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

Abstract

To provide a resin having an acid radical and a polymerizable unsaturated group, which has excellent alkali developability, whose cured product has excellent elongation, adhesion and dielectric properties, a curable resin composition, a cured product of the curable resin composition, an insulating material and a resist member.SOLUTION: The present invention provides a resin having an acid radical and a polymerizable unsaturated group, containing an indan bisphenol type epoxy resin (A) having an indan skeleton represented by the general formula (1), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) as essential starting reactive 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 are not only curable but also have heat resistance, photosensitivity, and alkali developability.

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

[0004] 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 properties such as elongation, adhesion to substrates, and dielectric properties, and are not sufficient for meeting current market demands.

[0005] Therefore, there has been a demand for a material that has excellent alkaline developability and is capable of forming a cured product that has excellent elongation, adhesion, and dielectric properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 Summary of the Invention [Problem to be solved by the invention]

[0007] 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 elongation, adhesion, and dielectric properties; a curable resin composition; a cured product of the curable resin composition; an insulating material; and a resist member. [Means for solving the problem]

[0008] 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.

[0009] 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 indane bisphenol-type epoxy resin (A) having an indane skeleton represented by the following general formula (1), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C); a curable resin composition containing the resin; and a cured product, insulating material, and resist member made of the curable resin composition.

[0010] [ka] (In the above formula (1), each Ra independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; q represents an integer value of 0 to 4. When q is 2 to 4, each Ra may be the same or different within the same ring. Each Rb independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; and r represents an integer value of 0 to 3. When r is 2 or 3, each Rb may be the same or different within the same ring. n is the average number of repeating units and represents a numerical value of 0.2 to 20.) [Effects of the Invention]

[0011] 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 elongation, adhesion, and dielectric properties. Therefore, a curable resin composition containing the resin and a photopolymerization initiator can be used as a coating agent or adhesive, and as a coating agent, it is particularly suitable for use in solder resist applications. Note that the "excellent dielectric properties" referred to in the present invention refer to a low dielectric constant and a low dielectric loss tangent. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a GPC chart of the indane bisphenol compound (1) obtained in Synthesis Example 1. [Figure 2] FIG. 1 is a GPC chart of the indane bisphenol epoxy resin (A-1) obtained in Synthesis Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0013] The resin having an acid group and a polymerizable unsaturated group of the present invention is characterized by using an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) as essential reaction raw materials.

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

[0015] The epoxy resin (A) is represented by the following general formula (1).

[0016] [ka] (In the above formula (1), each Ra independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; q represents an integer value of 0 to 4. When q is 2 to 4, each Ra may be the same or different within the same ring. Each Rb independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; and r represents an integer value of 0 to 3. When r is 2 or 3, each Rb may be the same or different within the same ring. n is the average number of repeating units and represents a numerical value of 0.2 to 20.)

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

[0018] Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, and an alkoxynaphthyl group.

[0019] In the general formula (1), Ra is preferably any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. When Ra is an alkyl group having 1 to 4 carbon atoms, etc., the planarity and crystallinity in the vicinity of the bisphenol group are reduced, which is a preferred embodiment that improves solvent solubility and enables a cured product to be obtained without impairing the reactivity of the bisphenol group.

[0020] In the general formula (1), q is preferably 1 to 3, and more preferably 2. When q is 2, the effect of steric hindrance is small, which is a more preferred embodiment in the production (synthesis) of the epoxy resin (A).

[0021] In the above general formula (1), it is preferable that r is 0 and Rb is a hydrogen atom, and it is also preferable that r is 1 to 3 and Rb is at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. In particular, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced during the formation of the indane skeleton in the epoxy resin (A), which is advantageous for the production (synthesis) of the epoxy resin (A) and is a preferred embodiment.

[0022] The epoxy resin (A) can be produced, for example, by epoxidizing a polyfunctional phenolic resin.

[0023] The epoxidation method is not particularly limited, and known techniques can be appropriately applied. For example, an epoxidation method may be used in which an indane bisphenol compound is reacted with epihalohydrin in the presence of a basic catalyst.

