Method for producing resin having acid group and polymerizable unsaturated group

Abstract

To provide a method for producing a resin having acid groups and polymerizable unsaturated groups, which has excellent alkali developability and high photosensitivity and a cured material of which is excellent in elongation, dielectric characteristics, and adhesion to a substrate.SOLUTION: A method for producing a resin having acid groups and polymerizable unsaturated groups, which is obtained by reacting a raw material comprising a polyol compound, an unsaturated monobasic acid, and a polybasic acid anhydride under an environment of a gas containing oxygen and an inert gas and under an agitation environment. An oxygen concentration in the reaction system is 3.5 to 12.5 mass%. Agitation power per unit volume in the reaction system is 0.5 to 5 kW / m3. The polyol compound is obtained by reacting a raw material comprising a compound having a phenolic hydroxyl group(s) and a cyclic carbonate compound under an inert gas atmosphere. A softening point of the compound having a phenolic hydroxy group(s) is 70°C or higher.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a resin having an acid group and a polymerizable unsaturated group, which has excellent alkaline developability and high photosensitivity, and in which the cured product has excellent elongation, dielectric properties, and substrate adhesion; a method for producing a curable resin composition containing the same; a method for producing a cured product made of the curable resin composition; and a method for producing an insulating material and a resist member using the cured product. [Background technology]

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

[0003] Conventionally known resin materials for solder resists include carboxyl group-containing photosensitive resins obtained by reacting a reaction product (c) of a compound (a) having two or more phenolic hydroxyl groups per molecule with a cyclic carbonate (b), with an unsaturated group-containing monocarboxylic acid (d) and / or its esters (e), and then reacting the resulting reaction product (f) with a polybasic acid anhydride (g) (see, for example, Patent Document 1 below). However, these resin materials do not satisfy the increasingly high requirements for properties in terms of elongation, dielectric properties, and substrate adhesion in the cured product, and are not sufficient for meeting current market demands.

[0004] Therefore, there has been a demand for a material that has excellent alkaline developability and high photosensitivity, and in the cured product, is even better in terms of elongation, dielectric properties, and substrate adhesion. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-359728 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a method for producing a resin having an acid group and a polymerizable unsaturated group, which has excellent alkaline developability and high photosensitivity, and which has excellent elongation, dielectric properties, and substrate adhesion in a cured product; a method for producing a curable resin composition containing the same; a method for producing a cured product made of the curable resin composition; and a method for producing an insulating material and a resist member using the cured product. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by reacting raw materials containing a specific polyol compound, an unsaturated monobasic acid, and a polybasic acid anhydride under an atmosphere of an oxygen-containing gas and an inert gas while stirring so that the oxygen concentration in the reaction system is within a specific range and so that the stirring power per unit volume is within a specific range, and have completed the present invention.

[0008] That is, the present invention provides a method for producing a resin having an acid group and a polymerizable unsaturated group, which is obtained by reacting raw materials containing a polyol compound (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) in an atmosphere of an oxygen-containing gas (g1) and an inert gas (g2) and in a stirring environment, wherein the oxygen concentration in the reaction system is in the range of 3.5 to 12.5 mass%, and the stirring power per unit volume in the reaction system is in the range of 0.5 to 5 kW / m 3the polyol compound (A) is obtained by reacting raw materials containing a compound (a1) having a phenolic hydroxyl group and a cyclic carbonate compound (a2) under an inert gas atmosphere, and the softening point of the compound (a1) having a phenolic hydroxyl group is 70°C or higher. The present invention relates to a method for producing a resin having an acid group and a polymerizable unsaturated group, a method for producing a curable resin composition containing the resin, a method for producing a cured product made of the curable resin composition, and a method for producing an insulating material and a resist member using the cured product. [Effects of the Invention]

[0009] The resin having an acid group and a polymerizable unsaturated group obtained by the production method of the present invention has excellent alkaline developability and high photosensitivity, and the cured product has excellent elongation, dielectric properties, and substrate adhesion, making it suitable for use in insulating materials and resist members. The "excellent dielectric properties" referred to in the present invention refer to a low dielectric constant and a low dielectric loss tangent. DETAILED DESCRIPTION OF THE INVENTION

[0010] The method for producing a resin having an acid group and a polymerizable unsaturated group of the present invention is characterized in that raw materials containing a polyol compound (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) are reacted with stirring in an atmosphere of an oxygen-containing gas (g1) and an inert gas (g2).

[0011] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among these, a carboxyl group is preferred.

[0012] Examples of the polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group.

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

[0014] The polyol compound (A) is obtained by reacting raw materials containing a compound (a1) having a phenolic hydroxyl group with a cyclic carbonate compound (a2).

[0015] The compound (a1) 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 (2-1) to (2-4).

[0016] [ka]

[0017] In the above structural formulas (1-1) to (1-4), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (1-2), the substituent may be on any ring. In structural formula (1-3), the substituent may be on any ring of the benzene ring present in one molecule. In structural formulas (1-4) and (1-5), the substituent may be on any ring of the benzene ring present in one molecule. The numbers p and q indicate the number of substituents in one molecule.

[0018] Examples of the compound (a1) having a phenolic hydroxyl group include a reaction product obtained by reacting the compound having at least one phenolic hydroxyl group in its molecule with a compound represented by any one of the following structural formulas (x-1) to (x-5) as essential reaction materials, a reaction product obtained by reacting the compound having at least one phenolic hydroxyl group in its molecule with an aldehyde compound or a divinyl compound as essential reaction materials, and a reaction product obtained by reacting the compound having at least one phenolic hydroxyl group in its molecule with a compound represented by any one of the following structural formulas (x-1) to (x-5) with an aldehyde compound or a divinyl compound as essential reaction materials. Also useful are novolac-type phenolic resins obtained by reacting one or more compounds having at least one phenolic hydroxyl group in its molecule as reaction materials.

[0019] [ka] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group. In formula (x-5), Y represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and j is an integer of 1 to 4.

[0020] Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyl aldehyde, isobutyl aldehyde, pentyl aldehyde, and hexyl aldehyde; hydroxybenzaldehydes such as salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde; Examples of suitable aldehyde compounds include benzaldehydes having both a hydroxy group and an alkoxy group, such as 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes, such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes, such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes, such as brombenzaldehyde. These aldehyde compounds can be used alone or in combination of two or more.

[0021] Examples of the divinyl compound include aromatic divinyl compounds such as divinylbenzene, alkyldivinylbenzene, diallyl phthalate, and diisopropenylbenzene, and aliphatic divinyl compounds such as glycerol diallyl ether and trimethylolpropane triacrylate.

[0022] Examples of the divinylbenzene include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, etc. These divinylbenzenes can be used alone or in combination of two or more.

[0023] Examples of the diisopropenylbenzene include 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, etc. These diisopropenylbenzenes can be used alone or in combination of two or more.

