy group per mole of the phenolic hydroxyl group in the aromatic compound (A) is preferably 0.4 or more, more preferably in the range of 0.5 to 2.5.

In the reaction of the reaction product (I) with the polybasic acid anhydride (D) in the method 2, the number of moles of the polybasic acid anhydride (D) per mole of hydroxyl groups in the reaction product (I) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

In the method 2, the reaction of the reaction product (II), the aromatic compound (A), and the aromatic compound (B) is preferably such that the number of moles of functional groups capable of reacting with the phenolic hydroxyl groups of the aromatic compound (B) is in the range of 0.8 to 1.3, more preferably in the range of 0.95 to 1.25, per mole of the total of the phenolic hydroxyl groups of the reaction product (II) and the aromatic compound (A). The aromatic compound (A) in the above reaction may be the same as or different from the aromatic compound (A) that is the reaction raw material of the reaction product (I). However, since a resin having high photosensitivity and excellent alkaline developability and excellent dielectric properties in the cured product can be obtained, the aromatic compound (A) that reacts with the reaction product (II) is preferably an aromatic compound having an aliphatic structure and/or an alicyclic structure.

In the reaction between the aromatic compound (A) and the aromatic compound (B) in the method 3, the mole number of functional groups capable of reacting with the phenolic hydroxyl groups of the aromatic compound (B) per mole of the phenolic hydroxyl groups of the aromatic compound (A) is preferably in the range of 0.5 to 1.5, and more preferably in the range of 0.8 to 1.2.

In the reaction of the reaction product (III) with the (meth)acrylate compound (C) having an epoxy group in the method 3, the number of moles of epoxy groups in the (meth)acrylate compound (a3) having an epoxy group is preferably in the range of 0.9 to 1.1, and more preferably in the range of 0.95 to 1.05, per mole of functional groups capable of reacting with the epoxy groups in the reaction product (III).

In the reaction of the reaction product (IV) with the polybasic acid anhydride (D) in the method 3, the number of moles of the polybasic acid anhydride (D) per mole of hydroxyl groups in the reaction product (IV) is preferably in the range of 0.5 to 1.2, and more preferably in the range of 0.8 to 1.1.

The reaction between the aromatic compound (A), the aromatic compound (B), the (meth)acrylate compound having an epoxy group (C), and the polybasic acid anhydride (D) can also be carried out in an organic solvent, if necessary.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; 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 of two or more.

The method for producing the resin (II) is not particularly limited, and any method may be used. For example, the resin (II) may be produced by a method in which all of the reaction raw materials containing the aromatic compound (A), the aromatic compound (B), and the unsaturated monobasic acid (E) are reacted at once, or the reaction raw materials are reacted sequentially. Examples of the reaction method include a method in which the aromatic compound (A), the aromatic compound (B), and the unsaturated monobasic acid (E) are reacted at 20 to 140°C under basic conditions. In addition, the resin (II) can be produced by using a polybasic acid anhydride (D) other than the aromatic compound (A), the aromatic compound (B), and the unsaturated monobasic acid (E) as a reaction raw material. For example, the aromatic compound (B) and the polybasic acid anhydride (D) are reacted in the presence of a basic catalyst at 60 to 140°C to obtain a reaction product (I), and then the reaction product (I), the aromatic compound (A), and the unsaturated monobasic acid (E) are reacted under basic conditions at 20 to 140°C to produce the resin (II).

In the production of the resin (I) and the resin (II), a polymerization inhibitor, an antioxidant, etc. may be used as necessary.

Examples of the polymerization inhibitor include phenolic compounds such as 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, and 6-ethoxy-2,2,4-trimethyl-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, and N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.3-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 product of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, and other amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl= Thioether compounds such as 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-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 compounds such as nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol; triphenyl phosphite; 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; trisnonylphenyl phosphite; and (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl phosphite. Examples of the polymerization inhibitor include phosphate compounds such as esters, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, and 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 3,3'-thiodipropionate distearyl. These polymerization inhibitors can be used alone or in combination of two or more.

The antioxidant may be the same as the compounds exemplified as the polymerization inhibitor, and the antioxidant may be used alone or in combination of two or more kinds.

In addition, examples of commercially available products of the polymerization inhibitor and the 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.

