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

Abstract

To provide a resin and a curable resin composition which have excellent alkali developability, and have excellent adhesion and dielectric characteristics in a cured product, a cured product of the curable resin composition, an insulation material, and a resist member.SOLUTION: A resin having an acid group and a polymerizable unsaturated group contains an indane bisphenol resin (A) having an indane skeleton represented by general formula (1), a (meth)acrylate compound (B) having an epoxy group, and a polybasic acid anhydride (C) as essential reaction raw materials.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, curable compositions, such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat, have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. In particular, for the coating agent applications, it is generally required that the compositions be capable of imparting design features to the surfaces of various substrates, have excellent curability, and be capable of forming coating films that can prevent deterioration of the substrate surfaces. Furthermore, in recent years, the industrial world has been demanding materials that can form cured coating films that not only have curability but also elongation, adhesion, a low dielectric constant, a low dielectric dissipation factor, and alkaline developability.

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

[0004] Therefore, there has been a demand for a material that has excellent alkaline developability and is capable of forming a cured product that has excellent elongation, adhesion, and dielectric properties. [Prior art documents] [Patent documents]

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

[0006] The problem to be solved by the present invention is to provide a resin having an acid group and a polymerizable unsaturated group, which has excellent alkaline developability, and in a cured product thereof has excellent 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]

[0007] As a result of intensive research into solving 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 phenolic resin, a compound having an epoxy group, and a polybasic acid anhydride as essential reaction raw materials, and have thus completed the present invention.

[0008] That is, 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 resin (A) having an indane skeleton represented by the following general formula (1), a (meth)acrylate compound (B) having an epoxy group, 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.

[0009] [ka] (In the above general 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 hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 or 3, Ra may be the same or different within the same ring. n represents the average number of repeating units and represents a value of 0.2 to 20. A 11 and A 12each independently represents a group selected from the following general formulae (A2) to (A6).

[0010] [ka] (In the above general formulas (A2) to (A6), Rb's each independently represent 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, or a mercapto group; q1's each independently represent an integer value of 0 to 4, and q2's each independently represent an integer value of 0 to 8. When q1 is 2 to 4 and when q2 is 2 to 8, Rb's may be the same or different within the same ring. Rc's each independently represent a hydrogen atom or a methyl group. * represents a connection point with general formula (1); x1's each independently represent an integer value of 1 to 5, and x2's each independently represent an integer value of 1 to 9.) [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 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 resin (A-1) obtained in Synthesis Example 1. 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 a phenolic resin (A), a (meth)acrylate compound having an epoxy group (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 phenol resin (A) is represented by the following general formula (1).

[0016] [ka] (In the above general 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 hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 or 3, Ra may be the same or different within the same ring. n represents the average number of repeating units and represents a value of 0.2 to 20. A 11 and A 12 each independently represents a group selected from the following general formulae (A2) to (A6).

[0017] [ka] (In the above general formulas (A2) to (A6), Rb's each independently represent 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, or a mercapto group; q1's each independently represent an integer value of 0 to 4, and q2's each independently represent an integer value of 0 to 8. When q1 is 2 to 4 and when q2 is 2 to 8, Rb's may be the same or different within the same ring. Rc's each independently represent a hydrogen atom or a methyl group. * represents a connection point with general formula (1); x1's each independently represent an integer value of 1 to 5, and x2's each independently represent an integer value of 1 to 9.)

[0018] Examples of the alkyl group in the general formula (1) and general formulae (A2) to (A6) 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.

[0019] Examples of the aryl group in the general formula (1) and general formulae (A2) to (A6) 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.

[0020] In the general formula (1), it is preferable that r is 0 and each of the Ra's is a hydrogen atom, and it is also preferable that r is 1 to 3 and each of the Ra's 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 Ra is a hydrogen atom, steric hindrance is reduced during the formation of the indane skeleton in the phenolic resin (A), which is advantageous for the production (synthesis) of the phenolic resin (A) and is a preferred embodiment.