[0024] Furthermore, examples of the compound (a1) having a phenolic hydroxyl group include bisphenol-type phenolic resins, phenylene ether-type phenolic resins, naphthalene-type phenolic resins, naphthylene ether-type phenolic resins, biphenyl-type phenolic resins, triphenylmethane-type phenolic resins, phenol novolac-type phenolic resins, cresol novolac-type phenolic resins, bisphenol novolac-type phenolic resins, naphthol novolac-type phenolic resins, naphthol-phenol co-condensed novolac-type phenolic resins, naphthol-cresol co-condensed novolac-type phenolic resins, phenol aralkyl-type phenolic resins, naphthol aralkyl-type phenolic resins, dicyclopentadiene-phenol addition reaction-type phenolic resins, biphenyl aralkyl-type phenolic resins, fluorene-type phenolic resins, xanthene-type phenolic resins, dihydroxybenzene-type phenolic resins, and trihydroxybenzene-type phenolic resins.

[0025] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0026] The softening point of the compound (a1) having a phenolic hydroxyl group is 70° C. or higher, and is preferably in the range of 70 to 150° C., more preferably in the range of 80 to 140° C., and even more preferably in the range of 80 to 120° C., because a resin having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent alkali developability, high photosensitivity, elongation, dielectric properties, and substrate adhesion can be obtained. In the present invention, the softening point is a value measured by the ring and ball method described in JIS K6910 (2007).

[0027] Examples of the cyclic carbonate compound (a2) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkali developability and high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion. These cyclic carbonate compounds can be used alone or in combination of two or more.

[0028] The amount of the cyclic carbonate compound (a2) used is preferably in the range of 0.9 to 2 mol, more preferably 0.9 to 1.2 mol, per mol of the hydroxyl group of the compound (a1) having a phenolic hydroxyl group, because a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion can be obtained.

[0029] As raw materials for the polyol compound (A), compounds other than the compound (a1) having a phenolic hydroxyl group and the cyclic carbonate compound (a2) can also be used.

[0030] Examples of the other compounds include polybasic acids, polybasic acid anhydrides, and epihalohydrins.

[0031] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of suitable polybasic acids include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0032] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0033] Examples of the aliphatic polybasic acid anhydrides include acid anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

[0034] In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0035] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0036] These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0037] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, etc. These epihalohydrins can be used alone or in combination of two or more.

[0038] The amount of the other compounds used is preferably 10% by mass or less in the raw materials for the polyol compound (A).

[0039] The method for producing the polyol compound (A) is not particularly limited, and any method may be used. For example, raw materials containing the compound (a1) having a phenolic hydroxyl group and the cyclic carbonate compound (a2) are reacted in the presence of a basic catalyst under an inert gas atmosphere at a temperature of preferably 100 to 200°C for a reaction time of preferably 1 to 30 hours.

[0040] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. Examples of basic catalysts include quaternary ammonium salts such as octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. These basic catalysts can be used alone or in combination. Among these, phosphine compounds are preferred because they can give resins having an acid group and a polymerizable unsaturated group that can form cured products having excellent alkali developability and high photosensitivity, as well as excellent elongation, dielectric properties, and substrate adhesion.

[0041] The amount of the basic catalyst used is preferably in the range of 0.01 to 1.0 part by mass, more preferably 0.05 to 0.8 part by mass, relative to 100 parts by mass of the total of raw materials including the compound (a1) having a phenolic hydroxyl group and the cyclic carbonate compound (a2), because a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkali developability and high photosensitivity, as well as excellent elongation, dielectric properties, and substrate adhesion, can be obtained.

[0042] The unsaturated monobasic acid (B) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. In the present invention, the term "polymerizable unsaturated bond" refers to an unsaturated bond that can be radically polymerized.

[0043] Examples of the acid group include those exemplified above as the acid group.

[0044] Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (2) can also be used.

[0045] [ka] [In formula (2), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

[0046] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0047] An example of the (poly)ester chain is a (poly)ester chain represented by the following structural formula (X-1).

[0048] [ka] [In formula (X-1), R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0049] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0050] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following structural formula (X-2).

[0051] [ka] [In formula (X-2), R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0052] The molecular weight of the compound represented by the structural formula (2) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0053] These unsaturated monobasic acids (B) can be used alone or in combination of two or more kinds.

[0054] The amount of the unsaturated monobasic acid (B) used is preferably in the range of 0.3 to 0.7 mol, more preferably 0.4 to 0.7 mol, of the acid groups of the unsaturated monobasic acid (B) per mol of hydroxyl groups of the polyol compound (A), because a resin having acid groups and polymerizable unsaturated groups capable of forming a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion can be obtained.

[0055] The polybasic acid anhydride (C) may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, cyclohexane-1,2-dicarboxylic anhydride, succinic anhydride, and 3-methyl-8-oxabicyclo[4.3.0]nonane-7,9-dione are preferred because they give resins having acid groups and polymerizable unsaturated groups that can form cured products having excellent alkali developability, high photosensitivity, elongation, dielectric properties, and substrate adhesion.

[0056] The amount of the polybasic acid anhydride (C) used is preferably in the range of 0.3 to 0.7 mol, more preferably 0.3 to 0.6 mol, of the acid anhydride groups of the polybasic acid anhydride (C) per mol of hydroxyl groups of the polyol compound (A), because a resin having acid groups and polymerizable unsaturated groups capable of forming a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion can be obtained.

[0057] Furthermore, since a resin having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion can be obtained, the total number of moles of the acid group of the unsaturated monobasic acid (B) and the acid anhydride group of the polybasic acid anhydride (C) is preferably in the range of 0.8 to 1.2 moles, more preferably in the range of 0.9 to 1.1 moles, per mole of hydroxyl group of the polyol compound (A).

[0058] As raw materials for the resin having an acid group and a polymerizable unsaturated group of the present invention, compounds other than the polyol compound (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) can also be used.

[0059] Examples of the other compounds include polyisocyanate compounds, epoxy compounds, and amine compounds.

[0060] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating unit represented by the following structural formula (3); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

[0061] [ka] [In the formula, R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 2 are each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0062] Examples of the epoxy compound include bisphenol-type epoxy compounds, phenylene ether-type epoxy compounds, naphthalene-type epoxy compounds, naphthylene ether-type epoxy compounds, biphenyl-type epoxy compounds, triphenylmethane-type epoxy compounds, phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol novolac-type epoxy compounds, naphthol novolac-type epoxy compounds, naphthol-phenol co-condensed novolac-type epoxy compounds, naphthol-cresol co-condensed novolac-type epoxy compounds, phenol aralkyl-type epoxy compounds, naphthol aralkyl-type epoxy compounds, dicyclopentadiene-phenol addition reaction-type epoxy compounds, biphenyl aralkyl-type epoxy compounds, fluorene-type epoxy compounds, xanthene-type epoxy compounds, dihydroxybenzene-type epoxy compounds, and trihydroxybenzene-type epoxy compounds.

