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

Abstract

To provide a resin that has high photosensitivity and excellent alkali developability, and gives a cured product having excellent thermostability; a curable resin composition, and a cured product of the curable resin composition; an insulating material; and a resist member.SOLUTION: A resin comprises an epoxy resin (A) represented by general formula (1), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) as essential reactive materials, the resin comprising an acid radical and a polymerizable unsaturated group. There are also provided a curable resin composition, and a cured product of the curable resin composition, an insulating material, and a resist member.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin, a curable resin composition, a cured product, an insulating material, and a resist member. [Background technology]

[0002] In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surfaces 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 a material that can form a cured coating film that has not only curability but also heat resistance, photosensitivity, and alkaline developability.

[0003] In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, etc. Among them, examples of the coating agent applications include solder resists for printed wiring boards, and when used as curable compositions for solder resists, they are required to have not only high photosensitivity and excellent alkaline developability, but also excellent heat resistance and the like in the cured product.

[0004] As a conventional curable composition for a solder resist, 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, is known (see, for example, Patent Document 1). However, there are problems such as insufficient photosensitivity and alkaline developability, and insufficient heat resistance in the cured product.

[0005] As a material capable of forming a cured coating film having the above-mentioned elasticity, there is known an active energy ray curable composition characterized by containing, as essential components, an epoxy acrylate resin (A) obtained by reacting a lactone adduct (a1) of a hydroxyalkyl (meth)acrylate, a dicarboxylic anhydride (a2) and an epoxy resin (a3), and a radical polymerizable monomer (B) (see, for example, Patent Document 2). However, this composition does not satisfy the increasingly high performance requirements of recent years.

[0006] Therefore, there has been a demand for a material that has high photosensitivity, excellent alkaline developability, and is capable of forming a cured product having even better heat resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 [Patent Document 2] JP 2003-105230 A Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a resin having high photosensitivity and excellent alkali developability, and having excellent heat resistance in a cured product; a curable resin composition; a cured product of the curable resin composition; an insulating material; and a resist member. [Means for solving the problem]

[0009] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that the above problems can be solved by using a resin containing a specific epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials, and have thus completed the present invention.

[0010] That is, the present invention relates to a resin having an acid group, which comprises an epoxy resin (A) represented by the following general formula (1), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) as essential reaction raw materials, and to a curable resin composition containing the resin, a cured product made of the curable resin composition, an insulating material, and a resist member.

[0011] [ka] [In formula (1), G is a glycidyl group, and R 1 are each independently a hydrogen atom or an alkyl group; R 2 are each independently a hydrogen atom or an alkyl group; R 3 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. Effect of the Invention

[0012] The resin of the present invention has high photosensitivity and excellent alkaline developability, and has excellent heat resistance in a cured product. Therefore, a curable resin composition containing the resin and a photopolymerization initiator can be used as a coating agent or an adhesive, and as a coating agent in particular, it can be suitably used in solder resist applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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 reaction raw materials.

[0014] In the present invention, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylic" means acrylic and / or methacrylic.

[0015] As the epoxy resin (A), one represented by the following general formula (1) is used.

[0016] [ka] [In formula (1), G is a glycidyl group, and R 1 are each independently a hydrogen atom or an alkyl group; R 2 are each independently a hydrogen atom or an alkyl group; R 3 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.

[0017] Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a cyclohexyl group.

[0018] 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.

[0019] 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 a resin having high photosensitivity and excellent alkali developability and excellent heat resistance in the cured product can be obtained.

[0020] 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 gives a resin having high photosensitivity and excellent alkali developability, and having excellent heat resistance in the cured product.

[0021] The epoxy resin (A) can be produced, for example, by epoxidizing a polyfunctional phenol resin.

[0022] The method of epoxidation is not particularly limited, and known techniques can be appropriately applied. For example, a method of epoxidizing a polyfunctional phenol resin by reacting it with epihalohydrin can be mentioned.

[0023] The polyfunctional phenol resin may, for example, be one represented by the following general formula (2).

