Resin, curable resin composition, cured product, insulating material, and resist member

Abstract

To provide a resin that has high luminous sensitivity and excellent alkali developability, and has excellent dielectric properties in a cured product; and a curable resin composition containing the same, a cured product, an insulation material composed of the cured product and a resist member.SOLUTION: A resin has, in one molecule, at least one polymerizable unsaturated group, at least one acid radical, and at least one structure represented by a general formula (1). There are also provided a curable resin composition containing the same, a cured product, an insulation material composed of the cured product and a resist member.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin having high photosensitivity and excellent alkali developability, and having excellent dielectric properties in a cured product, a curable resin composition containing the same, a cured product, an insulating material made of the cured product, and a resist member.

Background Art

[0002] In recent years, as a resin material for solder resist for printed wiring boards, a curable resin composition that can be cured by active energy rays such as ultraviolet rays has been widely used. Various required characteristics for the resin material for solder resist include curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, dielectric properties, etc. in a cured product.

[0003] As a conventional resin material for solder resist, a photosensitive resin composition containing an acid group-containing epoxy acrylate resin obtained by reacting an intermediate obtained by reacting a cresol novolak type epoxy resin, acrylic acid, and phthalic anhydride with tetrahydrophthalic anhydride is known (for example, see Patent Document 1), but it does not satisfy the increasingly demanding characteristics in terms of photosensitivity and alkali developability, and is also not sufficient for the current market requirements in terms of dielectric properties.

[0004] Therefore, there has been a demand for a material having high photosensitivity and excellent alkali developability, and having excellent dielectric properties in a cured product.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide a resin having high photosensitivity and excellent alkali developability, having excellent dielectric properties in the cured product, a curable resin composition containing the same, a cured product, an insulating material made of the cured product, and a resist member.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found 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 have completed the present invention.

[0008] 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.

[0009]

Chemical formula

Effects of the Invention

[0010] The resin of the present invention has high photosensitivity and excellent alkali developability, and can form a cured product having excellent dielectric properties. Therefore, it can be suitably used for insulating materials, solder resist resin materials, and resist members. Note that the "excellent dielectric properties" referred to in the present invention means low dielectric constant and low dielectric tangent.

Modes for Carrying Out the Invention

[0011] 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.

[0012]

Chemical formula

[0013] Examples of the polymerizable unsaturated group include, for example, (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, etc. In the present invention, “(meth)acryloyl” means acryloyl and / or methacryloyl. Also, “(meth)acrylate” means acrylate and / or methacrylate. Further, “(meth)acrylic” means acrylic and / or methacrylic.

[0014] Examples of the acid group include, for example, carboxyl group, sulfonic acid group, phosphoric acid group, etc.

[0015] Since the polymerizable unsaturated group equivalent in the resin of the present invention has high photosensitivity and excellent alkali developability, and a resin having excellent dielectric properties in the cured product can be obtained, the range of 250 to 1200 g / equivalent is preferable, the range of 300 to 1000 g / equivalent is more preferable, and the range of 400 to 1000 g / equivalent is even more preferable.

[0016] Also, since the acid value of the resin of the present invention has high photosensitivity and excellent alkali developability, and a resin having excellent dielectric properties in the cured product can be obtained, the range of 40 to 140 gKOH / g is preferable, the range of 50 to 130 mgKOH / g is more preferable, and the range of 60 to 120 mgKOH / g is even more preferable.

[0017] Furthermore, since the ester bond equivalent of the structure represented by the general formula (1) in the resin of the present invention has high photosensitivity and excellent alkali developability, and a resin having excellent dielectric properties in the cured product can be obtained, the range of 200 to 1000 g / equivalent is preferable, the range of 250 to 800 g / equivalent is more preferable, and the range of 250 to 600 g / equivalent is even more preferable.

[0018] The Ar in the formula (1) 1 and the Ar 2 Examples of the substituent that the carbon may have 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.

[0019] Examples of the resin of the present invention include a resin (I) using, 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); a resin (II) using, 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), an unsaturated monobasic acid, its acid halide and / or its ester (E), and the like.

[0020] Examples of the aromatic compound (A) include compounds represented by the following structural formulas (2-1) to (2-10). Among these, since a resin having high photosensitivity and excellent alkali developability and excellent dielectric properties in the cured product can be obtained, a compound having at least one hydroxyl group on the aromatic ring and at least one acid group in one molecule is preferable.

[0021]

Chemical formula

[0022] In the above structural formulas (2-1) to (2-10), R 1 is, independently of each other, any one of 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, independently of each other, a hydrogen atom or a methyl group. Further, p is, independently of each other, 0 or an integer of 1 or more, and q is, independently of each other, an integer of 1 or more. n is an integer of 1 to 10, and m is an integer of 1 to 5. Note that the positions of the substituent R 1 and the hydroxyl group on the aromatic ring in the above structural formula are arbitrary. For example, in the naphthalene ring of the structural formula (2-2), it may be substituted on any ring, and in the structural formulas (2-3) and (2-4), it may be substituted on any benzene ring existing in one molecule, indicating that the number of substituents on the benzene ring in one molecule is p + q.

[0023] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0024] The aromatic compound having the acid group, its acid halide and / or its esterified product (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 above aromatic compound (A), and examples thereof include compounds represented by the following structural formulas (3-1) to (3-5).

[0025]

Chemical formula

[0026] In the above structural formulas (3-1) to (3-5), R 3 is an acid group, and R 4 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, or a halogen atom, and R 5is independently a hydrogen atom or a methyl group. Further, r is an integer of 1 or more, and s is 0 or an integer of 1 or more. In the above structural formula, the substituents R 3 and R 4 at the positions are arbitrary. For example, in the naphthalene ring of the structural formula (3-2), they may be substituted on any ring, and in the structural formulas (3-3) to (3-5), they may be substituted on any benzene ring existing in one molecule, indicating that the number of substituents on the benzene ring in one molecule is r + s.

