JP7615864B2 - Resin, curable resin composition, cured product, insulating material, and resist member - Google Patents

Description

The present invention relates to a resin, a curable resin composition, a cured product, an insulating material, and a resist member.

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 heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical components, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surface of various substrates, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding materials that can form a cured coating film that is not only curable but also has heat resistance, photosensitivity, and alkaline developability.

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 heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical components, etc. Among them, an example of the coating agent application is solder resist for printed wiring boards. When used as a curable composition for solder resist, it is required not only to have high photosensitivity and excellent alkaline developability, but also to have excellent heat resistance in the cured product.

A known conventional curable composition for solder resist is a photosensitive resin composition containing a resin having an acid group and a polymerizable unsaturated group, which is obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride (see, for example, Patent Document 1). However, this composition has problems such as insufficient photosensitivity and alkaline developability, and insufficient heat resistance in the cured product.

As a material capable of forming a cured coating film having the above-mentioned elasticity, an active energy ray curable composition is known that is characterized by containing, as essential components, an epoxy acrylate resin (A) obtained by reacting a lactone adduct of a hydroxyalkyl (meth)acrylate (a1), a dicarboxylic anhydride (a2), and an epoxy resin (a3), and a radical polymerizable monomer (B) (see, for example, Patent Document 2). However, this does not satisfy the increasingly high performance requirements of recent years.

Therefore, there was a demand for a material that has high photosensitivity, excellent alkaline developability, and the ability to form a cured product with even better heat resistance.

Japanese Patent Application Publication No. 8-259663 JP 2003-105230 A

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

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using a resin whose essential reaction raw materials were a specific epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride, and thus completed the present invention.

That is, the present invention relates to a resin having an acid group, which is essentially made of an epoxy resin (A) represented by the following general formula (1), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C), a curable resin composition containing the resin, a cured product made of the curable resin composition, an insulating material, and a resist member.

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

The resin of the present invention has high photosensitivity and excellent alkaline developability, and the cured product has excellent heat resistance. Therefore, a curable resin composition containing the resin and a photopolymerization initiator can be used as a coating agent or adhesive, and as a coating agent, it is particularly suitable for use in solder resist applications.

The resin of the present invention is characterized in that it contains an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) as essential reactive raw materials.

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

The epoxy resin (A) is represented by the following general formula (1):

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and cyclohexyl groups.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, and an alkoxynaphthyl group.

The epoxy equivalent of the epoxy resin (A) is preferably in the range of 160 to 300 g/equivalent, more preferably in the range of 170 to 270 g/equivalent, and even more preferably in the range of 170 to 250 g/equivalent, since this gives a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

The melt viscosity of the epoxy resin (A) at 150°C is preferably in the range of 0.1 to 2 dPa·s, and more preferably in the range of 0.1 to 1 dPa·s, since this provides a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

The method for producing the epoxy resin (A) can be, for example, a method for epoxidizing a polyfunctional phenolic resin.

The epoxidation method is not particularly limited and any known technique can be used as appropriate. For example, a method of epoxidizing a polyfunctional phenolic resin by reacting it with epihalohydrin can be mentioned.

The polyfunctional phenolic resin may be, for example, one represented by the following general formula (2):

[In formula (2), R ¹ 's are each independently a hydrogen atom or an alkyl group, R ² 's are each independently a hydrogen atom or an alkyl group, R ³ 's are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

In addition, in the formula (2), the bonding position between the naphthalene ring and the methylene group, which may have a substituent, is arbitrary, and indicates that the bonding may be on a ring having a hydroxyl group or on a ring not having a hydroxyl group, and when l is 2 or more, the structures may be the same or different.

The alkyl group can be the same as the alkyl group described above.

The aryl group can be the same as the aryl group described above.

The method for producing the polyfunctional phenolic resin is not particularly limited, and any method may be used. For example, a method of reacting a naphthol compound, a catechol compound, and an aldehyde compound may be used.