The resin of the present invention has a polymerizable unsaturated group in its molecular structure, and therefore can be used as a curable resin composition, for example, by adding a photopolymerization initiator.

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.

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

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

The photopolymerization initiator may also be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound, if necessary.

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

The resin having an acid group and a polymerizable unsaturated group may be any resin having an acid group and a polymerizable unsaturated group in the resin, and examples thereof include epoxy resins having an acid group and a polymerizable unsaturated group, urethane resins having an acid group and a polymerizable unsaturated group, acrylic resins having an acid group and a polymerizable unsaturated group, amide-imide resins having an acid group and a polymerizable unsaturated group, acrylamide resins having an acid group and a polymerizable unsaturated group, and ester resins having an acid group and a polymerizable unsaturated group.

The acid group may be any of the acid groups exemplified above.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include epoxy (meth)acrylate resins having an acid group, which have epoxy resins, unsaturated monobasic acids, and polybasic acid anhydrides as essential reaction raw materials, and epoxy (meth)acrylate resins having an acid group and a urethane bond, which have epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and (meth)acrylate compounds having hydroxyl groups as reaction raw materials.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more. Among these, novolac type epoxy resins are preferred, and cresol novolac type epoxy resins are more preferred, since they have excellent alkaline developability and provide a resin with excellent dielectric properties in the cured product.

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, bisphenol S type epoxy resin, etc.

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.

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.

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, hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified as the unsaturated monobasic acid (E) described above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above as polybasic acid anhydride (D), and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

Examples of the polyisocyanate compounds 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 structure represented by the following structural formula (5); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more types.

[In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 4 carbon atoms. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

Examples of the (meth)acrylate compound having a hydroxyl group 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 is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure is 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.

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

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

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

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

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

The polybasic acid anhydride may be the same as those exemplified as the polybasic acid anhydride (D) described above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

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

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

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acrylic resin having an acid group and a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing an essential component of 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 intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups 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; (meth)acrylates having an alicyclic structure such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; (meth)acrylates having an aromatic ring such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

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

The polybasic acid anhydride may be the same as the polybasic acid anhydride (D) exemplified above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

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

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The amide-imide resin having an acid group and a polymerizable unsaturated group may be, for example, one obtained by reacting an amide-imide resin having an acid group and/or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and/or a (meth)acrylate compound having an epoxy group, 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 a reactive functional group may or may not have a (meth)acryloyl group.

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

The amide-imide resin can be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride.

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified as the polybasic acid anhydride (D) described above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

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

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. 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 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

The (meth)acrylate compound having an epoxy group may be the same as the one exemplified as the (meth)acrylate compound having an epoxy group (C) described above, and the (meth)acrylate compound having an epoxy group may be used alone or in combination of two or more kinds.

The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated group 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 group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

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

The compound having a phenolic hydroxyl group 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 (6-1) to (6-4).

In the above structural formulas (6-1) to (6-4), R ¹ is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and R ² is each independently a hydrogen atom or a methyl group. Furthermore, p is an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of structural formula (6-2), it may be substituted on any ring, in structural formula (6-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (6-4), it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is indicated as p and q.

As the compound having a phenolic hydroxyl group, for example, a reaction product in which a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) are used as essential reaction raw materials can also be used. In addition, a novolac-type phenolic resin in which one or more compounds having at least one phenolic hydroxyl group in the molecule are used as reaction raw materials can also be used.

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

These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more.

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 provides a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent dielectric properties. The alkylene oxides can be used alone or in combination of two or more kinds.

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 provides a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

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

The polybasic acid anhydride may be the same as those exemplified as the polybasic acid anhydride (D) described above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified as the unsaturated monobasic acid (E) described above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

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

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

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. In addition, solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acid catalysts can be used alone or in combination of two or more.

The ester resin having an acid group and a polymerizable unsaturated group may be, for example, one obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.

The compound having a phenolic hydroxyl group may be the same as the compounds exemplified above as compounds having a phenolic hydroxyl group, and the compound having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

As the alkylene oxide, the same alkylene oxides as those exemplified above can be used. Among these, ethylene oxide or propylene oxide is preferred because it gives a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent dielectric properties. The alkylene oxides can be used alone or in combination of two or more kinds.