[0024] Examples of the indane bisphenol compound include a compound represented by the following general formula (2) and a compound represented by the following general formula (5).

[0025] [ka] ····(2)

[0026] [In formula (2), each Rc is independently a monovalent functional group represented by the following structural formula (3) or (4), and at least one Rc has a hydrogen atom at the ortho position. Each Rb is independently an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and r is an integer value of 0 to 3.]

[0027] [ka] ····(3)

[0028] [ka] ····(4)

[0029] [ka] ····(5) [In formula (5), each Ra independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, q is an integer value of 0 to 4, and x is 1 or 2.]

[0030] The compound of general formula (2) and the compound of general formula (5) are reacted in the presence of an acid catalyst to obtain an indane bisphenol compound represented by the following general formula (6): where Ra, Rb, q, r, x, and n are as defined above.

[0031] [ka] ····(6)

[0032] In the indane skeleton (see general formula (7) below) which is a characteristic of the indane bisphenol compound, the average number of repeating units n (average value) is 0.2 to 20, preferably 0.5 to 10, and more preferably 1 to 8, because a curable resin composition can be obtained which has excellent alkali developability and is capable of forming a cured product which is excellent in elongation, adhesion, and dielectric properties.

[0033] [ka] ····(7)

[0034] Examples of compounds represented by the general formula (2) (hereinafter referred to as "compound (a)") include p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene, p- and m-bis(α-chloroisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene, and mixtures thereof. Nuclear alkyl group-substituted products of these compounds, such as diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, can also be used, as can nuclear halogen-substituted products, such as chlorodiisopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene.

[0035] Other examples of the compound (a) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 5-bromo-1 ,3-Diisopropenylbenzene, 5-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methoxy-1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzenethiol, 2,4-biisopropenylbenzene Bis(α-hydroxyisopropyl)benzenethiol, 2,5-diisopropenylbenzenethiol, 2,5-bis(α-hydroxyisopropyl)benzenethiol, 2-methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis(α-hydroxyisopropyl)benzene, 2-phenylthio-1,3-diisopropenylbenzene, 2-phenylthio-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis(α-hydroxyisopropyl)benzene Benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene, 5-cyclohexyl-1,Examples include 3-diisopropenylbenzene and 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene.

[0036] The substituent contained in the compound (a) is not particularly limited, and the compounds exemplified above can be used. However, in the case of a substituent with large steric hindrance, stacking of the resulting indane bisphenol compounds is less likely to occur and crystallization of the indane bisphenol compounds is less likely to occur compared to a substituent with small steric hindrance. In other words, the solvent solubility of the indane bisphenol compound is improved, which is a preferred embodiment.

[0037] The compound represented by the above general formula (5) (hereinafter referred to as "compound (b)") is phenol or a derivative thereof, for example, cresols such as o-cresol, m-cresol, and p-cresol; phenol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and pt-butylphenol; p-pentylphenol, p Examples of suitable phenols include alkylphenols such as p-octylphenol, p-nonylphenol, and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; mono-substituted phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; and polyhydric phenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, and phloroglucinol. These phenols or their derivatives may be used alone or in combination of two or more. Among these, the use of compounds such as 2,6-xylenol and 2,4-xylenol, which are alkyl-substituted at two of the ortho and para positions relative to the phenolic hydroxyl group, is preferred. However, excessive steric hindrance may inhibit the reactivity of the indane bisphenol compound during synthesis. Therefore, it is preferable to use, for example, a compound (b) having an alkyl group having 1 to 4 carbon atoms.

[0038] Examples of the method for producing an indane bisphenol compound represented by the general formula (6) include a method in which the compound (a) and the compound (b) are charged in a molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a)) of preferably 0.1 to 10, more preferably 0.2 to 8, and reacted in the presence of an acid catalyst to obtain an indane bisphenol compound having an indane skeleton.

[0039] Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acid. These acid catalysts can be used alone or in combination of two or more. Furthermore, homogeneous catalysts such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid (especially p-toluenesulfonic acid) are preferred because they can be easily removed after the reaction by neutralization with a base and washing with water.