Examples of the naphthol compound include α-naphthol, β-naphthol, and various dihydroxynaphthalenes, which may have a substituent. These naphthol compounds may be used alone or in combination of two or more. Among these, it is preferable to use unsubstituted β-naphthol, since it has high photosensitivity and excellent alkaline developability, and a resin with excellent heat resistance in the cured product can be obtained.

Examples of the catechol compounds include catechol, methylcatechol, n-butylcatechol, sec-butylcatechol, t-butylcatechol, 4-octylcatechol, and 3,5-di-t-butylcatechol. These catechol compounds can be used alone or in combination of two or more.

Examples of the aldehyde compounds include formaldehyde, trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, and hexamethylenetetramine. These aldehyde compounds can be used alone or in combination of two or more. Among these, formaldehyde is preferably used because it has high photosensitivity and excellent alkaline developability, and a resin with excellent heat resistance in the cured product can be obtained. The formaldehyde may be used as formalin in the form of an aqueous solution, or as paraformaldehyde in the form of a solid.

The molar ratio of naphthol compound to catechol compound is preferably in the range of 7/3 to 3/7, since this produces a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

From the viewpoint of controlling the molecular weight distribution, the ratio of the raw materials used is preferably in the range of 0.1 to 1.1 moles of the aldehyde compound per 1 mole of the naphthol compound and catechol compound combined.

The reaction between the naphthol compound, the catechol compound, and the aldehyde compound can be carried out under the same conditions as in a normal novolak reaction. If necessary, the reaction may be carried out in an organic solvent, and if necessary, a reaction catalyst may be used.

Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; 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; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of suitable organic solvents include alcohol solvents such as propylene glycol monomethyl ether and propyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of 10 to 1,000 parts by mass per 100 parts by mass of the total amount of the naphthol compound and the catechol compound used.

Examples of the reaction catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as oxalic acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These reaction catalysts can be used alone or in combination of two or more. The amount of the reaction catalyst used is preferably in the range of 1 to 20 parts by mass per 100 parts by mass of the total amount of the naphthol compound and the catechol compound used.

The reaction temperature in the reaction between the naphthol compound, the catechol compound, and the aldehyde compound is preferably in the range of 60 to 180°C, and the reaction is preferably carried out while distilling off the water produced in the reaction. The reaction time is preferably 1 to 16 hours, and more preferably 2 to 12 hours.

The above reaction produces a polyfunctional phenolic resin represented by the general formula (2), which may contain other by-products. The by-products may be removed to extract and use only the compound represented by the general formula (2), but it may also be used as a precursor to the epoxy resin (A) while still containing the by-products.

In addition, the polyfunctional phenolic resin may be used in combination with other compounds having a phenolic hydroxyl group as long as the effects of the present invention are not impaired.

As the other compound having a phenolic hydroxyl group, for example, a compound having at least one phenolic hydroxyl group in the molecule can be used.

Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (1-1) to (1-4).

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

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

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

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

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and β-methylepibromohydrin. These epihalohydrins can be used alone or in combination of two or more. Among these, epichlorohydrin is preferred.

The reaction between the polyfunctional phenolic resin and the epihalohydrin can be carried out, for example, by adding 1 to 10 moles of the epihalohydrin per mole of hydroxyl groups contained in the polyfunctional phenolic resin, and then reacting for 0.5 to 10 hours at a temperature of 20 to 120°C while adding 0.9 to 2.0 moles of a basic catalyst per mole of hydroxyl groups in the raw material all at once or gradually. The basic catalyst may be in the form of a solid or an aqueous solution. When an aqueous solution is used, it may be added continuously, and water and epihalohydrin may be continuously distilled from the reaction mixture under reduced pressure or normal pressure, and the water may be removed by liquid separation while the epihalohydrin is continuously returned to the reaction mixture.

