Resin having acid group and polymerizable unsaturated group, curable resin composition, cured product, insulating material and resist member

Abstract

To provide a resin having excellent alkali developability and having excellent heat resistance and high elastic modulus in a cured product, a curable resin composition, a cured product of the curable resin composition, an insulation material, and a resist member.SOLUTION: There is provided a resin having an acid group and a polymerizable unsaturated group which contains a phenolic resin having at least two catechol skeletons and an epoxy resin (A) containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin, an unsaturated monobasic acid (B) and a polybasic acid anhydride (C) as essential reaction raw materials.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin having an acid group and a polymerizable unsaturated group, 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 thermosetting compositions that can be cured by heat, have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. In particular, for the coating agent applications, it is generally required that the coating agent be capable of imparting design properties to the surfaces of various substrates, have excellent curability, and be capable of forming a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding materials that can form cured coating films that not only have curability but also have high elastic modulus, heat resistance, photosensitivity, and alkali developability.

[0003] Known conventional curable compositions for solder resists include photosensitive resin compositions containing a resin having an acid group and a polymerizable unsaturated group, which is obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride (see, for example, Patent Document 1). However, these compositions do not satisfy the increasingly high requirements for elastic modulus and heat resistance, and are not sufficient for meeting current market demands.

[0004] Therefore, there has been a demand for a material that has excellent alkaline developability and is capable of forming a cured product having excellent heat resistance and a high elastic modulus. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a resin having an acid group and a polymerizable unsaturated group, which has excellent alkaline developability, and in a cured product thereof has excellent heat resistance and a high elastic modulus; a curable resin composition; a cured product of the curable resin composition; an insulating material; and a resist member. [Means for solving the problem]

[0007] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a resin having an acid group and a polymerizable unsaturated group, which is produced from 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.

[0008] Specifically, the present invention relates to a resin having an acid group and a polymerizable unsaturated group, characterized in that the resin contains, as essential reaction raw materials, an epoxy resin (A) containing a phenolic resin having at least two catechol skeletons derived from a catechol compound and a glycidyl ether group-containing compound obtained by reacting epihalohydrin, an unsaturated monobasic acid (B), and a polybasic acid anhydride (C); a curable resin composition containing the resin; and a cured product, insulating material, and resist member made from the curable resin composition.

[0009] More specifically, Aspect 1 of the present invention relates to a resin having an acid group and a polymerizable unsaturated group, characterized in that the essential reaction raw materials used are an epoxy resin (A) containing a phenolic resin having at least two catechol skeletons derived from a catechol compound and a glycidyl ether group-containing compound obtained by reacting epihalohydrin with an unsaturated monobasic acid (B), and a polybasic acid anhydride (C).

[0010] A second aspect of the present invention relates to the resin having an acid group and a polymerizable unsaturated group according to the first aspect, wherein the phenolic resin according to the first aspect is a reaction product of a catechol compound and a ketone group-containing compound.

[0011] A third aspect of the present invention relates to the resin having an acid group and a polymerizable unsaturated group according to the first or second aspect, wherein the unsaturated monobasic acid (B) is used in an amount of 0.9 to 1.1 moles of acid groups per mole of epoxy group in the epoxy resin (A).

[0012] A fourth aspect of the present invention relates to the resin having an acid group and a polymerizable unsaturated group according to any one of the first to third aspects, wherein the amount of the polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 mol per 1 mol of the epoxy group in the epoxy resin (A).

[0013] A fifth aspect of the present invention relates to a curable resin composition comprising the resin having an acid group and a polymerizable unsaturated group according to any one of the first to fourth aspects, and a photopolymerization initiator.

[0014] A sixth aspect of the present invention relates to the curable resin composition according to the fifth aspect, further comprising a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group.

[0015] A seventh aspect of the present invention relates to a cured product of the curable resin composition according to the fifth or sixth aspect.

[0016] An eighth aspect of the present invention relates to an insulating material comprising the cured product according to the seventh aspect.

[0017] A ninth aspect of the present invention relates to a resist member comprising the cured product according to the seventh aspect. [Effects of the Invention]

[0018] The resin having an acid group and a polymerizable unsaturated group of the present invention is an alkali-soluble resin having excellent alkali developability, and the cured product has excellent heat resistance and a high elastic modulus. 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. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a GPC chart of the phenol resin obtained in Synthesis Example 1. [Figure 2] FIG. 1 is a GPC chart of the epoxy resin obtained in Synthesis Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0020] The resin having an acid group and a polymerizable unsaturated group of the present invention is characterized by using, as essential reaction raw materials, an epoxy resin (A) containing a phenolic resin having at least two catechol skeletons derived from a catechol compound and a glycidyl ether group-containing compound obtained by reacting epihalohydrin with an unsaturated monobasic acid (B), and a polybasic acid anhydride (C).

[0021] 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.

[0022] [Phenol resin] The phenolic resin used in the epoxy resin (A) is characterized by having at least two catechol skeletons derived from a catechol compound. The phenolic resin is a reaction product of a catechol compound and a ketone group-containing compound, and contains at least two or more independent ring structures of catechol skeletons derived from the catechol compound (having two hydroxyl groups as substituents on the aromatic ring, with the two hydroxyl groups in an ortho-position relationship to each other), making it polyfunctional, and therefore the resulting cured product exhibits high heat resistance, which is preferable. Note that the phenolic resin contains at least two catechol skeletons, and although three or more may be acceptable, two catechol skeletons are particularly preferred, as they result in a low melt viscosity.

[0023] In the present invention, the "phenolic resin" refers to a resin containing a phenolic hydroxyl group, and the "epoxy resin" refers to a resin containing a glycidyl ether group. The "catechol skeleton" refers to a skeleton "having two hydroxyl groups as substituents on an aromatic ring, with the two hydroxyl groups in an ortho-position relationship to each other," or a skeleton from which the hydrogen atoms constituting the hydroxyl groups have been removed.

[0024] [Catechol compounds] The phenolic resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound. The catechol compound is a dihydroxybenzene having hydroxyl groups at the 1st and 2nd positions. The catechol compound may have a substituent on the aromatic ring, but from the viewpoint of bending properties, an unsubstituted catechol (catechol) is particularly preferred. By using the catechol compound, the phenolic resin contains a catechol skeleton, which is presumed to increase intermolecular density due to intermolecular π-π interactions based on the aromatic ring, and thus a cured product with excellent mechanical strength and heat resistance can be obtained, which is preferable.

[0025] The substituent may be a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and may be an alkyl group such as a methyl group, and the position and number of the substituent are not particularly limited. Note that if the number of carbon atoms in the hydrocarbon group or the like exceeds 4, steric hindrance becomes too great, which is undesirable because it results in excessively low reactivity during synthesis of the phenolic resin or the epoxy resin described below, and reduces the mechanical strength of the resulting cured product.

[0026] The catechol compound may be used alone or in combination with a plurality of compounds having different positions of substituents.