[0063] Examples of the bisphenol type epoxy compound include bisphenol A type epoxy compounds, bisphenol AP type epoxy compounds, bisphenol B type epoxy compounds, bisphenol BP type epoxy compounds, bisphenol E type epoxy compounds, bisphenol F type epoxy compounds, and bisphenol S type epoxy compounds.

[0064] Examples of the hydrogenated bisphenol epoxy compound include hydrogenated bisphenol A epoxy compounds, hydrogenated bisphenol B epoxy compounds, hydrogenated bisphenol E epoxy compounds, hydrogenated bisphenol F epoxy compounds, and hydrogenated bisphenol S epoxy compounds.

[0065] Examples of the biphenol type epoxy compound include 4,4'-biphenol type epoxy compounds, 2,2'-biphenol type epoxy compounds, tetramethyl-4,4'-biphenol type epoxy compounds, and tetramethyl-2,2'-biphenol type epoxy compounds.

[0066] Examples of the hydrogenated biphenol type epoxy compound include hydrogenated 4,4'-biphenol type epoxy compound, hydrogenated 2,2'-biphenol type epoxy compound, hydrogenated tetramethyl-4,4'-biphenol type epoxy compound, and hydrogenated tetramethyl-2,2'-biphenol type epoxy compound.

[0067] These epoxy compounds can be used alone or in combination of two or more.

[0068] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more.

[0069] The amount of the other compounds used is preferably 10% by mass or less in the raw material for the resin having an acid group and a polymerizable unsaturated group.

[0070] Examples of the gas (g1) include oxygen gas and air.

[0071] The inert gas (g2) may be any gas that is inert in the reaction system, and examples thereof include hydrogen, nitrogen, carbon dioxide, carbon monoxide, helium, neon, argon, etc. These inert gases may be used alone or as a mixed gas of two or more kinds.

[0072] The gas (g1) and the inert gas (g2) may be prepared in advance as a mixed gas and introduced into the reaction apparatus, or the gas (g1) and the inert gas (g2) may be introduced separately into the reaction apparatus and mixed in the reaction system.

[0073] When the gas (g1) and the inert gas (g2) are introduced separately into the reaction apparatus, the introduction nozzles for the gas (g1) and the inert gas (g2) may be separate or may be combined, as long as the introduction nozzles are present in the reaction apparatus, but it is preferable that they are separate. In addition, the position of the introduction nozzles in this case is preferably such that the gas (g1) is introduced below the liquid surface of the reaction system and the inert gas (g2) is introduced above the liquid surface of the reaction system, because this results in a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion.

[0074] The oxygen concentration in the reaction apparatus, i.e., the oxygen concentration in the reaction system, is in the range of 3.5 to 12.5 mass %, preferably 4 to 10 mass %, more preferably 5 to 9 mass %, and particularly preferably 6 to 9 mass %, because a resin having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent alkali developability and high photosensitivity, as well as excellent elongation, dielectric properties, and substrate adhesion, can be obtained.

[0075] The method for adjusting the oxygen concentration in the reaction system to 3.5 to 12.5% ​​by mass is not particularly limited, and examples thereof include a method of blowing the gas (g1) from above the liquid surface in the reaction system, a method of bubbling the gas from a gas inlet nozzle set below the liquid surface, etc. Among these, a method of blowing the gas (g1) and the inert gas (g2) from above the liquid surface in the reaction system is preferred, because it produces a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkali developability and high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion, and a method of blowing the inert gas (g2) from above the liquid surface in the reaction system and bubbling the gas (g1) from a gas inlet nozzle set below the liquid surface is more preferred.

[0076] The total amount of the gas (g1) and the inert gas (g2) introduced is preferably 1×10 per 1 kg of the total amount of the polyol compound (A) and the unsaturated monobasic acid (B), because a resin having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion can be obtained. -12 ~1×10 -3 / min is preferred, and 1×10 -11 ~1×10 -3 / min is more preferable. The gas (g1) and the inert gas (g2) may be introduced continuously or intermittently, as long as the average amount introduced is within this range.

[0077] The method for producing a resin having an acid group and a polymerizable unsaturated group of the present invention comprises reacting raw materials containing a polyol compound (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) in the presence of an acidic catalyst and / or a basic catalyst under an atmosphere of an oxygen-containing gas (g1) and an inert gas (g2), wherein the oxygen concentration in the reaction system is in the range of 3.5 to 12.5 mass%, and the stirring power per unit volume in the reaction system is in the range of 0.5 to 5 kW / m 3 The "stirring power per unit volume" in the present invention is a value calculated from the following formula (1).

[0078]

number

[0079] The stirring power is 0.5 to 5 kW / m 3However, the range of 1 to 4 kW / m is 1 to 4 kW / m because it is possible to obtain a resin having an acid group and a polymerizable unsaturated group that can form a cured product having excellent alkaline developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion. 3 The range is preferably 2 to 4 kW / m 3 The range is more preferable.

[0080] As a method for producing the resin having an acid group and a polymerizable unsaturated group, a method in which a polyol compound (A) is reacted with an unsaturated monobasic acid (B) in advance to obtain a reaction product, and then a polybasic acid anhydride (C) is reacted therewith is preferred, because this method can produce a resin having an acid group and a polymerizable unsaturated group that has excellent alkali developability, high photosensitivity, and is capable of forming a cured product having excellent elongation, dielectric properties, and substrate adhesion.

[0081] The reaction temperature in the reaction between the polyol compound (A) and the unsaturated monobasic acid (B) is, for example, preferably in the range of 60 to 150° C., and the reaction time is preferably in the range of 1 to 30 hours.

[0082] In the reaction of the polyol compound (A) with the unsaturated monobasic acid (B), a method is preferred in which the reaction is carried out in the presence of an acid catalyst, under reduced pressure, by azeotroping water with a water-insoluble solvent while removing water from the system, and then washing with water to remove the acid catalyst.

[0083] Examples of the non-water-soluble solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and aromatic solvents such as toluene, xylene and solvent naphtha.

[0084] The reaction of the polybasic acid anhydride (C) with the reaction product obtained by reacting the polyol compound (A) with the unsaturated monobasic acid (B) is preferably carried out in the presence of a basic catalyst at a temperature in the range of 70 to 160°C, and the reaction time is preferably in the range of 1 to 20 hours.

[0085] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0086] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0087] The curable resin composition of the present invention contains the resin having an acid group and a polymerizable unsaturated group, and a photopolymerization initiator.

[0088] Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0089] Commercially available photopolymerization initiators include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); and "Vicure 10" and "Vicure 55" (manufactured by Stoffa Examples of photopolymerization initiators include "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop), and "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

[0090] The amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15 mass %, more preferably in the range of 0.1 to 10 mass %, of the total of the components other than the solvent of the curable resin composition.

[0091] The photopolymerization initiator may also be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound, if necessary.