In industrial production, all of the epihalohydrin used in the first batch of epoxy resin production is new, but from the next batch onwards, it is preferable to use epihalohydrin recovered from the crude reaction product in combination with new epihalohydrin equivalent to the amount consumed and lost in the reaction. In this case, it may contain impurities such as glycidol that are derived from the reaction of epichlorohydrin with water, organic solvents, etc.

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

The reaction between the polyfunctional phenolic resin and the epihalohydrin may be carried out in an organic solvent as necessary. The organic solvent may be the same as the organic solvent exemplified above. The organic solvent may be used alone or in combination of two or more. The reaction product obtained by the reaction may be washed with water, and then the unreacted epihalohydrin and the organic solvent used may be distilled off by heating under reduced pressure. Furthermore, in order to obtain an epoxy resin with a low hydrolyzable halogen content, the reaction product obtained, i.e., the epoxy resin, may be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to further react. In this case, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present in order to improve the reaction rate. When a phase transfer catalyst is used, the amount of the catalyst used is preferably in the range of 0.1% by mass to 3.0% by mass relative to the epoxy resin used. After the reaction is complete, the salts formed are removed by filtration and washing with water, and the solvents such as toluene and methyl isobutyl ketone are distilled off under heating and reduced pressure to obtain a high-purity epoxy resin.

In addition, in the reaction between the polyfunctional phenolic resin and the epihalohydrin, a side reaction may occur, causing cyclization between adjacent hydroxyl groups in the catechol structure, or between a hydroxyl group on a benzene ring and a hydroxyl group on a naphthalene ring. Such by-products may be removed, or may be used as they are as epoxy resin (A).

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. Acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (3) can also be used.

[In formula (3), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

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

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

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

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

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

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

The molecular weight of the compound represented by the general formula (3) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400.

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

The amount of the unsaturated monobasic acid (B) used is preferably in the range of 0.9 to 1.1 moles of acid groups in the unsaturated monobasic acid (B) per mole of epoxy groups in the epoxy resin (A), since this produces a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

Examples of the polybasic acid anhydride (C) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

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

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

Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid.

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

The amount of the polybasic acid anhydride (C) used is preferably in the range of 0.2 to 1 mol, and more preferably in the range of 0.25 to 0.95 mol, per mol of epoxy groups in the epoxy resin (A), since this gives a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

The resin of the present invention can also use compounds other than the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) as raw materials, if necessary.

Examples of the other compounds include unsaturated monobasic acid anhydrides.

Examples of the unsaturated monobasic acid anhydride include acrylic acid anhydride and methacrylic acid anhydride. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more kinds.

The total mass ratio of the epoxy resin (A), the unsaturated monobasic acid (B) and the polybasic acid anhydride (C) in the raw material (solid content) of the resin of the present invention is preferably 70 mass% or more, since this gives a resin with high photosensitivity and excellent alkaline developability, and excellent heat resistance in the cured product.

The method for producing the resin of the present invention is not particularly limited, and any method may be used. For example, the resin may be produced by a method in which all of the reaction raw materials containing the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) are reacted at once, or the reaction raw materials may be reacted sequentially. Among these, a method in which the epoxy resin (A) and the unsaturated monobasic acid (B) are reacted first in the presence of a basic catalyst at a temperature range of 80 to 140°C, and then the polybasic acid anhydride (C) is added and reacted at a temperature range of 80 to 140°C is preferred, since this method makes it easier to control the reaction.

The reaction between the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) can also be carried out in an organic solvent, if necessary.

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

The amount of the basic catalyst used is preferably in the range of 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.8 parts by mass, per 100 parts by mass of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) in total, since this produces a resin with high photosensitivity, excellent alkaline developability, and excellent heat resistance in the cured product.

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

The resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

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

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

The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the curable resin composition.

The curable resin composition of the present invention may contain resin components other than the resin of the present invention described above (hereinafter, may be referred to as "other resin components"). Examples of the other resin components include a resin (D) having an acid group and a polymerizable unsaturated group, various (meth)acrylate monomers, etc.

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

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

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

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

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.