[0027] [Ketone group-containing compounds] As described above, the phenolic resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound. Introducing a skeleton (e.g., —C(—R)(—R’)—) resulting from the reaction between the catechol compound and the ketone group-containing compound (e.g., represented by RC(═O)—R’, where R is a hydrocarbon group and R’ is a hydrocarbon group or a hydrogen atom) into the phenolic resin moderately weakens intermolecular interactions, resulting in a phenolic resin with low melt viscosity and excellent handleability, which is preferable. Furthermore, the resulting cured product is useful because it has an excellent balance between heat resistance and mechanical strength. The ketone group-containing compound is preferably an aliphatic ketone or a formyl group-containing aromatic compound.

[0028] Examples of the aliphatic ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone (2-heptanone), cyclopentanone, cyclohexanone, isophorone, cycloheptanone, cyclooctanone, etc. Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are preferred from the viewpoints of reactivity during synthesis of the phenolic resin and synthesis of the epoxy resin, and ease of availability. The aliphatic ketones may be used alone or in combination of two or more compounds.

[0029] The formyl group-containing aromatic compound is preferably a compound having a benzene ring substituted with at least one aldehyde group, such as benzaldehyde, 4-methylbenzaldehyde, 4-methoxybenzaldehyde, etc. Among these, benzaldehyde is more preferred from the viewpoints of reactivity during epoxy resin synthesis and ease of handling.

[0030] [Phenol resin 1] The phenolic resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound. Specifically, for example, a catechol compound represented by the following general formula (1) is reacted with an aliphatic ketone represented by the following general formula (2) to obtain a phenolic resin 1 represented by the following general formula (3).

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] In the above general formula (1), the substituent R 1 may be a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. From the viewpoint of reactivity when used as a raw material and bending properties of a cured product, preferably, the hydrocarbon group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, etc., the alkoxy group having 1 to 4 carbon atoms includes a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc., and the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, etc. Among these, the R 1 However, when the aryl group is a hydrogen atom, the melt viscosity is low, the handling property is excellent, and the balance between the bending property and the heat resistance is excellent, which is a preferred embodiment.

[0035] In the above general formula (1), m is preferably an integer of 0 to 3, and more preferably an integer of 0 or 1, from the viewpoint of reactivity when used as a raw material and bending properties of the cured product.

[0036] In the above general formula (2), R 2 and R 3are each independently preferably a hydrocarbon group having 1 to 4 carbon atoms, and from the viewpoint of the heat resistance and bending properties of the cured product, it is more preferable that the R 2 and R 3 are each independently a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably, 2 and R 3 are both methyl groups. 2 and R 3 However, by using a methyl group or the like, the cured product has a good balance between heat resistance and bending properties, and among these, the R 2 and R 3 When both R are methyl groups, the melt viscosity is low, the handling property is excellent, and the balance between the bending property and the heat resistance is excellent, which is a preferred embodiment. 2 and R 3 may be bonded to form a cyclic structure (the aliphatic ketone includes an alicyclic ketone).

[0037] In the above general formula (3), n is preferably an integer of 0 to 3. In the case where the resulting phenolic resin or epoxy resin is easily adjusted to a low viscosity and has excellent fluidity and handling properties, n is an integer of 0 or 1, and n is preferably 0 (biscatechol A).

[0038] In addition, R in the above general formula (3) 1 , R 2 , R 3 and m are the same as in the above general formulas (1) and (2).

[0039] The reaction ratio of the catechol compound to the aliphatic ketone is preferably in the range of 0.01 to 0.9 mol, more preferably 0.1 to 0.7 mol, and even more preferably 0.2 to 0.6 mol, of the aliphatic ketone relative to 1 mol of the catechol compound, since this gives an epoxy resin having an excellent balance between melt viscosity and heat resistance in the cured product.

[0040] The reaction between the catechol compound and the aliphatic ketone is preferably carried out in the presence of an acid catalyst, as this promotes efficient reaction. 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 to the acid catalyst, a co-catalyst can be used, such as a mercaptocarboxylic acid such as thioglycolic acid, thiolactic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid; or an alkyl mercaptan such as propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, or dodecyl mercaptan. The amount of the acid catalyst used is preferably 0.01 to 5.0% by mass based on the total mass of the reaction raw materials (including the solvent).

[0041] The reaction between the catechol compound and the aliphatic ketone can usually be carried out at a temperature of 30 to 80°C for 1 to 20 hours. The reaction may be carried out in an organic solvent, if necessary. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the temperature conditions described above. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When using these organic solvents, it is preferable to use them in an amount of 10 to 500% by mass relative to the total mass of the reaction raw materials.

[0042] After the reaction between the catechol compound and the aliphatic ketone is completed, unreacted reactant materials and by-products are distilled off to obtain the purified phenolic resin. If a portion of the catechol compound remains unreacted after the reaction between the catechol compound and the aliphatic ketone is complete, it may volatilize during the production of a cured product, causing voids or stoichiometric errors that could adversely affect the flexural properties of the resulting epoxy resin. Therefore, it is preferable that the amount of the catechol compound remaining be kept small. Therefore, the content of the remaining (unreacted) catechol compound is preferably 20% or less, more preferably 10% or less, in terms of GPC area %. Here, GPC area % refers to the value obtained by dividing the GPC peak area value of the remaining (unreacted) catechol compound by the sum of the GPC peak area values ​​of all components.

[0043] The hydroxyl equivalent of the phenolic resin 1 is preferably 50 to 110 g / equivalent, more preferably 60 to 100 g / equivalent, and even more preferably 65 to 90 g / equivalent. When the hydroxyl equivalent is within the above range, the functional group density in the cured product increases, and the heat resistance and mechanical strength of the resulting cured product are excellent, which is preferable. The hydroxyl equivalent of the phenolic resin 1 here is measured based on the method for measuring the "hydroxyl equivalent of a phenolic resin" in the Examples below.

[0044] The melt viscosity (150°C) of the phenolic resin 1 is preferably 5.0 dPa·s or less, more preferably 0.1 to 4.0 dPa·s, and even more preferably 0.5 to 3.0 dPa·s. When the melt viscosity of the phenolic resin is within the above range, the resin has low viscosity and excellent fluidity and handleability, which is preferable because it also provides excellent handleability during epoxy resin synthesis and during the preparation of a cured product. The melt viscosity (150°C) here is measured using an ICI viscometer in accordance with ASTM D4287.

[0045] [Phenol resin 2] The phenolic resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound. In another example, specifically, a phenolic resin having a triphenylmethane skeleton represented by the following general formula (6) can be obtained by reacting a catechol compound represented by the following general formula (4) with a formyl group-containing aromatic compound represented by the following general formula (5).

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] In the above general formula (4), the substituent R 2 is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. From the viewpoint of reactivity when used as a raw material and bending properties of the cured product, the hydrocarbon group having 1 to 4 carbon atoms preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, etc. The alkoxy group having 1 to 4 carbon atoms preferably includes a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. The halogen atom preferably includes a fluorine atom, a chlorine atom, a bromine atom, etc. Among these, the R 2 However, when the aryl group is a hydrogen atom, the melt viscosity is low, the handling property is excellent, and the balance between the bending property and the heat resistance is excellent, which is a preferred embodiment.

[0050] In the above general formula (4), m represents an integer of 0 to 3, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending properties of the cured product.