[0027] Further, the acid group that the aromatic compound (B) has may have at least one in one molecule.

[0028] These aromatic compounds (B) can be used alone or in combination of two or more.

[0029] The amount of the aromatic compound (B) used is such that a resin having high photosensitivity, excellent alkali developability, and excellent dielectric properties in the cured product can be obtained. Therefore, with respect to 1 mol of the phenolic hydroxyl group that the aromatic compound (A) has, the number of moles of the functional group capable of reacting with the phenolic hydroxyl group that the aromatic compound (B) has is preferably in the range of 0.9 to 1.5, and more preferably in the range of 0.95 to 1.25.

[0030] 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, and mono(meth)acrylate compounds 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.

[0031] 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, and the like.

[0032] Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, acid anhydrides of 1,2,3,4-butanetetracarboxylic acid, and the like. Further, as the aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure.

[0033] In the present invention, the alicyclic polybasic acid anhydride is defined as one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural parts is not limited. Examples of the alicyclic polybasic acid anhydride include acid 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, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and the like.

[0034] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like.

[0035] These polybasic acid anhydrides (D) can be used alone or in combination of two or more. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred because a resin having high photosensitivity, excellent alkali developability, and excellent dielectric properties in the cured product can be obtained.

[0036] Examples of the unsaturated monobasic acid, its acid halide and / or its esterified product (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, and the like. Further, the acid halide and esterified product of the unsaturated monobasic acid can also be used. Furthermore, compounds represented by the following structural formula (4) and the like can also be used.

[0037]

Chemical formula

[0038] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0039] Examples of the (poly)ester chain include a (poly)ester chain represented by the following structural formula (X-1).

[0040]

Chemical formula

[0041] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, and the like. As a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

[0042] Examples of the (poly)carbonate chain include a (poly)carbonate chain represented by the following structural formula (X-2).

[0043] [Chemical formula] [In formula (X-2), R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0044] 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.

[0045] These unsaturated monobasic acids can be used alone or in combination of two or more.

[0046] Examples of the resin (I) include a resin having a structure represented by the following general formula (I) in one molecule.

[0047] [Chemical formula] [In formula (I), Ar 1 represents a substituted or unsubstituted aromatic ring, and Ar 2 represents a substituted or unsubstituted aromatic ring. Z 1 represents any one of the following formulas (z-1) to (z-27), and R 1 represents a hydrogen atom or a methyl group.]

[0048] [Chemical formula] [In formulas (z-1) to (z-27), "*" indicates the bonding point with the oxygen atom.]

[0049] Examples of the resin (II) include resins having a structure represented by the following general formula (I) in one molecule.

[0050] [Chemical formula] [In formula (II), Ar 1 represents a substituted or unsubstituted aromatic ring, and Ar 2 represents a substituted or unsubstituted aromatic ring. Z 2 represents any one of those represented by the formulas (z-1) to (z-27) in the same manner as Z 1 in the formula (I), W represents any one of those represented by the following formulas (w-1) to (w-10), 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. ]

[0051] [Chemical formula] [In the formulas (w-1) to (w-10), R 3 each independently represents any one of 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 each independently represents a hydrogen atom or a methyl group. Also, p each independently represents 0 or an integer of 1 or more. n is an integer of 1 to 10, and m is an integer of 1 to 5. Note that the positions of the substituents R 3 and hydroxyl groups on the aromatic ring in the above structural formula are arbitrary. For example, in the naphthalene ring of the structural formula (w-2), it may be substituted on any ring, and in the structural formulas (w-3) and (w-4), it may be substituted on any benzene ring present in one molecule, indicating that the number of substituents on the benzene ring in one molecule is p + q. Note that "*" indicates the bonding point with the oxygen atom, and s and r each independently represent an integer of 1 or more, and s + r is in the range of 2 to 20. ]

[0052] The method for producing the resin (I) is not particularly limited, and it may be produced by any method. For example, it may be produced by a method in which 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) are reacted all at once, or it may be produced by a method in which the reaction raw materials are reacted sequentially. As the method for sequentially reacting the reaction raw materials, for example, first, the aromatic compound (A) and the (meth)acrylate compound (C) having an epoxy group are reacted at 60 to 140°C in the presence of a basic catalyst to obtain a reaction product (I), then the reaction product (I) and the polybasic acid anhydride (D) are reacted at 60 to 140°C under a basic catalyst to obtain a reaction product (II), and further, the reaction product (II) and the aromatic compound (B) are reacted at 20 to 140°C under basic conditions to produce (Method 1), first, the aromatic compound (A) and the (meth)acrylate compound (C) having an epoxy group are reacted at 60 to 140°C in the presence of a basic catalyst to obtain a reaction product (I), then the reaction product (I) and the polybasic acid anhydride (D) are reacted at 60 to 140°C under a basic catalyst to obtain a reaction product (II), and the reaction product (II), the aromatic compound (A), and the aromatic compound (B) are reacted at 20 to 140°C under basic conditions to produce (Method 2), first, the aromatic compound (A) and the aromatic compound (B) are reacted at 60 to 140°C in the presence of a basic catalyst to obtain a reaction product (III), then the reaction product (III) and the (meth)acrylate compound (C) having an epoxy group are reacted at 20 to 140°C under basic conditions to obtain a reaction product (IV), and further, the reaction product (IV) and the polybasic acid anhydride (D) are reacted at 60 to 140°C under a basic catalyst to produce (Method 3), etc. Among these, since a resin having high photosensitivity, excellent alkali developability, and excellent dielectric properties in the cured product can be obtained, Method 1 or Method 2 is preferable, and Method 2 is more preferable.

