Curable resin composition, cured product and related products

Abstract

To provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric characteristics, a cured product thereof, and an article having a coating film comprising the cured product.SOLUTION: The curable resin composition which contains a curable resin (A) having an indane skeleton represented by general formula (1) and a photopolymerization initiator (B) is used. [In the formula (1), X is a polymerizable unsaturated group; Ra and Rb are each independently a C1-12 alkyl group, an aryl group, an aralkyl group or a cycloalkyl group; j is an integer of 1-3; k and l are each independently an integer of 0-4; n is an average repeating unit number and is a numerical value of 0.5-20; and m is an integer of 0-2.]SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, a cured product of the curable resin composition, and an article having a coating film made of the cured product. [Background technology]

[0002] In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. In particular, for the coating agent applications, it is generally required that the coating agent be capable of imparting design features to the surfaces of various substrates, have excellent curability, and be capable of forming a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding materials that can form cured coating films that not only have curability but also have performance such as heat resistance at a level that can protect the coated object even under various temperature environments.

[0003] Known techniques for improving the heat resistance of cured coating films include curable compositions containing di(meth)acrylates represented by the following general formula (see, for example, Patent Document 1).

[0004] [ka] [In the above formula, R1 represents a hydrogen atom or a methyl group.]

[0005] However, the heat resistance of the curable composition in the cured coating film is insufficient, and the dielectric properties do not satisfy the increasingly high performance requirements of today.

[0006] Therefore, there is a need for a material that has excellent heat resistance and dielectric properties. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-314320 Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, a cured product of the curable resin composition, and an article having a coating film made of the cured product. [Means for solving the problem]

[0009] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a curable resin composition containing a specific curable resin having an indane skeleton and a photopolymerization initiator, and have completed the present invention.

[0010] That is, the present invention relates to a curable resin composition characterized by containing a curable resin (A) having an indane skeleton represented by the following general formula (1) and a photopolymerization initiator (B), a cured product of the curable resin composition, an insulating material, and a resist member:

[0011] [ka]

[0012] [In formula (1), X represents a polymerizable unsaturated group. Ra and Rb each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, j represents an integer of 1 to 3, and k and l each independently represent an integer of 0 to 4. n represents the average number of repeating units and is a number of 0.5 to 20, and m is an integer of 0 to 2.] [Effects of the Invention]

[0013] The curable resin composition of the present invention can form a cured product having excellent heat resistance and dielectric properties, and therefore can be used as a coating agent or adhesive. As the coating agent, the composition is particularly suitable for use as a solder resist. In the present invention, "excellent dielectric properties" refer to a low dielectric constant and a low dielectric loss tangent. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a GPC chart of the curable resin having an indane skeleton obtained in Synthesis Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0015] The curable resin composition of the present invention is characterized by containing a curable resin (A) having an indane skeleton represented by general formula (1) and a photopolymerization initiator (B).

[0016] The curable resin (A) used has an indane skeleton represented by the following general formula (1).

[0017] [ka]

[0018] [In formula (1), X represents a polymerizable unsaturated group. Ra and Rb each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, j represents an integer of 1 to 3, and k and l each independently represent an integer of 0 to 4. n represents the average number of repeating units and is a number of 0.5 to 20, and m is an integer of 0 to 2.]

[0019] In the above formula (1), X is a polymerizable unsaturated group, examples of which include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, etc. Among these, a (meth)acryloyl group is preferred, and a methacryloyl group is more preferred, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0020] In the above formula (1), Ra and Rb are preferably alkyl groups, aryl groups, or cycloalkyl groups having 1 to 4 carbon atoms, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0021] In the above formula (1), j is preferably 1 or 2, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0022] In the above formula (1), k and l are preferably integers of 0 to 2, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0023] In the above formula (1), when m is 0 it is a benzene ring, when m is 1 it is a naphthalene ring, and when m is 2 it is an anthracene ring. A benzene ring in which m is 0 is preferred, as this gives a curable resin composition that can form a cured product having excellent heat resistance and dielectric properties.

[0024] In the above formula (1), n ​​is preferably from 0.5 to 5, and more preferably from 0.95 to 2.5, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0025] Furthermore, the curable resin (A) preferably has an indane skeleton represented by the following general formula (2), since this gives a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties.