As the alkylene carbonate, the same alkylene carbonates as those exemplified above can be used. Among these, ethylene carbonate or propylene carbonate is preferred because it gives a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent dielectric properties. The alkylene carbonates can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified as the unsaturated monobasic acid (E) described above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified as the polybasic acid anhydride (D) described above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

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

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The acid catalyst may be the same as those exemplified above, and the acid catalyst may be used alone or in combination of two or more.

The amount of the resin having an acid group and a polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the resin of the present invention.

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; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; Alicyclic mono(meth)acrylate compounds such as acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, 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 mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenoxybenzyl (meth)acrylate and phenylphenoxyethyl (meth)acrylate; (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 various mono(meth)acrylate monomers described above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds described above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane di(meth)acrylate, Alicyclic di(meth)acrylate compounds such as arylbornane 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; aliphatic tri(meth)acrylate compounds in which 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. (Poly)oxyalkylene-modified tri(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxytetramethylene chains introduced; lactone-modified tri(meth)acrylate compounds having (poly)lactone structures 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 having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; tetrafunctional or higher lactone-modified poly(meth)acrylate compounds having (poly)lactone structures introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

In addition to the above, the other (meth)acrylate monomers that can be used include (meth)acrylate monomers that have a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

Examples of the phenolic compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 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 phenol resin having a cyclo ring structure.

Examples of the cyclic carbonate compounds 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.

Examples of the cyclic ether compounds include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more.

The unsaturated monocarboxylic acid may be the same as those exemplified above as the unsaturated monobasic acid (E).

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

The curable resin composition of the present invention may also contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

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

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

Examples of the polybasic acids 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, bicyclo[2.2.1]hepta Examples of the polybasic acid include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, 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 the polybasic acid include copolymers of conjugated diene vinyl monomers and acrylonitrile, and polymers having carboxyl groups in the molecule. These polybasic acids can be used alone or in combination of two or more.

The unsaturated monobasic acid may be the same as those exemplified above as the unsaturated monobasic acid, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

Examples of the amine compounds 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 kinds.

Examples of the amide-based compounds include dicyandiamide, polyamide resins synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, alkyl peroxycarbonates, etc. These organic peroxides can be used alone or in combination of two or more kinds.

Examples of the polyol compounds 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 polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation 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 reaction of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; 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.

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

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

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, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc.

The pigment may be any known inorganic or organic pigment.

Examples of the inorganic pigments include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

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 reacted 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 glass. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, the amount is preferably in the range of 0.1 to 20% by mass in the total resin composition.

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 curing reaction by ultraviolet rays.

As a source of ultraviolet light, ultraviolet lamps are generally used from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , and more preferably 0.5 to 10 kJ/m ^2. When the cumulative light amount is within the above range, it is preferable because the occurrence of uncured portions can be prevented or suppressed.

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

The cured product of the present invention has high photosensitivity, excellent alkaline developability, and excellent dielectric properties, and can therefore 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, and 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, resists for black matrices, spacers, and the like. Among these, it is particularly suitable for use as a solder resist.

The resist member of the present invention can be obtained, for example, by applying the curable resin composition onto a substrate, evaporating and drying the organic solvent at a temperature range of about 60 to 100°C, exposing the composition to active energy rays through a photomask on which a desired pattern has been formed, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the composition at a temperature range of about 140 to 200°C.

Examples of the substrate include metal-clad laminates such as copper and aluminum.

The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the examples listed below.

(Synthesis Example 1: Production of reaction product (I-1))
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of methyl isobutyl ketone, 138 parts by mass of salicylic acid, 145 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, and 0.9 parts by mass of triphenylphosphine were added, and the mixture was reacted for 25 hours at 70° C. while blowing in air and stirring. Next, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the mixture was reacted for 5 hours at 110° C. to obtain the target reaction product (I-1).

(Synthesis Example 2: Production of reaction product (I-2))
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 105 parts by mass of methyl isobutyl ketone, 154 parts by mass of 3,4-dihydroxybenzoic acid, 145 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, and 1.0 part by mass of triphenylphosphine were added, and the mixture was reacted for 25 hours at 70° C. while blowing in air and stirring. Next, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the mixture was reacted for 5 hours at 110° C. to obtain the target reaction product (I-2).