[0053] 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, tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride, trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organometallic compounds such as zinc octylate, bismuth octylate; inorganic tin compounds such as tin octoate; inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. An alkali metal hydroxide is particularly preferred because of its excellent catalytic activity in the epoxy resin synthesis reaction. For example, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts can be used alone or in combination of two or more.

[0054] In the above method 1, in the reaction between the aromatic compound (A) and the (meth)acrylate compound (C) having an epoxy group, the number of moles of the epoxy group in the (meth)acrylate compound (C) having an epoxy group is preferably 0.4 or more, more preferably in the range of 0.5 to 2.5, relative to 1 mole of the phenolic hydroxyl group in the aromatic compound (A).

[0055] In the above method 1, in the reaction between the reaction product (I) and the polybasic acid anhydride (D), the number of moles of the polybasic acid anhydride (D) is preferably in the range of 0.5 to 1.2, more preferably in the range of 0.8 to 1.1, relative to 1 mole of the hydroxyl group in the reaction product (I).

[0056] In the above method 1, in the reaction between the reaction product (II) and the aromatic compound (B), the number of moles of the functional group capable of reacting with the phenolic hydroxyl group in the aromatic compound (B) is preferably in the range of 0.8 to 1.3, more preferably 0.95 to 1.25, relative to 1 mole of the phenolic hydroxyl group in the reaction product (II).

[0057] In the above method 2, in the reaction between the aromatic compound (A) and the (meth)acrylate compound (C) having an epoxy group, the number of moles of the epoxy group in the (meth)acrylate compound (C) having an epoxy group is preferably 0.4 or more, more preferably in the range of 0.5 to 2.5, relative to 1 mole of the phenolic hydroxyl group in the aromatic compound (A).

[0058] In the above method 2, in the reaction between the reaction product (I) and the polybasic acid anhydride (D), the number of moles of the polybasic acid anhydride (D) is preferably in the range of 0.5 to 1.2, more preferably in the range of 0.8 to 1.1, relative to 1 mole of the hydroxyl group in the reaction product (I).

[0059] In the above-mentioned 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 the functional group capable of reacting with the phenolic hydroxyl group 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, with respect to a total of 1 mole of the phenolic hydroxyl groups of the reaction product (II) and the aromatic compound (A). Note that as the aromatic compound (A) in the above reaction, the same one as the aromatic compound (A) which is the reaction raw material of the reaction product (I) may be used, or a different one may be used. However, since a resin having high photosensitivity, excellent alkali developability, and excellent dielectric properties in the cured product can be obtained, as the aromatic compound (A) that reacts with the reaction product (II), an aromatic compound having an aliphatic structure and / or an alicyclic structure is preferred.

[0060] In the above-mentioned Method 3, the reaction of the aromatic compound (A) and the aromatic compound (B) is preferably such that the number of moles of the functional group capable of reacting with the phenolic hydroxyl group of the aromatic compound (B) is in the range of 0.5 to 1.5, more preferably in the range of 0.8 to 1.2, with respect to 1 mole of the phenolic hydroxyl group of the aromatic compound (A).

[0061] In the above-mentioned Method 3, the reaction of the reaction product (III) and the (meth)acrylate compound (C) having an epoxy group is preferably such that the number of moles of the epoxy group of the (meth)acrylate compound (a3) having an epoxy group is in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05, with respect to 1 mole of the functional group capable of reacting with the epoxy group of the reaction product (III).

[0062] In the above-mentioned Method 3, the reaction of the reaction product (IV) and the polybasic acid anhydride (D) is preferably such that the number of moles of the polybasic acid anhydride (D) is in the range of 0.5 to 1.2, more preferably in the range of 0.8 to 1.1, with respect to 1 mole of the hydroxyl group of the reaction product (IV).

[0063] In addition, the reaction of the aromatic compound (A), the aromatic compound (B), the (meth)acrylate compound (C) having an epoxy group, and the polybasic acid anhydride (D) can also be carried out in an organic solvent if necessary.

[0064] 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, propylene glycol monomethyl ether acetate, and the like. These organic solvents can be used alone or in combination of two or more.

[0065] The method for producing the resin (II) is not particularly limited, and it may be produced by any method. For example, it 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 together, or by a method in which the reaction raw materials are reacted sequentially. Examples of the method of reacting together include a method of producing by reacting the aromatic compound (A), the aromatic compound (B), and the unsaturated monobasic acid (E) at 20 to 140°C under basic conditions. Further, as the resin (II), a polybasic acid anhydride (D) other than the aromatic compound (A), the aromatic compound (B), and the unsaturated monobasic acid (E) may be used as a reaction raw material. For example, the aromatic compound (B) and the polybasic acid anhydride (D) are reacted at 60 to 140°C in the presence of a basic catalyst to obtain a reaction product (I), and then the reaction product (I), the aromatic compound (A), and the unsaturated monobasic acid (E) are reacted at 20 to 140°C under basic conditions to produce it.

[0066] In the production of the resin (I) and the resin (II), a polymerization inhibitor, an antioxidant, etc. may be used as necessary.

[0067] 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)dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 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, diphenoquinone; and melamine, p-phenylenediamine, 4-aminodiphenylamine, 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, the reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, amine compounds such as the reaction product of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl = bis[3-(dodecylthio)propionate], thioether compounds such as ditridecan-1-yl = 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitroso benzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrone dimethylamine, p-nitrone-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, dinitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, nitroso compounds such as 2-nitroso-5-methylaminophenol hydrochloride, the ester of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecyl-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5) Phosphite compounds such as undecane, tris(nonylphenyl) phosphite, (1-methylethylidene)-di-4,1-phenylene tetra-C12-15-alkyl ester phosphite, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite; zinc compounds such as zinc bis(dimethyldithiocarbamate-κ(2)S,S’), zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate; nickel compounds such as nickel bis(N,N-dibutylcarbamodithioato-S,S’); 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, distearyl 3,3’-thiodipropionate, etc. These polymerization inhibitors can be used alone or in combination of two or more.

