JP7806552B2 - Resin having polymerizable unsaturated group, curable resin composition, cured product and article - Google Patents

Description

The present invention relates to a resin having a polymerizable unsaturated group, a curable resin composition, a cured product, and an article.

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, coatings, adhesives, and optical components. In particular, for coating applications, there is a general demand for compositions that can impart design features to the surface of various substrates, have excellent curing properties, and are capable of forming coating films that can prevent deterioration of the substrate surface. Furthermore, in recent years, there has been a demand in industry for materials that not only have excellent heat resistance in the cured product but also excellent dielectric properties.

A known conventional active energy ray-curable composition is a photosensitive resin composition containing an epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride (see, for example, Patent Document 1). However, this composition does not satisfy the increasingly high heat resistance requirements, and its dielectric properties are also insufficient to meet current market demands.

Therefore, there was a need for a material that not only had heat resistance but also excellent dielectric properties.

Japanese Patent Application Publication No. 8-259663

The problem that the present invention aims to solve is to provide a resin having a polymerizable unsaturated group that can form a cured product with excellent adhesion and dielectric properties, a curable resin composition, a cured product, and an article.

As a result of extensive research into resolving the above-mentioned problems, the inventors discovered that the above-mentioned problems could be solved by using a resin having a polymerizable unsaturated group, the essential reaction ingredients of which were a specific phenolic resin and a (meth)acrylate compound having an epoxy group, and thus completed the present invention.

That is, the present invention relates to a resin having a polymerizable unsaturated group, a curable resin composition, a cured product, and an article, characterized in that the essential reaction raw materials are a phenolic resin (A) represented by the following general formula (1) and a (meth)acrylate compound (B) having an epoxy group.

(In the above general formula (1), Ra each 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; 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 is the average number of repeating units and represents a value of 0.2 to 20. A ₁₁ and A ₁₂ each independently represent a group selected from the following general formulae (A2) to (A6).)

(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.)

The resin having a polymerizable unsaturated group of the present invention can form a cured product with excellent adhesion and dielectric properties. Therefore, a curable resin composition containing the resin having a polymerizable unsaturated group and a photopolymerization initiator can be suitably used as a coating agent or adhesive. In this invention, "excellent dielectric properties" refers to a low dielectric constant and a low dielectric loss tangent.

FIG. 1 is a GPC chart of the indane bisphenol resin (A-1) obtained in Synthesis Example 1.

The resin having a polymerizable unsaturated group of the present invention is characterized by having a phenolic resin (A) and a (meth)acrylate compound having an epoxy group (B) as essential reaction raw materials.

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

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

(In the above general formula (1), Ra each 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; 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 is the average number of repeating units and represents a value of 0.2 to 20. A ₁₁ and A ₁₂ each independently represent a group selected from the following general formulae (A2) to (A6).)

(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.)

Examples of the alkyl group in general formula (1) and general formulas (A2) to (A6) include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and cyclohexyl groups.

Examples of the aryl group in general formula (1) and general formulas (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.

In the above general formula (1), it is preferable that r is 0 and each of the Ra's is a hydrogen atom. 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.

A ₁₁ and A ₁₂ in the general formula (1) each independently represent 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, but in the general formulae (A2), (A4) to (A6), q1 is preferably 0 to 2, and more preferably 0 or 2. In the general formula (A3), q2 is an integer value of 0 to 8, but is preferably 0 to 2, and more preferably 0 or 2. When q1 and q2 are other than 0, it is preferable that Rb is either 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. When Rb is an alkyl group having 1 to 4 carbon atoms or the like, the planarity and crystallinity in the vicinity of the phenol group are reduced, thereby improving solvent solubility and enabling a cured product to be obtained without impairing the reactivity of the phenol group.

In the above general formula (1), n is the average number of repeating units and is a value between 0.2 and 20, but n is preferably between 1 and 10, more preferably between 1 and 5, and even more preferably between 1 and 2.

In the above general formulas (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 formulas (A2) to (A6).