[0092] The curable resin composition of the present invention may contain other resin components in addition to the resin having an acid group and a polymerizable unsaturated group described above. Examples of the other resin components include epoxy resins having an acid group and a polymerizable unsaturated group, urethane resins having an acid group and a polymerizable unsaturated group, acrylic resins having an acid group and a polymerizable unsaturated group, amide-imide resins having an acid group and a polymerizable unsaturated group, acrylamide resins having an acid group and a polymerizable unsaturated group, and various (meth)acrylate monomers.

[0093] Examples of the acid group include those exemplified above as the acid group.

[0094] Examples of the polymerizable unsaturated group include those exemplified above as the polymerizable unsaturated group.

[0095] Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include an epoxy (meth)acrylate resin having an acid group, which is produced from 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, which is produced from 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.

[0096] Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, etc. These epoxy resins (A1) can be used alone or in combination of two or more. Among these, novolac-type epoxy resins and naphthalene-type epoxy resins are preferred because they give resins having an acid group and a polymerizable unsaturated group that have excellent alkali developability and high photosensitivity and are capable of forming a cured product having excellent elongation, dielectric properties, and substrate adhesion.

[0097] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0098] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0099] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0100] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0101] These epoxy resins can be used alone or in combination of two or more.

[0102] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0103] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0104] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0105] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Also usable are (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0106] The method for producing the epoxy resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0107] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, as this improves reaction efficiency.

[0108] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0109] 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, with 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.

[0110] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0111] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

[0112] 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.

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

[0114] Examples of polyol compounds other than the polyol compounds having a carboxyl group include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various polyol compounds; and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the polyol compounds having a carboxyl group can be used alone or in combination of two or more.

[0115] The method for producing the urethane resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0116] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0117] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0118] Examples of the acrylic resin having an acid group and a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

[0119] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; (meth)acrylates having an alicyclic structure such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; (meth)acrylates having an aromatic ring such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0120] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferred 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 preferred 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 preferred to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

[0121] The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more.

[0122] The method for producing the acrylic resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0123] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0124] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0125] Examples of the amide-imide resin having an acid group and a polymerizable unsaturated group include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group.

[0126] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with (meth)acrylate compounds having hydroxyl groups or epoxy compounds having (meth)acryloyl groups, it is preferable for the resin to have an acid anhydride group, and it is more preferable for the resin to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0127] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0128] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0129] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0130] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0131] As the polybasic acid, the same polybasic acids as those exemplified above can be used, and the polybasic acids can be used alone or in combination of two or more kinds.

[0132] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

[0133] The (meth)acrylate compound having an epoxy group is not particularly limited in its specific structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more. Among these, (meth)acrylate compounds having one epoxy group are preferred because the reaction can be easily controlled, and (meth)acrylate monomers having a glycidyl group are preferred because they can provide curable resin compositions that have excellent alkali developability and high photosensitivity and can form cured products with excellent elongation, dielectric properties, and substrate adhesion. The molecular weight of the (meth)acrylate monomer having a glycidyl group is preferably 500 or less. Furthermore, the proportion of the (meth)acrylate monomer having a glycidyl group relative to the total mass of the (meth)acrylate compound having an epoxy group is preferably 70% by mass or more, and more preferably 90% by mass or more.

[0134] The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0135] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0136] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0137] Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, a polybasic acid anhydride, and, if necessary, an unsaturated monobasic acid.

[0138] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified as the compound (a1) having a phenolic hydroxyl group described above can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0139] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition that has excellent alkali developability and high photosensitivity and can form a cured product having excellent elongation, dielectric properties, and substrate adhesion. The alkylene oxides can be used alone or in combination of two or more.

[0140] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition that has excellent alkali developability and high photosensitivity and can form a cured product having excellent elongation, dielectric properties, and substrate adhesion. The alkylene carbonates can be used alone or in combination of two or more.

[0141] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0142] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0143] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0144] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

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

[0146] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0147] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0148] The amount of the resin having an acid group and a polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the resin having an acid group and a polymerizable unsaturated group of the present invention.

[0149] Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono(meth)acrylate compounds such as the aromatic mono(meth)acrylate compounds of the above: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

[0150] In addition to the above-mentioned other (meth)acrylate monomers, (meth)acrylate monomers having 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.

[0151] Examples of the phenol 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 novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

[0152] As the cyclic carbonate compound, the same compounds as those exemplified as the cyclic carbonate compound (a2) above can be used, and the cyclic carbonate compounds can be used alone or in combination of two or more kinds.

[0153] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran, etc. These cyclic ether compounds can be used alone or in combination of two or more.

[0154] As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used.

[0155] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0156] Furthermore, the curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as needed.

[0157] Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

[0158] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0159] As the polybasic acid, the same polybasic acids as those exemplified above can be used, and the polybasic acids can be used alone or in combination of two or more kinds.

[0160] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0161] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more.

[0162] Examples of the amide compounds include dicyandiamide, polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more.

[0163] Examples of the azo compounds include azobisisobutyronitrile.

[0164] Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, alkyl peroxycarbonate, etc. These organic peroxides can be used alone or in combination of two or more.

[0165] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. Examples of suitable polyols include polyester polyols obtained by co-condensation of the above polyol monomers with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

[0166] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0167] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0168] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0169] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,3-diphenyl-4-phenylenediamine), and methyl-p-benzoquinone.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination.

[0170] As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0171] Commercially available examples of the polymerization inhibitor and antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0172] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0173] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0174] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0175] Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0176] 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, and zinc sulfide.

[0177] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

[0178] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0179] The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0180] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0181] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0182] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0183] Furthermore, the cured product of the present invention has excellent alkali developability, high photosensitivity, and excellent elongation, dielectric properties, and substrate adhesion, and therefore can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, etc., or adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCDs and OELDs as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. Among these, it can be particularly suitably used in solder resist applications.

[0184] The resin material for a solder resist of the present invention comprises the above-mentioned curable resin composition.

[0185] The resist member of the present invention can be obtained, for example, by applying the solder resist resin material to a substrate, evaporating and drying the organic solvent at a temperature in the range of about 60 to 100°C, exposing the material to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the material at a temperature in the range of about 140 to 200°C.

[0186] Examples of the substrate include a metal-clad laminate made of copper, aluminum, or the like. [Example]

[0187] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0188] (Synthesis Example 1: Synthesis of Polyol Compound (1)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 116 parts by mass of orthocresol novolac phenolic resin (softening point: 70°C, phenolic hydroxyl group equivalent: 116 g / equivalent), and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 10 hours to obtain polyol compound (1). The hydroxyl group equivalent of this polyol compound (1) was 180 g / equivalent. The amount of propylene carbonate used was 1.05 moles per mole of hydroxyl groups in the orthocresol novolac phenolic resin. In the present synthesis examples, examples, and comparative examples, a mixed gas of hydrogen (3% by mass) and nitrogen (97% by mass) was used as the inert gas.