[0068] As the antioxidant, the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant can be used alone or in combination of two or more.

[0069] Moreover, as commercially available products of the polymerization inhibitor and the antioxidant, for example, "Q-1300", "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S", "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd., etc. can be mentioned.

[0070] Since the resin of the present invention has a polymerizable unsaturated group in its molecular structure, for example, it can be used as a curable resin composition by adding a photoinitiator.

[0071] Examples of the photopolymerization initiator include photo radical 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-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, etc.

[0072] Examples of commercially available products of the other photoinitiators 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" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), etc. These photoinitiators can be used alone or in combination of two or more.

[0073] The addition amount of the photoinitiator is preferably in the range of 0.05 to 15% by mass, more preferably in the range of 0.1 to 10% by mass, for example, in the total of the components other than the solvent of the curable resin composition.

[0074] In addition, the photoinitiator can 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, a nitrile compound, etc., if necessary.

[0075] The curable resin composition of the present invention may contain other resin components other than 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, and the like.

[0076] As the resin having an acid group and a polymerizable unsaturated group, any resin having an acid group and a polymerizable unsaturated group in the resin may be used. For example, an epoxy resin having an acid group and a polymerizable unsaturated group, a urethane resin having an acid group and a polymerizable unsaturated group, an acrylic resin having an acid group and a polymerizable unsaturated group, an amide-imide resin having an acid group and a polymerizable unsaturated group, an acrylamide resin having an acid group and a polymerizable unsaturated group, an ester resin having an acid group and a polymerizable unsaturated group, and the like can be mentioned.

[0077] Examples of the acid group include those exemplified as the acid group above.

[0078] Examples of the epoxy (meth)acrylate resin having an acid group and a polymerizable unsaturated group include an epoxy (meth)acrylate resin having an acid group using an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials, and an epoxy (meth)acrylate resin having an acid group and a urethane bond using an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group as reaction raw materials.

[0079] 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 resin is preferred and cresol novolac type epoxy resin is more preferred because a resin having excellent alkali developability and excellent dielectric properties in the cured product can be obtained.

[0080] 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.

[0081] 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, hydrogenated bisphenol S type epoxy resin, etc.

[0082] 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, tetramethyl-2,2'-biphenol type epoxy resin, and the like.

[0083] 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, and the like. These epoxy resins can be used alone or in combination of two or more.

[0084] As the unsaturated monobasic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid (E) can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

[0085] As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0086] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene 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); isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like of these. These polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0087]

Chemical formula

[0088] 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, ditrimethylolpropane tri(meth)acrylate, and the like. In addition, (poly)oxyalkylene modified products obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the above-mentioned (meth)acrylate compound having various hydroxyl groups, and lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned (meth)acrylate compound having various hydroxyl groups can also be used. These (meth)acrylate compounds having a hydroxyl group can be used alone or in combination of two or more.

[0089] The method for producing the epoxy resin having an acid group and a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the epoxy resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

[0090] As the organic solvent, the same solvents as those exemplified above as the organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

[0091] As the basic catalyst, the same ones as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0092] 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 the polyol compound having a carboxyl group.

[0093] As the polyisocyanate compound, the same ones as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

[0094] As the (meth)acrylate compound having a hydroxyl group, the same ones as those exemplified as the above-mentioned (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

[0095] Examples of the polyol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The polyol compound having a carboxyl group can be used alone or in combination of two or more kinds.

[0096] As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds..

[0097] Examples of polyol compounds other than the polyol compound 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 products obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structures of the various polyol compounds; lactone modified products obtained by introducing (poly)lactone structures into the molecular structures of the various polyol compounds, and the like. The polyol compounds other than the polyol compound having a carboxyl group can be used alone or in combination of two or more.

[0098] The method for producing the urethane resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method can be used. In the production of the urethane resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0099] As the organic solvent, the same solvents as those exemplified as the above-mentioned organic solvents can be used, and the organic solvents can be used alone or in combination of two or more.

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

[0101] Examples of the acrylic resin having an acid group and a polymerizable unsaturated group include a reaction product obtained by introducing a (meth)acryloyl group by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups into an acrylic resin intermediate obtained by polymerizing 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 as an essential component, and a product obtained by reacting a polybasic acid anhydride with a hydroxyl group in the reaction product.

[0102] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, a compound having another polymerizable unsaturated group. Examples of the compound having another polymerizable unsaturated group 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 can be used alone or in combination of two or more.

[0103] The above-mentioned (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 from the perspective of reactivity, it is preferably the following combination. 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.

[0104] The above-mentioned polybasic acid anhydride can be the same as those exemplified as the above-mentioned polybasic acid anhydride (D), and the polybasic acid anhydride can be used alone or in combination of two or more.

[0105] The method for producing the acrylic resin having the acid group and the polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the acrylic resin having the acid group and the polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0106] The above-mentioned organic solvent can be the same as those exemplified as the above-mentioned organic solvent, and the organic solvent can be used alone or in combination of two or more.

[0107] As the basic catalyst, the same ones as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0108] Examples of the amide-imide resin having an acid group and a polymerizable unsaturated group include an amide-imide resin having an acid group and / or an acid anhydride group, a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, 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, which is obtained by reacting them. Note that the compound having a reactive functional group may or may not have a (meth)acryloyl group.

[0109] The amide-imide resin may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoints 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 preferably one having an acid anhydride group, and more preferably one having 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 mgKOH / g as measured under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mgKOH / g as measured under conditions where the acid anhydride group is ring-opened, such as in the presence of water.