[0040] The amount of the acid catalyst to be added is preferably in the range of 0.001 to 40 parts by mass, and more preferably 0.001 to 5 parts by mass from the viewpoint of economy, relative to 100 parts by mass of the total amount of the compound (a) and the compound (b) that are initially charged as raw materials.

[0041] The reaction temperature in the production of the indane bisphenol compound represented by the general formula (6) is usually in the range of 50 to 300°C, but in order to suppress the formation of isomeric structures, avoid side reactions such as thermal decomposition, and obtain a high-purity indane bisphenol compound, a temperature of 80 to 200°C is preferred.

[0042] Regarding the reaction time in the production of the indane bisphenol compound represented by the above general formula (6), the reaction does not proceed completely if it is short, and if it is long, side reactions such as thermal decomposition of the product occur. Therefore, under the above reaction temperature conditions, the reaction time is usually preferably in the range of 0.5 to 24 hours in total, and more preferably in the range of 0.5 to 12 hours in total.

[0043] In the method for producing an indane bisphenol compound, since phenol or its derivative also serves as a solvent, other solvents do not necessarily have to be used, but it is possible to use a solvent. For example, in the case of a reaction system that also serves as a dehydration reaction, specifically, when a compound having an α-hydroxypropyl group is reacted as a raw material, a method may be adopted in which an azeotropically dehydratable solvent such as toluene, xylene, or chlorobenzene is used, the dehydration reaction is completed, the solvent is distilled off, and then the reaction is carried out within the above reaction temperature range.

[0044] Examples of organic solvents that can be used to synthesize the indane bisphenol compound include ketone compounds such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ether compounds such as dioxane and tetrahydrofuran; ester compounds such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0045] The hydroxyl equivalent of the indane bisphenol compound is preferably 100 to 1,000 g / equivalent, more preferably 150 to 800 g / equivalent, because this provides a curable resin composition that has excellent alkali developability and is capable of forming a cured product that is excellent in elongation, adhesion, and dielectric properties. The hydroxyl equivalent of the indane bisphenol compound refers to the value calculated by neutralization titration in accordance with JIS K 0070 (1992).

[0046] 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.

[0047] 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. In particular, alkali metal hydroxides are preferred because of their excellent catalytic activity in the epoxy resin synthesis reaction, such as sodium hydroxide and potassium hydroxide.When used, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

[0048] The reaction between the indane bisphenol compound and the epihalohydrin can be carried out, for example, by adding 1 to 10 moles of the epihalohydrin per mole of hydroxyl groups contained in the indane bisphenol compound, and then adding 0.9 to 2 moles of a basic catalyst per mole of hydroxyl groups of the indane bisphenol compound all at once or gradually, and carrying out the reaction for 0.5 to 10 hours at a temperature of 20 to 120° C. The basic catalyst may be a solid or an aqueous solution thereof. When an aqueous solution is used, the basic catalyst may be added continuously, and water and epihalohydrin may be continuously distilled from the reaction mixture under reduced pressure or normal pressure, followed by liquid separation to remove water and continuously return the epihalohydrin to the reaction mixture.

[0049] The reaction rate of the epoxy resin synthesis can be increased by using an organic solvent during the epoxidation reaction. Examples of such organic solvents include, but are not limited to, ketone compounds such as acetone and methyl ethyl ketone; alcohol compounds such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol; cellosolve compounds such as methyl cellosolve and ethyl cellosolve; ether compounds such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents may be used alone or in combination with two or more of them to adjust the polarity.

[0050] 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.

[0051] 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.

[0052] When the indane bisphenol epoxy resin is industrially produced, all of the epihalohydrin used for charging in the first batch of epoxy resin production is fresh, but from the next batch onwards, it is preferred to use epihalohydrin recovered from the crude reaction product in combination with fresh epihalohydrin equivalent to the amount consumed and lost in the reaction.