[0021] A in the above general formula (1) 11 and A 12each independently represents a group selected from the general formulae (A2) to (A6). In the general formulae (A2), (A4), to (A6), q1 each independently represents an integer value of 0 to 4. In the general formulae (A2), (A4), to (A6), q1 is preferably an integer value of 0 to 2, and more preferably 0 or 2. In the general formula (A3), q2 is an integer value of 0 to 8. In the general formula (A3), q2 is preferably an integer value of 0 to 2, and more preferably 0 or 2. When q1 and q2 are other than 0, Rb is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. By using the alkyl group having 1 to 4 carbon atoms, the planarity and crystallinity in the vicinity of the phenol group are reduced, which improves solvent solubility. This is a preferred embodiment in which a cured product can be obtained without impairing the reactivity of the phenol group.

[0022] In the general formula (1), n ​​is the average number of repeating units and is a value of 0.2 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.

[0023] In the above general formulae (A2) to (A6), * represents the point of connection to general formula (1), and the other end is connected to any part of the ring structure of general formulae (A2) to (A6).

[0024] In the above general formulas (A2) to (A6), x1 represents an integer value of 1 to 5, and x2 represents an integer value of 1 to 9. When general formula (A2) is used, x1 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. When general formula (A3) is used, x2 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. When any of general formulas (A4) to (A6) is used, it is preferable that both of the two x1s are 1 or 2.

[0025] In the above general formula (1), A 11 and A12 are preferably groups each having the same structure selected from general formulae (A2) to (A6), and A 11 and A 12 are preferably groups represented by general formula (A2), general formula (A3) or general formula (A5), and A 11 and A 12 are more preferably groups represented by general formula (A2) or general formula (A5), and the preferred embodiments of Rb, Rc, q1, q2, x1, and x2 when groups represented by these general formulas are used are as described above.

[0026] The phenolic resin (A) can be produced by a method such as a conventional method for producing a polyfunctional phenolic resin.

[0027] As the indane bisphenol compound constituting the phenol resin (A), for example, an indane bisphenol compound represented by the following general formula (6) can be obtained by reacting a compound represented by the following general formula (2) with a compound selected from the following general formulas (5-A2) to (5-A6) in the presence of an acid catalyst.

[0028] [ka]

[0029] [In general formula (2), each Rd is independently a monovalent functional group represented by the following structural formula (3) or (4), and the ortho-position of at least one Rd is a hydrogen atom. Each Ra 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.]

[0030] [ka]

[0031] [ka]

[0032] [ka] (In the above general formulas (5-A2) to (5-A6), 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 nitro group, or a mercapto group; each q1 independently represents an integer value of 0 to 4, and q2 independently represents an integer value of 0 to 8. When q1 is 2 to 4 and when q2 is 2 to 8, Rbs may be the same or different within the same ring. Each Rc independently represents a hydrogen atom or a methyl group. * represents a connection point with the above general formula (2); each x1 independently represents an integer value of 1 to 5, and x2 independently represents an integer value of 1 to 9.)

[0033] As described above, the compound of the general formula (2) above can be reacted with a compound selected from the general formulae (5-A2) to (5-A6) above in the presence of an acid catalyst to obtain an indane bisphenol compound represented by the following general formula (6). 11 , A 12 , Ra, Rb, q1, r, x1 and n are the same as those defined in the general formula (1) above.

[0034] [ka]

[0035] 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 1 to 10, and more preferably 1 to 5, 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.

[0036] [ka]

[0037] 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.

[0038] 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.

[0039] 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.