[0024] [ka] [In formula (2), R 1 are each independently a hydrogen atom or an alkyl group; R 2 are each independently a hydrogen atom or an alkyl group; R 3 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.

[0025] 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 they may be bonded to a ring having a hydroxyl group or to a ring not having a hydroxyl group, and when l is 2 or more, they may be the same structure or different structures.

[0026] As the alkyl group, the same alkyl groups as those described above can be used.

[0027] As the aryl group, the same aryl groups as those described above can be used.

[0028] 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.

[0029] Examples of the naphthol compound include α-naphthol, β-naphthol, and various dihydroxynaphthalenes that may have a substituent. These naphthol compounds can 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 alkali developability, and a resin with excellent heat resistance in the cured product can be obtained.

[0030] Examples of the catechol compound include catechol, methylcatechol, n-butylcatechol, sec-butylcatechol, t-butylcatechol, 4-octylcatechol, 3,5-di-t-butylcatechol, etc. These catechol compounds can be used alone or in combination of two or more kinds.

[0031] Examples of the aldehyde compound 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.

[0032] The ratio of the naphthol compound to the catechol compound used is preferably in the molar ratio of naphthol compound / catechol compound=7 / 3 to 3 / 7, since this gives a resin having high photosensitivity and excellent alkaline developability, and excellent heat resistance in the cured product.

[0033] The ratio of the raw materials used is preferably within a range of 0.1 to 1.1 moles of the aldehyde compound per mole of the naphthol compound and the catechol compound in total, from the viewpoint of controlling the molecular weight distribution.

[0034] The reaction of the naphthol compound, the catechol compound, and the aldehyde compound can be carried out under the same conditions as those of a normal novolak reaction, and may be carried out in an organic solvent as required, and may further include a reaction catalyst as required.

[0035] 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 organic solvents include alcohol solvents such as propylene glycol monomethyl 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 1000 parts by mass relative to 100 parts by mass of the total amount of the naphthol compound and the catechol compound used.

[0036] 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.

[0037] The reaction temperature in the reaction of 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 water generated in the reaction. The reaction time is preferably 1 to 16 hours, more preferably 2 to 12 hours.

[0038] The 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 the by-products may also be used as a precursor of the epoxy resin (A).

[0039] The polyfunctional phenolic resin may be used in combination with other compounds having a phenolic hydroxyl group within the scope of not impairing the effects of the present invention.

[0040] 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.

[0041] 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).

[0042] [ka]

[0043] In the above general formulas (1-1) to (1-4), R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above 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 numbers of the substituents in one molecule are p and q.

[0044] As the other compound having a phenolic hydroxyl group, for example, a reaction product obtained by using 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) as essential reaction raw materials can be used. In addition, a novolac-type phenolic resin obtained by using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials can be used.

[0045] [ka]

[0046] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is 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 of 1 to 4.]

[0047] These other compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0048] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, etc. These epihalohydrins can be used alone or in combination of two or more. Among these, epichlorohydrin is preferred.

[0049] The reaction between the polyfunctional phenol resin and the epihalohydrin may be carried out, for example, by adding 1 to 10 moles of the epihalohydrin per mole of hydroxyl groups contained in the polyfunctional phenol resin, and further 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, while reacting for 0.5 to 10 hours at a temperature of 20 to 120° C. The basic catalyst may be a solid or an aqueous solution thereof. When an aqueous solution is used, the basic catalyst may be added continuously, and water and epihalohydrin may be continuously distilled from the reaction mixture under reduced pressure or normal pressure, and further the mixture may be separated to remove water and return epihalohydrin to the reaction mixture continuously.

[0050] In industrial production, all of the epihalohydrin used for charging 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 fresh epihalohydrin equivalent to the amount consumed and lost in the reaction. In this case, impurities derived from the reaction of epichlorohydrin with water, organic solvents, etc., such as glycidol, may be contained.

[0051] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri Examples of 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 kinds.