[0053] After the epoxidation reaction is complete, the reaction product is washed with water and the unreacted epihalohydrin and the organic solvent used are distilled off under heated and reduced pressure. To further reduce the hydrolyzable halogen content in the resulting indane bisphenol-type epoxy resin, the indane bisphenol-type epoxy resin can be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added for further reaction. To improve the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When a phase transfer catalyst is used, its amount is preferably in the range of 0.1 to 3% by mass relative to the indane bisphenol-type epoxy resin used. After the reaction is complete, the resulting salt is removed by filtration or washing with water, and the organic solvent is distilled off under heated and reduced pressure to obtain the desired indane bisphenol-type epoxy resin with a low hydrolyzable chlorine content.

[0054] After the reaction is complete, the reaction product is washed with water, and unreacted epihalohydrin and the organic solvent used are distilled off under heated and reduced pressure conditions. Furthermore, to further reduce the hydrolyzable halogen content in the resulting indane bisphenol-type epoxy resin, the indane bisphenol-type epoxy resin can be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added for further reaction. 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 parts by mass per 100 parts by mass of the indane bisphenol-type epoxy resin used. After the reaction is complete, the resulting salt is removed by filtration or washing with water, and the organic solvent is distilled off under heated and reduced pressure conditions to obtain the desired indane bisphenol-type epoxy resin.

[0055] The epoxy equivalent of the indane bisphenol type epoxy resin is preferably 150 to 1000 g / equivalent, and more preferably 200 to 800 g / equivalent, because a curable resin composition can be obtained that has excellent alkali developability and is capable of forming a cured product that is excellent in elongation, adhesion, and dielectric properties.

[0056] The softening point of the indane bisphenol type epoxy resin is preferably 200°C or lower, more preferably 30 to 180°C, because a curable resin composition can be obtained that has excellent alkali developability and is capable of forming a cured product that is excellent in elongation, adhesion, and dielectric properties.

[0057] 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 (8) can also be used.

[0058] [ka] [In formula (8), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

[0059] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0060] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (X-1).

[0061] [ka] [In formula (X-1), R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0062] 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.

[0063] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (X-2).

[0064] [ka] [In formula (X-2), R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0065] The molecular weight of the compound represented by the general formula (8) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0066] These unsaturated monobasic acids (B) can be used alone or in combination of two or more kinds.

[0067] 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 elongation, adhesion, and dielectric properties can be obtained.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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 alkaline developability and can form a cured product that is excellent in elongation, adhesion, and dielectric properties.

[0073] 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 elongation, adhesion, and dielectric properties can be obtained.

[0074] 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.

[0075] Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0076] 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.

[0077] 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 elongation, adhesion, and dielectric properties.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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 elongation, adhesion, and dielectric properties can be obtained.

[0082] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of suitable organic solvents include alcohol solvents such as ethanol 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 ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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 epoxy resins having an acid group and a polymerizable unsaturated group, urethane resins having an acid group and a polymerizable unsaturated group, acrylic resins having an acid group and a polymerizable unsaturated group, amide-imide resins having an acid group and a polymerizable unsaturated group, acrylamide resins having an acid group and a polymerizable unsaturated group, and ester resins having an acid group and a polymerizable unsaturated group.

[0094] Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

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

[0096] 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.

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

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

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

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

[0101] 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.

[0102] 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.

[0103] 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.

[0104] [ka] [In formula (9), each R1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Each R2 is 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.]

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

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

[0107] 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.

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

[0109] Examples of the urethane resin having an acid group and a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and, if necessary, a polybasic acid anhydride, with a polyol compound other than the polyol compound having a carboxyl group; and those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polybasic acid anhydride, and a polyol compound other than the polyol compound having a carboxyl group.

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

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

[0112] Examples of the polyol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The polyol compound having a carboxyl group can be used alone or in combination of two or more kinds.

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

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

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

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

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

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

[0119] The acrylic resin intermediate may be 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.

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

[0121] The polybasic acid anhydride 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.

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

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

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

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

[0126] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with 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.

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

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

[0129] As the polybasic acid anhydride, the same 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.

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

[0131] 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.

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

[0133] 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.

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

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

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

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

[0138] The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (10-1) to (10-4).