[0051] In the above general formula (5), the substituent R3 is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. From the viewpoint of reactivity when used as a raw material and bending properties of the cured product, the hydrocarbon group having 1 to 4 carbon atoms preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, etc. The alkoxy group having 1 to 4 carbon atoms preferably includes a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. The halogen atom preferably includes a fluorine atom, a chlorine atom, a bromine atom, etc. Among these, the R 3 However, when the aryl group is a hydrogen atom, the melt viscosity is low, the handling property is excellent, and the balance between the bending property and the heat resistance is excellent, which is a preferred embodiment.

[0052] In the above general formula (5), n represents an integer of 0 to 5, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending properties of the cured product.

[0053] In the above general formula (6), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of the bending properties of the cured product, preferably, R 1 is represented by a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. 1 is preferably a hydrogen atom or the like, since the cured product has a good balance between heat resistance and bending properties. 1 However, when the substituent is a hydrogen atom, the melt viscosity is low and the handling properties are improved, which is a preferred embodiment. In the general formula (6), R 2 , R 3 , m, and n are the same as those in the general formulae (4) and (5) above.

[0054] The reaction ratio of the catechol compound to the formyl group-containing aromatic compound is preferably in the range of 0.01 to 0.9 mol, more preferably 0.05 to 0.8 mol, even more preferably 0.1 to 0.7 mol, and even more preferably 0.1 to 0.5 mol, of the formyl group-containing aromatic compound relative to 1 mol of the catechol compound, since this results in an epoxy resin having an excellent balance between melt viscosity and heat resistance in the cured product.

[0055] The reaction between the catechol compound and the formyl group-containing aromatic compound is preferably carried out in the presence of an acid catalyst, since this allows the reaction to proceed efficiently. 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 this case, the amount of the reaction catalyst used is preferably in the range of 0.01 to 5% by mass based on the total mass of the reaction raw materials.

[0056] The reaction between the catechol compound and the formyl group-containing aromatic compound can usually be carried out at a temperature of 80 to 200°C for 1 to 20 hours. The reaction may be carried out in an organic solvent, if necessary. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the temperature conditions described above. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When using these organic solvents, it is preferable to use them in an amount of 10 to 500% by mass relative to the total mass of the reaction raw materials.

[0057] After the reaction between the catechol compound and the formyl group-containing aromatic compound is completed, the unreacted reaction raw materials and by-products are distilled off to obtain the phenolic resin 2 containing the phenolic hydroxyl group-containing compound. If a portion of the catechol compound remains unreacted after the reaction between the catechol compound and the formyl group-containing aromatic compound is complete, this may contaminate the reactor used for the reaction, adversely affect the surrounding environment, or result in stoichiometric errors, resulting in reduced physical properties. Furthermore, the residual catechol compound may volatilize during the production of a cured product, potentially causing voids. Therefore, a large amount of the catechol compound is undesirable. Therefore, the content of the remaining (unreacted) catechol compound calculated by GPC measurement is preferably 5 area% or less in terms of GPC area %. Examples of by-products other than the phenolic hydroxyl group-containing compound include compounds represented by the following general formula (7). The by-products may be present to an extent that does not impair the effects of the present invention. Specifically, the total amount of the by-products is preferably less than 30 area% in terms of GPC area %. Here, the term "GPC area %" refers to the value obtained by dividing the GPC peak area value of the by-product by the sum of the GPC peak area values ​​of all components.

[0058] [ka]

[0059] The hydroxyl equivalent of the phenolic resin 2 is preferably 60 to 110 g / eq, more preferably 70 to 100 g / eq, and even more preferably 75 to 90 g / eq. When the hydroxyl equivalent of the phenolic resin 2 is within the above range, the functional group density in the cured product increases, and the heat resistance and mechanical strength of the obtained cured product are also excellent, which is preferable. The hydroxyl equivalent of the phenolic resin 2 here is based on the measurement method for "hydroxyl equivalent of phenolic resin" in the examples below.

[0060] The melt viscosity (150°C) of the phenolic resin 2 is preferably 5.0 dPa·s or less, more preferably 0.1 to 4.5 dPa·s, and even more preferably 1.0 to 4.0 dPa·s. When the melt viscosity of the epoxy resin is within the above range, the epoxy resin has low viscosity and excellent fluidity and handleability, which is preferable because it also provides excellent handleability during epoxy resin synthesis and during preparation of a cured product. The melt viscosity (150°C) here is measured using an ICI viscometer in accordance with ASTM D4287.

[0061] The softening point of the phenolic resin 2 is preferably 50 to 110° C., more preferably 60 to 100° C. If the softening point of the phenolic resin 2 is within the above range, it is preferable because the phenolic resin 2 has excellent handling properties and storage stability. The softening point here is measured based on JIS K 7234 (ring and ball method).

[0062] <Epoxy resin (A)> The present invention relates to an epoxy resin which is a reaction product of a catechol compound and a ketone group-containing compound, and which is characterized by being a reaction product having a phenolic resin having at least two catechol skeletons derived from the catechol compound, and a glycidyl ether group formed by a reaction between a phenolic hydroxyl group of the phenolic resin and an epihalohydrin. The epoxy resin is an epoxy resin into which a glycidyl ether group has been introduced by reacting a phenolic hydroxyl group of the phenol resin with epihalohydrin (epoxidation reaction), and a cured product using the epoxy resin is excellent in high heat resistance and high elastic modulus, and is therefore preferred.

[0063] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. These may be used alone or in combination. Among these, epichlorohydrin is preferred because it is easily available industrially.

[0064] The reaction rate in the synthesis of the epoxy resin can be increased by using an organic solvent during the epoxidation reaction. Examples of such organic solvents include, but are not limited to, 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 cyclohexane. Examples of suitable organic solvents include alcohol solvents such as cyclohexanol and 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 ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; 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.

[0065] In addition, commercially available organic solvents can also be used. Examples of commercially available organic solvents include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphtesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and "ExxonMobil Examples include Exxor D80, Exxor D110, Exxor D120, Exxor D130, Exxor D160, Exxor D100K, Exxor D120K, Exxor D130K, Exxor D280, Exxor D300, and Exxor D320 manufactured by Exxor Chemical Co., Ltd. The organic solvents can be used alone or in combination of two or more. In the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, as this improves the reaction efficiency.

[0066] The organic solvent may be used in combination with water, and the proportion of water in the mixed solvent is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the mixed solvent.

[0067] When the basic catalyst used in the epoxidation reaction is in the form of an aqueous solution, the content of water contained in the aqueous solution is not included in the amount of water in the mixed solvent.

[0068] [Epoxy resin 1] As the epoxy resin, for example, an epoxy resin 1 having a glycidyl ether group (the "OX group" in formula (9)) represented by the following general formula (8) introduced therein can be obtained by reacting the phenolic hydroxyl group of a phenol resin represented by the above general formula (3) with epihalohydrin.

[0069] [ka]

[0070] [ka]

[0071] In the general formula (8), X is represented by the general formula (9), and R 4 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. 4 However, when X is a hydrogen atom or the like, the bending properties and heat resistance are excellent, and therefore it is preferable. Among these, when X is a hydrogen atom, the melt viscosity is low, and this is a particularly preferable embodiment. Note that all or some of the X may be substituted with a glycidyl ether group represented by the above formula (9). When not substituted, X represents a hydrogen atom.