[0052] The reaction between the polyfunctional phenol resin and the epihalohydrin may be carried out in an organic solvent as necessary, and 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. In addition, the reaction product obtained by the reaction may be washed with water, and then the unreacted epihalohydrin and the organic solvent used in combination may be distilled off by heating under reduced pressure. Furthermore, in order to obtain an epoxy resin with a small amount of hydrolyzable halogen, 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. At this time, 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 completed, the salt formed is removed by filtration, washing with water, etc., and the solvent such as toluene or methyl isobutyl ketone is further distilled off under heating and reduced pressure to obtain a high purity epoxy resin.

[0053] In addition, in the reaction between the polyfunctional phenol resin and the epihalohydrin, a side reaction may occur, resulting in 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 a by-product may be removed, or may be used as it is as the epoxy resin (A).

[0054] 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.

[0055] [ka] [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.]

[0056] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0057] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (X-1).

[0058] [ka] [In formula (X-1), R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0059] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. 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.

[0060] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (X-2).

[0061] [ka] [In formula (X-2), R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0062] The molecular weight of the compound represented by the general formula (3) is preferably in the range of 100-500, and more preferably in the range of 150-400.

[0063] These unsaturated monobasic acids (B) can be used alone or in combination of two or more kinds.

[0064] The amount of the unsaturated monobasic acid (B) used is preferably in the range of 0.9 to 1.1 mol of the acid group of the unsaturated monobasic acid (B) per 1 mol of the epoxy group of the epoxy resin (A), since a resin having high photosensitivity and excellent alkali developability and having excellent heat resistance in the cured product can be obtained.

[0065] 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.

[0066] Examples of the aliphatic polybasic acid anhydride 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, 1,2,3,4-butanetetracarboxylic acid, etc. In addition, the aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight-chain type or a branched type, and may have an unsaturated bond in the structure.

[0067] 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 tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0068] Examples of the aromatic polybasic acid anhydride 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.

[0069] 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 a resin having excellent heat resistance in the cured product.

[0070] 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 a resin having high photosensitivity and excellent alkali developability and having excellent heat resistance in the cured product can be obtained.

[0071] The resin of the present invention may contain, as required, compounds other than the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) as raw materials.

[0072] Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0073] Examples of the unsaturated monobasic acid anhydride include acrylic acid anhydride, methacrylic acid anhydride, etc. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more kinds.

[0074] 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 having high photosensitivity and excellent alkali developability, and having excellent heat resistance in the cured product.

[0075] 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 them, the method in which the epoxy resin (A) and the unsaturated monobasic acid (B) are reacted 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 because it is easy to control the reaction.

[0076] Furthermore, 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.

[0077] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0078] The amount of the basic catalyst used is preferably in the range of 0.01 to 1.0 part by mass, and more preferably in the range of 0.05 to 0.8, relative to 100 parts by mass in total of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C), since a resin having high photosensitivity and excellent alkali developability and having excellent heat resistance in the cured product can be obtained.

[0079] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0080] The resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

[0081] 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.

[0082] Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); and "Vicure 10" and "Vicure 55" (manufactured by Stoffa Examples of photopolymerization initiators include "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop), and "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more kinds.

[0083] The amount of the photopolymerization initiator added is preferably within a range of, for example, 0.5 to 20% by mass in the curable resin composition.

[0084] 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.

[0085] 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.

[0086] Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0087] 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 as essential raw materials an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride; and epoxy (meth)acrylate resins having an acid group and a urethane group, which have as reaction raw materials an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group.

[0088] 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.

[0089] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

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

[0095] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, cyclohexane diisocyanate, and cyclohexane 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.

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

[0097] 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.

[0098] 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 may also use a basic catalyst as necessary.

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

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

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

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

[0103] As the (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.

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

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

[0106] Examples of polyol compounds other than the 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 products 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 products 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.

[0107] 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 may also use a basic catalyst as necessary.

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

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

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

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

[0112] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group 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.

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

[0114] 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 may also use a basic catalyst as necessary.

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

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

[0117] The amide-imide resin having an acid group and a polymerizable unsaturated group may be, for example, a product 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, 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.

[0118] 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 mgKOH / g under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mgKOH / g under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

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

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

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

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

[0123] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -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.