[0139] [ka]

[0140] In the above general formulas (10-1) to (10-4), R1 is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and R2 is each independently a hydrogen atom or a methyl group. p is an integer of 0 or 1 or greater, 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 greater, preferably 2 or 3. The position of the substituent on the aromatic ring in the above general formulas is arbitrary. For example, in the naphthalene ring of general formula (10-2), the substituent may be on any ring; in general formula (10-3), the substituent may be on any ring of the benzene ring present in one molecule; and in general formula (10-4), 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.

[0141] The compound having a phenolic hydroxyl group may also be, for example, a reaction product obtained by using, as essential reaction raw materials, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general formulas (x-1) to (x-5): Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule.

[0142] [ka]

[0143] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R3 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is each independently any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (x-5), Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer of 1 to 4.]

[0144] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0145] 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 elongation, adhesion, and dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

[0146] 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 elongation, adhesion, and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used.

[0171] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0179] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] The integrated light quantity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m2, and more preferably 0.5 to 10 kJ / m2. When the integrated light quantity is within the above range, it is preferable because generation or suppression of uncured portions can be prevented.

[0187] Note that the irradiation of the active energy rays may be performed in one step or may be performed in two or more steps.

[0188] In addition, since the cured product of the present invention has excellent alkali developability and is excellent in elongation, adhesion, and dielectric properties, for example, in semiconductor device applications, solder resist, interlayer insulating material, package material, underfill material, package adhesion layers such as circuit elements, and integrated circuit elements and circuit boards. It can be suitably used as an adhesive layer. Further, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. in thin display applications typified by LCD and OELD. Among these, it can be particularly suitably used for solder resist applications.

[0189] 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, and then exposing it to active energy rays through a photomask having a desired pattern, developing the unexposed portion with an aqueous alkali solution, and further heating and curing it in a temperature range of about 140 to 200°C.

[0190] Examples of the substrate include metal-clad laminates such as copper and aluminum.

Examples

[0191] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below. <Evaluation of GPC measurement)> Measurements were performed using the following measuring equipment and conditions, and GPC charts (FIGS. 1 and 2) were obtained for the indane bisphenol compound (1) and indane bisphenol-type epoxy resin (A-1) obtained in the following Synthesis Examples. From the results of the GPC charts, the average number of repeating units (n) contributing to the indane skeleton in the indane bisphenol compound was calculated based on the number-average molecular weight (Mn) of the indane bisphenol compound. (Note that the average number of repeating units (n) of the indane bisphenol-type epoxy resin is the same as the average number of repeating units (n) of the indane bisphenol compound.) Specifically, for compounds where n is 0 to 4, the theoretical molecular weight and each measured molecular weight in GPC were plotted on a scatter diagram, an approximation line was drawn, and the number-average molecular weight (Mn) was determined from the point on the line indicated by the measured value (Mn(1)), and n was calculated. 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℃ 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: A tetrahydrofuran solution (50 μl) containing 1.0 mass % of the indane bisphenol compound (1) and the indane bisphenol epoxy resin (A-1) obtained in the synthesis example shown below, converted into a solid content, was filtered through a microfilter.

[0192] <Softening point> Measurement method: The softening points (° C.) of the indane bisphenol type epoxy resins obtained in the synthesis examples shown below were measured according to JIS K7234 (ring and ball method).

[0193] (Synthesis Example 1: Synthesis of indane bisphenol compound (1)) A flask equipped with a stirrer, Dean-Stark apparatus, condenser, and nitrogen inlet was charged with 244 parts by mass of 2,6-xylenol, 388 parts by mass of m-bis(α-hydroxyisopropyl)benzene, 633 parts by mass of toluene, and 19 parts by mass of paratoluenesulfonic acid monohydrate, and heated while nitrogen gas was blown in. The temperature was raised to 120 °C and held for 10 hours while removing the water generated during the reaction using a Dean-Stark apparatus. After cooling, the reaction mixture was neutralized with 49% aqueous sodium hydroxide until the pH was neutral. After washing with water to remove the catalyst residue, the mixture was heated and reduced pressure was used to distill off the volatiles, yielding indane bisphenol compound (1). The average repeating unit number n of the resulting indane bisphenol compound (1) was 1.50, and the hydroxyl equivalent weight was 342 g / eq. A GPC chart of the resulting indane bisphenol compound (1) is shown in Figure 1.