[0072] In the general formula (8), R 1 , R 2 , R 3 , m, and n are the same as those in the above general formulae (1) to (3).

[0073] [Epoxy resin 2] The epoxy resin is also characterized by containing a glycidyl ether group-containing compound represented by the following general formula (10) and obtained by reacting the phenolic resin 2 with epihalohydrin. By reacting the phenolic resin 2 with epihalohydrin, an epoxy resin containing a glycidyl ether group-containing compound having a glycidyl ether group introduced therein can be obtained, and this is preferable because it allows for the production of a cured product with low melt viscosity and excellent bending properties.

[0074] [ka]

[0075] [ka]

[0076] In the general formula (10), X is represented by the general formula (9), and R 4 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. 4 However, when X is a hydrogen atom or the like, the bending properties and heat resistance are excellent, and therefore it is preferable. Among these, when X is a hydrogen atom, the melt viscosity is low, and this is a particularly preferable embodiment. Note that all or some of the X may be substituted with a glycidyl ether group represented by the above formula (9). When not substituted, X represents a hydrogen atom. In the general formula (10), R 1 , R 2 , R 3 , m, and n are the same as those in the general formula (6) above.

[0077] The target epoxy resin 1 and / or epoxy resin 2 can be obtained by reacting the phenolic resin 1 and / or phenolic resin 2 with epihalohydrin. The reaction can be carried out, for example, by using 1 to 10 moles of epihalohydrin per mole of phenolic hydroxyl groups in the phenolic resin 1 and / or phenolic resin 2, and reacting at a temperature of 20 to 120°C for 0.5 to 30 hours while adding 0.9 to 2.0 moles of a basic catalyst per mole of phenolic hydroxyl groups all at once or in portions.

[0078] Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred because of their excellent catalytic activity, and specific examples thereof include sodium hydroxide and potassium hydroxide.

[0079] After the reaction is complete, the reaction mixture is washed with water, and then unreacted epihalohydrin and the organic solvent are removed by distillation under heating and reduced pressure. Alternatively, to obtain an epoxy resin with even fewer hydrolyzable halogens, the resulting epoxy resin can be dissolved again in an organic solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to further react. In this case, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present to improve the reaction rate. When a phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of the epoxy resin. After the reaction is complete, the resulting salt is removed by filtration or washing with water, and the organic solvent is removed by distillation under heating and reduced pressure, thereby obtaining the desired epoxy resin of the present invention.

[0080] The epoxy equivalent of each of the epoxy resins 1 and 2 is preferably 120 to 400 g / equivalent, more preferably 130 to 300 g / equivalent, and even more preferably 120 to 200 g / equivalent. It is preferable that the epoxy equivalent of the epoxy resins be within the above range, since this increases the crosslink density of the cured product and provides excellent heat resistance to the resulting cured product. The epoxy equivalent here is measured in accordance with JIS K7236.

[0081] The melt viscosity (150°C) of each of the epoxy resins 1 and 2 is preferably 2.0 dPa·s or less, more preferably 0.01 to 1.0 dPa·s, and even more preferably 0.1 to 0.6 dPa·s. It is preferable that the melt viscosity of the epoxy resins be within the above range, since they have low viscosity, excellent fluidity, and excellent handleability, and the moldability of the resulting cured product is also excellent. The melt viscosity (150°C) here is measured using an ICI viscometer in accordance with ASTM D4287.

[0082] <Unsaturated monobasic acid (B)> 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 (11) can also be used.

[0083] [ka]

[0084] [In general formula (11), 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 its structure. Y represents a hydrogen atom or a methyl group.]

[0085] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0086] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (12).

[0087] [ka] [In general formula (12), R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0088] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0089] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (13).

[0090] [ka]

[0091] [In general formula (13), R 2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0092] The molecular weight of the compound represented by the general formula (11) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0093] These unsaturated monobasic acids (B) can be used alone or in combination of two or more kinds.

[0094] The amount of the unsaturated monobasic acid (B) used is preferably in the range of 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol, of acid groups in the unsaturated monobasic acid (B) per 1 mol of epoxy groups in the epoxy resin (A), since a curable resin composition having excellent alkali developability and capable of forming a cured product excellent in heat resistance and high elastic modulus can be obtained.

[0095] <Polybasic acid anhydride (C)> 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.

[0096] Examples of the aliphatic polybasic acid anhydrides include acid anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

[0097] In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0098] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0099] 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 can give a curable resin composition that has excellent alkali developability and can form a cured product that is excellent in heat resistance and high elastic modulus.

[0100] The amount of the polybasic acid anhydride (C) used is preferably in the range of 0.2 to 1.05 mol, more preferably 0.25 to 0.95 mol, per mol of epoxy groups in the epoxy resin (A), since a curable resin composition having excellent alkali developability and capable of forming a cured product excellent in heat resistance and high elastic modulus can be obtained.

[0101] The resin having an acid group and a polymerizable unsaturated group of the present invention may, if necessary, use compounds other than the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) as raw materials.

[0102] Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0103] 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.

[0104] The total mass proportion 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 having an acid group and a polymerizable unsaturated group of the present invention is preferably 70 mass% or more, since this gives a curable resin composition that has excellent alkali developability and is capable of forming a cured product that is excellent in heat resistance and high elastic modulus.

[0105] The method for producing the resin having an acid group and a polymerizable unsaturated group of the present invention is not particularly limited, and any method may be used. For example, the resin may be produced by reacting all of the reaction raw materials containing the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) all at once, or by sequentially reacting the reaction raw materials. Among these, a preferred method is one in which the epoxy resin (A) and the unsaturated monobasic acid (B) are first reacted in the presence of a basic catalyst at a temperature of 80 to 140°C, and then the polybasic acid anhydride (C) is added and reacted at a temperature of 80 to 140°C, because this method makes it easier to control the reaction.

[0106] The reaction of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) can be carried out in an organic solvent, if necessary, and a polymerization inhibitor or an antioxidant can also be used, if necessary.

[0107] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. Examples of suitable ammonium salts include quaternary ammonium salts such as octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. 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. When used, these basic catalysts can be used in the form of an aqueous solution of about 10 to 55 mass %, or in the form of a solid.

[0108] The amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, more preferably in the range of 0.05 to 0.8 parts by mass, relative to 100 parts by mass of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) in total, since a curable resin composition having excellent alkali developability and capable of forming a cured product excellent in heat resistance and high elastic modulus can be obtained.

[0109] 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 the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, in order to improve the reaction efficiency.

[0110] The organic solvent may be used in combination with water, and the proportion of water in the mixed solvent is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the mixed solvent.

[0111] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,3-diphenyl-4-phenylenediamine), and methyl-p-benzoquinone.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination.

[0112] 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.

[0113] Commercially available examples of the polymerization inhibitor and antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0114] The resin having an acid group and a polymerizable unsaturated group of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] <Other resin components: resin (D) having an acid group and a polymerizable unsaturated group, etc.> The curable resin composition of the present invention may contain resin components other than the resin having an acid group and a polymerizable unsaturated group of the present invention (hereinafter, these 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.