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. However, when general formula (A2) is used, x1 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. When general formula (A3) is used, x2 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. Furthermore, when any of general formulas (A4) to (A6) is used, it is preferable that both of the two x1s are 1 or 2.

In the above general formula (1), A ₁₁ and A ₁₂ are preferably both groups representing the same structure selected from general formulae (A2) to (A6), A ₁₁ and A ₁₂ are preferably both groups represented by general formula (A2), general formula (A3) or general formula (A5), A ₁₁ and A ₁₂ are more preferably both groups represented by general formula (A2) or general formula (A5), and preferred aspects of Rb, Rc, q1, q2, x1 and x2 when groups represented by these general formulae are adopted are as described above.

Examples of the production method for the phenolic resin (A) include methods for producing conventional polyfunctional phenolic resins.

As the indane bisphenol compound constituting the phenolic 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.

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

(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.)

By reacting the compound of general formula (2) above with a compound selected from the general formulae (5-A2) to (5-A6) above in the presence of an acid catalyst, it is possible to obtain, for example, an indane bisphenol compound represented by the following general formula (6): In general formula (6), A ₁₁ , A ₁₂ , Ra, Rb, q1, r, x1, and n are the same as defined in general formula (1).

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 this allows for the production of a curable resin composition capable of forming a cured product with excellent elongation, adhesion, and dielectric properties.

Examples of compounds represented by the above 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.

Other examples of 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, and 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-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, 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-1,3-diisopropenylbenzene, 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene, etc.

The substituents contained in compound (a) are not particularly limited, and the compounds exemplified above can be used. However, when the substituents have a 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 than when the substituents have a small steric hindrance. In other words, the solvent solubility of the indane bisphenol compounds is improved, making this a preferred embodiment.

The compounds represented by the above general formulas (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 p-t-butylphenol; p-pentylphenol, p-octylphenol, and p-nonylphenol. Examples of suitable phenols include alkylphenols such as benzophenone 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 derivatives thereof 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 a more preferred embodiment. However, if the steric hindrance is too great, there is a concern that it may inhibit the reactivity during the synthesis of the indane bisphenol compound, so it is preferable to use, for example, a compound (b) having an alkyl group with 1 to 4 carbon atoms.

Examples of methods for producing an indane bisphenol compound represented by the above general formula (6) include a method in which compound (a) and compound (b) are charged in a molar ratio of compound (b) to 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.

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.

The amount of the acid catalyst is preferably in the range of 0.001 to 40 parts by mass per 100 parts by mass of the total amount of the initially charged raw materials, compound (a) and compound (b), and from an economic standpoint, 0.001 to 5 parts by mass is more preferable.

The reaction temperature for producing the indane bisphenol compound represented by the above 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.

When producing the indane bisphenol compound represented by the general formula (6) above, the reaction will not proceed completely if the reaction time is short, and side reactions such as thermal decomposition of the product will occur if the reaction time is long. Therefore, under the reaction temperature conditions described above, a total reaction time of 0.5 to 24 hours is usually preferred, and a total reaction time of 0.5 to 12 hours is more preferred.

In the method for producing an indane bisphenol compound, since phenol or its derivative doubles as a solvent, it is not necessary to use other solvents, but it is possible to use a solvent. For example, in the case of a reaction system that also performs a dehydration reaction, specifically when a compound having an α-hydroxypropyl group is used as a raw material, a method can be used 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 the reaction is then carried out within the reaction temperature range mentioned above.

Organic solvents 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.

The hydroxyl group equivalent of the indane bisphenol compound is preferably 100 to 1,000 g/equivalent, and more preferably 150 to 800 g/equivalent, since this results in a curable resin composition that can form a cured product with excellent elongation, adhesion, and dielectric properties. The hydroxyl group equivalent of the indane bisphenol compound is calculated using the neutralization titration method in accordance with JIS K 0070 (1992).

The (meth)acrylate compound (B) having an epoxy group is not particularly limited in its specific structure, as long as it contains 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 of two or more.