[0194] [ka] ····(1)

[0195] (Synthesis Example 2: Synthesis of indane bisphenol type epoxy resin (A-1)) A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas. 342 parts by mass of the indane bisphenol compound (1) obtained in Synthesis Example 1 (hydroxyl equivalent: 342 g / equivalent), 370 parts by mass of epichlorohydrin, and 27 parts by mass of n-butanol were charged and dissolved. After heating to 50°C, 220 parts by mass of a 20% aqueous sodium hydroxide solution was added over 3 hours, and the mixture was further reacted at 50°C for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 800 parts by mass of methyl isobutyl ketone and 120 parts by mass of n-butanol were added and dissolved. To this solution, 15 parts by mass of a 10 wt% aqueous sodium hydroxide solution was added, and the mixture was reacted at 80°C for 2 hours. The mixture was then washed with 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 indane bisphenol-type epoxy resin (A-1). The softening point of the obtained indane bisphenol-type epoxy resin (A-1) was 73°C, the epoxy equivalent was 419 g / equivalent, and the average number of repeating units n was the same as that of indane bisphenol compound (1). The GPC chart of the obtained indane bisphenol-type epoxy resin (A-1) is shown in Figure 2.

[0196] [ka] ····(A-1)

[0197] (Synthesis Example 3: Production of phenolic resin (r1)) A flask equipped with a stirrer, a condenser, and a nitrogen inlet was charged with 360 parts by weight of α-naphthol, 586 parts by weight of toluene, and 377 parts by weight of bischloromethylbiphenyl while blowing in nitrogen gas and heated to 80°C. 245 parts by weight of 49% aqueous sodium hydroxide solution was added dropwise over 1 hour, then the mixture was heated to 90°C and held for 11 hours. The mixture was neutralized using 85% phosphoric acid until the pH was neutral, stirring was stopped, and the lower layer was removed. 15 parts by weight of paratoluenesulfonic acid was added, and the mixture was heated to 180°C over 2 hours while distilling off the volatile components. The mixture was then neutralized using 49% aqueous sodium hydroxide solution until the pH was neutral. The pressure was reduced while maintaining the internal temperature, and the volatile components were distilled off to obtain phenolic resin (r1). The hydroxyl group equivalent was 272 g / eq.

[0198] (Synthesis Example 4: Production of Epoxy Resin (A-2)) A flask equipped with a thermometer, a condenser, and a stirrer was charged with 272 parts by weight of the phenolic resin (r1) obtained in Synthesis Example 3, 740 parts by weight of epichlorohydrin, and 53 parts by weight of n-butanol, and dissolved while purging with nitrogen gas. After heating to 50°C, 220 parts by weight of 20% aqueous sodium hydroxide was added over 3 hours, and the mixture was then allowed to react at 50°C for an additional 1 hour. After the reaction was completed, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 600 parts by weight of methyl isobutyl ketone and 100 parts by weight of n-butanol were added and dissolved. 15 parts by weight of 10 wt% aqueous sodium hydroxide was added to the solution, and the mixture was allowed to react for 2 hours at 80°C. The mixture was then repeatedly washed with 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 epoxy resin (A-2). The resulting epoxy resin (A-2) had a softening point of 100°C and an epoxy equivalent of 325 g / equivalent.

[0199] (Synthesis Example 5: Preparation of Resin (D-1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of diethylene glycol monoethyl ether acetate and dissolved in 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). 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 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 reacted at 110°C for 3 hours to obtain Resin (D) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this Resin (D-1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

[0200] (Example 1: Preparation of Resin (1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 122.8 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 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 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Subsequently, 212.8 parts by weight of diethylene glycol monoethyl ether acetate and 132.2 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.87 moles.

[0201] (Example 2: Preparation of Resin (2) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 122.8 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 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 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Subsequently, 184.7 parts by weight of diethylene glycol monoethyl ether acetate and 80.0 parts by weight of succinic anhydride were added, and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (2) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 82 mgKOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.80 moles.