[0119] 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 the above-mentioned epoxy resins having an acid group and a polymerizable unsaturated group other than those of the present invention, urethane resins having an acid group and a polymerizable unsaturated group, acrylic resins having an acid group and a polymerizable unsaturated group, amide-imide resins having an acid group and a polymerizable unsaturated group, acrylamide resins having an acid group and a polymerizable unsaturated group, and ester resins having an acid group and a polymerizable unsaturated group.

[0120] Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0121] Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include an epoxy (meth)acrylate resin having an acid group, which is made from an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential raw materials, and an epoxy (meth)acrylate resin having an acid group and a urethane group, which is made from an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group as reaction raw materials.

[0122] Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0129] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

[0130] [ka]

[0131] [In general formula (14), R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0132] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Also usable are (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0133] The method for producing the epoxy resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0134] 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.

[0135] 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.

[0136] Examples of the urethane resin having an acid group and a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and, if necessary, a polybasic acid anhydride, with a polyol compound other than the polyol compound having a carboxyl group; and those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polybasic acid anhydride, and a polyol compound other than the polyol compound having a carboxyl group.

[0137] 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.

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

[0139] 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.

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

[0141] Examples of polyol compounds other than the polyol compounds having a carboxyl group include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various polyol compounds; and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the polyol compounds having a carboxyl group can be used alone or in combination of two or more.

[0142] The method for producing the urethane resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

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

[0146] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0147] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

[0148] The polybasic acid anhydride can be the same as those exemplified above as the polybasic acid anhydride (C), and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0149] The method for producing the acrylic resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0150] 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.

[0151] 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.

[0152] Examples of the amide-imide resin having an acid group and a polymerizable unsaturated group include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group.

[0153] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, it is preferable for the resin to have an acid anhydride group, and it is more preferable for the resin to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0154] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0155] 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.

[0156] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0157] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0158] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of suitable polybasic acids include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0159] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

[0160] 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 types.

[0161] The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (4-1) to (4-5).

[0166] [ka]

[0167] In the above structural formulas (4-1) to (4-5), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, 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 structural formula is arbitrary. For example, in the naphthalene ring of structural formula (4-2), the substituent may be on any ring; in structural formula (4-3), the substituent may be on any ring of the benzene ring present in one molecule; in structural formula (4-4), the substituent may be on any ring of the benzene ring present in one molecule; and in structural formula (4-5), the substituent may be on any ring of the benzene ring present in one molecule; and p and q indicate the number of substituents in one molecule.

[0168] The compound having a phenolic hydroxyl group may also 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 structural formulas (5-1) to (5-5) and / or formaldehyde as essential reaction raw materials. Also usable are novolac-type phenolic resins obtained by using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials.

[0169] [ka]

[0170] [In structural formula (5-1), h is 0 or 1. In structural formulas (5-2) to (5-5), R 1is 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 structural formulas (5-2), (5-3), and (5-5), each W is independently any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (5-5), V 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.

[0171] Specific examples of the compounds represented by the above general formulas (5-1) to (5-5) and the reaction products thereof include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzyl phenol ... Examples of the phenol resin include benzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

[0172] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0173] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition that has excellent alkali developability and can form a cured product that is excellent in heat resistance and high elastic modulus. The alkylene oxides can be used alone or in combination of two or more.

[0174] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition that has excellent alkaline developability and can form a cured product that is excellent in heat resistance and high elastic modulus. The alkylene carbonates can be used alone or in combination of two or more.

[0175] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0176] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0177] 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.

[0178] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0179] 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.

[0180] 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.

[0181] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0182] 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.

[0183] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as compounds 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 types.

[0184] 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 that has excellent alkali developability and can form a cured product that is excellent in elongation, adhesion, and dielectric properties. The alkylene oxide may be used alone or in combination of two or more.

[0185] 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 that has excellent alkaline developability and can form a cured product that is excellent in elongation, adhesion, and dielectric properties. The alkylene carbonate may be used alone or in combination of two or more.

[0186] 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.

[0187] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0188] 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 needed, and a basic catalyst and an acidic catalyst may be used as needed.

[0189] 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.

[0190] 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.

[0191] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0192] The amount of the resin (D) having an acid group and a polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the resin having an acid group and a polymerizable unsaturated group of the present invention.

[0193] Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono(meth)acrylate compounds such as the aromatic mono(meth)acrylate compounds of the above: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

[0194] In addition to the above-mentioned other (meth)acrylate monomers, (meth)acrylate monomers having a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials can be used.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used.

[0199] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0200] Furthermore, 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 modifier, a leveling agent, a flame retardant, and a storage stabilizer, as needed.

[0201] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0202] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0203] As the polymerization inhibitor, the same ones as those exemplified above as polymerization inhibitors can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds.

[0204] As the antioxidant, the same antioxidants as those exemplified above can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0205] 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.

[0206] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0207] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0208] Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0209] 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.

[0210] 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.

[0211] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0212] The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0213] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0214] The integrated light quantity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 and more preferably 0.5 to 10 kJ / m 2 . When the integrated light quantity is within the above range, it is preferable because generation or suppression of uncured portions can be prevented.

[0215] Note that the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

[0216] In addition, the cured product of the present invention has excellent alkali developability and excellent heat resistance and high elastic modulus. Therefore, for example, in semiconductor device applications, it can be suitably used as a solder resist, an interlayer insulating material, a packaging material, an underfill material, a package adhesive layer such as a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer, etc. in thin display applications typified by LCD and OELD. Among these, it can be particularly suitably used for solder resist applications.

[0217] The resist member of the present invention can be obtained, for example, by applying the resin material for solder resist on a substrate, volatilizing and drying an organic solvent in a temperature range of about 60 to 100°C, then exposing with active energy rays through a photomask having a desired pattern formed thereon, developing an unexposed portion with an aqueous alkali solution, and further heating and curing in a temperature range of about 140 to 200°C.

[0218] Examples of the substrate include metal-clad laminates such as copper and aluminum.

Examples

[0219] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples given below. <(Evaluation of GPC measurement)> Measurements were carried out using the following measuring apparatus and under the following measuring conditions, and the synthesis of the phenolic resin obtained by the synthesis method shown below and the epoxy resin obtained using the phenolic resin was confirmed based on GPC measurement. Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Sample: 1.0 mass % tetrahydrofuran solution (equivalent to epoxy resin solid content) filtered through a microfilter (50 μl). Regarding the content (area %) of residual (unreacted) catechol compounds in the phenolic resin, it is preferable that the content of residual catechol compounds is 5.0 area % or less, from the viewpoint of reducing volatile content during curing.

[0220] <Softening point> Measurement method: The softening points (° C.) of the phenolic resins obtained in the synthesis examples shown below were measured according to JIS K7234 (ring and ball method).