[0040] The compounds represented by the above general formulae (5-A2) to (5-A6) (hereinafter referred to as "compound (b)") are phenols or derivatives thereof, such as cresols such as o-cresol, m-cresol, and p-cresol; phenols; 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-octylphenol, and p-nonylphenol. Examples of suitable phenols include alkylphenols such as p-cumylphenol 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; bisphenols such as bisphenol A, bisphenol C, bisphenol E, bisphenol F, and bisphenol S; 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 in which two of the ortho- and para-positions relative to the phenolic hydroxyl group are alkyl-substituted, such as 2,6-xylenol and 2,4-xylenol, is more preferred. However, if the steric hindrance is too large, there is a concern that the reactivity during synthesis of the indane bisphenol compound may be inhibited, so it is preferable to use, for example, a compound (b) having an alkyl group having 1 to 4 carbon atoms.

[0041] Examples of the method for producing an indane bisphenol compound represented by the general formula (1) 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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).

[0049] The (meth)acrylate compound (B) having an epoxy group is not particularly limited in structure, as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Among these, glycidyl (meth)acrylate and / or 4-hydroxybutyl (meth)acrylate glycidyl ether and / or epoxycyclohexylmethyl (meth)acrylate are preferred. These (meth)acrylate compounds having an epoxy group can be used alone or in combination.

[0050] The amount of the (meth)acrylate compound (B) having an epoxy group used is preferably in the range of 0.9 to 1.1 moles, more preferably 0.95 to 1.1 moles, of the epoxy groups in the (meth)acrylate compound (B) having an epoxy group per mole of the phenolic hydroxyl groups in the phenolic resin (A), because 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] The amount of the polybasic acid anhydride (C) used is preferably in the range of 0.2 to 1.05 mol, more preferably 0.3 to 0.95, and even more preferably 0.3 to 0.9 mol per mol of the phenolic hydroxyl groups in the phenolic 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.

[0057] The resin having an acid group and a polymerizable unsaturated group of the present invention can also use, as raw materials, compounds other than the phenolic resin (A), the (meth)acrylate compound having an epoxy group (B), and the polybasic acid anhydride (C), if necessary.

[0058] Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0059] 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.

[0060] The total mass proportion of the phenolic resin (A), the (meth)acrylate compound (B) having an epoxy group, 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.

[0061] 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 phenolic resin (A), the (meth)acrylate compound having an epoxy group (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 phenolic resin (A) and the (meth)acrylate compound having an epoxy group (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.

[0062] The reaction of the phenolic resin (A), the (meth)acrylate compound (B) having an epoxy group, 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.

[0063] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. Examples of suitable ammonium salts include quaternary ammonium salts such as octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts can be used alone or in combination of two or more. When used, these basic catalysts can be used in the form of an aqueous solution of about 10 to 55 mass %, or in the form of a solid.

[0064] 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 total of the phenolic resin (A), the (meth)acrylate compound having an epoxy group (B), and the polybasic acid anhydride (C), because 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (11) can also be used.

[0085] [ka] [In general formula (11), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in its structure. Y represents a hydrogen atom or a methyl group.]

[0086] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0087] An example of the (poly)ester chain is a (poly)ester chain represented by the following structural formula (12).

[0088] [ka] [In general formula (12), R 1 are each independently an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0089] 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.

[0090] These unsaturated monobasic acids can be used alone or in combination of two or more.

[0091] 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.

[0092] 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.

[0093] [ka] [In formula (9), R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[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 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (4-1) to (4-5).

[0128] [ka]

[0129] In the above structural formulas (4-1) to (4-5), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (4-2), the substituent may be on any ring; in structural formula (4-3), the substituent may be on any ring of the benzene ring present in one molecule; in structural formula (4-4), the substituent may be on any ring of the benzene ring present in one molecule; and in structural formula (4-5), the substituent may be on any ring of the benzene ring present in one molecule; and p and q indicate the number of substituents in one molecule.

[0130] The compound having a phenolic hydroxyl group may also be, for example, a reaction product obtained by using a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (5-1) to (5-5) and / or formaldehyde as essential reaction raw materials. Also usable are novolac-type phenolic resins obtained by using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials.