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

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

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

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

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

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

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１～４のアルキル基、又は一般式（４）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１～３の整数であり、ｍは１～１５の整数である。］

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

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

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

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

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

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

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

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

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

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

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

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

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it provides a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent heat resistance. The alkylene oxides can be used alone or in combination of two or more kinds.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it provides a curable resin composition that has high photosensitivity and excellent alkaline developability and can form a cured product with excellent heat resistance. The alkylene carbonates can be used alone or in combination of two or more kinds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The amount of the resin (D) 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 (meth)acrylate resin having an acid group of the present invention.

Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; Alicyclic mono(meth)acrylate compounds such as acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenoxybenzyl (meth)acrylate and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various mono(meth)acrylate monomers described above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds described above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, nor Alicyclic di(meth)acrylate compounds such as bornane 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 having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds having a (poly)lactone structure 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; aliphatic tri(meth)acrylate compounds having a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds. (Poly)oxyalkylene-modified tri(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxytetramethylene chains; lactone-modified tri(meth)acrylate compounds having (poly)lactone structures in the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structure of the aliphatic poly(meth)acrylate compounds; tetrafunctional or higher lactone-modified poly(meth)acrylate compounds having (poly)lactone structures in the molecular structure of the aliphatic poly(meth)acrylate compounds.

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

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

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

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

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

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

The curable resin composition of the present invention may also contain various additives, such as curing accelerators, ultraviolet absorbers, polymerization inhibitors, antioxidants, organic solvents, inorganic fillers, polymer particles, pigments, defoamers, viscosity adjusters, leveling agents, flame retardants, and storage stabilizers, as necessary.

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

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

Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, and N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, and other amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl= Thioether compounds such as 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N- Nitroso compounds such as nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol; triphenyl phosphite; 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; trisnonylphenyl phosphite; and (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl phosphite. Examples of the polymerization inhibitor include phosphate compounds such as esters, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, and zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and 3,3'-thiodipropionate distearyl. These polymerization inhibitors can be used alone or in combination of two or more.

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

In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

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

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

As the pigment, known inorganic pigments or organic pigments can be used.

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

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

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

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

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

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

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

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

The cured product of the present invention has excellent alkaline developability and excellent heat resistance and elasticity, 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., and adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin display applications such as LCD and OELD as thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. Among these, it can be particularly suitably used for solder resist applications.

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

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

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

(Synthesis Example 1: Synthesis of phenolic resin (a-1))
216.2 parts by mass of β-naphthol, 412.9 parts by mass of catechol, and 4.1 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. 140.4 parts by mass of 37% by mass formalin was added dropwise over 3 hours while maintaining the temperature. The reaction was further carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off while blowing in water vapor under reduced pressure at 150 ° C., thereby obtaining the desired phenolic resin (a-1). The phenolic hydroxyl group equivalent was 92 g / equivalent, the softening point was 94 ° C., and the melt viscosity at 150 ° C. was 5.6 dPa · s.

(Synthesis Example 2: Synthesis of phenolic resin (a-2))
216.2 parts by mass of β-naphthol, 330.3 parts by mass of catechol, and 6.6 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. 140.4 parts by mass of 37% by mass formalin was added dropwise over 3 hours while maintaining the temperature. The reaction was further carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off at 150 ° C. under reduced pressure while blowing in water vapor, thereby obtaining the desired phenolic resin (a-2). The phenolic hydroxyl group equivalent was 93 g / equivalent, the softening point was 101 ° C., and the melt viscosity at 150 ° C. was 8.8 dPa · s.

(Synthesis Example 3: Synthesis of phenolic resin (a-3))
216.2 parts by mass of β-naphthol, 495.5 parts by mass of catechol, and 9.9 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. While maintaining the temperature, 140.4 parts by mass of 37% by mass formalin was dropped over 3 hours. Furthermore, the reaction was carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off while blowing in water vapor under reduced pressure at 150 ° C., thereby obtaining the desired phenolic resin (a-3). The phenolic hydroxyl group equivalent was 93 g / equivalent, the softening point was 91 ° C., and the melt viscosity at 150 ° C. was 4.5 dPa · s.