[0221] [Synthesis Example 1] Synthesis of phenolic resin (a-1) A 2L flask equipped with a thermometer, condenser, and stirrer was charged with 330.3 parts by mass (3.00 mol) of catechol, 328.3 parts by mass of toluene, and 0.95 parts by mass (0.05 mol) of paratoluenesulfonic acid, and the mixture was heated to 100°C while dissolving. While maintaining the temperature, 106.1 parts by mass (1.00 mol) of benzaldehyde was added dropwise over 1 hour, and the mixture was allowed to react for an additional 3 hours. After the reaction, 616.2 parts by mass of methyl isobutyl ketone was added, and the mixture was washed with water until neutral. The mixture was then concentrated under reduced pressure at 150°C, and unreacted catechol was removed by distillation while blowing in steam, yielding 261 parts by mass of the target phenolic resin (a-1). The resulting phenolic resin (a-1) had a hydroxyl equivalent of 86 g / eq, a softening point of 96°C, and a melt viscosity of 3.6 dPa·s at 150°C. The GPC chart of the obtained phenolic resin (a-1) is shown in Figure 1. Formation was confirmed by the main peak at the peak top of 34.1 min. The term "major component" as used herein means a component that accounts for 50% or more of a GPC area percentage, and the GPC area percentage of each component refers to the value obtained by dividing the GPC peak area value of each component by the total GPC peak area value of all components.

[0222] [Synthesis Example 2] Synthesis of phenolic resin (a-2) Synthesis was performed in the same manner as in Synthesis Example 1, except that the amount of catechol added was changed to 440.4 parts by mass (4.00 mol), to obtain 275 parts by mass of phenolic resin (a-2). The hydroxyl group equivalent of the obtained phenolic resin (a-2) was 82 g / eq, the softening point was 89°C, and the melt viscosity at 150°C was 1.9 dPa s.

[0223] [Synthesis Example 3] Synthesis of phenolic resin (a-3) Synthesis was performed in the same manner as in Synthesis Example 1, except that the amount of catechol added was changed to 550.6 parts by mass (5.00 mol), to obtain 260 parts by mass of phenolic resin (a-3). The hydroxyl group equivalent of the obtained phenolic resin (a-3) was 80 g / eq, the softening point was 92°C, and the melt viscosity at 150°C was 2.6 dPa s.

[0224] [Synthesis Example 4] Synthesis of phenolic resin (a-4) Synthesis was performed in the same manner as in Synthesis Example 1, except that the amount of catechol added was changed to 660.7 parts by mass (6.00 mol), to obtain 260 parts by mass of phenolic resin (a-4). The hydroxyl group equivalent of the obtained phenolic resin (a-4) was 82 g / eq, the softening point was 91°C, and the melt viscosity at 150°C was 2.3 dPa s.

[0225] [Synthesis Example 5] Synthesis of phenolic resin (a-5) A 2L flask equipped with a thermometer, condenser, and stirrer was charged with 495.5 parts by mass (4.50 mol) of catechol, 4.9 parts by mass (0.046 mol) of 3-mercaptopropionic acid, 247.8 parts by mass of 1,4-dioxane, and 52.5 parts by mass (0.54 mol) of 98% sulfuric acid. The temperature was raised to 40°C under a nitrogen inflow. While maintaining the temperature, 87.0 parts by mass (1.55 mol) of acetone was added dropwise over 1 hour, and the reaction was continued for another 3 hours. After the reaction, 520.0 parts by mass of methyl isobutyl ketone was added and the mixture was washed with water until neutral. The system was then dehydrated by azeotropy, microfiltrated, and concentrated under reduced pressure at 150°C. Unreacted catechol was removed by distillation while blowing in water vapor, yielding 236 parts by mass of phenolic resin (a-5). The hydroxyl equivalent of the obtained phenolic resin (a-5) was 72 g / eq, and the melt viscosity (150°C) was 0.7 dPa·s.

[0226] [Synthesis Example 6] Synthesis of phenolic resin (a-6) A 2-L flask equipped with a thermometer, condenser, and stirrer was charged with 200.0 parts by mass (1.82 mol) of catechol, 220.0 parts by mass of 1,4-dioxane, and 35.0 parts by mass (0.36 mol) of 98% sulfuric acid. The temperature was raised to 40°C under a nitrogen inflow. While maintaining the temperature, 60.0 parts by mass (1.07 mol) of acetone was added dropwise over 1 hour, and the reaction was continued for an additional 3 hours. After the reaction, 300.0 parts by mass of methyl isobutyl ketone was added and the mixture was washed with water until neutral. The system was then dehydrated by azeotropy, microfiltrated, and concentrated under reduced pressure at 150°C to obtain 160 parts by mass of phenolic resin (a-6). The hydroxyl equivalent of the resulting phenolic resin (a-6) was 71 g / eq and the melt viscosity (150°C) was 0.6 dPa·s.

[0227] [Synthesis Example 7] Synthesis of epoxy resin (A-1) A 2-L flask equipped with a thermometer, a condenser, and a stirrer was charged with 180.0 parts by mass of the phenolic resin (a-1) obtained in Synthesis Example 1 and 774.4 parts by mass (8.37 mol) of epichlorohydrin, and the mixture was heated to 50°C while stirring and dissolving. Next, 9.74 parts by mass of a 50% aqueous solution of benzyltrimethylammonium chloride was charged, and the mixture was allowed to react for 24 hours while maintaining the temperature at 50°C. Furthermore, 199.2 parts by mass of a 49% aqueous solution of sodium hydroxide (1.10 equivalents relative to the hydroxyl groups) was added dropwise over 3 hours, and the mixture was allowed to react for an additional hour at 50°C. After the reaction was completed, 246.7 parts by mass of isopropyl alcohol was added, stirring was stopped, and the aqueous layer that had accumulated in the lower layer was removed. Stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. The resulting crude epoxy resin was dissolved in 517.6 parts by mass of methyl isobutyl ketone and repeatedly washed with 152.2 parts by mass of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 273.0 parts by mass of the target epoxy resin (A-1). The resulting epoxy resin (A-1) had an epoxy equivalent of 159 g / eq and a melt viscosity of 0.52 dPa·s at 150°C. The GPC chart of the epoxy resin (A-1) is shown in Figure 2. Formation was confirmed by the main peak at 32.4 min.

[0228] [Synthesis Example 8] Synthesis of epoxy resin (A-2) Synthesis was performed in the same manner as in Synthesis Example 7, except that the charged amounts of phenol resin (a-2) obtained in Synthesis Example 2 were 175 parts by mass and epichlorohydrin were 793.4 parts by mass (8.58 mol), to obtain 255 parts by mass of epoxy resin (A-2). The epoxy equivalent was 163 g / eq, and the melt viscosity at 150°C was 0.50 dPa s.

[0229] [Synthesis Example 9] Synthesis of epoxy resin (A-3) Synthesis was performed in the same manner as in Synthesis Example 7, except that the charged amounts of phenol resin (a-3) obtained in Synthesis Example 3 were 180 parts by mass and epichlorohydrin were 832.5 parts by mass (9 mol), to obtain 271 parts by mass of epoxy resin (A-3). The epoxy equivalent was 154 g / eq, and the melt viscosity at 150°C was 0.48 dPa s.