[0110] Examples of the amide-imide resin include those obtained using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

[0111] As the polyisocyanate compound, the same ones as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

[0112] As the polybasic acid anhydride, the same ones as those exemplified as the above polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0113] In addition, the amide imide resin can, if necessary, be used in combination with a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride.

[0114] 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, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. can be mentioned. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile and having a carboxyl group in its molecule can also be used. These polybasic acids can be used alone or in combination of two or more.

[0115] As the (meth)acrylate compound having a hydroxyl group, the same ones as those exemplified as the above (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more.

[0116] As the (meth)acrylate compound having an epoxy group, those similar to those exemplified as the (meth)acrylate compound (C) having an epoxy group described above can be used, and the (meth)acrylate compound having an epoxy group can be used alone or in combination of two or more.

[0117] The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the amide-imide resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0118] As the organic solvent, those similar to those exemplified as the organic solvent described above can be used, and the organic solvent can be used alone or in combination of two or more.

[0119] As the basic catalyst, those similar to those exemplified as the basic catalyst described above can be used, and the basic catalyst can be used alone or in combination of two or more.

[0120] 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 an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, a polybasic acid anhydride, and an unsaturated monobasic acid as necessary.

[0121] 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).

[0122]

Chemical formula

[0123] In the above structural formulas (6-1) to (6-4), R 1 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 R 2 are each independently a hydrogen atom or a methyl group. Also, p is an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 3, more preferably 0 or 1. Note that the position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (6-2), it may be substituted on any ring, and in structural formula (6-3), it may be substituted on any of the benzene rings present in one molecule, and in structural formula (6-4), it may be substituted on any of the benzene rings present in one molecule, indicating that the number of substituents in one molecule is p and q.

[0124] Further, as the compound having a phenolic hydroxyl group, for example, a reaction product using a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) as essential reaction raw materials can also be used. Also, a novolak-type phenol resin using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials can also be used.

[0125] [Chemical formula] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3is 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 of 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 of 1 to 4.

[0126] These compounds having phenolic hydroxyl groups can be used alone or in combination of two or more.

[0127] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product having high photosensitivity, excellent alkali developability, and excellent dielectric properties can be obtained. The alkylene oxide can be used alone or in combination of two or more.

[0128] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product having high photosensitivity, excellent alkali developability, and excellent dielectric properties can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

[0129] Examples of the N - alkoxyalkyl (meth) acrylamide compound include N - methoxymethyl (meth) acrylamide, N - ethoxymethyl (meth) acrylamide, N - butoxymethyl (meth) acrylamide, N - methoxyethyl (meth) acrylamide, N - ethoxyethyl (meth) acrylamide, N - butoxyethyl (meth) acrylamide, and the like. The N - alkoxyalkyl (meth) acrylamide compound can be used alone or in combination of two or more.

[0130] As the polybasic acid anhydride, the same ones as those exemplified as the above - mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0131] As the unsaturated monobasic acid, the same ones as those exemplified as the above - mentioned unsaturated monobasic acid (E) can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

[0132] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the acrylamide resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

[0133] As the organic solvent, the same ones as those exemplified as the above - mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

[0134] As the basic catalyst, the same ones as those exemplified as the above - mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.

[0135] Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, aluminum chloride anhydride, and zinc chloride. Further, solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acidic catalysts can be used alone or in combination of two or more.

[0136] Examples of the ester resin having the acid group and the polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.

[0137] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as the compound having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more.

[0138] As the alkylene oxide, the same compounds as those exemplified above as the alkylene oxide can be used. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition having high photosensitivity, excellent alkali developability, and capable of forming a cured product having excellent dielectric properties can be obtained. The alkylene oxide can be used alone or in combination of two or more.

[0139] As the alkylene carbonate, the same compounds as those exemplified above as the alkylene carbonate can be used. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition having high photosensitivity, excellent alkali developability, and capable of forming a cured product having excellent dielectric properties can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

[0140] As the unsaturated monobasic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid (E) can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more kinds.

[0141] As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.

[0142] The method for producing the ester resin having the acid group and the polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the ester resin having the acid group and the polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

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

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

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

[0146] The amount of the resin having the acid group and the polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the resin of the present invention.

[0147] Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate; aromatic mono(meth)acrylate compounds such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc.; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, etc. into the molecular structure of the various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the various mono(meth)acrylate compounds; 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, neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenyl 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 is introduced into the molecular structure of the various di(meth)acrylate compounds; Lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the various di(meth)acrylate compounds; Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; Lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; Tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; Tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds, etc. can be mentioned.;

[0148] In addition, as the other (meth)acrylate monomers, in addition to those described above, (meth)acrylate monomers using a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials can be used.

[0149] Examples of the phenolic compound 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 novolak resin, cresol novolak resin, bisphenol novolak type resin, naphthol novolak type resin, phenol aralkyl type resin, naphthol aralkyl type resin, phenolic resin having a cyclo ring structure, and the like.

[0150] Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. These cyclic carbonate compounds can be used alone or in combination of two or more.

[0151] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran and the like. These cyclic ether compounds can be used alone or in combination of two or more.

[0152] As the unsaturated monocarboxylic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid (E) can be used.

[0153] The content of the other (meth)acrylate monomer is preferably 90% by mass or less in the curable resin composition of the present invention.

[0154] In addition, the curable resin composition of the present invention can contain various additives such as a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, etc., if necessary.

[0155] Examples of the hardener include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, epoxy resins, and the like.

[0156] As the epoxy resin, those similar to those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin can be used alone or in combination of two or more.

[0157] Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, 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, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

[0158] As the unsaturated monobasic acid, those similar to those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

[0159] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative, etc. These amine compounds can be used alone or in combination of two or more.