[0189] (Synthesis Example 2: Synthesis of Polyol Compound (2)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 117 parts by mass of orthocresol novolac phenolic resin (PHENOLITE KA-1160 manufactured by DIC Corporation, softening point: 85°C, phenolic hydroxyl group equivalent: 117 g / eq., hereinafter abbreviated as "orthocresol novolac phenolic resin (1)") and heated to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 10 hours to obtain polyol compound (2). The hydroxyl group equivalent of this polyol compound (2) was 181 g / eq. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in the orthocresol novolac phenolic resin.

[0190] (Synthesis Example 3: Synthesis of polyol compound (3)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 118 parts by mass of orthocresol novolac phenolic resin (PHENOLITE KA-1163 manufactured by DIC Corporation, softening point 110°C, phenolic hydroxyl group equivalent: 118 g / equivalent), and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate were added in three portions. The reaction was carried out for 11 hours to obtain polyol compound (3). The hydroxyl group equivalent of this polyol compound (3) was 183 g / equivalent. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in the orthocresol novolac phenolic resin.

[0191] (Synthesis Example 4: Synthesis of polyol compound (4)) 117 parts by mass of orthocresol novolac phenolic resin (1) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 92 parts by mass of ethylene carbonate was added in three portions. The reaction was carried out for 10 hours to obtain polyol compound (4). The hydroxyl group equivalent of this polyol compound (4) was 168 g / equivalent. The amount of ethylene carbonate used was 1.05 mol per mol of hydroxyl groups in the orthocresol novolac phenolic resin.

[0192] (Synthesis Example 5: Synthesis of polyol compound (5)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 104 parts by mass of phenol novolac phenolic resin (PHENOLITE TD-2106 manufactured by DIC Corporation, softening point 90°C, phenolic hydroxyl group equivalent: 104 g / equivalent), and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate were added in three portions. The reaction was carried out for 12 hours to obtain polyol compound (5). The hydroxyl group equivalent of this polyol compound (5) was 167 g / equivalent. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in the phenol novolac phenolic resin.

[0193] (Synthesis Example 6: Synthesis of polyol compound (6)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 118 parts by mass of bisphenol A novolac phenolic resin (PHENOLITE VH-4170 manufactured by DIC Corporation, softening point 105°C, phenolic hydroxyl group equivalent: 118 g / equivalent), and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate were added in three portions. The reaction was carried out for 13 hours to obtain polyol compound (6). The hydroxyl group equivalent of this polyol compound (6) was 182 g / equivalent. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in the bisphenol A novolac phenolic resin.

[0194] (Synthesis Example 7: Synthesis of polyol compound (7)) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 240 parts by weight of 2,7-dihydroxynaphthalene, 85 parts by weight of 37% by weight aqueous formaldehyde solution, 376 parts by weight of isopropyl alcohol, and 88 parts by weight of 48% aqueous potassium hydroxide solution. Stirring was started while blowing in an inert gas, and the mixture was heated to 75°C and stirred for 2 hours. After the reaction was completed, 108 parts by weight of sodium phosphate monobasic was added to neutralize the mixture. The isopropyl alcohol was removed under reduced pressure, and 480 parts by weight of methyl isobutyl ketone was added. This water-washing process with 200 parts by weight of water was repeated three times, after which the methyl isobutyl ketone was removed under reduced pressure with heating, yielding intermediate (x1) with a phenolic hydroxyl group equivalent of 84 g / equivalent and a softening point of 110°C. Next, 84 parts by mass of intermediate (x1) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.5 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 11 hours to obtain polyol compound (7). The hydroxyl equivalent of this polyol compound (7) was 149 g / equivalent. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in "intermediate (X1)".

[0195] (Synthesis Example 8: Synthesis of polyol compound (8)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 285 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid, and the mixture was heated to 115°C under an inert gas atmosphere. 208 parts by mass of 1,4-divinylbenzene was added dropwise over 2 hours, and the mixture was maintained at 115°C for 5 hours. 2.3 parts by mass of a 20% aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain an intermediate (x2) having a phenolic hydroxyl group equivalent of 108 g / equivalent and a softening point of 110°C. Next, 108 parts by mass of intermediate (x2) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.5 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 13 hours to obtain polyol compound (8). The hydroxyl group equivalent of this polyol compound (8) was 170 g / equivalent. The amount of propylene carbonate used was 1.05 mol per 1 mol of hydroxyl groups in "intermediate (X2)".

[0196] (Synthesis Example 9: Synthesis of polyol compound (9)) 117 parts by mass of orthocresol novolac phenolic resin (1) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 122 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 15 hours to obtain polyol compound (9). The hydroxyl group equivalent of this polyol compound (9) was 192 g / equivalent. The amount of propylene carbonate used was 1.2 moles per mole of hydroxyl groups in the orthocresol novolac phenolic resin.

[0197] (Synthesis Example 10: Synthesis of polyol compound (10)) 117 parts by mass of orthocresol novolac phenolic resin (1) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 97 parts by mass of propylene carbonate was added in three portions. The reaction was carried out for 9 hours to obtain polyol compound (10). The hydroxyl group equivalent of this polyol compound (10) was 179 g / equivalent. The amount of propylene carbonate used was 0.95 mol per 1 mol of hydroxyl groups in the orthocresol novolac phenolic resin.

[0198] (Synthesis Example 11: Synthesis of polyol compound (11)) 120 parts by mass of orthocresol novolac phenolic resin (softening point: 65°C, phenolic hydroxyl group equivalent: 120 g / equivalent) was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 170°C while blowing in an inert gas. 0.6 parts by mass of a 50% by mass aqueous potassium hydroxide solution was added, and 107 parts by mass of propylene carbonate were added in three portions. The reaction was carried out for 10 hours to obtain polyol compound (11). The hydroxyl group equivalent of this polyol compound (11) was 179 g / equivalent. The amount of propylene carbonate used was 1.05 mol per mol of hydroxyl groups in the orthocresol novolac phenolic resin.

[0199] (Example 1: Preparation of Resin (1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 148 parts by mass of toluene, 180 parts by mass of the polyol compound (1) obtained in Synthesis Example 1, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 117 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (1) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (1), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (1), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (1).

[0200] (Example 2: Preparation of Resin (2) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (2) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0201] (Example 3: Preparation of Resin (3) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 148 parts by mass of toluene, 183 parts by mass of the polyol compound (3) obtained in Synthesis Example 3, 42.5 parts by mass of acrylic acid, 6.8 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 154 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (3) having acid groups and polymerizable unsaturated groups was 65% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (3), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (3), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (3).

[0202] (Example 4: Preparation of Resin (4) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 142 parts by mass of toluene, 168 parts by mass of the polyol compound (4) obtained in Synthesis Example 4, 44.6 parts by mass of acrylic acid, 6.4 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 111 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 58 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (4) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 78 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (4), the number of moles of the acid groups in acrylic acid was 0.62 mole per mole of the hydroxyl groups in polyol compound (4), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.38 mole per mole of the hydroxyl groups in polyol compound (4).