[0124] 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.

[0125] 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.

[0126] 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 may also use a basic catalyst as necessary.

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

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

[0129] Examples of the acrylamide resin having an acid group and a polymerizable unsaturated 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.

[0130] 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).

[0131] [ka]

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

[0133] The compound having a phenolic hydroxyl group may be, for example, a reaction product obtained by using 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) as essential reaction raw materials. Also usable is a novolac-type phenolic resin obtained by using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials.

[0134] [ka]

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

[0136] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0137] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it provides a curable resin composition that has high photosensitivity and excellent alkali 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.

[0138] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide 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.

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

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

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

[0142] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated 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.

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

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

[0145] 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 a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0146] Examples of the ester resin having an acid group and a polymerizable unsaturated group include those 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.

[0147] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as the compound having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0148] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition having high photosensitivity and excellent alkaline developability, and capable of forming a cured product having excellent heat resistance. The alkylene oxide may be used alone or in combination of two or more kinds.

[0149] The alkylene carbonate may be the same as those exemplified above. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition having high photosensitivity and excellent alkaline developability, and capable of forming a cured product having excellent heat resistance. The alkylene carbonate may be used alone or in combination of two or more kinds.

[0150] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0151] As the polybasic acid anhydride, the same as those exemplified as the polybasic acid anhydride (C) described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0152] 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.

[0153] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0154] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0155] As the acid catalyst, the same as those exemplified above as the acid catalyst can be used, and the acid catalyst can be used alone or in combination of two or more kinds.

[0156] The amount of the resin (D) having an acid group and a polymerizable unsaturated group used is preferably within a range of 10 to 900 parts by mass relative to 100 parts by mass of the (meth)acrylate resin having an acid group of the present invention.

[0157] Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono(meth)acrylate compounds such as the aromatic mono(meth)acrylate compounds of the above: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds Examples of the alkylene-modified tri(meth)acrylate compound include: a lactone-modified tri(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the aliphatic tri(meth)acrylate compound; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as (poly)oxyalkylene chains, such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains, obtained by introducing a (poly)oxyalkylene chain into the molecular structure of the aliphatic poly(meth)acrylate compound; and a lactone-modified poly(meth)acrylate compound having 4 or more functional groups, such as (poly)lactone structure into the molecular structure of the aliphatic poly(meth)acrylate compound.

[0158] In addition to the above, the other (meth)acrylate monomers that can be used include (meth)acrylate monomers having a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

[0159] Examples of the phenol compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and cyclo ring structure-containing phenol resin.

[0160] Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. These cyclic carbonate compounds can be used alone or in combination of two or more kinds.

[0161] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran, etc. These cyclic ether compounds can be used alone or in combination of two or more kinds.

[0162] As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used.

[0163] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0164] In addition, the curable resin composition of the present invention may contain various additives, such as a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

[0165] The curing accelerator is one that accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % based on the solid content of the curable resin composition.

[0166] Examples of the ultraviolet absorbent 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 absorbents can be used alone or in combination of two or more.

[0167] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite and other phosphite compounds, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, diethyldithiocarbamate , zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more.

[0168] As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0169] 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.

[0170] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0171] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0172] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0173] Examples of the inorganic pigment 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.

[0174] Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide.

[0175] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds.

[0176] 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, and the like. 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 oils, silicone rubbers, and silicone resins; 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 these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total resin composition.

[0177] 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 under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0178] As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

[0179] The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0180] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0181] In addition, 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., or adhesive layer between integrated circuit elements and circuit boards. In addition, in thin display applications such as LCD and OELD, it can be suitably used as thin film transistor protective film, liquid crystal color filter protective film, pigment resist for color filter, resist for black matrix, spacer, etc. Among these, it can be particularly suitably used for solder resist applications.

[0182] 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 having a desired pattern formed thereon, 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.