[0230] [Synthesis Example 10] Synthesis of epoxy resin (A-4) Synthesis was performed in the same manner as in Synthesis Example 7, except that the charged amounts of phenol resin (a-4) obtained in Synthesis Example 4 were 180 parts by mass and epichlorohydrin were 794.5 parts by mass (8.59 mol), to obtain 266 parts by mass of epoxy resin (A-4). The epoxy equivalent was 161 g / eq, and the melt viscosity at 150°C was 0.48 dPa s.

[0231] [Synthesis Example 11] Synthesis of epoxy resin (A-5) A 2-L flask equipped with a thermometer, a condenser, and a stirrer was charged with 170.0 parts by mass (2.36 mol as hydroxyl groups) of the phenolic resin (a-5) obtained in Synthesis Example 5 and 873.6 parts by mass (9.44 mol) of epichlorohydrin, and the mixture was heated to 50°C while stirring and dissolving. Next, 10.35 parts by mass of a 50% aqueous tetramethylammonium solution was added, and the mixture was allowed to react for 24 hours. Furthermore, 211.6 parts by mass of a 49% aqueous sodium hydroxide solution (1.10 equivalents relative to the hydroxyl groups) was added dropwise over 3 hours, and the mixture was allowed to react for an additional 1 hour at 50°C. After the reaction was completed, 262.1 parts by mass of isopropyl alcohol was added, stirring was stopped, and the aqueous layer that had accumulated at the bottom was removed. Stirring was resumed, and unreacted epichlorohydrin was distilled off at 150°C under reduced pressure. The resulting crude epoxy resin was dissolved in 517.8 parts by mass of methyl isobutyl ketone and repeatedly washed with 152.3 parts by mass of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 270.0 parts by mass of the desired epoxy resin (A-5). The resulting epoxy resin (A-5) was a viscous semi-solid at room temperature, with an epoxy equivalent of 152 g / eq and a melt viscosity (150°C) of 0.2 dPa·s.

[0232] [Synthesis Example 12] Synthesis of epoxy resin (A-6) A 2-L flask equipped with a thermometer, a condenser, and a stirrer was charged with 100.0 parts by mass of the phenolic resin (a-6) obtained in Synthesis Example 6 (1.41 mol as hydroxyl groups) and 513.9 parts by mass (5.56 mol) of epichlorohydrin, and the mixture was heated to 50°C while stirring and dissolving. Next, 6.09 parts by mass of a 50% aqueous tetramethylammonium solution was charged, and the mixture was allowed to react for 24 hours. Furthermore, 124.7 parts by mass of a 49% aqueous sodium hydroxide solution (1.10 equivalents relative to the hydroxyl groups) was added dropwise over 3 hours, and the mixture was allowed to react for another hour at 50°C. After the reaction was completed, 154.2 parts by mass of isopropyl alcohol was added, stirring was stopped, and the aqueous layer that had accumulated at the bottom was removed. Stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. The resulting crude epoxy resin was dissolved in 614.1 parts by mass of methyl isobutyl ketone and repeatedly washed with 180.6 parts by mass of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 160.0 parts by mass of the desired epoxy resin (A-6). The resulting epoxy resin (A-6) had an epoxy equivalent of 158 g / eq and a melt viscosity (150°C) of 0.1 dPa·s.

[0233] [Synthesis Example 13] Resin (C-1) having an acid group and a polymerizable unsaturated group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of diethylene glycol monoethyl ether acetate, and 214 parts by weight of orthocresol novolac epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) (hereinafter referred to as "epoxy resin (1)") was dissolved therein. 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 72 parts by weight of diethylene glycol monoethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (C-1) having acid groups and polymerizable unsaturated groups. The resin (C-1) having an acid group and a polymerizable unsaturated group had a nonvolatile content of 65 mass % and an acid value of the solid content of 80 mgKOH / g.

[0234] Example 1: Resin (B-1) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.8 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 100.2 parts by weight of diethylene glycol monoethyl ether acetate and 62.3 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g.

[0235] Example 2: Resin (B-2) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 58.8 parts by weight of diethylene glycol monoethyl ether acetate, and 163 parts by weight of the epoxy resin (A-2) obtained in Synthesis Example 8 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 101.3 parts by weight of diethylene glycol monoethyl ether acetate and 62.3 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-2) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0236] Example 3: Resin (B-3) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56.5 parts by weight of diethylene glycol monoethyl ether acetate, and 154 parts by weight of the epoxy resin (A-3) obtained in Synthesis Example 9 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 97.9 parts by weight of diethylene glycol monoethyl ether acetate and 60.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-3) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0237] Example 4: Resin (B-4) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 58.3 parts by weight of diethylene glycol monoethyl ether acetate, and 161 parts by weight of the epoxy resin (A-4) obtained in Synthesis Example 10 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 100.8 parts by weight of diethylene glycol monoethyl ether acetate and 62.3 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-4) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g.

[0238] Example 5: Resin (B-5) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 97.4 parts by weight of diethylene glycol monoethyl ether acetate and 60.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-5) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 82 mgKOH / g.

[0239] Example 6: Resin (B-6) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.5 parts by weight of diethylene glycol monoethyl ether acetate, and 158 parts by weight of the epoxy resin (A-6) obtained in Synthesis Example 12 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 99.1 parts by weight of diethylene glycol monoethyl ether acetate and 60.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-6) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-6) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0240] Example 7 Resin (B-7) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.4 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 70.6 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 8 hours while blowing in air. Next, 100.6 parts by weight of diethylene glycol monoethyl ether acetate and 63.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-7) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-7) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0241] Example 8 Resin (B-8) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 58.7 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 75.6 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 8 hours while blowing in air. Next, 99.6 parts by weight of diethylene glycol monoethyl ether acetate and 59.3 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-8) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-8) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 82 mgKOH / g.

[0242] Example 9: Resin (B-9) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.8 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was reacted for 10 hours at 120°C while blowing in air. Next, 86 parts by weight of diethylene glycol monoethyl ether acetate and 36 parts by weight of succinic anhydride were added, and the mixture was reacted for 3 hours at 110°C to obtain a resin (B-9) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-9) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 79 mgKOH / g.

[0243] Example 10: Resin (B-10) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.8 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted for 10 hours at 120°C while blowing in air. Next, 99.8 parts by weight of diethylene glycol monoethyl ether acetate and 61.6 parts by weight of hexahydrophthalic anhydride were added, and the mixture was reacted for 3 hours at 110°C to obtain a resin (B-10) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-10) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0244] Example 11 Resin (B-11) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.8 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 86.3 parts by weight of diethylene glycol monoethyl ether acetate and 36.5 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-11) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-11) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 52 mgKOH / g.

[0245] Example 12 Resin (B-12) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 57.8 parts by weight of diethylene glycol monoethyl ether acetate, and 159 parts by weight of the epoxy resin (A-1) obtained in Synthesis Example 7 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.2 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 126.4 parts by weight of diethylene glycol monoethyl ether acetate and 111 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-12) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-12) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 122 mg KOH / g.

[0246] Example 13 Resin (B-13) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 70.6 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 96.9 parts by weight of diethylene glycol monoethyl ether acetate and 60.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-13) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-13) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 78 mgKOH / g.