[0203] (Example 5: Preparation of Resin (5) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 142 parts by mass of toluene, 167 parts by mass of the polyol compound (5) obtained in Synthesis Example 5, 44.6 parts by mass of acrylic acid, 6.4 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 111 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 58 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (5) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 78 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (5), the number of moles of the acid groups in acrylic acid was 0.62 mole per mole of the hydroxyl groups in polyol compound (5), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.38 mole per mole of the hydroxyl groups in polyol compound (5).

[0204] (Example 6: Preparation of Resin (6) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 150 parts by mass of toluene, 182 parts by mass of the polyol compound (6) obtained in Synthesis Example 6, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (6) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (6) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (6), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (6), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (6).

[0205] (Example 7: Preparation of Resin (7) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 130 parts by mass of toluene, 149 parts by mass of the polyol compound (7) obtained in Synthesis Example 7, 46.1 parts by mass of acrylic acid, 5.9 parts by mass of paratoluenesulfonic acid, and 1.0 part by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 102 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 55 parts by mass of tetrahydrophthalic anhydride and 1.0 part by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (7) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (7) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (7), the number of moles of the acid groups in acrylic acid was 0.64 mole per mole of the hydroxyl groups in polyol compound (7), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.36 mole per mole of the hydroxyl groups in polyol compound (7).

[0206] (Example 8: Preparation of Resin (8) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 143 parts by mass of toluene, 170 parts by mass of the polyol compound (8) obtained in Synthesis Example 8, 43.9 parts by mass of acrylic acid, 6.4 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 112 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 59 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (8) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (8) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (8), the number of moles of the acid groups in acrylic acid was 0.61 mole per mole of the hydroxyl groups in polyol compound (8), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.39 mole per mole of the hydroxyl groups in polyol compound (8).

[0207] (Example 9: Preparation of Resin (9) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 156 parts by mass of toluene, 192 parts by mass of the polyol compound (9) obtained in Synthesis Example 9, 41.8 parts by mass of acrylic acid, 7.0 parts by mass of paratoluenesulfonic acid, and 1.2 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 123 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 64 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (9) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (9) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (9), the number of moles of the acid groups in acrylic acid was 0.58 mole per mole of the hydroxyl groups in polyol compound (9), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.42 mole per mole of the hydroxyl groups in polyol compound (9).

[0208] (Example 10: Preparation of Resin (10) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 148 parts by mass of toluene, 179 parts by mass of the polyol compound (10) obtained in Synthesis Example 10, 43.2 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 116 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 61 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (10) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (10) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (10), the number of moles of the acid groups in acrylic acid was 0.6 mole per mole of the hydroxyl groups in polyol compound (10), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.4 mole per mole of the hydroxyl groups in polyol compound (10).

[0209] (Example 11: Preparation of Resin (11) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 44.6 parts by mass of acrylic acid, 6.8 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 108 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 38 parts by mass of succinic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (11) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (11) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in succinic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.62 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in succinic anhydride was 0.38 mole per mole of the hydroxyl groups in polyol compound (2).

[0210] (Example 12: Preparation of Resin (12) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 63 parts by mass of cyclohexanedicarboxylic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (12) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (12) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in cyclohexanedicarboxylic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in cyclohexanedicarboxylic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0211] (Example 13: Preparation of Resin (13) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 154 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 50.4 parts by mass of acrylic acid, 6.9 parts by mass of paratoluenesulfonic acid, and 1.2 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 22 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 113 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 46 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (13) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (13) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 60 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (13), the number of moles of the acid groups in acrylic acid was 0.7 mole per mole of the hydroxyl groups in polyol compound (13), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.3 mole per mole of the hydroxyl groups in polyol compound (13).

[0212] (Example 14: Preparation of Resin (14) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 144 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 34.6 parts by mass of acrylic acid, 6.5 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 18 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 122 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 79 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 12 hours to obtain the desired resin (14) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (14) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 100 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.48 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.52 mole per mole of the hydroxyl groups in polyol compound (2).

[0213] (Example 15: Preparation of Resin (15) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface using a stainless steel tube with an inner diameter of 0.5 mm at a rate of 0.16 L / min, and an inert gas was blown in from above the liquid surface at a rate of 0.64 L / min, to adjust the oxygen concentration to 4.2% by mass. The stirring was carried out with a stirring power per unit volume of 3 kW / m 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (15) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (15) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 78 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0214] (Example 16: Preparation of Resin (16) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.46 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.34 L / min to adjust the oxygen concentration to 12% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (16) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (16) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0215] (Example 17: Preparation of Resin (17) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring power per unit volume was 0.5 kW / m 3The mixture was stirred at 85°C under reduced pressure to azeotrope toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (17) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (17) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 82 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0216] (Example 18: Preparation of resin (18) having an acid group and a polymerizable unsaturated group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 5 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (18) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (18) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0217] (Example 19: Preparation of Resin (19) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 147 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 39.6 parts by mass of acrylic acid, 6.6 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 116 parts by mass of diethylene glycol monoethyl ether acetate, 0.5 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 61 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain the desired resin (19) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (19) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 0.95 moles per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.55 moles per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.4 moles per mole of the hydroxyl groups in polyol compound (2).

[0218] (Example 20: Preparation of resin (20) having an acid group and a polymerizable unsaturated group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 154 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 49.9 parts by mass of methacrylic acid, 6.9 parts by mass of paratoluenesulfonic acid, and 1.2 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 25 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 121 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 64 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 10 hours to obtain the desired resin (20) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (20) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 80 mgKOH / g. The total number of moles of the acid groups in methacrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in methacrylic acid was 0.58 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.42 mole per mole of the hydroxyl groups in polyol compound (2).

[0219] (Comparative Example 1: Production of Resin (R1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 148 parts by weight of toluene, 179 parts by weight of the polyol compound (11) obtained in Synthesis Example 11, 39.6 parts by weight of acrylic acid, 6.6 parts by weight of paratoluenesulfonic acid, and 1.1 parts by weight of methylhydroquinone. Air was blown in from below the liquid surface at 0.3 L / min using a 0.5 mm inner diameter stainless steel tube while stirring, and the reaction was carried out at 85 °C for 20 hours. The reaction solution was then cooled to 50 °C and washed with water. 115.1 parts by weight of diethylene glycol monoethyl ether acetate, 0.5 parts by weight of dibutylhydroxytoluene, and 0.1 parts by weight of methoquinone were added, and the toluene was removed at 80 °C. Next, 60.8 parts by weight of tetrahydrophthalic anhydride and 1.1 parts by weight of triphenylphosphine were added, and the reaction was carried out at 110 °C for 8 hours to obtain the desired resin (R1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R1) having an acid group and a polymerizable unsaturated group was 70% by mass, and the acid value of the solid content was 81 mg KOH / g. The total number of moles of the acid groups of the acrylic acid and the acid anhydride groups of the tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups of the polyol compound (11), the number of moles of the acid groups of the acrylic acid was 0.59 mole per mole of the hydroxyl groups of the polyol compound (11), and the number of moles of the acid anhydride groups of the tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups of the polyol compound (11).