[0183] Examples of the substrate include a metal-clad laminate of copper, aluminum, or the like. EXAMPLES

[0184] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0185] (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 condenser, a Dean-Stark trap, and a stirrer, and the mixture was heated to 150°C while being dissolved. While maintaining the temperature, 140.4 parts by mass of 37% by mass formalin was added dropwise over a period of 3 hours. The mixture was further reacted at 150°C for 6 hours while the distilled water was expelled from the system. After the reaction, the unreacted catechol was distilled off at 150°C under reduced pressure while blowing in steam, to obtain 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.

[0186] (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 condenser, a Dean-Stark trap, and a stirrer, and the mixture was heated to 150°C while being dissolved. While maintaining the temperature, 140.4 parts by mass of 37% by mass formalin was added dropwise over 3 hours. The mixture was further reacted at 150°C for 6 hours while the distilled water was expelled from the system. After the reaction, the unreacted catechol was distilled off at 150°C under reduced pressure while blowing in steam, to obtain 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.

[0187] (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 condenser, 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 added dropwise over 3 hours. The reaction was further carried out at 150°C for 6 hours while the distilled water was expelled from the system. After the reaction, the unreacted catechol was distilled off at 150°C under reduced pressure while blowing in steam, to obtain 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.

[0188] (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. Furthermore, 47.0 parts by mass of a 10% by mass aqueous solution of sodium hydroxide was added to this solution and 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 solution became neutral. Next, the system was dehydrated by azeotropy, and after 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.

[0189] (Synthesis Example 5: Synthesis of epoxy resin (A-2)) Epoxy resin (A-2) was obtained by the same procedure as in Example 3, except that 230.0 parts by mass of phenolic resin (a-1) was changed to 232.5 parts by mass of phenolic 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.

[0190] (Synthesis Example 6: Synthesis of epoxy resin (A-3)) Epoxy resin (A-3) was obtained by the same procedure as in Example 3, except that 230.0 parts by mass of phenolic resin (a-1) was changed to 232.5 parts by mass of phenolic 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.

[0191] (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 20% by mass aqueous sodium hydroxide solution were charged and heated 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 the methyl isobutyl ketone was distilled off under reduced pressure. Next, 1174.8 parts by mass of epichlorohydrin was charged and heated to 50°C while stirring and dissolving. Next, 9.47 parts by mass of benzyltrimethylammonium chloride was charged and reacted for 24 hours 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 reaction was carried out at 80 ° C for 2 hours, and then the solution 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.

[0192] (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 dibutyl hydroxytoluene 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).

[0193] (Example 1: Preparation 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. Then, 56 parts by mass of diethylene glycol monoethyl ether acetate and 70 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0194] (Example 2: Preparation 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. Then, 65 parts by mass of diethylene glycol monoethyl ether acetate and 73 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0195] (Example 3: Preparation 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. Then, 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.

[0196] (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. Then, 56 parts by mass of diethylene glycol monoethyl ether acetate and 70 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0197] (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. Then, 56 parts by mass of diethylene glycol monoethyl ether acetate and 67 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0198] (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. Then, 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 mgKOH / 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.

[0199] (Example 7: Preparation 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. Then, 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.

[0200] (Example 8: Preparation 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. Then, 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.

[0201] (Example 9: Preparation 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. Then, 46 parts by mass of diethylene glycol monoethyl ether acetate and 41 parts by mass of succinic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0202] (Example 10: Preparation 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. Then, 69 parts by mass of diethylene glycol monoethyl ether acetate and 85 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0203] (Example 11: Preparation of Resin (11) Having Acid Group and Polymerizable Unsaturated Group) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 67 parts by mass of diethylene glycol monoethyl ether acetate was placed, 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. Then, 58 parts by mass of diethylene glycol monoethyl ether acetate and 71.4 parts by mass of tetrahydrophthalic anhydride were added and the reaction was carried out for 3 hours at 110 ° C. 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.

[0204] (Comparative Example 1: Production of Resin (R1) Having Acid Groups and Polymerizable Unsaturated Groups) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 70 parts by mass of diethylene glycol monoethyl ether acetate was placed, 208 parts by mass of t-butylcatechol type epoxy resin (DIC Corporation's "EPICLON HP-820", epoxy equivalent: 208) 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 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 molar number 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 molar number of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the t-butylcatechol type epoxy resin was 0.5 mole.