[0131] [ka]

[0132] [In structural formula (5-1), h is 0 or 1. In structural formulas (5-2) to (5-5), R 1is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer of 1 to 4. In structural formulas (5-2), (5-3), and (5-5), each W is independently any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (5-5), V is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer of 1 to 4.

[0133] Specific examples of the compounds represented by the above general formulas (5-1) to (5-5) and the reaction products thereof include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzyl phenol ... Examples of the phenol resin include benzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

[0134] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0149] 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.

[0150] 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.

[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] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid (B) can be used.

[0161] The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0169] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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 carried out in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

[0175] 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.

[0176] The integrated light quantity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 and more preferably 0.5 to 10 kJ / m 2 . When the integrated light quantity is within the above range, it is preferable because generation or suppression of uncured portions can be prevented.

[0177] Note that the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

[0178] In addition, the cured product of the present invention has excellent alkali developability and is excellent in elongation, adhesion, and dielectric properties. Therefore, for example, in semiconductor device applications, it can be suitably used as a solder resist, an interlayer insulating material, a package material, an underfill material, a package adhesive layer such as a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. Also, in thin display applications typified by LCD and OELD, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer, and the like. Among these, it can be particularly suitably used for solder resist applications.

[0179] The resist member of the present invention can be obtained, for example, by applying the resin material for solder resist on a substrate, volatilizing and drying an organic solvent in a temperature range of about 60 to 100°C, then exposing with active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed portions with an aqueous alkali solution, and further heating and curing in a temperature range of about 140 to 200°C.

[0180] Examples of the substrate include metal-clad laminated boards such as copper and aluminum.

Examples

[0181] 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 a GPC chart (Figure 1) of the indane bisphenol resin (A-1) obtained in the following synthesis example was obtained. From the results of the GPC chart, the average number of repeating units n contributing to the indane skeleton in the indane bisphenol resin was calculated based on the number-average molecular weight (Mn) of the indane bisphenol resin. Specifically, for compounds where n is 0 to 4, the theoretical molecular weight and the 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°C Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution (50 μl) containing 1.0 mass % of the indane bisphenol resin (A-1) obtained in the synthesis example shown below, calculated as a solid content, was filtered through a microfilter.

[0182] <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).

[0183] (Synthesis Example 1: Synthesis of indane bisphenol resin (A-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 2,2'-(1,3-phenylene)bis(propan-2-ol), 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 6 hours, while the water generated during the reaction was removed using a Dean-Stark apparatus. After cooling, the reaction solution was neutralized with 49% aqueous sodium hydroxide until the pH was neutral. After washing with water to remove catalyst residue, the volatiles were distilled off by heating and reduced pressure to obtain indane bisphenol resin (A-1). The average repeating unit number n of the resulting indane bisphenol resin (A-1) was 1.5, and the hydroxyl equivalent was 342 g / eq. A GPC chart of the resulting indane bisphenol resin (A-1) is shown in Figure 1.

[0184] [ka]

[0185] (Synthesis Example 2: Synthesis of indane bisphenol resin (A-2)) A flask equipped with a stirrer, Dean-Stark apparatus, condenser, and nitrogen inlet was charged with 220 parts by weight of resorcinol, 194 parts by weight of 2,2'-(1,3-phenylene)bis(propan-2-ol), 414 parts by weight of toluene, 83 parts by weight of methanol, and 3 parts by weight of paratoluenesulfonic acid monohydrate while blowing in nitrogen gas. The mixture was stirred at 50°C for 20 hours. After cooling the reaction solution, 414 parts by weight of methyl isobutyl ketone was added and the mixture was neutralized with 49% aqueous sodium hydroxide solution until the pH was neutral. After removing the catalyst residue by washing with water, the volatiles were distilled off by heating and reducing the pressure to obtain indane bisphenol resin (A-2). The average repeating unit number (n) of the resulting indane bisphenol resin (A-2) was 1, and the hydroxyl group equivalent was 120 g / eq.