(Synthesis Example 3: Production of reaction product (I-3))
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 180 parts by mass of methyl isobutyl ketone, 182 parts by mass of 5-hydroxyisophthalic acid, 291 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted for 25 hours at 70° C. while blowing in air and stirring. Next, 148 parts by mass of tetrahydrophthalic anhydride and 97 parts by mass of succinic anhydride were added, and the mixture was reacted for 5 hours at 110° C. to obtain the target reaction product (I-3).

(Synthesis Example 4: Production of reaction product (I-4))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 108 parts by mass of methyl isobutyl ketone, 138 parts by mass of salicylic acid, 145 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, and 0.9 parts by mass of triphenylphosphine, and the mixture was reacted for 25 hours at 70° C. while blowing in air and stirring. Next, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the mixture was reacted for 5 hours at 110° C. Next, 28 parts by mass of glycidyl methacrylate was added, and the mixture was reacted for 5 hours at 110° C. to obtain the desired reaction product (I-4).

(Synthesis Example 5: Production of reaction product (I-5))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 71 parts by mass of methyl isobutyl ketone, 138 parts by mass of 2-(4-hydroxyphenyl)ethanol, 145 parts by mass of tetrahydrophthalic anhydride, 0.1 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methoquinone, and 0.9 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours with stirring under a nitrogen atmosphere, to obtain the target reaction product (I-5).

(Synthesis Example 6: Synthesis of aromatic ester compound (R))
244 parts by mass of 2,5-xylenol and 1120 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 203 parts by mass of isophthalic acid chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 0.6 parts by mass of tetrabutylammonium bromide was added, and while performing a nitrogen gas purging treatment, the inside of the system was controlled to 60°C or less, and 410 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained toluene layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer became 7. Then, the mixture was heated and dried under reduced pressure to obtain an aromatic ester compound (R) represented by the following structural formula.

(Synthesis Example 7: Synthesis of Resin (1) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was placed, and 428 parts by mass of orthocresol novolac type epoxy resin (DIC Corporation "EPICLON N-680", epoxy equivalent: 214) was dissolved. 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor were added, and then 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 10 hours while blowing in air. Thereafter, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a resin (1) having an acid group and a polymerizable unsaturated group with a solid content of 64.0% by mass. The solid content acid value of this resin (1) having an acid group and a polymerizable unsaturated group was 85 mg KOH / g.

(Example 1: Production of Resin (1))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 500 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1, 165 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 1519 parts by mass of methyl isobutyl ketone were added. Then, 202 parts by mass of isophthalic acid chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 618 parts by mass of a 20% aqueous sodium hydroxide solution were dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methoquinone, and 297 parts by mass of diethylene glycol monomethyl ether acetate were added, and methyl isobutyl ketone was desolvated at 80° C. while blowing air into the mixture, to obtain resin (1). The non-volatile content of this resin (1) was 70% by mass, the solid content acid value was 80 mg KOH/g, the methacryloyl group equivalent was 691 g/equivalent, and the ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention was 347 g/equivalent. In the present invention, the methacryloyl group equivalent and the ester bond equivalent are values calculated from the amount of raw materials charged.

(Example 2: Production of Resin (2))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 260 parts by mass of the reaction product (I-2) obtained in Synthesis Example 2, 165 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 1119 parts by mass of methyl isobutyl ketone were added. Then, 202 parts by mass of isophthalic acid chloride and 0.8 parts by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 515 parts by mass of a 20% aqueous sodium hydroxide solution were dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.5 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 270 parts by mass of diethylene glycol monomethyl ether acetate were added, and the methyl isobutyl ketone was desolvated at 80° C. while blowing in air to obtain resin (2). This resin (2) had a non-volatile content of 65% by mass, a solid content acid value of 56 mg KOH/g, a methacryloyl group equivalent of 999 g/equivalent, and an ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention of 251 g/equivalent.

(Example 3: Production of resin (3))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 898 parts by mass of the reaction product (I-3) obtained in Synthesis Example 3, 165 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 2182 parts by mass of methyl isobutyl ketone were added. Then, 202 parts by mass of isophthalic acid chloride and 1.5 parts by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 824 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 1.0 part by mass of dibutylhydroxytoluene, 0.5 part by mass of methoquinone, and 434 parts by mass of diethylene glycol monomethyl ether acetate were added, and the methyl isobutyl ketone was desolvated at 80° C. while blowing in air to obtain resin (3). This resin (3) had a nonvolatile content of 70% by mass, a solid content acid value of 110 mg KOH/g, a methacryloyl group equivalent of 481 g/equivalent, and an ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention of 506 g/equivalent.