The amount of the (meth)acrylate compound (B) having an epoxy group used is preferably in the range where the number of moles of epoxy groups in the (meth)acrylate compound (B) having an epoxy group is 0.9 to 1.1 moles per mole of phenolic hydroxyl groups in the phenolic resin (A), and more preferably 0.95 to 1.1 moles, since this results in an epoxy (meth)acrylate resin capable of forming a cured product with excellent elongation, adhesion, and dielectric properties.

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

Examples of the other compounds include unsaturated monobasic acid anhydrides.

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

The total mass proportion of the phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group in the raw material (solid content) of the resin having a polymerizable unsaturated group of the present invention is preferably 60 mass% or more, since this results in a resin having a polymerizable unsaturated group that can form a cured product having adhesive properties and dielectric properties.

The resin having a polymerizable unsaturated group of the present invention may be produced by any method without particular limitations. For example, a preferred production method involves reacting all of the reaction raw materials containing the phenolic resin (A) and the (meth)acrylate compound having an epoxy group (B) all at once in the presence of an acidic or basic catalyst at a temperature in the range of 70 to 140°C.

Furthermore, the reaction between the phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group can also be carried out in an organic solvent, if necessary.

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 containing strong acids such as sulfonyl groups can also be used. These acid catalysts can be used alone or in combination of two or more.

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, ... Examples of suitable quaternary ammonium salts include 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. Additionally, 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% by mass, or in solid form.

The amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, and more preferably in the range of 0.05 to 0.8 parts by mass, per 100 parts by mass of the phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group, since this results in a resin having a polymerizable unsaturated group that can form a cured product with excellent adhesion and dielectric properties.

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 propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; 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.

In addition, commercially available products can also be used as the organic solvent. Examples of commercially available products include "No. 1 Spindle Oil,""No. 3 Solvent,""No. 4 Solvent,""No. 5 Solvent,""No. 6 Solvent,""NaphtesolH,""Alkene56NT,""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 may be used alone or in combination of two or more. In the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, in order to improve the reaction efficiency.

The organic solvent may also be used in combination with water. In this case, the ratio of water used in the mixed solvent is preferably in the range of 5 to 60 parts by weight, and more preferably 10 to 50 parts by weight, per 100 parts by weight of the mixed solvent.

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

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

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

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

The curable resin composition of the present invention may contain resin components other than the resin having a polymerizable unsaturated group of the present invention described above (hereinafter, these may be referred to as "other resin components"). Examples of such other resin components include epoxy resins, resins having a polymerizable unsaturated group, and (meth)acrylate compounds, which are resin constituents.

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.

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.

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

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

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

The resin having a polymerizable unsaturated group may be any resin that has a polymerizable unsaturated group within it, and examples thereof include epoxy resins having a polymerizable unsaturated group, urethane resins having a polymerizable unsaturated group, acrylic resins having a polymerizable unsaturated group, amide-imide resins having a polymerizable unsaturated group, acrylamide resins having a polymerizable unsaturated group, and ester resins having a polymerizable unsaturated group.

Examples of epoxy resins having polymerizable unsaturated groups include epoxy (meth)acrylate resins obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, a polybasic acid anhydride, and epoxy (meth)acrylate resins having urethane groups obtained by reacting an epoxy resin with an unsaturated monobasic acid, a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polybasic acid anhydride.

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

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.

[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 the structure. Y represents a hydrogen atom or a methyl group.]

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

An example of the (poly)ester chain is the (poly)ester chain represented by the following structural formula (12):

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

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

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

Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

Examples of the aliphatic polybasic acid anhydrides include the anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,2,3,4-butanetetracarboxylic acid. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydrides may be either linear or branched, and may contain unsaturated bonds within the structure.

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

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

These polybasic acid anhydrides can be used alone or in combination of two or more.