[0247] Example 14 Resin (B-14) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56.9 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 75.6 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 96.8 parts by weight of diethylene glycol monoethyl ether acetate and 57.8 parts by weight of tetrahydrophthalic anhydride were added and the reaction was continued at 110°C for 3 hours to obtain a resin (B-14) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-14) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g.

[0248] Example 15: Resin (B-15) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was reacted for 10 hours at 120°C while blowing in air. Next, 83.5 parts by weight of diethylene glycol monoethyl ether acetate and 35 parts by weight of succinic anhydride were added, and the mixture was reacted for 3 hours at 110°C to obtain a resin (B-15) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-15) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0249] Example 16: Resin (B-16) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was reacted for 10 hours at 120°C while blowing in air. Next, 97 parts by weight of diethylene glycol monoethyl ether acetate and 60.1 parts by weight of hexahydrophthalic anhydride were added and the mixture was reacted for 3 hours at 110°C to obtain a resin (B-16) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-16) was 65% by weight, and the acid value of the solid content was 81 mgKOH / g.

[0250] Example 17 Resin (B-17) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was reacted for 10 hours at 120°C while blowing in air. Next, 83.4 parts by weight of diethylene glycol monoethyl ether acetate and 35 parts by weight of tetrahydrophthalic anhydride were added, and the reaction was continued for 3 hours at 110°C to obtain a resin (B-17) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-17) was 65% by weight, and the acid value of the solid content was 51 mgKOH / g.

[0251] Example 18: Resin (B-18) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56 parts by weight of diethylene glycol monoethyl ether acetate, and 152 parts by weight of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.1 parts by weight of triphenylphosphine. The mixture was reacted for 10 hours at 120°C while blowing in air. Next, 122.7 parts by weight of diethylene glycol monoethyl ether acetate and 107.9 parts by weight of tetrahydrophthalic anhydride were added and the reaction was continued for 3 hours at 110°C to obtain a resin (B-18) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-18) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 122 mg KOH / g.

[0252] Example 19: Preparation of curable resin composition (1) 100 parts by mass (65 parts by mass as solids) of the resin (B-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Example 1, 19.9 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.7 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, 0.4 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).

[0253] (Examples 20 to 37: Preparation of curable resin compositions (2) to (19)) Curable resin compositions (2) to (19) were obtained in the same manner as in Example 19, except that the resins (B-2) to (B-18) and (C-1) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 18 and Synthesis Example 13 were used in the blending amounts shown in Tables 1 and 2, instead of the resin (B-1) having an acid group and a polymerizable unsaturated group used in Example 1.

[0254] (Comparative Example 1: Preparation of curable resin composition (C2)) A curable resin composition (C2) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (C-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Synthesis Example 13, 19.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.6 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, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green.

[0255] The curable resin compositions (1) to (19) and (C2) obtained in the above examples and comparative examples were evaluated as follows.

[0256] [Method for evaluating alkaline developability] The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 60, 70, 80, 90, 100, 110, 120, 130, or 140 minutes, respectively, to prepare samples with different drying times. These were then developed with a 1% by mass aqueous sodium carbonate solution at 30°C for 180 seconds, and the drying time at 80°C of samples that left no residue on the substrate was evaluated as the drying control range. Note that a longer drying control range indicates better alkaline developability.

[0257] The compositions and evaluation results of the curable resin compositions (1) to (19) prepared in Examples 19 to 37 and the curable resin composition (C2) prepared in Comparative Example 1 are shown in Tables 1 and 2.

[0258] [Table 1]

[0259] [Table 2]

[0260] (Example 38: Preparation of curable resin composition (20)) A curable resin composition (20) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (B-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Example 1, 19.9 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.7 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).

[0261] (Examples 39 to 56: Preparation of curable resin compositions (21) to (38)) Curable resin compositions (21) to (38) were obtained in the same manner as in Example 38, except that the resins (B-2) to (B-18) and (C-1) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 18 and Synthesis Example 13 were used in the blending amounts shown in Tables 3 and 4, instead of the resin (B-1) having an acid group and a polymerizable unsaturated group used in Example 38.

[0262] (Comparative Example 2: Preparation of curable resin composition (C3)) A curable resin composition (C3) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (C-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Synthesis Example 13, 19.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.6 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).

[0263] The curable resin compositions (20) to (38) and (C3) obtained in the above examples and comparative examples were evaluated as follows.

[0264] [Heat resistance evaluation method] The curable resin compositions obtained in each of the Examples and Comparative Examples were 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 curable resin compositions to a copper foil to a thickness of 50 μm. 2 After irradiating the film with ultraviolet light, the film 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 maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics 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.

[0265] [Elasticity evaluation method] The elasticity was evaluated by measuring the elastic modulus through a tensile test.

[0266] <Tensile test> The test piece 1 was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece under the following measurement conditions using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

[0267] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between supports 20mm, tensile speed 10mm / min

[0268] Tables 3 and 4 show the compositions and evaluation results of the curable resin compositions (20) to (38) prepared in Examples 38 to 56 and the curable resin composition (C3) prepared in Comparative Example 3.

[0269] [Table 3]

[0270] [Table 4]

[0271] In Tables 1 to 4, the parts by mass of the resin having an acid group and a polymerizable unsaturated group are solid content values.

[0272] "Curing agent" in Tables 1 to 4 refers to an orthocresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0273] "Organic solvent" in Tables 1 to 4 refers to diethylene glycol monoethyl ether acetate.

[0274] "Photopolymerization initiator" in Tables 1 to 4 refers to "Omnirad-907" manufactured by IGM Resins.

[0275] Examples 19 to 37 shown in Tables 1 and 2 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that these curable resin compositions had excellent alkaline developability.

[0276] Examples 38 to 56 shown in Tables 3 and 4 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance and a high elastic modulus.

[0277] On the other hand, Comparative Examples 2 and 3 shown in Tables 3 and 4 are examples of curable resin compositions that do not use a phenolic resin having at least two catechol skeletons and an epoxy resin containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin as raw materials for a resin having an acid group and a polymerizable unsaturated group. It was confirmed that the cured product of the curable resin composition obtained in Comparative Example 3 had insufficient heat resistance and elastic modulus.

Claims

1. an epoxy resin (A) containing a phenolic resin having at least two catechol skeletons derived from a catechol compound and a glycidyl ether group-containing compound obtained by reacting epihalohydrin; an unsaturated monobasic acid (B); A resin having an acid group and a polymerizable unsaturated group, characterized in that it contains a polybasic acid anhydride (C) as an essential reactant.

2. 2. The resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the phenolic resin is a reaction product of a catechol compound and a ketone group-containing compound.

3. 3. The resin having an acid group and a polymerizable unsaturated group according to claim 1 or claim 2, wherein the amount of the unsaturated monobasic acid (B) used is in a range such that the number of moles of the acid group in the unsaturated monobasic acid (B) is 0.9 to 1.1 moles per mole of the epoxy group in the epoxy resin (A).

4. 3. The resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the amount of the polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 mol per 1 mol of the epoxy group contained in the epoxy resin (A).

5. A curable resin composition comprising the resin having an acid group and a polymerizable unsaturated group according to claim 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 having an acid group and a polymerizable unsaturated group.

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