(Example 4: Production of resin (4))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 500 parts by mass of the reaction product (I-4) obtained in Synthesis Example 4, 165 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 1519 parts by mass of methyl isobutyl ketone were added. Then, 202 parts by mass of isophthalic acid chloride and 1.0 part by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 618 parts by mass of a 20% aqueous sodium hydroxide solution were dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methoquinone, and 374 parts by mass of diethylene glycol monomethyl ether acetate were added, and the methyl isobutyl ketone was desolvated at 80° C. while blowing in air, to obtain resin (4). This resin (4) had a nonvolatile content of 65% by mass, a solid content acid value of 61 mg KOH/g, a methacryloyl group equivalent of 620 g/equivalent, and an ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention of 347 g/equivalent.

(Example 5: Production of resin (5))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 363 parts by mass of the reaction product (I-5) obtained in Synthesis Example 5, 330 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 1801 parts by mass of methyl isobutyl ketone. Then, 202 parts by mass of isophthalic acid chloride, 91 parts by mass of acrylic acid chloride, and 1.2 parts by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 824 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 parts by mass of dibutylhydroxytoluene, 0.4 parts by mass of methoquinone, and 305 parts by mass of diethylene glycol monomethyl ether acetate were added, and the methyl isobutyl ketone was desolvated at 80° C. while blowing in air, to obtain resin (5). This resin (5) had a nonvolatile content of 70% by mass, a solid content acid value of 70 mg KOH/g, an acryloyl group equivalent of 803 g/equivalent, and an ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention of 402 g/equivalent.

(Example 6: Production of resin (6))
190 parts by mass of 4-hydroxyphenylacetic acid, 330 parts by mass of a polyaddition product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq), and 1514 parts by mass of methyl isobutyl ketone were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. Then, 202 parts by mass of isophthalic acid chloride, 91 parts by mass of acrylic acid chloride, and 0.9 parts by mass of tetrabutylammonium bromide were added, and the temperature in the system was controlled to 60° C. or less, and 824 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained methyl isobutyl ketone layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 246 parts by mass of diethylene glycol monomethyl ether acetate were added, and the methyl isobutyl ketone was desolvated at 80° C. while blowing in air, to obtain resin (6). This resin (6) had a non-volatile content of 70% by mass, a solid content acid value of 87 mg KOH/g, an acryloyl group equivalent of 665 g/equivalent, and an ester bond equivalent of the structure represented by general formula (1) in the resin specified in the present invention of 333 g/equivalent.

(Comparative Example 1: Synthesis of aromatic ester compound (R1) having a polymerizable unsaturated group)
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 268 parts by mass of ortho-allylphenol and 1200 parts by mass of toluene, and the system was replaced with nitrogen under reduced pressure. Then, 203 parts by mass of isophthalic acid chloride was charged, and the system was replaced with nitrogen under reduced pressure. Then, 0.6 parts by mass of tetrabutylammonium bromide was added, and while performing a nitrogen gas purging treatment, the system was controlled to 60°C or less, and 412 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by static separation. Water was further added to the obtained toluene layer and stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer reached 7. Then, by heating and drying under reduced pressure, an aromatic ester compound (R1) having a polymerizable unsaturated group represented by the following chemical formula was obtained. The ester bond equivalent of this aromatic ester compound (R1) having a polymerizable unsaturated group was 199 g/equivalent.

(Comparative Example 2: Production of methacrylate resin (R2) having polymerizable unsaturated group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 85 parts by mass of methyl isobutyl ketone, 122 parts by mass of benzoic acid, 145 parts by mass of glycidyl methacrylate, 0.2 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, and 0.8 parts by mass of triphenylphosphine were added, and the mixture was reacted for 8 hours at 110 ° C. while blowing in air and stirring. Next, 74 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted for 5 hours at 110 ° C. to obtain a methacrylate resin (R2) having a polymerizable unsaturated group. The non-volatile content of this methacrylate resin (R2) having a polymerizable unsaturated group was 80% by mass, and the solid acid value was 83 mg KOH / g.