[0220] (Comparative Example 2: Production of Resin (R2) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface using a stainless steel tube with an inner diameter of 0.5 mm at a rate of 0.08 L / min, and an inert gas was blown in from above the liquid surface at a rate of 0.72 L / min, to adjust the oxygen concentration to 2.1% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 148 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain a resin (R2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R2) having acid groups and polymerizable unsaturated groups was 65% by mass, and the acid value of the solid content was 83 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0221] (Comparative Example 3: Production of Resin (R3) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface using a stainless steel tube with an inner diameter of 0.5 mm at a rate of 0.53 L / min, and an inert gas was blown in from above the liquid surface at a rate of 0.27 L / min, to adjust the oxygen concentration to 13.9% by mass. The stirring was carried out at a stirring power per unit volume of 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain a resin (R3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R3) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 78 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0222] (Comparative Example 4: Production of Resin (R4) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring power per unit volume was 0.3 kW / m 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 148 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain a resin (R4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R4) having acid groups and polymerizable unsaturated groups was 65% by mass, and the acid value of the solid content was 84 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0223] (Comparative Example 5: Production of Resin (R5) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface at a rate of 0.3 L / min using a stainless steel tube with an inner diameter of 0.5 mm, and an inert gas was blown in from above the liquid surface at a rate of 0.5 L / min to adjust the oxygen concentration to 7.9% by mass. The stirring was carried out at a stirring power per unit volume of 7 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture with toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain a resin (R5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R5) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 77 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0224] (Comparative Example 6: Production of Resin (R6) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 149 parts by mass of toluene, 181 parts by mass of the polyol compound (2) obtained in Synthesis Example 2, 42.5 parts by mass of acrylic acid, 6.7 parts by mass of paratoluenesulfonic acid, and 1.1 parts by mass of methylhydroquinone. Air was blown in from below the liquid surface using a stainless steel tube with an inner diameter of 0.5 mm at a rate of 0.8 L / min, and the stirring power per unit volume was 3 kW / m. 3The mixture was stirred at 85°C under reduced pressure to form an azeotropic mixture of toluene and water, and the reaction was continued for 20 hours while distilling off the water. The mixture was then cooled to 50°C, and sodium phosphate dibasic was added to the resulting reaction solution, followed by washing with water. Next, 118 parts by mass of diethylene glycol monoethyl ether acetate, 0.6 parts by mass of dibutylhydroxytoluene, and 0.1 parts by mass of methoquinone were added, and the toluene was removed at 80°C. Next, 62 parts by mass of tetrahydrophthalic anhydride and 1.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 8 hours to obtain a resin (R6) having acid groups and polymerizable unsaturated groups. The nonvolatile content of the resin (R6) having acid groups and polymerizable unsaturated groups was 70% by mass, and the acid value of the solid content was 79 mgKOH / g. The total number of moles of the acid groups in acrylic acid and the acid anhydride groups in tetrahydrophthalic anhydride was 1.0 mole per mole of the hydroxyl groups in polyol compound (2), the number of moles of the acid groups in acrylic acid was 0.59 mole per mole of the hydroxyl groups in polyol compound (2), and the number of moles of the acid anhydride groups in tetrahydrophthalic anhydride was 0.41 mole per mole of the hydroxyl groups in polyol compound (2).

[0225] (Example 21: Preparation of curable resin composition (1)) The resin (1) having an acid group and a polymerizable unsaturated group obtained in Example 1, an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, dipentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, a photopolymerization initiator (Omnirad 907 manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green were blended in the parts by mass shown in Table 1 and kneaded using a roll mill to obtain a curable resin composition (1).

[0226] (Examples 22 to 40: Preparation of curable resin compositions (2) to (20)) Using the compositions and blending ratios shown in Tables 1 and 2, curable resin compositions (2) to (20) were obtained in the same manner as in Example 21.

[0227] Comparative Examples 7 to 12: Preparation of Curable Resin Compositions (R1) to (R6) Using the compositions and blending ratios shown in Table 2, curable resin compositions (R1) to (R6) were obtained in the same manner as in Example 21.

[0228] The following evaluations were carried out using the curable resin compositions (1) to (20) and (R1) to (R6) obtained in the above examples and comparative examples.

[0229] [Method for evaluating alkaline developability] The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, or 160 minutes, respectively, to prepare samples with different drying times. These were then developed with a 1% by mass aqueous sodium carbonate solution at 30°C for 180 seconds, and the drying time at 80°C of samples that left no residue on the substrate was evaluated as the drying control range. Note that a longer drying control range indicates better alkaline developability.

[0230] [Photosensitivity evaluation method] The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Then, the composition was irradiated with 10 kJ / m 2 of a metal halide lamp through a Kodak Step Tablet No. 2. 2 The film was then developed for 180 seconds in a 1% by mass aqueous solution of sodium carbonate, and the remaining number of steps was evaluated. The greater the number of remaining steps, the higher the photosensitivity.

[0231] Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (20) and (R1) to (R6) obtained in the above examples and comparative examples.

[0232] [Table 1]

[0233] [Table 2]

[0234] (Example 41: Preparation of curable resin composition (21)) Resin (1) having an acid group and a polymerizable unsaturated group obtained in Example 1, an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907 manufactured by IGM Resins) as a photopolymerization initiator, and diethylene glycol monoethyl ether acetate as an organic solvent were mixed in the parts by mass shown in Table 3 to obtain a curable resin composition (21).

[0235] (Examples 42 to 60: Preparation of curable resin compositions (22) to (40)) Curable resin compositions (22) to (40) were obtained using the compositions and blendings shown in Tables 3 and 4 in the same manner as in Example 11.

[0236] (Comparative Examples 13 to 18: Preparation of Curable Resin Compositions (R7) to (R12)) Curable resin compositions (R7) to (R12) were obtained using the compositions and blendings shown in Table 4 in the same manner as in Example 11.

[0237] The curable resin compositions (22) to (40) and (R7) to (R12) obtained in the above Examples and Comparative Examples were evaluated as follows.

[0238] [Method for measuring elongation] The elongation was measured based on a tensile test. <Preparation of test piece 1> The curable resin compositions obtained in the examples and comparative examples were applied onto copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then heated at 10 kJ / m using a metal halide lamp. 2After irradiating with ultraviolet light, the product was heated for 1 hour at 160° C. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product).

[0239] <Tensile test> The test piece 1 was cut into a size of 10 mm × 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured.

[0240] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm / min

[0241] [Method for measuring dielectric constant] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored for 24 hours in a room at 23°C and 50% humidity to prepare a test piece. The dielectric constant of the test piece at 1 GHz was measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. by the cavity resonance method.