(Synthesis Example 4: Synthesis of epoxy resin (A-1))
A flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 230.0 parts by mass of phenolic resin (a-1) and 925.0 parts by mass of epichlorohydrin, and the temperature was raised to 50 ° C. while stirring and dissolving. Next, 2.30 parts by mass of benzyltrimethylammonium chloride was charged and reacted for 24 hours at 50 ° C. Furthermore, 224.5 parts by mass of 49% by mass aqueous sodium hydroxide solution was dropped over 3 hours, and the reaction was further carried out at 50 ° C. for 1 hour. After the reaction was completed, 185.0 parts by mass of n-butanol was added, stirring was stopped, the water layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 629.0 parts by mass of methyl isobutyl ketone and 105.0 parts by mass of n-butanol were added to the crude epoxy resin obtained and dissolved. Further, 47.0 parts by mass of a 10% by mass aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80°C for 2 hours, after which washing with 185.0 parts by mass of water was repeated until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin (A-1) was 181 g/equivalent, and the melt viscosity at 150°C was 0.5 dPa·s.

(Synthesis Example 5: Synthesis of epoxy resin (A-2))
The same operation as in Example 3 was carried out except that 230.0 parts by mass of the phenolic resin (a-1) was changed to 232.5 parts by mass of the phenolic resin (a-2), to obtain an epoxy resin (A-2). The epoxy equivalent of the obtained epoxy resin (A-2) was 192 g/equivalent, and the melt viscosity at 150° C. was 0.9 dPa·s.

(Synthesis Example 6: Synthesis of epoxy resin (A-3))
The same operation as in Example 3 was carried out except that 230.0 parts by mass of the phenolic resin (a-1) was changed to 232.5 parts by mass of the phenolic resin (a-3), to obtain an epoxy resin (A-3). The epoxy equivalent of the obtained epoxy resin (A-3) was 181 g/equivalent, and the melt viscosity at 150°C was 0.4 dPa·s.

(Synthesis Example 7: Synthesis of epoxy resin (A-4))
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 122.5 parts by mass of β-naphthol, 141.2 parts by mass of t-butylcatechol (DIC Corporation, "DIC-TBC"), and 38.3 parts by mass of a 20% by mass aqueous solution of sodium hydroxide were charged, and the temperature was raised to 100°C while dissolving. While maintaining the temperature, 71.0 parts by mass of 37% by mass formalin was dropped over 2 hours. Then, the mixture was reacted at 100°C for 6 hours and cooled to room temperature. After neutralization with 26.4 parts by mass of sodium dihydrogen phosphate, 380 parts by mass of methyl isobutyl ketone was added and dissolved, washed with water, and methyl isobutyl ketone was distilled off under reduced pressure. Next, 1174.8 parts by mass of epichlorohydrin was charged, and the temperature was raised to 50°C while stirring and dissolving. Next, 9.47 parts by mass of benzyltrimethylammonium chloride was charged, and the mixture was reacted for 24 hours while maintaining the temperature at 50°C. Further, 238.2 g parts by mass of 49% by mass aqueous sodium hydroxide was dropped over 3 hours, and further reacted at 50 ° C. for 1 hour. After the reaction was completed, 117.4 parts by mass of n-butanol was added, stirring was stopped, the water layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. The crude epoxy resin thus obtained was dissolved by adding 708.9 parts by mass of methyl isobutyl ketone and 105.0 parts by mass of n-butanol. Further, 33.8 parts by mass of 10% by mass aqueous sodium hydroxide was added to this solution, and the mixture was reacted at 80 ° C. for 2 hours, after which the mixture was repeatedly washed with 209.0 parts by mass of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin (A-4). The epoxy equivalent of the obtained epoxy resin (A-4) was 237 g/equivalent, and the melt viscosity at 150° C. was 0.2 dPa·s.