[0202] (Example 3: Preparation of Resin (3) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 122.8 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 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 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Subsequently, 213.8 parts by weight of diethylene glycol monoethyl ether acetate and 134.0 parts by weight of hexahydroisobenzofuran-1,3-dione were added, and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (3) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1 mole, and the number of moles of hexahydroisobenzofuran-1,3-dione relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.87 moles.

[0203] (Example 4: Preparation of Resin (4) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 122.8 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 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 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Subsequently, 219.4 parts by weight of diethylene glycol monoethyl ether acetate and 144.4 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (4) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 86 mgKOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.95 moles.

[0204] (Example 5: Preparation of Resin (5) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 122.8 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 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 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Subsequently, 192.4 parts by weight of diethylene glycol monoethyl ether acetate and 94.2 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (5) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 61 mgKOH / g. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.62 moles.

[0205] (Example 6: Preparation of Resin (6) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 121.9 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 68.4 parts by weight of acrylic acid and 2.4 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 8 hours while blowing in air. Subsequently, 214.3 parts by weight of diethylene glycol monoethyl ether acetate and 136.8 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (6) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (6) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 78 mgKOH / g. The number of moles of acid groups in acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.95 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.90 moles.

[0206] (Example 7: Preparation of Resin (7) Having Acid Group and Polymerizable Unsaturated Group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123.7 parts by weight of diethylene glycol monoethyl ether acetate, and 419 parts by weight of the indane bisphenol-type epoxy resin (A-1) obtained in Synthesis Example 2 was dissolved therein. 1.0 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 75.6 parts by weight of acrylic acid and 2.5 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 8 hours while blowing in air. Subsequently, 210.6 parts by weight of diethylene glycol monoethyl ether acetate and 126.2 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours to obtain the desired resin (7) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (7) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The number of moles of acid groups in acrylic acid relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 1.05 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of epoxy groups in the indane bisphenol type epoxy resin (A-1) was 0.83 moles.

[0207] (Comparative Example 1: Production of Resin (R1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 99.3 parts by weight of diethylene glycol monoethyl ether acetate, and 325 parts by weight of the epoxy resin (A-2) obtained in Synthesis Example 4 was dissolved therein. 0.8 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 2.0 parts by weight of triphenylphosphine. The mixture was then reacted at 120 °C for 10 hours while blowing in air. Subsequently, 171.8 parts by weight of diethylene glycol monoethyl ether acetate and 106.4 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110 °C for 3 hours to obtain the desired resin (R1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (R1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mg KOH / g.

[0208] (Example 8: Preparation of curable resin composition (1)) 100 parts by mass (65 parts by mass as solids) of the resin (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).

[0209] (Examples 9 to 15: Preparation of curable resin compositions (2) to (8)) Curable resin compositions (2) to (8) were obtained in the same manner as in Example 8, except that the resins (2) to (7) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 7 were used in the amounts shown in Table 1 instead of the resin (1) having an acid group and a polymerizable unsaturated group used in Example 8.

[0210] (Comparative Example 2: Preparation of curable resin composition (R1)) A curable resin composition (R1) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (R1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Comparative Example 1, 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.

[0211] The curable resin compositions (1) to (8) and (R1) obtained in the above examples and comparative examples were evaluated as follows.

[0212] [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, or 110 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 for 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.

[0213] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (8) prepared in Examples 8 to 15 and the curable resin composition (R1) prepared in Comparative Example 2.

[0214] [Table 1]

[0215] (Example 16: Preparation of curable resin composition (9)) A curable resin composition (9) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (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).

[0216] (Examples 17 to 23: Preparation of curable resin compositions (10) to (16)) Curable resin compositions (10) to (16) were obtained in the same manner as in Example 16, except that resins (2) to (7) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 7 were used in the blending amounts shown in Table 2 instead of resin (1) having an acid group and a polymerizable unsaturated group used in Example 16.

[0217] (Comparative Example 3: Preparation of curable resin composition (R2)) A curable resin composition (R2) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (R1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Comparative Example 1, 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).

[0218] The following evaluations were carried out using the curable resin compositions (9) to (16) and (R2) obtained in the above examples and comparative examples.