[0242] [Method for measuring dielectric loss tangent] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0243] [Method for evaluating adhesion to substrate] The adhesion to the substrate was evaluated by measuring the peel strength. <Preparation of test piece 2> The active energy ray-curable resin compositions obtained in the examples and comparative examples were applied to copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then heated at 10 kJ / m using a metal halide lamp. 2 After irradiating with ultraviolet light, the specimen was heated at 160°C for 1 hour to obtain a test piece 2.

[0244] <Method for measuring peel strength> The test piece 2 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength was measured using a peel tester ("A&D Tensilon" manufactured by A&D Co., Ltd., peel speed 50 mm / min).

[0245] Tables 3 and 4 show the compositions and evaluation results of the curable resin compositions (22) to (40) prepared in Examples 41 to 60 and the curable resin compositions (R7) to (R12) prepared in Comparative Examples 13 to 18.

[0246] [Table 3]

[0247] [Table 4]

[0248] In Tables 1 to 4, the parts by mass of the resin having an acid group and a polymerizable unsaturated group are solid content values.

[0249] "Curing agent" in Tables 1 to 4 refers to an orthocresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0250] "Organic solvent" in Tables 1 to 4 refers to diethylene glycol monoethyl ether acetate.

[0251] The "photopolymerization initiator" in Tables 1 to 4 is "Omnirad-907" manufactured by IGM Resins.

[0252] Examples 21 to 40 shown in Tables 1 and 2 are examples of curable resin compositions using resins having an acid group and a polymerizable unsaturated group obtained by the production method of the present invention. It was confirmed that these curable resin compositions had high photosensitivity and excellent alkaline developability.

[0253] Examples 41 to 60 shown in Tables 3 and 4 are examples of curable resin compositions using resins having an acid group and a polymerizable unsaturated group obtained by the production method of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent elongation, dielectric properties, and substrate adhesion.

[0254] On the other hand, Comparative Example 1 is an example of a resin having an acid group and a polymerizable unsaturated group, which is made from a compound having a phenolic hydroxyl group and a softening point of less than 70°C. It was confirmed that the curable resin composition using this resin having an acid group and a polymerizable unsaturated group (Comparative Example 7) had insufficient photosensitivity. Furthermore, it was confirmed that the cured product of the curable resin composition using this resin having an acid group and a polymerizable unsaturated group (Comparative Example 13) had insufficient substrate adhesion, and it was confirmed that the various performance properties were not balanced.

[0255] Comparative Examples 2 and 3 are examples of resins having acid groups and polymerizable unsaturated groups in which the oxygen concentration in the reaction system was outside the oxygen concentration range specified in the present invention (2.1% by mass, 13.9% by mass). It was confirmed that the curable resin composition using the resin having acid groups and polymerizable unsaturated groups obtained in Comparative Example 2 (Comparative Example 8) had significantly insufficient alkaline developability, and the curable resin composition using the resin having acid groups and polymerizable unsaturated groups obtained in Comparative Example 3 (Comparative Example 9) had significantly insufficient photosensitivity. Furthermore, it was confirmed that the cured products (Comparative Examples 14 and 15) of the curable resin compositions using these resins having acid groups and polymerizable unsaturated groups were insufficient in dielectric properties and substrate adhesion.

[0256] In Comparative Examples 4 and 5, the stirring power per unit volume in the reaction system was outside the range of the stirring power specified in the present invention (0.3 kW / m 3 , 7kW / m 3 ) are examples of resins having an acid group and a polymerizable unsaturated group. It was confirmed that the curable resin composition (Comparative Example 10) using the resin having an acid group and a polymerizable unsaturated group obtained in Comparative Example 4 had significantly insufficient alkaline developability, and the curable resin composition (Comparative Example 11) using the resin having an acid group and a polymerizable unsaturated group obtained in Comparative Example 5 had significantly insufficient photosensitivity. It was also confirmed that the cured products (Comparative Examples 16 and 17) of the curable resin compositions using these resins having an acid group and a polymerizable unsaturated group were insufficient in dielectric properties and substrate adhesion.

[0257] Comparative Example 6 is an example of a resin having an acid group and a polymerizable unsaturated group prepared in an air atmosphere without injecting an inert gas. It was confirmed that the curable resin composition (Comparative Example 12) using the resin having an acid group and a polymerizable unsaturated group obtained in Comparative Example 6 had significantly insufficient photosensitivity. Furthermore, it was confirmed that the cured product (Comparative Example 18) of the curable resin composition using this resin having an acid group and a polymerizable unsaturated group had insufficient dielectric properties and substrate adhesion.

Claims

1. A method for producing a resin having an acid group and a polymerizable unsaturated group, which is obtained by reacting raw materials including a polyol compound (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) in an atmosphere of an oxygen-containing gas (g1) and an inert gas (g2) and in a stirring environment, comprising: The oxygen concentration in the reaction system is in the range of 3.5 to 12.5 mass%, The stirring power per unit volume in the reaction system is in the range of 0.5 to 5 kW / m3, the polyol compound (A) is obtained by reacting raw materials containing a compound (a1) having a phenolic hydroxyl group and a cyclic carbonate compound (a2) under an inert gas atmosphere; a method for producing a resin having an acid group and a polymerizable unsaturated group, wherein the compound (a1) having a phenolic hydroxyl group has a softening point of 70°C or higher, The method for producing a resin having an acid group and a polymerizable unsaturated group, wherein the gas (g1) is introduced from below the liquid surface in the reaction system, and the inert gas (g2) is introduced from above the liquid surface.

2. 2. The method for producing a resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the total number of moles of the acid group of the unsaturated monobasic acid (B) and the acid anhydride group of the polybasic acid anhydride (C) is in the range of 0.8 to 1.2 moles per mole of the hydroxyl group of the polyol compound (A).

3. 3. The method for producing a resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the amount of the acid group contained in the unsaturated monobasic acid (B) is in the range of 0.3 to 0.7 moles per mole of the hydroxyl group contained in the polyol compound (A).

4. 4. The method for producing a resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the amount of acid anhydride groups contained in the polybasic acid anhydride (C) is in the range of 0.3 to 0.7 moles per mole of hydroxyl groups contained in the polyol compound (A).

5. 5. The method for producing a resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the amount of the cyclic carbonate compound (a2) used is in the range of 0.9 to 2 moles per mole of the hydroxyl group of the compound (a1) having a phenolic hydroxyl group.

6. A method for producing a curable resin composition, comprising mixing a resin having an acid group and a polymerizable unsaturated group, obtained by the method for producing a resin having an acid group and a polymerizable unsaturated group according to any one of claims 1 to 5, with a photopolymerization initiator.

7. A method for producing a cured product by curing the curable resin composition obtained by the method for producing a curable resin composition according to claim 6.

8. A method for producing an insulating material, comprising using the cured product according to claim 7.

9. A method for producing a resist member, comprising using the cured product according to claim 7.

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