[0026] [ka]

[0027] In the above formula (2), R1 and R2 are preferably an alkyl group, an aryl group, or a cycloalkyl group having 1 to 4 carbon atoms, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0028] In the above formula (2), n is preferably from 0.5 to 5, and more preferably from 0.95 to 2.5, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0029] In the above formula (2), R3 is preferably a methyl group, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0030] <Method for producing intermediate phenol compounds> As a method for producing the curable resin (A) having an indane skeleton, first, a method for producing an intermediate phenol compound, which is a raw material (precursor) of the curable resin having an indane skeleton, will be described below.

[0031] Examples of the method for producing the intermediate phenol compound include a method of reacting a compound represented by the following general formula (3) (hereinafter referred to as "compound (a)") with a compound represented by any one of the following general formulas (4-1) to (4-3) (hereinafter referred to as "compound (b)") in the presence of an acidic catalyst to obtain an intermediate phenol compound having an indane skeleton.

[0032] [ka] ····(3)

[0033] [In formula (3), R c each independently represents a monovalent functional group selected from the group consisting of the following general formulas (3-1) and (3-2), and two R cAt least one of the Rc's is ortho-positioned with a hydrogen atom. Rb's are each independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and 1 is an integer of 0 to 4.

[0034] [ka] (3-1)

[0035] [ka] (3-2)

[0036] [ka] (4-1)

[0037] [ka] (4-2)

[0038] [ka] (4-3)

[0039] [In formulas (4-1) to (4-3), each Ra is independently an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, each k is independently an integer of 0 to 4, and each i is independently 1 or 2.]

[0040] The general formula (4-1) is used when m in the general formula (1) is 0, that is, when the curable resin having an indane skeleton is a benzene ring, and i is preferably 1. The general formula (4-2) is used when m in the general formula (1) is 1, that is, when the curable resin is a naphthalene ring, and i is preferably 1. The general formula (4-3) is used when m in the general formula (1) is 2, that is, when the curable resin is an anthracene ring, and i is preferably 1.

[0041] Examples of the compound (a) include p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene (α,α'-dihydroxy-1,3-diisopropylbenzene), 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.

[0042] Other examples of the compound (a) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 5-bromo-1 ,3-Diisopropenylbenzene, 5-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methoxy-1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzenethiol, 2,4-biisopropenylbenzene Bis(α-hydroxyisopropyl)benzenethiol, 2,5-diisopropenylbenzenethiol, 2,5-bis(α-hydroxyisopropyl)benzenethiol, 2-methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis(α-hydroxyisopropyl)benzene, 2-phenylthio-1,3-diisopropenylbenzene, 2-phenylthio-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis(α-hydroxyisopropyl)benzene Benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene, 5-cyclohexyl-1,3-Diisopropenylbenzene, 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene, etc. can also be used. These compounds (a) can be used alone or in combination of two or more.

[0043] Examples of the compound (b) include cresols such as o-cresol, m-cresol, and p-cresol; phenol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol (2,6-dimethylphenol), 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and pt-butylphenol; and alkylphenols such as p-pentylphenol, p-octylphenol, p-nonylphenol, and p-cumylphenol. Examples of suitable compounds include halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; mono-substituted phenols such as o-phenylphenol, p-phenylphenol, 2-cyclohexylphenol, 2-benzylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; condensed polycyclic phenols such as 1-naphthol, 2-naphthol, 1-anthracenol, and 2-anthracenol; and polyhydric phenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, and phloroglucinol. These compounds (b) can be used alone or in combination of two or more. Among these, 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, are preferred. The use of the compounds (b) is a more preferred embodiment. However, if the steric hindrance is too large, there is a concern that the reactivity may be inhibited during the synthesis of the intermediate phenol compound, so it is preferable to use, for example, a compound (b) having an alkyl group having 1 to 4 carbon atoms.

[0044] Examples of the intermediate phenol compound include compounds represented by the following general formula (5).

[0045] [ka] ····(5)

[0046] [In formula (5), Ra and Rb each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and k and l each independently represent an integer of 0 to 4. n is the average number of repeating units and is a number of 0.5 to 20.]