(Example 7: Preparation of curable resin composition (1))
70 parts by mass of the resin (1) having a nonvolatile content of 70% by mass obtained in Example 1, 21.2 parts by mass of an orthocresol novolac type epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 11.6 parts by mass of diethylene glycol monoethyl ether acetate, 3.5 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 7.0 parts by mass of dipentaerythritol hexaacrylate, 0.5 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (1).

(Examples 8 to 13: Preparation of curable resin compositions (2) to (7))
Curable resin compositions (2) to (7) were obtained in the same manner as in Example 7, except that the resins (2) to (6) obtained in Examples 2 to 6 were used in place of the resin (1) used in Example 7 in the amounts shown in Table 1.

(Comparative Example 3: Preparation of Curable Resin Composition (R1))
100 parts by mass of the aromatic ester compound (R1) having a polymerizable unsaturated group obtained in Comparative Example 1, 22.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.4 parts by mass of diethylene glycol monoethyl ether acetate, 5.0 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 10.0 parts by mass of dipentaerythritol hexaacrylate, 0.5 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 (R1).

(Comparative Example 4: Preparation of Curable Resin Composition (R2))
A curable resin composition (R2) was obtained in the same manner as in Comparative Example 3, except that the methacrylate resin (R2) having a polymerizable unsaturated group obtained in Comparative Example 2 was used in place of the aromatic ester compound (R1) having a polymerizable unsaturated group used in Comparative Example 3 in the blending amount shown in Table 1.

The following evaluations were carried out using the curable resin compositions (1) to (7), (R1) and (R2) obtained in the above examples and comparative examples.

[Method for evaluating photosensitivity]
The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate with an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Then, ultraviolet rays of 10 kJ/m ² were irradiated using a metal halide lamp through a Kodak Step Tablet No. 2. This was developed for 180 seconds with a 1% by mass aqueous solution of sodium carbonate, and the number of remaining steps was evaluated. The more the number of remaining steps, the higher the photosensitivity.

[Method for evaluating alkaline developability]
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 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, and 140 minutes, respectively, to prepare samples with different drying times. These were developed with a 1% aqueous sodium carbonate solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample that did not leave a residue on the substrate was evaluated as the drying control width. Note that a longer drying control width indicates better alkaline developability.

The compositions and evaluation results of the curable resin compositions (1) to (13) prepared in Examples 7 to 13 and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 3 and 4 are shown in Table 1.

Note that "-" in Table 1 indicates that the film cannot be developed.

(Example 14: Preparation of curable resin composition (8))
A curable resin composition (8) was obtained by mixing 70 parts by mass of the resin (1) obtained in Example 1, 21.2 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 11.6 parts by mass of diethylene glycol monoethyl ether acetate, 3.5 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), and 1.4 parts by mass of 4-dimethylaminopyridine.

(Examples 15 to 20: Preparation of curable resin compositions (9) to (14))
Curable resin compositions (9) to (14) were obtained in the same manner as in Example 14, except that the resins (2) to (6) obtained in Examples 2 to 6 were used in place of the resin (1) used in Example 14 in the blending amounts shown in Table 2.

(Comparative Example 5: Preparation of Curable Resin Composition (R3))
A curable resin composition (R3) was obtained by mixing 100 parts by mass of the aromatic ester compound (R1) having a polymerizable unsaturated group obtained in Comparative Example 1, 22.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.4 parts by mass of diethylene glycol monoethyl ether acetate, 5.0 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), and 2.0 parts by mass of 4-dimethylaminopyridine.

(Comparative Example 6: Preparation of Curable Resin Composition (R4))
A curable resin composition (R4) was obtained in the same manner as in Comparative Example 5, except that the methacrylate resin (R2) having a polymerizable unsaturated group obtained in Comparative Example 2 was used in place of the aromatic ester compound (R1) having a polymerizable unsaturated group used in Comparative Example 5 in the blending amount shown in Table 2.

The following evaluations were carried out using the curable resin compositions (8) to (14), (R3) and (R4) obtained in the above examples and comparative examples.