(Synthesis Example 8: Preparation of Resin (D) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 123 parts by mass of diethylene glycol monoethyl ether acetate was placed, and 214 parts by mass of orthocresol novolac type epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86 ° C., epoxy equivalent: 214 g / eq.) was dissolved. After adding 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 72 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain a resin (D) having an acid group and a polymerizable unsaturated group. The non-volatile content of this resin (D) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid acid value was 80 mg KOH / g. The acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

(Example 1: Production of Resin (1) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 56 parts by mass of diethylene glycol monoethyl ether acetate and 70 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (1) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (1) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 83 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.46 moles.

(Example 2: Production of Resin (2) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 66 parts by mass of diethylene glycol monoethyl ether acetate was placed, 192 parts by mass of epoxy resin (A-2) was dissolved, 0.7 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 65 parts by mass of diethylene glycol monoethyl ether acetate and 73 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (2) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (2) having an acid group and a polymerizable unsaturated group was 72% by mass, and the solid acid value was 83 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-2) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-2) was 0.48 moles.

(Example 3: Production of Resin (3) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-3) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 56 parts by mass of diethylene glycol monoethyl ether acetate and 70 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (3) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (3) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 84 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-3) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-3) was 0.46 moles.

(Example 4: Preparation of Resin (4) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 68.4 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out for 7 hours at 120 ° C. while blowing in air. Thereafter, 56 parts by mass of diethylene glycol monoethyl ether acetate and 70 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (4) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (4) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 79 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.95 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.46 moles.

(Example 5: Preparation of Resin (5) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 64 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 75.6 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 7 hours at 120 ° C. while blowing in air. Thereafter, 56 parts by mass of diethylene glycol monoethyl ether acetate and 67 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (5) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (5) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 82 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1.05 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.44 moles.

(Example 6: Preparation of Resin (6) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 45 parts by mass of diethylene glycol monoethyl ether acetate and 39.5 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (6) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (6) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 52 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.26 moles.

(Example 7: Production of Resin (7) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 107 parts by mass of diethylene glycol monoethyl ether acetate and 144 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (7) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (7) having an acid group and a polymerizable unsaturated group was 70% by mass, and the solid acid value was 136 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.95 moles.

(Example 8: Production of Resin (8) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 57 parts by mass of diethylene glycol monoethyl ether acetate and 72 parts by mass of 1,2-cyclohexanedicarboxylic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. to obtain the resin (8) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (8) having an acid group and a polymerizable unsaturated group was 73 mass%, and the solid acid value was 83 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of 1,2-cyclohexanedicarboxylic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.46 moles.

(Example 9: Production of Resin (9) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 63 parts by mass of diethylene glycol monoethyl ether acetate was placed, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 46 parts by mass of diethylene glycol monoethyl ether acetate and 41 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (9) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (9) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 80 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of succinic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.41 moles.

(Example 10: Production of Resin (10) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 77 parts by mass of diethylene glycol monoethyl ether acetate was placed, 237 parts by mass of epoxy resin (A-4) was dissolved, 0.7 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out for 10 hours at 120 ° C. while blowing in air. Thereafter, 69 parts by mass of diethylene glycol monoethyl ether acetate and 85 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (10) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (10) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 82 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-4) was 1.02 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.56 moles.

(Example 11: Production of Resin (11) Having Acid Group and Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 67 parts by mass of diethylene glycol monoethyl ether acetate, 181 parts by mass of epoxy resin (A-1) was dissolved, 0.7 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 86 parts by mass of methacrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out for 8 hours at 120 ° C. while blowing in air. Thereafter, 58 parts by mass of diethylene glycol monoethyl ether acetate and 71.4 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (11) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (11) having an acid group and a polymerizable unsaturated group was 73% by mass, and the solid acid value was 80 mg KOH / g. The number of moles of acid groups in the methacrylic acid relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the epoxy resin (A-1) was 0.47 moles.