[0219] [Method for measuring elongation] The elongation was measured based on a tensile test. <Preparation of test piece 1> The curable resin compositions obtained in the Examples and Comparative Examples were applied to copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, irradiated with ultraviolet light at 10 kJ / m using a metal halide lamp, and then heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product).

[0220] <Tensile test> The test piece 1 was cut into a size of 10 mm × 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured.

[0221] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between supports 20mm, tensile speed 10mm / min

[0222] [Method for evaluating adhesion] The adhesion was evaluated by measuring the peel strength. <Preparation of test piece 2> The curable resin compositions obtained in the Examples and Comparative Examples were applied to copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, irradiated with ultraviolet light of 10 kJ / m2 using a metal halide lamp, and then heated at 160°C for 1 hour to obtain test piece 2.

[0223] <Method for measuring peel strength> The test piece 2 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength was measured using a peel tester ("A&D Tensilon" manufactured by A&D Co., Ltd., peel speed 50 mm / min).

[0224] [Method for measuring dielectric constant] 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 dried at 80°C for 30 minutes. Next, the composition was irradiated with 10 kJ / m2 of ultraviolet light using a metal halide lamp and then heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The specimens were then stored for 24 hours in a room at 23°C and 50% humidity, and their dielectric constants at 1 GHz were measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. using a cavity resonance method.

[0225] [Method for measuring dielectric loss tangent] 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 dried at 80°C for 30 minutes. Next, the composition was irradiated with 10 kJ / m2 of ultraviolet light using a metal halide lamp and then heated at 160°C for 1 hour to obtain a cured coating. The cured coating was then peeled off from the glass substrate to obtain a cured product. The specimens were then stored for 24 hours in a room at 23°C and 50% humidity, and their dielectric loss tangents at 1 GHz were measured using an Agilent Technologies Network Analyzer E8362C by the cavity resonance method.

[0226] Table 2 shows the compositions and evaluation results of the curable resin compositions (13) to (24) prepared in Examples 24 to 35 and the curable resin compositions (R3) and (R4) prepared in Comparative Examples 5 and 6.

[0227] [Table 2]

[0228] In Tables 1 and 2, the parts by mass of the resin having an acid group and a polymerizable unsaturated group are solid content values.

[0229] "Curing agent" in Tables 1 and 2 refers to an orthocresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0230] "Organic solvent" in Tables 1 and 2 refers to diethylene glycol monoethyl ether acetate.

[0231] The "photopolymerization initiator" in Tables 1 and 2 refers to "Omnirad-907" manufactured by IGM Resins.

[0232] Examples 8 to 15 shown in Table 1 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that these curable resin compositions had excellent alkaline developability.

[0233] Furthermore, Examples 16 to 23 shown in Table 2 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that the cured products of these curable resin compositions had excellent elongation, adhesion, and dielectric properties.

[0234] On the other hand, Comparative Examples 2 and 3 shown in Tables 1 and 2 are examples of curable resin compositions that do not use an indane bisphenol epoxy resin having an indane skeleton represented by general formula (1) as a raw material for the resin having an acid group and a polymerizable unsaturated group. It was confirmed that the cured product of the curable resin composition obtained in Comparative Example 3 was insufficient in elongation, adhesion, and dielectric properties.

Claims

1. an indane bisphenol type epoxy resin (A) having an indane skeleton represented by the following general formula (1); 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. 【Chemical 1】 ・・・（１） (In the above formula (1), each Ra independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; q is 2; each Ra may be the same or different within the same ring; each Rb independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; and r represents an integer value of 0 to 3. When r is 2 or 3, each Rb may be the same or different within the same ring; and n is the average number of repeating units and represents a value of 0.2 to 20.)

2. 2. The resin having an acid group and a polymerizable unsaturated group according to claim 1, 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).

3. 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).

4. A curable resin composition comprising the resin having an acid group and a polymerizable unsaturated group according to any one of claims 1 to 3 and a photopolymerization initiator.

5. The curable resin composition according to claim 4, 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.

6. A cured product of the curable resin composition according to claim 4 or 5.

7. An insulating material comprising the cured product according to claim 6.

8. A resist member comprising the cured product according to claim 6.

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