Examples of the polyisocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, Examples of suitable polyisocyanate compounds 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 polyisocyanates having a repeating structure represented by the following general formula (9); and isocyanurate-, biuret-, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

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

The (meth)acrylate compound that is a component of the resin is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof 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; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate; and heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate. mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 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, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)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; Oxyalkylene-modified mono(meth)acrylate compounds; 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; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. alicyclic di(meth)acrylate compounds such as those listed above; 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-modified tri(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 tri(meth)acrylate compound; 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 compound; tetra- or higher functional aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, or dipentaerythritol hexa(meth)acrylate; aliphatic poly(meth)acrylate compounds in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, or the like has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; (Poly)oxyalkylene-modified poly(meth)acrylate compounds having tetrafunctional or higher functional groups in which a (poly)oxyalkylene chain such as a tramethylene chain has been introduced; lactone-modified poly(meth)acrylate compounds having tetrafunctional or higher functional groups in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; 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 di(meth)acrylate, (Meth)acrylate compounds having a hydroxyl group, such as dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (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 above-mentioned (meth)acrylate compounds having a hydroxyl group; lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned (meth)acrylate compounds having a hydroxyl group; 2-acryloyl Examples of suitable (meth)acrylate compounds include (meth)acrylate compounds having an isocyanate group, such as 2-hydroxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and (meth)acrylate compounds having an epoxy group, such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These various (meth)acrylate monomers can be used alone or in combination of two or more.

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

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

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

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

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

The (meth)acrylate compound having a hydroxyl group can be the same as the above-mentioned examples of the (meth)acrylate compound having a hydroxyl group, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

Examples of the polyol compounds 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; lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various polyol compounds; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds can be used alone or in combination of two or more.

The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydrides can be used alone or in combination of two or more.

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

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

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

Examples of the acrylic resin having 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, carboxyl group, isocyanate group, or 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, if necessary, a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

The acrylic resin intermediate may be obtained by copolymerizing the (meth)acrylate compound (α) with, 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.

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 standpoint of reactivity. That is, when water (meth)acrylate 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 water (meth)acrylate 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 compounds (β) can be used alone or in combination of two or more types.

The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydrides can be used alone or in combination of two or more.

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

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

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

Examples of the amide-imide resin having 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 a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the standpoint of reactivity and reaction control with (meth)acrylate compounds having hydroxyl groups and epoxy compounds having (meth)acryloyl groups, 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 that do not cause ring-opening of the acid anhydride group), is preferably in the range of 60 to 350 mg KOH/g. On the other hand, it is preferable for the acid value measured under conditions that cause ring-opening of the acid anhydride group, such as in the presence of water, to be in the range of 61 to 360 mg KOH/g.

Examples of the amide-imide resin include those obtained by reacting a polyisocyanate compound with a polybasic acid anhydride.

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

The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydrides can be used alone or in combination of two or more.

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

Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid. Examples include 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, and 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 of two or more.

The (meth)acrylate compound having a hydroxyl group can be the same as the above-mentioned examples of the (meth)acrylate compound having a hydroxyl group, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

Examples of the (meth)acrylate compound having an epoxy group 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. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more.

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

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

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

Examples of the acrylamide resin having 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, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

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

In the 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, and R ² is each independently a hydrogen atom or a methyl group. p is 0 or an integer of 1 or greater, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or greater, preferably 2 or 3. The position of the substituent on the aromatic ring in the structural formulas 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.

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

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

Specific examples of the compounds represented by the above general formulas (5-1) to (5-5) and the reaction products 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 include benzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether diol, polynaphthylene ether diol, phenol novolac resin, cresol novolac resin, bisphenol novolac resin, naphthol novolac resin, phenol aralkyl resin, naphthol aralkyl resin, and phenol resins having a cyclocyclic structure.

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

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 produces a curable resin composition that can form a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

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 allows for the production of a curable resin composition that can form a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more types.

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

The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydrides can be used alone or in combination of two or more.

The unsaturated monobasic acids can be the same as those exemplified above, and the unsaturated monobasic acids can be used alone or in combination of two or more.

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

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

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

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

Examples of the ester resin having 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, if necessary, a polybasic acid anhydride.

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

The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can yield a curable resin composition capable of forming a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene oxides may be used alone or in combination of two or more.

The alkylene carbonate may be the same as those exemplified above. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a curable resin composition capable of forming a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene carbonates may be used alone or in combination of two or more.