(Comparative Example 1: Production of Resin (R1) Having Acid Group and Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 70 parts by mass of diethylene glycol monoethyl ether acetate, and 208 parts by mass of t-butylcatechol type epoxy resin (DIC Corporation "EPICLON HP-820", epoxy equivalent: 208) was dissolved therein. After adding 0.7 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 9 hours while blowing in air. Thereafter, 49 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (R1) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (R1) having an acid group and a polymerizable unsaturated group was 75% by mass, and the solid acid value was 82 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the t-butylcatechol type epoxy resin was 1.0 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the t-butylcatechol type epoxy resin was 0.5 mole.

(Comparative Example 2: Production of Resin (R2) Having Acid Group and Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 118 parts by mass of diethylene glycol monoethyl ether acetate, 204 parts by mass of naphthalene-type epoxy resin (DIC Corporation "EPICLON HP-4770", epoxy equivalent: 204) was dissolved, 0.7 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 11 hours while blowing in air. Thereafter, 63 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain the resin (R2) having the desired acid group and polymerizable unsaturated group. The non-volatile content of this resin (R2) having an acid group and a polymerizable unsaturated group was 66% by mass, and the solid acid value was 83 mg KOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the naphthalene type epoxy resin was 1.0 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the naphthalene type epoxy resin was 0.5 mole.

(Example 12: Preparation of curable resin composition (1))
100 parts by mass of the resin (1) having an acid group and a polymerizable unsaturated group and a non-volatile content of 73% by mass obtained in Example 1 (73 parts by mass as solid content), 22.9 parts by mass of an orthocresol novolac type epoxy resin (DIC Corporation's "EPICLON N-680", epoxy equivalent: 214) as a curing agent, 12.3 parts by mass of diethylene glycol monoethyl ether acetate, 3.25 parts by mass of a photopolymerization initiator (IGM Resins'"Omnirad907"), 6.5 parts by mass of dipentaerythritol hexaacrylate, 0.5 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (1).

(Examples 13 to 23: Preparation of curable resin compositions (2) to (12))
Curable resin compositions (2) to (12) were obtained in the same manner as in Example 12, except that the resins (2) to (12) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 11 were used in the blending amounts shown in Table 1 instead of the resin (1) having an acid group and a polymerizable unsaturated group used in Example 12.

(Comparative Example 3: Preparation of Curable Resin Composition (R1))
100 parts by mass of the resin (R1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 75% by mass obtained in Comparative Example 1 (75 parts by mass as solid content), 23.2 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.5 parts by mass of diethylene glycol monoethyl ether acetate, 3.25 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 6.5 parts by mass of dipentaerythritol hexaacrylate, 0.5 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green were mixed to obtain a curable resin composition (R1).

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

The following evaluations were carried out using the curable resin compositions (1) to (12), (R1) and (R2) obtained in the above examples and comparative examples.

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

[Method for evaluating alkaline developability]
The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, and 170 minutes, respectively, to prepare samples with different drying times. These were developed with a 1% by mass aqueous sodium carbonate solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample that did not leave a residue on the substrate was evaluated as the drying control width. Note that the longer the drying control width, the better the alkaline developability.

The compositions and evaluation results of the curable resin compositions (1) to (12) prepared in Examples 12 to 23 and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 3 and 4 are shown in Table 1.

(Example 24: Preparation of curable resin composition (13))
100 parts by mass (73 parts by mass as solid content) of the resin (1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 73% by mass obtained in Example 1, 22.9 parts by mass of an orthocresol novolac type epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.3 parts by mass of diethylene glycol monoethyl ether acetate, and 3.25 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins) were mixed to obtain a curable resin composition (13).

(Examples 25 to 35: Preparation of curable resin compositions (14) to (24))
Curable resin compositions (14) to (24) were obtained in the same manner as in Example 24, except that the resins (2) to (11) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 11 were used in the blending amounts shown in Table 2 instead of the resin (1) having an acid group and a polymerizable unsaturated group used in Example 24.