[0186] (Synthesis Example 3: Synthesis of indane bisphenol resin (A-3)) A flask equipped with a stirrer, Dean-Stark apparatus, condenser, and nitrogen inlet was charged with 220 parts by weight of resorcinol, 259 parts by weight of 2,2'-(1,3-phenylene)bis(propan-2-ol), 479 parts by weight of toluene, 96 parts by weight of methanol, and 3 parts by weight of paratoluenesulfonic acid monohydrate while blowing in nitrogen gas. The mixture was stirred at 50°C for 20 hours. After cooling the reaction solution, 479 parts by weight of methyl isobutyl ketone was added and the mixture was neutralized using 49% aqueous sodium hydroxide until the pH was neutral. After removing the catalyst residue by washing with water, the volatiles were distilled off by heating and reducing the pressure to obtain indane bisphenol resin (A-3). The average repeating unit number (n) of the resulting indane bisphenol resin (A-3) was 1.7, and the hydroxyl equivalent was 138 g / eq.

[0187] (Synthesis Example 4: Synthesis of indane bisphenol resin (A-4)) A flask equipped with a stirrer, Dean-Stark apparatus, condenser, and nitrogen inlet was charged with 320 parts by mass of 2,7-dihydroxynaphthalene, 582 parts by mass of 2,2'-(1,3-phenylene)bis(propan-2-ol), 902 parts by mass of xylene, and 16 parts by mass of paratoluenesulfonic acid monohydrate, and heated while nitrogen gas was blown in. The temperature was raised to 140°C and held for 6 hours, while the water generated during the reaction was removed using a Dean-Stark apparatus. After cooling, the reaction solution was neutralized with 49% aqueous sodium hydroxide until the pH was neutral. After washing with water to remove catalyst residue, the volatiles were distilled off by heating and reduced pressure to obtain indane bisphenol resin (A-4). The average repeating unit number n of the resulting indane bisphenol resin (A-4) was 1.5, and the hydroxyl group equivalent was 242 g / equivalent.

[0188] (Synthesis Example 5: Production of Resin (C-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 monomethyl ether acetate, and 214 parts by weight of orthocresol novolac epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) (hereinafter referred to as "epoxy resin (1)") was dissolved therein. 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 72 parts by weight of diethylene glycol monomethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (C-1) having acid groups and polymerizable unsaturated groups. The resin (C-1) having an acid group and a polymerizable unsaturated group had a nonvolatile content of 65 mass % and an acid value of the solid content of 80 mgKOH / g.

[0189] (Example 1: Preparation of Resin (B-1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 207.4 parts by weight of diethylene glycol monoethyl ether acetate, and 342 parts by weight of the indane bisphenol resin (A-1) obtained in Synthesis Example 1 was dissolved therein. 1.2 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 2.4 parts by weight of triethylamine. The mixture was then reacted at 120°C for 15 hours while blowing in air. Next, 122.8 parts by weight of diethylene glycol monoethyl ether acetate and 122.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 2.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 82 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-1) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-1) was 0.85 moles.

[0190] (Example 2: Preparation of Resin (B-2) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 113.5 parts by weight of diethylene glycol monoethyl ether acetate, and 120 parts by weight of the indane bisphenol resin (A-2) obtained in Synthesis Example 2 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.3 parts by weight of triethylamine. The mixture was then reacted at 120°C for 20 hours while blowing in air. Next, 66.4 parts by weight of diethylene glycol monoethyl ether acetate and 69.9 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.3 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-2) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-2) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-2) was 0.46 moles.

[0191] (Example 3: Preparation of Resin (B-3) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was then reacted at 120°C for 20 hours while blowing in air. Next, 70.9 parts by weight of diethylene glycol monoethyl ether acetate and 74.5 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-3) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.49 moles.