The unsaturated monobasic acids can be the same as those exemplified above, and the unsaturated monobasic acids can be used alone or in combination of two or more.

The polybasic acid anhydride can be the same as those exemplified above, and the polybasic acid anhydrides can be used alone or in combination of two or more.

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

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

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

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

The amount of the other resin components 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.

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

The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus-based compounds, amine-based 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% by mass of the solid content of the curable resin composition.

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

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

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

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.

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

Examples of inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

The pigment may be any known or commonly used inorganic or organic pigment.

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

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.

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

Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphate 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. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma 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 to efficiently carry out the ultraviolet curing reaction.

As a source of ultraviolet light, ultraviolet lamps are commonly used due to their practicality and economical efficiency. 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.

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

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

In addition, because the cured product of the present invention has excellent elongation, adhesion, and dielectric properties, it can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, packaging adhesive layer for circuit elements, etc., or as an adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCDs and OELDs as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. Among these, it is particularly suitable for use as a solder resist.

The article of the present invention has a coating film made of the cured product. Examples of such articles include plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.
<Evaluation of GPC Measurement>
Measurements were performed using the following measuring equipment and conditions, and a GPC chart (FIG. 1) was obtained for the indane bisphenol resin (A-1) obtained in the following Synthesis Example. 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 each measured molecular weight in GPC were plotted on a scatter diagram, an approximation line was drawn, and the number-average molecular weight (Mn) was determined from the point on the line indicated by the measured value Mn(1), and n was calculated.
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation
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: 1.0 ml/min. Standard: The following monodisperse polystyrene with known molecular weight was used in accordance with the measurement manual for the "GPC Workstation EcoSEC-Workstation."
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
Tosoh Corporation "F-4"
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
Tosoh Corporation "F-40"
"F-80" manufactured by Tosoh Corporation
Tosoh Corporation "F-128"
Sample: A tetrahydrofuran solution of 1.0% by mass (solid content equivalent) of the indane bisphenol resin (A-1) obtained in the synthesis example shown below was filtered through a microfilter (50 μl).

(Synthesis Example 1: Synthesis of indane bisphenol resin (A-1))
A flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a 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 blowing in nitrogen gas. The temperature was raised to 120°C and held for 6 hours, while removing water generated during the reaction using a Dean-Stark apparatus. After cooling the reaction solution, it was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. After removing catalyst residue by washing with water, volatiles were distilled off by heating and reduced pressure, yielding an 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 group equivalent was 342 g/equivalent. A GPC chart of the resulting indane bisphenol resin (A-1) is shown in Figure 1.

(Synthesis Example 2: Synthesis of indane bisphenol resin (A-2))
A flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet was charged with 220 parts by mass of resorcinol, 194 parts by mass of 2,2'-(1,3-phenylene)bis(propan-2-ol), 414 parts by mass of toluene, 83 parts by mass of methanol, and 3 parts by mass of paratoluenesulfonic acid monohydrate while blowing nitrogen gas into the flask, and the mixture was stirred at 50 ° C. for 20 hours. After cooling the reaction solution, 414 parts by mass of methyl isobutyl ketone was added, and the mixture was neutralized using a 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 an indane bisphenol resin (A-2). The average number of repeating units n of the obtained indane bisphenol resin (A-2) was 1, and the hydroxyl group equivalent was 120 g / eq.

(Synthesis Example 3: Synthesis of indane bisphenol resin (A-3))
A flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet was charged with 220 parts by mass of resorcinol, 259 parts by mass of 2,2'-(1,3-phenylene)bis(propan-2-ol), 479 parts by mass of toluene, 96 parts by mass of methanol, and 3 parts by mass of paratoluenesulfonic acid monohydrate while blowing nitrogen gas into the flask, and the mixture was stirred at 50 ° C. for 20 hours. After cooling the reaction solution, 479 parts by mass of methyl isobutyl ketone was added, and the mixture was neutralized using a 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 an indane bisphenol resin (A-3). The average number of repeating units n of the obtained indane bisphenol resin (A-3) was 1.7, and the hydroxyl group equivalent was 138 g / eq.