[0047] In addition, the reaction of compound (a) with compound (b) in the production of the intermediate phenol compound is preferably carried out in such a manner that the molar ratio of compound (b) to compound (a) [compound (b) / compound (a)] is in the range of 0.1 to 10, more preferably 0.2 to 8.

[0048] 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 acids. Among these, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid are preferred.

[0049] The amount of the acidic catalyst to be added is in the range of 0.001 to 40 parts by mass relative to 100 parts by mass of the total amount of the compound (a) and the compound (b) that are the raw materials initially charged, and from the viewpoints of handleability and economy, the amount is preferably 0.001 to 25 parts by mass.

[0050] The reaction temperature in the reaction between the compound (a) and the compound (b) 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 intermediate phenol compound, a temperature of 80 to 200°C is preferred.

[0051] The reaction time for the reaction of the compound (a) with the compound (b) is usually in the range of 0.5 to 24 hours in total under the reaction temperature conditions, preferably in the range of 0.5 to 12 hours in total, since the reaction does not proceed completely in a short time and side reactions such as thermal decomposition of the product occur in a long time.

[0052] In the method for producing the intermediate phenol compound, since phenol or a derivative thereof also serves as a solvent, other solvents are not necessarily used, but it is possible to use a solvent. For example, in the case of a reaction system that also serves as a dehydration reaction, specifically, when a compound having an α-hydroxypropyl group is used as a raw material for the reaction, a method may be adopted in which an azeotropically dehydratable organic solvent such as toluene, xylene, or chlorobenzene is used, the dehydration reaction is completed, the solvent is distilled off, and then the reaction is carried out within the above reaction temperature range.

[0053] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; 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; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; and 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. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, as this improves reaction efficiency.

[0054] The hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is preferably 200 to 2000 g / equivalent, more preferably 220 to 500 g / equivalent, because a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. In the present invention, the hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is calculated by titration, and refers to the neutralization titration method in accordance with JIS K0070.

[0055] <Method for producing curable resin (A) having an indane skeleton> The method for producing the curable resin (A) (introduction of a (meth)acryloyl group) will be described below.

[0056] The curable resin (A) can be obtained by a known method such as reacting the intermediate phenol compound with (meth)acrylic anhydride or (meth)acrylic acid chloride in the presence of a basic catalyst or an acid catalyst.

[0057] Examples of the (meth)acrylic anhydride include acrylic anhydride and methacrylic anhydride. Examples of the (meth)acrylic acid chloride include methacrylic acid chloride and acrylic acid chloride. These (meth)acrylic anhydrides can be used alone or in combination of two or more. Among these, methacrylic anhydride is preferred because it can provide a curable resin composition that can form a cured product having excellent heat resistance and dielectric properties.

[0058] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. Examples of suitable ammonium salts include quaternary ammonium salts such as octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts can be used alone or in combination of two or more. When using the basic catalyst, it may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or in the form of a solid.

[0059] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0060] The reaction of the intermediate phenol compound with the (meth)acrylic anhydride or the (meth)acrylic acid chloride (hereinafter sometimes referred to as "(meth)acrylic anhydride, etc.") may be carried out by adding 1 to 5 moles of the (meth)acrylic anhydride, etc., per mole of hydroxyl group contained in the intermediate phenol compound, and reacting the mixture at a temperature of 30 to 150°C for 1 to 40 hours while adding 0.03 to 1 mole of a basic catalyst all at once or gradually.

[0061] Furthermore, by using an organic solvent in the reaction with (meth)acrylic anhydride or the like (introduction of a (meth)acryloyl group), the reaction rate in the synthesis of the curable resin (A) can be increased. As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more.

[0062] After the reaction with (meth)acrylic anhydride or the like (introduction of (meth)acryloyl groups) is completed, the reaction product is washed with water, and then unreacted (meth)acrylic anhydride or the like and the organic solvent used are distilled off under heated and reduced pressure conditions. Furthermore, to further reduce the hydrolyzable halogen in the resulting curable resin (A), the curable resin (A) can be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to further carry out the reaction. In this case, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present to improve the reaction rate. When a phase transfer catalyst is used, its amount is preferably in the range of 0.1 to 10% by mass relative to the curable resin (A) used. After the reaction is completed, the resulting salt is removed by filtration or washing with water, and the organic solvent is distilled off under heated and reduced pressure conditions to obtain the desired curable resin (A) with a low content of hydrolyzable chlorine.