[0192] (Example 4: Preparation of Resin (B-4) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 164.6 parts by weight of diethylene glycol monoethyl ether acetate, and 242 parts by weight of the indane bisphenol resin (A-4) obtained in Synthesis Example 4 was dissolved therein. 1 part by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.9 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into the mixture. Next, 97 parts by weight of diethylene glycol monoethyl ether acetate and 101.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.9 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-4) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 82 mgKOH / g. Furthermore, the number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-4) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-4) was 0.67 moles.

[0193] (Example 5: Preparation of Resin (B-5) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was then reacted at 120°C for 20 hours while blowing in air. Next, 70.9 parts by weight of diethylene glycol monoethyl ether acetate and 74.5 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (B-5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-5) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 79 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.49 moles.

[0194] (Example 6: Preparation of Resin (B-6) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 118.8 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 139.2 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing in air. Next, 69.7 parts by weight of diethylene glycol monoethyl ether acetate and 73 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-6) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-6) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.98 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.48 moles.

[0195] (Example 7: Preparation of Resin (B-7) 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 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 149.1 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing in air. Next, 72.5 parts by weight of diethylene glycol monoethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-7) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-7) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1.05 moles, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.5 moles.

[0196] (Example 8: Preparation of Resin (B-8) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into the mixture. Next, 54.5 parts by weight of diethylene glycol monoethyl ether acetate and 44.1 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-8) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-8) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 52 mgKOH / g. Furthermore, the number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.29 moles.

[0197] (Example 9: Preparation of Resin (B-9) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into the mixture. Next, 108.5 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 5 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-9) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-9) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 127 mgKOH / g. Furthermore, the number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of tetrahydrophthalic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.95 moles.

[0198] (Example 10: Preparation of Resin (B-10) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing in air. Next, 54.5 parts by weight of diethylene glycol monoethyl ether acetate and 44 parts by weight of succinic anhydride were added, and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added, and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-10) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-10) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. Furthermore, the number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of succinic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.44 moles.

[0199] (Example 11: Preparation of Resin (B-11) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120 parts by weight of diethylene glycol monoethyl ether acetate, and 138 parts by weight of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into it. Next, 71.4 parts by weight of diethylene glycol monoethyl ether acetate and 75.5 parts by weight of 1,2-cyclohexanedicarboxylic anhydride were added and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added and the mixture was stirred at 80°C for 1 hour to obtain a resin (B-11) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-11) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 81 mgKOH / g. Furthermore, the number of moles of epoxy groups in glycidyl methacrylate relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole, and the number of moles of 1,2-cyclohexanedicarboxylic anhydride relative to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 0.49 moles.

[0200] (Example 12: Preparation of curable resin composition (1)) A curable resin composition (1) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (B-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Example 1, 20.1 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.8 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, 3.3 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.

[0201] (Examples 13 to 23: Preparation of curable resin compositions (2) to (12)) Curable resin compositions (2) to (12) were obtained in the same manner as in Example 12, except that the resins (B-2) to (B-11) and (C-1) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 11, etc. were used in the blending amounts shown in Tables 1 and 2, instead of the resin (B-1) having an acid group and a polymerizable unsaturated group used in Example 12.

[0202] (Comparative Example 1: Preparation of curable resin composition (C1)) A curable resin composition (C1) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (C-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Synthesis Example 5 above, 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, 3.3 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.

[0203] The curable resin compositions (1) to (12) and (C1) obtained in the above examples and comparative examples were evaluated as follows.

[0204] [Method for evaluating alkaline developability] The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 minutes, respectively, to prepare samples with different drying times. These were then developed with a 1% by mass aqueous sodium carbonate solution at 30°C for 180 seconds, and the drying time at 80°C of samples that left no residue on the substrate was evaluated as the drying control range. Note that a longer drying control range indicates better alkaline developability.

[0205] Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (12) prepared in Examples 12 to 23 and the curable resin composition (C1) prepared in Comparative Example 1.