[0160] Examples of the amide compound include dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more.

[0161] Examples of the azo compound include azobisisobutyronitrile, etc.

[0162] Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, alkylperoxycarbonate, etc. These organic peroxides can be used alone or in combination of two or more.

[0163] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; polyester polyols obtained by co-condensation of the polyol monomers with dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, 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 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 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.

[0164] As the epoxy resin, those similar to the ones exemplified as the above epoxy resin can be used, and the epoxy resin can be used alone or in combination of two or more.

[0165] As the hardening accelerator, it promotes the hardening reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, metal organic salts, Lewis acids, amine complex salts, etc. These hardening accelerators can be used alone or in combination of two or more. Further, the addition amount of the hardening accelerator is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.

[0166] 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, benzotriazoles such as 2-(2'-xanthene carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, benzophenones such as 2-xanthene carboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

[0167] As the organic solvent, those similar to those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0168] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc.

[0169] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0170] Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, ultramarine blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0171] 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.

[0172] Examples of the organic pigment include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone 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.

[0173] Examples of the flame retardant include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as amide phosphates; phosphate 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-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and organic phosphorus compounds such as derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glasses. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

[0174] 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 radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When ultraviolet rays are used as the active energy rays, in order to efficiently carry out the curing reaction by ultraviolet rays, it may be irradiated in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

[0175] As the ultraviolet light source, an ultraviolet lamp is generally used from the viewpoints of practicality and economy. Specifically, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, and the like.

[0176] The integrated light quantity 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 integrated light quantity is within the above range, it is preferable because generation or suppression of uncured portions can be prevented.

[0177] Note that the irradiation of the active energy rays may be performed in one step or may be performed in two or more steps.

[0178] In addition, since the cured product of the present invention has high photosensitivity, excellent alkali developability, and excellent dielectric properties, for example, in semiconductor device applications, solder resist, interlayer insulating material, package material, underfill material, package adhesive layer such as circuit elements, and integrated circuit elements and circuit boards. It can be suitably used as an adhesive layer. Further, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. in thin display applications typified by LCD and OELD. Among these, it can be particularly suitably used for solder resist applications.

[0179] The resist member of the present invention can be obtained, for example, by applying the curable resin composition onto a substrate, volatilizing and drying the organic solvent in a temperature range of about 60 to 100 ° C, and then exposing it to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed portion with an aqueous alkali solution, and further heating and curing it in a temperature range of about 140 to 200 ° C.

[0180] Examples of the substrate include metal-clad laminates such as copper and aluminum.

Examples

[0181] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below.

[0182] (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. Air was blown in, and the mixture was reacted at 70 °C for 25 hours while stirring. Then, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the mixture was reacted at 110 °C for 5 hours to obtain the target reaction product (I-1).

[0183] (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 parts by mass of triphenylphosphine were added. Air was blown in, and the mixture was reacted at 70 °C for 25 hours while stirring. Then, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the mixture was reacted at 110 °C for 5 hours to obtain the target reaction product (I-2).

[0184] (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. Air was blown in, and the mixture was reacted at 70 °C for 25 hours while stirring. Then, 148 parts by mass of tetrahydrophthalic anhydride and 97 parts by mass of succinic anhydride were added, and the mixture was reacted at 110 °C for 5 hours to obtain the target reaction product (I-3).

[0185] (Synthesis Example 4: Production of Reaction Product (I-4)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 108 parts by mass of methyl isobutyl ketone, 138 parts by mass of salicylic acid, 145 parts by mass of glycidyl methacrylate, 0.2 part by mass of dibutylhydroxytoluene, 0.2 part by mass of methoquinone, and 0.9 part by mass of triphenylphosphine were added. Air was blown in, and while stirring, the reaction was carried out at 70 °C for 25 hours. Next, 74 parts by mass of tetrahydrophthalic anhydride and 49 parts by mass of succinic anhydride were added, and the reaction was carried out at 110 °C for 5 hours. Then, 28 parts by mass of glycidyl methacrylate was added, and the reaction was carried out at 110 °C for 5 hours to obtain the target reaction product (I-4).

[0186] (Synthesis Example 5: Production of Reaction Product (I-5)) Into 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 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methoquinone, and 0.9 part by mass of triphenylphosphine were added. Under a nitrogen atmosphere, while stirring, the reaction was carried out at 110 °C for 5 hours to obtain the target reaction product (I-5).

[0187] (Synthesis Example 6: Synthesis of Aromatic Ester Compound (R)) Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 244 parts by mass of 2,5-xylenol and 1120 parts by mass of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 parts by mass of isophthaloyl chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 0.6 part by mass of tetrabutylammonium bromide was added, and while performing a nitrogen gas purge treatment, the inside of the system was controlled to 60 °C or lower, and 410 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, stirring was carried out 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 stirring was carried out for 15 minutes. The aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Then, by heating and drying under reduced pressure, the aromatic ester compound (R) represented by the following structural formula was obtained.

[0188] [Chemistry]

[0189] (Synthesis Example 7: Synthesis of Resin (1) Having Acid Group and Polymerizable Unsaturated Group) Into 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 an ortho-cresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214) was dissolved. After adding 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 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 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 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 mgKOH / g.

[0190] (Example 1: Production of Resin (1)) Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 500 parts by mass of the reaction product (I-1) obtained in Synthesis Example 1, 165 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 1519 parts by mass of methyl isobutyl ketone were added. Subsequently, 202 parts by mass of isophthaloyl chloride and 1.1 parts by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60 °C or lower. 618 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and after completion of the dropwise addition, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Subsequently, 0.7 part by mass of dibutylhydroxytoluene, 0.4 part by mass of methoquinone, and 297 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed as a solvent at 80 °C to obtain Resin (1). The nonvolatile content of this Resin (1) was 70% by mass, the solid acid value was 80 mgKOH / g, the methacryloyl group equivalent was 691 g / eq, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 347 g / eq. In the present invention, the methacryloyl group equivalent and the ester bond equivalent are values calculated from the charged amounts of the raw materials.