[Method of measuring dielectric constant]
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 dried at 80° C. for 30 minutes. Then, after irradiating ultraviolet rays of 10 kJ/m ² using a metal halide lamp, the coating was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Then, the test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the dielectric constant of the test piece at 1 GHz was measured by a cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[Method of measuring dielectric tangent]
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 dried at 80° C. for 30 minutes. Then, after irradiating ultraviolet rays of 10 kJ/m ² using a metal halide lamp, the coating was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Then, the test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by a cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

The compositions and evaluation results of the curable resin compositions (8) to (14) prepared in Examples 14 to 20 and the curable resin compositions (R3) and (R4) prepared in Comparative Examples 5 and 6 are shown in Table 2.

The parts by mass of resin listed in Tables 1 and 2 are solid content values.

The "hardener" in Tables 1 and 2 refers to orthocresol novolac epoxy resin (EPICLON N-680, manufactured by DIC Corporation).

"Organic solvent" in Tables 1 and 2 refers to diethylene glycol monomethyl ether acetate.

The "photopolymerization initiator" in Tables 1 and 2 refers to "Omnirad 907" manufactured by IGM Resins.

Examples 7 to 13 shown in Table 1 are examples of curable resin compositions using the resin of the present invention. It was confirmed that the cured products of these curable resin compositions have high sensitivity and excellent alkaline developability.

In addition, Examples 14 to 20 shown in Table 2 are examples of curable resin compositions using the resin of the present invention. It was confirmed that the cured products of these curable resin compositions have excellent dielectric properties.

On the other hand, Comparative Example 3 is an example of a curable resin composition that does not have an acid group and contains an aromatic ester compound that has a polymerizable unsaturated group. It was confirmed that this curable resin composition has extremely insufficient photosensitivity and alkaline developability.

Comparative Example 4 is an example of a curable resin composition containing a methacrylate resin having an acid group and a polymerizable unsaturated group that does not have a structure represented by the general formula (1). It was confirmed that this curable resin composition has insufficient photosensitivity.

Comparative Example 5, like Comparative Example 3, is an example of a curable resin composition that does not have an acid group and contains an aromatic ester compound that has a polymerizable unsaturated group. It was confirmed that the cured product of this curable resin composition has insufficient dielectric properties.

Similar to Comparative Example 4, Comparative Example 6 is an example of a curable resin composition containing a methacrylate resin having an acid group and a polymerizable unsaturated group that does not have the structure represented by the general formula (1). It was confirmed that the cured product of this curable resin composition has insufficient dielectric properties.

Claims (10)

At least one polymerizable unsaturated group in one molecule;
A resin having at least one acid group and at least one structure represented by the following general formula (1):
An aromatic compound (A) having a phenolic hydroxyl group;
an aromatic compound having an acid group other than the aromatic compound (A), an acid halide thereof and/or an ester thereof (B);
(C) a (meth)acrylate compound having an epoxy group;
A polybasic acid anhydride (D),
is a resin that is a reaction product obtained by using the following as an essential reaction raw material:
The polybasic acid anhydride (D) is at least one compound selected from the group consisting of an aliphatic polybasic acid anhydride, an alicyclic polybasic acid anhydride, an acid halide of an aliphatic polybasic acid anhydride, and an acid halide of an alicyclic polybasic acid anhydride.

[In formula (1), Ar1 represents a substituted or unsubstituted aromatic ring, and Ar2 represents a substituted or unsubstituted aromatic ring.] The resin according to claim 1, wherein the polymerizable unsaturated group equivalent is in the range of 250 to 1200 g/equivalent. The resin according to claim 1 or 2, having an acid value in the range of 40 to 140 mg KOH/g. The resin according to any one of claims 1 to 3, wherein the ester bond equivalent of the ester bond in the general formula (1) is in the range of 200 to 1000 g/equivalent. 2. The resin according to claim 1 , wherein the aromatic compound (A) having a phenolic hydroxyl group includes a compound having at least one hydroxyl group on an aromatic ring and at least one acid group in one molecule. A curable resin composition comprising the resin according to any one of claims 1 to 5 and a resin having an acid group and a polymerizable unsaturated group other than the resin. A curable resin composition comprising the resin according to any one of claims 1 to 5 and a photopolymerization initiator. A cured product of the curable resin composition according to claim 6 or 7 . An insulating material comprising the cured product according to claim 8 . A resist member comprising the cured product according to claim 8 .