(Synthesis Example 4: Synthesis of indane bisphenol resin (A-4))
A flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a 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 blowing in nitrogen gas. During the reaction, the temperature was raised to 140°C and held for 6 hours while removing water generated by the reaction using a Dean-Stark apparatus. After cooling the reaction solution, it was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. After removing catalyst residue by washing with water, the volatiles were distilled off by heating and reduced pressure, yielding an 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.

(Synthesis Example 5: Production of Resin (C-1) Having a Polymerizable Unsaturated Group)
A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of butyl 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 abbreviated 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 the addition of 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The reaction was carried out at 120°C for 10 hours while blowing in air, yielding a resin (C-1) having a polymerizable unsaturated group. The nonvolatile content of this resin (C-1) having a polymerizable unsaturated group was 70% by weight.

(Example 1: Production of Resin (B-1) Having a Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 207.4 parts by weight of butyl 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 the addition of 142 parts by weight of glycidyl methacrylate and 2.4 parts by weight of triethylamine. The reaction was carried out for 15 hours at 120 ° C. while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-1) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar ratio of epoxy groups in the glycidyl methacrylate to 1 mole of phenolic hydroxyl groups in the indane bisphenol resin (A-1) was 1 mole.

(Example 2: Production of Resin (B-2) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 113.5 parts by weight of butyl 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 the addition of 142 parts by weight of glycidyl methacrylate and 1.3 parts by weight of triethylamine. The reaction was carried out at 120 ° C. for 20 hours while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-2) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar number of epoxy groups in the glycidyl methacrylate per mole of phenolic hydroxyl groups in the indane bisphenol resin (A-2) was 1 mole.

(Example 3: Production of Resin (B-3) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 120 parts by weight of butyl 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 the addition of 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The reaction was carried out at 120 ° C. for 20 hours while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-3) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar number of epoxy groups in the glycidyl methacrylate per mole of phenolic hydroxyl groups in the indane bisphenol resin (A-3) was 1 mole.

(Example 4: Production of Resin (B-4) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 164.6 parts by weight of butyl 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 the addition of 142 parts by weight of glycidyl methacrylate and 1.9 parts by weight of triethylamine. The reaction was carried out at 120 ° C. for 20 hours while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-4) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar ratio of epoxy groups in the glycidyl methacrylate to 1 mole of phenolic hydroxyl groups in the indane bisphenol resin (A-4) was 1 mole.

(Example 5: Production of Resin (B-5) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 120 parts by mass of butyl acetate, and 138 parts by mass of the indane bisphenol resin (A-3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by the addition of 142 parts by mass of glycidyl methacrylate and 1.4 parts by mass of triethylamine. The reaction was carried out at 120°C for 20 hours while blowing in air. The nonvolatile content of this resin (B-5) having a polymerizable unsaturated group was 70% by mass. Furthermore, the molar ratio of epoxy groups in glycidyl methacrylate to 1 mole of phenolic hydroxyl groups in indane bisphenol resin (A-3) was 1 mole.

(Example 6: Production of Resin (B-6) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 118.8 parts by weight of butyl 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 the addition of 139.2 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The reaction was carried out at 120 ° C. for 20 hours while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-6) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar number of epoxy groups in the glycidyl methacrylate per mole of phenolic hydroxyl groups in the indane bisphenol resin (A-3) was 0.98 moles.

(Example 7: Production of Resin (B-7) Having Polymerizable Unsaturated Group)
A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of butyl 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 the addition of 149.1 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The reaction was carried out at 120 ° C. for 20 hours while blowing in air. 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 a polymerizable unsaturated group. The nonvolatile content of this resin (B-7) having a polymerizable unsaturated group was 70% by weight. Furthermore, the molar ratio of epoxy groups in glycidyl methacrylate to 1 mole of phenolic hydroxyl groups in the indane bisphenol resin (A-3) was 1.05 moles.