[0191] (Example 2: Production of Resin (2)) In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 260 parts by mass of the reaction product (I-2) obtained in Synthesis Example 2, 165 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 1119 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthaloyl chloride and 0.8 part by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60°C or lower. 515 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes. The aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.5 part by mass of dibutylhydroxytoluene, 0.3 part by mass of methoquinone, and 270 parts by mass of diethylene glycol monomethyl ether acetate were added. While blowing air, methyl isobutyl ketone was removed as a solvent at 80°C to obtain Resin (2). The nonvolatile content of this Resin (2) was 65% by mass, the solid acid value was 56 mgKOH / g, the methacryloyl group equivalent was 999 g / eq, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 251 g / eq.

[0192] (Example 3: Production of Resin (3)) 898 parts by mass of the reaction product (I-3) obtained in Synthesis Example 3, 165 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 2,182 parts by mass of methyl isobutyl ketone were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer. Next, 202 parts by mass of isophthaloyl chloride and 1.5 parts by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60°C or lower. 824 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was complete, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes. The aqueous layer was removed by standing and liquid separation. 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. While blowing air, the methyl isobutyl ketone was removed as a solvent at 80°C to obtain Resin (3). The nonvolatile content of this Resin (3) was 70% by mass, the solid acid value was 110 mgKOH / g, the methacryloyl group equivalent was 481 g / equivalent, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 506 g / equivalent.

[0193] (Example 4: Production of Resin (4)) 500 parts by mass of the reaction product (I-4) obtained in Synthesis Example 4, 165 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 1519 parts by mass of methyl isobutyl ketone were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer. Subsequently, 202 parts by mass of isophthaloyl chloride and 1.0 part by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60°C or lower. Then, 618 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes. Then, the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 part by mass of dibutylhydroxytoluene, 0.4 part by mass of methoquinone, and 374 parts by mass of diethylene glycol monomethyl ether acetate were added. While blowing air, methyl isobutyl ketone was removed as a solvent at 80°C to obtain Resin (4). The non-volatile content of this Resin (4) was 65% by mass, the solid acid value was 61 mgKOH / g, the methacryloyl group equivalent was 620 g / equivalent, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 347 g / equivalent.

[0194] (Example 5: Production of Resin (5)) In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 363 parts by mass of the reaction product (I-5) obtained in Synthesis Example 5, 330 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 1801 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthaloyl chloride, 91 parts by mass of acryloyl chloride, and 1.2 parts by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60°C or lower. 824 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and after completion of the dropwise addition, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.7 part by mass of dibutylhydroxytoluene, 0.4 part by mass of methoquinone, and 305 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, the methyl isobutyl ketone was removed as a solvent at 80°C to obtain Resin (5). The nonvolatile content of this Resin (5) was 70% by mass, the solid acid value was 70 mgKOH / g, the acryloyl group equivalent was 803 g / equivalent, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 402 g / equivalent.

[0195] (Example 6: Production of Resin (6)) Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 190 parts by mass of 4-hydroxyphenylacetic acid, 330 parts by mass of an adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq), and 1514 parts by mass of methyl isobutyl ketone were added. Next, 202 parts by mass of isophthaloyl chloride, 91 parts by mass of acryloyl chloride, and 0.9 part by mass of tetrabutylammonium bromide were added, and the temperature inside the system was controlled to 60°C or lower. Then, 824 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and after the addition was completed, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained methyl isobutyl ketone layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Next, 0.6 part by mass of dibutylhydroxytoluene, 0.3 part by mass of methoquinone, and 246 parts by mass of diethylene glycol monomethyl ether acetate were added, and while blowing air, methyl isobutyl ketone was removed as a solvent at 80°C to obtain Resin (6). The nonvolatile content of this Resin (6) was 70% by mass, the solid acid value was 87 mgKOH / g, the acryloyl group equivalent was 665 g / eq, and the ester bond equivalent of the structure represented by the general formula (1) in the resin defined in the present invention was 333 g / eq.

[0196] (Comparative Example 1: Synthesis of an aromatic ester compound (R1) having a polymerizable unsaturated group) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer was charged with 268 parts by mass of orthoallylphenol and 1200 parts by mass of toluene, and the inside of the system was purged with nitrogen under reduced pressure. Next, 203 parts by mass of isophthaloyl chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure. Then, 0.6 part by mass of tetrabutylammonium bromide was added, and while performing a nitrogen gas purge treatment, the inside of the system was controlled to 60 °C or lower, and 412 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. 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 liquid 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.

[0197] [Chemical formula]

[0198] (Comparative Example 2: Production of methacrylate resin (R2) having a polymerizable unsaturated group) 85 parts by mass of methyl isobutyl ketone, 122 parts by mass of benzoic acid, 145 parts by mass of glycidyl methacrylate, 0.2 part by mass of dibutylhydroxytoluene, 0.2 part by mass of methoquinone, and 0.8 part by mass of triphenylphosphine were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser. Air was blown in, and the mixture was reacted at 110 °C for 8 hours while stirring. Next, 74 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110 °C for 5 hours 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 mgKOH / g.

[0199] (Example 7: Preparation of curable resin composition (1)) 70 parts by mass of the resin (1) with a non-volatile content of 70% by mass obtained in Example 1, 21.2 parts by mass of an orthocresol novolak 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-methylimidazole, and 0.5 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (1).

[0200] (Examples 8 to 13: Preparation of curable resin compositions (2) to (7)) Except that the resins (2) to (6) obtained in Examples 2 to 6 were used in the compounding amounts shown in Table 1 instead of the resin (1) used in Example 7, curable resin compositions (2) to (7) were obtained in the same manner as in Example 7.