[0206] [Table 1]

[0207] [Table 2]

[0208] (Example 24: Preparation of curable resin composition (13)) A curable resin composition (13) 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, 20.1 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 10.8 parts by mass of diethylene glycol monoethyl ether acetate, and 3.3 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins).

[0209] (Examples 25 to 35: Preparation of curable resin compositions (14) to (24)) Curable resin compositions (13) to (24) were obtained in the same manner as in Example 24, except that the resins (B-2) to (B-11) having an acid group and a polymerizable unsaturated group obtained in Examples 1 to 11 were used in the blending amounts shown in Tables 3 and 4 instead of the resin (1) having an acid group and a polymerizable unsaturated group used in Example 1.

[0210] (Comparative Example 2: Preparation of curable resin composition (C2)) A curable resin composition (C2) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (C-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Synthesis Example 5 above, 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 3.3 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins).

[0211] The curable resin compositions (13) to (24) and (C2) obtained in the above Examples and Comparative Examples were evaluated as follows.

[0212] [Method for evaluating adhesion] The adhesion was evaluated by measuring the peel strength. <Preparation of test specimens> The curable resin compositions obtained in the examples and comparative examples were applied onto copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then heated at 10 kJ / m using a metal halide lamp. 2 After irradiating with ultraviolet light, the specimen was heated at 160°C for 1 hour to obtain a test piece.

[0213] <Method for measuring peel strength> The test piece 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).

[0214] [Method for measuring dielectric constant] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored for 24 hours in a room at 23°C and 50% humidity to prepare a test piece. The dielectric constant of the test piece at 1 GHz was measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. by the cavity resonance method.

[0215] [Method for measuring dielectric loss tangent] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0216] (Examples 24 to 35, Comparative Example 2) Tables 3 and 4 show the compositions and evaluation results of the curable resin compositions (13) to (24) prepared in Examples 24 to 35 and the curable resin composition (C2) prepared in Comparative Example 2.

[0217] [Table 3]

[0218] [Table 4]

[0219] In Tables 1 to 4, the parts by mass of the resin having an acid group and a polymerizable unsaturated group are solid content values.

[0220] "Curing agent" in Tables 1 to 4 refers to an orthocresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0221] "Organic solvent" in Tables 1 to 4 refers to diethylene glycol monoethyl ether acetate.

[0222] "Photopolymerization initiator" in Tables 1 to 4 refers to "Omnirad 907" manufactured by IGM Resins.

[0223] Examples 12 to 23 shown in Tables 1 and 2 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that these curable resin compositions had excellent alkaline developability.

[0224] Furthermore, Examples 24 to 35 shown in Tables 3 and 4 are examples of curable resin compositions using the resin of the present invention having an acid group and a polymerizable unsaturated group. It was confirmed that the cured products of these curable resin compositions had excellent elongation, adhesion, and dielectric properties.

[0225] On the other hand, Comparative Examples 1 and 2 shown in Tables 2 and 4 are examples of curable resin compositions that do not use an indane bisphenol 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 2 had insufficient adhesion and dielectric properties.

Claims

1. an indane bisphenol resin (A) having an indane skeleton represented by the following general formula (1); a (meth)acrylate compound (B) having an epoxy group; 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. 【Chemistry 1】 (In the above general 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 hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 or 3, Ra may be the same or different within the same ring. n represents the average number of repeating units and represents a value of 0.2 to 20. １１ and A １２ each independently represents a group selected from the following general formulas (A2) to (A3): 【Chemistry 2】 (In the above general formulas (A2) to (A3), Rb's each independently represent 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, or a mercapto group; q1's each independently represent an integer value of 0 to 4, and q2's each independently represent an integer value of 0 to 8. When q1 is 2 to 4 and when q2 is 2 to 8, Rb's may be the same or different within the same ring. * represents a connection point with general formula (1); each x1's independently represent an integer value of 1 to 5, and x2's each independently represent an integer value of 1 to 9.)

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