(Comparative Example 5: Preparation of Curable Resin Composition (R3))
A curable resin composition (R3) was obtained by mixing 100 parts by mass (75 parts by mass as solid content) of the resin (R1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 75% by mass obtained in Comparative Example 1, 23.2 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.5 parts by mass of diethylene glycol monoethyl ether acetate, and 3.25 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins).

(Comparative Example 6: Preparation of curable resin composition (R4))
A curable resin composition (R4) was obtained in the same manner as in Comparative Example 5, except that the resin (R2) having an acid group and a polymerizable unsaturated group obtained in Comparative Example 2 was used in place of the resin (R1) having an acid group and a polymerizable unsaturated group used in Comparative Example 5 in the blending amount shown in Table 2.

The following evaluations were carried out using the curable resin compositions (13) to (24), (R3) and (R4) obtained in the above examples and comparative examples.

[Method for evaluating heat resistance]
The curable resin composition obtained in each Example and Comparative Example was applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. Next, after irradiating with ultraviolet light of 10 kJ / m ² using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm x 35 mm was cut out from the cured product, and the temperature at which the elastic modulus change was maximum was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometrics Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C. / min). Note that a higher glass transition temperature indicates better heat resistance.

The compositions and evaluation results of the curable resin compositions (13) to (24) prepared in Examples 24 to 35 and the curable resin compositions (R3) and (R4) prepared in Comparative Examples 5 and 6 are shown in Table 2.

The parts by weight of the resin having an acid group and a polymerizable unsaturated group in Tables 1 and 2 are solids values.

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

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

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

Examples 12 to 23 shown in Table 1 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that these curable resin compositions have high photosensitivity and excellent alkaline developability.

In addition, Examples 24 to 35 shown in Table 2 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that the cured products of these curable resin compositions have excellent heat resistance.

On the other hand, Comparative Examples 3 and 4 shown in Table 1 are examples of curable resin compositions that do not use the epoxy resin represented by general formula (1) as the raw material for the resin having an acid group and a polymerizable unsaturated group. It was confirmed that the curable resin composition obtained in Comparative Example 3 had insufficient photosensitivity, and that the curable resin composition obtained in Comparative Example 3 had significantly insufficient alkaline developability.

Comparative Examples 5 and 6 shown in Table 2 are examples of curable resin compositions that do not use an epoxy resin represented by general formula (1) as a raw material for a resin having an acid group and a polymerizable unsaturated group, similar to Comparative Examples 3 and 4. The cured product of the curable resin composition obtained in Comparative Example 5 had extremely insufficient heat resistance, and it was also confirmed that the cured product of the curable resin composition obtained in Comparative Example 6 also had insufficient heat resistance.

Claims (9)

An epoxy resin (A) represented by the following general formula (1);
An unsaturated monobasic acid (B);
The reaction requires a polybasic acid anhydride (C) as an essential reaction raw material,
A resin having an acid group and a polymerizable unsaturated group.

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.] The resin according to claim 1, wherein ^R2 and ^R3 in the general formula (1) are hydrogen atoms. The resin according to claim 1 or 2, wherein the number of moles of acid groups in the unsaturated monobasic acid (B) is in the range of 0.9 to 1.1 moles per mole of epoxy groups in the epoxy resin (A). The resin according to any one of claims 1 to 3, wherein the number of moles of the polybasic acid anhydride (C) is in the range of 0.2 to 1 mole per mole of epoxy groups in the epoxy resin (A). A curable resin composition comprising the resin according to any one of claims 1 to 4 and a photopolymerization initiator. The curable resin composition according to claim 5, further comprising a resin (D) having an acid group and a polymerizable unsaturated group other than the resin. A cured product of the curable resin composition according to claim 5 or 6. An insulating material comprising the cured product according to claim 7. A resist member comprising the cured product according to claim 7.