[0205] (Comparative Example 2: Production of Resin (R2) Having Acid Groups and Polymerizable Unsaturated Groups) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 118 parts by mass of diethylene glycol monoethyl ether acetate was placed, 204 parts by mass of naphthalene-type epoxy resin (DIC Corporation's "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 desired resin (R2) having an acid group and a 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 molar number 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 molar number of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the naphthalene-type epoxy resin was 0.5 mole.

[0206] (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 having 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 (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, 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 (1).

[0207] (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 amounts shown in Table 1 instead of the resin (1) having an acid group and a polymerizable unsaturated group used in Example 12.

[0208] (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 non-volatile 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 type 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).

[0209] (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.

[0210] 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.

[0211] [Method of evaluating light sensitivity] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Then, the composition was exposed to 10 kJ / m 2 of a metal halide lamp through a Kodak Step Tablet No. 2. 2The film was developed for 180 seconds in a 1% by weight aqueous solution of sodium carbonate, and the remaining number of steps was evaluated. The greater the number of remaining steps, the higher the photosensitivity.

[0212] [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 any residue on the substrate was evaluated as the drying control width. Note that the longer the drying control width, the better the alkaline developability.

[0213] 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.

[0214] [Table 1]

[0215] (Example 24: Preparation of curable resin composition (13)) A curable resin composition (13) was obtained by mixing 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 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).

[0216] (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.

[0217] (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).

[0218] (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.

[0219] 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.

[0220] [Heat resistance evaluation method] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied coating to the copper foil. 2After irradiating with ultraviolet light of 1000 nm, the sample was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 35 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics Corp. solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). Note that a higher glass transition temperature indicates better heat resistance.

[0221] 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.

[0222] [Table 2]

[0223] The parts by mass of the resin having an acid group and a polymerizable unsaturated group in Tables 1 and 2 are solid content values.

[0224] "Curing agent" in Tables 1 and 2 refers to an orthocresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0225] "Organic solvent" in Tables 1 and 2 refers to diethylene glycol monoethyl ether acetate.

[0226] "Photopolymerization initiator" in Tables 1 and 2 refers to "Omnirad-907" manufactured by IGM Resins.

[0227] Examples 12 to 23 shown in Table 1 are examples of curable resin compositions using the resin having an acid group and a polymerizable unsaturated group of the present invention. It was confirmed that these curable resin compositions had high photosensitivity and excellent alkaline developability.

[0228] Moreover, Examples 24 to 35 shown in Table 2 are examples of curable resin compositions using the resin having an acid group and a polymerizable unsaturated group of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance.

[0229] 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 a 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 alkali developability.

[0230] 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. It was confirmed that the cured product of the curable resin composition obtained in Comparative Example 5 had extremely insufficient heat resistance, and that the cured product of the curable resin composition obtained in Comparative Example 6 also had insufficient heat resistance.

Claims

1. 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. 【Chemistry 1】 [In formula (1), G is a glycidyl group, R １ are each independently a hydrogen atom or an alkyl group; R ２ are each independently a hydrogen atom or an alkyl group; R ３ are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer from 0 to 3, m is an integer from 0 to 6, l is an integer from 1 to 4, and n+l is 4.

2. R in the general formula (1) ２ and R ３ The resin according to claim 1, wherein is a hydrogen atom.

3. 3. The resin according to claim 1, wherein the number of moles of the acid group in the unsaturated monobasic acid (B) is in the range of 0.9 to 1.1 moles per mole of the epoxy group in the epoxy resin (A).

4. 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 the epoxy group of the epoxy resin (A).

5. A curable resin composition comprising the resin according to any one of claims 1 to 4 and a photopolymerization initiator.

6. 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.

7. A cured product of the curable resin composition according to claim 5 or 6.

8. An insulating material comprising the cured product according to claim 7.

9. A resist member comprising the cured product according to claim 7.

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