(Example 8: Preparation of curable resin composition (1))
100 parts by mass (70 parts by mass as solids) of the resin (B-1) having a polymerizable unsaturated group and having a nonvolatile content of 70% by mass obtained in Example 1, 30 parts by mass of an acrylate monomer, 5 parts by mass of a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins), and 1.6 parts by mass of 2-ethyl-4-methylimidazole were mixed to obtain a curable resin composition (1).

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

(Comparative Example 1: Preparation of curable resin composition (C1))
A curable resin composition (C1) was obtained by mixing 100 parts by mass (70 parts by mass as solids) of the resin (C-1) having a polymerizable unsaturated group and having a nonvolatile content of 70% by mass obtained in Synthesis Example 5 above, 30 parts by mass of an acrylate monomer, 5 parts by mass of a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins), and 1.6 parts by mass of 2-ethyl-4-methylimidazole.

The following evaluations were carried out using the curable resin compositions (1) to (8) and (C1) obtained in the above examples and comparative examples.

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

<Method for measuring peel strength>
The test piece 1 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 rate 50 mm/min).

[Method for measuring dielectric constant]
The curable resin compositions obtained in each example and comparative example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 30 minutes. Next, the composition was irradiated with 10 kJ/ ^m2 ultraviolet light using a metal halide lamp, and then heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The specimens were then stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours to prepare test specimens, and the dielectric constant of the test specimens at 1 GHz was measured by a cavity resonance method using a Network Analyzer E8362C manufactured by Agilent Technologies, Inc.

[Method for measuring dielectric loss tangent]
The curable resin compositions obtained in each example and comparative example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 30 minutes. Next, the composition was irradiated with 10 kJ/ ^m2 ultraviolet light using a metal halide lamp, and then heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The specimens were then stored in a room at 23°C and 50% humidity for 24 hours to prepare test pieces, and the dielectric loss tangent of the test pieces at 1 GHz was measured by the cavity resonance method using a Network Analyzer E8362C manufactured by Agilent Technologies, Inc.

The compositions and evaluation results of the curable resin compositions (1) to (8) prepared in Examples 8 to 15 and the curable resin composition (C1) prepared in Comparative Example 1 are shown in Table 1.

The parts by mass of resins having polymerizable unsaturated groups in Table 1 are solids values.

In Table 1, "Acrylate Monomer" refers to an EO-modified diacrylate of bisphenol A ("Miramaer M240" manufactured by Miwon Specialty Chemical Co., Ltd.).

The "photopolymerization initiator" in Table 1 refers to "Omnirad 907" manufactured by IGM Resins.

Examples 8 to 15 shown in Table 1 are examples of curable resin compositions using resins having polymerizable unsaturated groups according to the present invention. It was confirmed that the cured products of these curable resin compositions have excellent adhesion and dielectric properties.

On the other hand, Comparative Example 1 shown in Table 1 is an example of a curable resin composition that does not use an indane bisphenol resin having an indane skeleton represented by general formula (1). It was confirmed that the cured product of this curable resin composition had insufficient adhesion and dielectric properties.

Claims (6)

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 a polymerizable unsaturated group, characterized in that the above is used as an essential reaction raw material.
(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, each Ra in the same ring may be the same or different. n is the average number of repeating units and represents a value of 0.2 to 20. A ₁₁ and A ₁₂ independently represent a group selected from the following general formulae (A2) to (A 3 ).)
(In the above general formulas (A2) to ( A3 ), 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 . * represents a connection point with general formula (1); each x1 independently represents an integer value of 1 to 5, and x2 independently represents an integer value of 1 to 9.) The resin having a polymerizable unsaturated group according to claim 1, wherein the amount of the (meth)acrylate compound (B) having an epoxy group used is in the range of 0.9 to 1.1 moles of epoxy groups per mole of phenolic hydroxyl group in the phenolic resin (A). A curable resin composition comprising the resin having a polymerizable unsaturated group according to claim 1 or 2 and a photopolymerization initiator. The curable resin composition according to claim 3, further comprising other resin components. A cured product of the curable resin composition according to claim 3 or 4. An article having a coating film made from the cured product of claim 5.