[0201] (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 novolak type 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-methylimidazole, and 0.6 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (R1).

[0202] (Comparative Example 4: Preparation of curable resin composition (R2)) Except that the methacrylate resin (R2) having a polymerizable unsaturated group obtained in Comparative Example 2 was used in the compounding amount shown in Table 1 instead of the aromatic ester compound (R1) having a polymerizable unsaturated group used in Comparative Example 3, a curable resin composition (R2) was obtained in the same manner as in Comparative Example 3.

[0203] Using the curable resin compositions (1) to (7), (R1), and (R2) obtained in the above Examples and Comparative Examples, the following evaluations were conducted.

[0204] [Method for Evaluating Photosensitivity] The curable resin compositions obtained in each Example and Comparative Example were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and then dried at 80°C for 30 minutes each. Next, ultraviolet rays of 10 kJ / m 2 were irradiated using a metal halide lamp through a step tablet No. 2 manufactured by Eastman Kodak Company. This was developed with a 1% aqueous sodium carbonate solution for 180 seconds, and the remaining number of steps was evaluated. Note that the higher the remaining number of steps, the higher the photosensitivity.

[0205] [Method for Evaluating Alkaline Developability] The curable resin compositions obtained in each Example and Comparative Example were applied onto a glass substrate using an applicator so as to have 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 create 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 with no residue remaining on the substrate was evaluated as the drying control width. Note that the longer the drying control width, the better the alkaline developability.

[0206] Table 1 shows 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.

[0207]

Table 1

[0208] Note that "-" in Table 1 indicates undevelopable.

[0209] (Example 14: Preparation of Curable Resin Composition (8)) 70 parts by mass of the resin (1) obtained in Example 1, 21.2 parts by mass of an orthocresol novolak 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), and 1.4 parts by mass of 4-dimethylaminopyridine were mixed to obtain a curable resin composition (8).

[0210] (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 the blending amounts shown in Table 2 instead of the resin (1) used in Example 14.

[0211] (Comparative Example 5: Preparation of curable resin composition (R3)) 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 novolak type 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 were mixed to obtain a curable resin composition (R3).

[0212] (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 the blending amount shown in Table 2 instead of the aromatic ester compound (R1) having a polymerizable unsaturated group used in Comparative Example 5.

[0213] Using the curable resin compositions (8) to (14), (R3) and (R4) obtained in the above Examples and Comparative Examples, the following evaluations were conducted.

[0214] [Method for Measuring Dielectric Constant] The curable resin compositions obtained in each of the examples and comparative examples were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating with ultraviolet rays of 10 kJ / m 2 using a metal halide lamp, it was heated at 160° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a sample stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours was used as a test piece, and the dielectric constant of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[0215] [Method for Measuring Dielectric Loss Tangent] The curable resin compositions obtained in each of the examples and comparative examples were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating with ultraviolet rays of 10 kJ / m 2 using a metal halide lamp, it was heated at 160° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a sample stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours was used as a test piece, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[0216] Table 2 shows 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.

[0217]

Table 2

[0218] Note that the description of the parts by mass of the resin in Tables 1 and 2 is the solid content value.

[0219] The "curing agent" in Tables 1 and 2 refers to orthocresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0220] The "organic solvent" in Tables 1 and 2 refers to diethylene glycol monomethyl ether acetate.

[0221] The "photoinitiator" in Tables 1 and 2 refers to "Omnirad 907" manufactured by IGM Resins.

[0222] 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 alkali developability.

[0223] Also, 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.

[0224] On the other hand, Comparative Example 3 is an example of a curable resin composition containing an aromatic ester compound having no acid group and having a polymerizable unsaturated group. It was confirmed that this curable resin composition is extremely insufficient in both photosensitivity and alkali developability.

[0225] Also, Comparative Example 4 is an example of a curable resin composition containing a methacrylate resin having an acid group and a polymerizable unsaturated group not having the structure represented by the general formula (1). It was confirmed that this curable resin composition has insufficient photosensitivity.

[0226] Comparative Example 5 is, like Comparative Example 3, an example of a curable resin composition containing an aromatic ester compound having no acid group and having a polymerizable unsaturated group. It was confirmed that the cured product of this curable resin composition has insufficient dielectric properties.

[0227] Comparative Example 6 is an example of a curable resin composition containing a methacrylate resin having an acid group and a polymerizable unsaturated group not having the structure represented by the general formula (1), like Comparative Example 4. It was confirmed that the cured product of this curable resin composition had insufficient dielectric properties.

Claims

1. A resin having at least one polymerizable unsaturated group, at least one acid group, and at least one structure represented by the following general formula (1), characterized in that it is a resin which is a reaction product using 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 esterified product (B), a (meth)acrylate compound (C) having an epoxy group, a polybasic acid anhydride (D), as essential reaction raw materials, wherein 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. 【Chemical 1】 [In formula (1), Ar1 represents a substituted or unsubstituted aromatic ring, and Ar2 represents a substituted or unsubstituted aromatic ring.]

2. The resin according to Claim 1, wherein the polymerizable unsaturated group equivalent is in the range of 250 to 1200 g / equivalent.

3. The resin according to Claim 1 or 2, wherein the acid value is in the range of 40 to 140 mgKOH / g.

4. 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.

5. 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 the aromatic ring and at least one acid group in one molecule.

6. 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.

7. A curable resin composition comprising the resin according to any one of Claims 1 to 5 and a photoinitiator.

8. A cured product of the curable resin composition according to Claim 6 or 7.

9. An insulating material comprising the cured product according to Claim 8.

10. A resist member comprising the cured product according to Claim 8.

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