[0063] The softening point of the curable resin (A) is preferably 150° C. or lower, more preferably 30 to 100° C., since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0064] The content of the curable resin (A) in the curable resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more.

[0065] Examples of the photopolymerization initiator (B) 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.

[0066] Commercially available products of the photopolymerization initiator (B) 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" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure Examples of suitable photopolymerization initiators (B) include "Quantacure 55" (manufactured by Stoffa Chemical Co.), "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ Co.), "DEAP" (manufactured by Upjohn Chemical Co.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop Co.), and "Runtecure 1104" (manufactured by Runtec Co.). These photopolymerization initiators (B) can be used alone or in combination of two or more.

[0067] The amount of the photopolymerization initiator (B) added is, for example, preferably in the range of 0.05 to 15 mass %, more preferably in the range of 0.1 to 10 mass %, of the total of the components other than the solvent of the curable resin composition.

[0068] The method for producing the curable resin composition of the present invention is not particularly limited, and any method may be used. For example, the curable resin composition may be produced by mixing the components including the curable resin (A) and the photopolymerization initiator (B). The mixing method is not particularly limited, and a paint shaker, disperser, roll mill, bead mill, ball mill, attritor, sand mill, bead mill, etc. may be used.

[0069] The curable resin composition of the present invention may contain other resin components in addition to the curable resin (A). Examples of the other resin components include a resin (C) having a polymerizable unsaturated group.

[0070] The resin (C) having a polymerizable unsaturated group may be any resin having a polymerizable unsaturated group in the resin, 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, ester resins having a polymerizable unsaturated group, etc. Examples of the polymerizable unsaturated group include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, etc.

[0071] Examples of the epoxy resin having a polymerizable unsaturated group include an epoxy (meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, a polybasic acid anhydride; and an epoxy (meth)acrylate resin having a urethane group obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group and, if necessary, a polybasic acid anhydride.

[0072] 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.

[0073] 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.

[0074] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0075] 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.

[0076] 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.

[0077] 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. Acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (6) can also be used.

[0078] [ka] [In formula (6), 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.]

[0079] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0080] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (X-1).

[0081] [ka] [In formula (X-1), R1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0082] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0083] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (X-2).

[0084] [ka] [In formula (X-2), R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

[0085] The molecular weight of the compound represented by the general formula (6) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0086] These unsaturated monobasic acids can be used alone or in combination of two or more.

[0087] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0088] Examples of the aliphatic polybasic acid anhydrides include acid anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

[0089] In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0090] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0091] These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0092] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (7); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

[0093] [ka] [In formula (7), R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0094] The (meth)acrylate compound having a hydroxyl group is not particularly limited in its specific structure as long as it has a hydroxyl group and a (meth)acryloyl group in its molecular structure, and a wide variety of compounds can be used. Examples of such acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Also usable are (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0095] The method for producing the epoxy resin having 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 may also use a basic catalyst, if necessary.

[0096] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0097] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0098] Examples of the urethane resin having 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.

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

[0100] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound (C) having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

[0101] Examples of the polyol 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 above-mentioned various polyol compounds; lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various polyol compounds; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The above-mentioned polyol compounds can be used alone or in combination of two or more.

[0102] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0103] 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 may also use a basic catalyst, if necessary.

[0104] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0105] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0106] 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, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product, if necessary.

[0107] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0108] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when 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 preferred 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 kinds.

[0109] The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more.

[0110] 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 may also use a basic catalyst, if necessary.

[0111] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0112] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0113] 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.

[0114] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, it is preferable for the resin to have an acid anhydride group, and it is more preferable for the resin to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0115] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

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

[0117] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0118] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0119] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of suitable polybasic acids include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0120] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more types.

[0121] 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.

[0122] 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 may also use a basic catalyst, if necessary.

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

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

[0125] Examples of the 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.

[0126] 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 (8-1) to (8-4).

[0127] [ka]

[0128] In the above structural formulas (8-1) to (8-4), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (8-2), the substituent may be on any ring; in structural formula (8-3), the substituent may be on any ring of the benzene ring present in one molecule; and in structural formula (8-4), the substituent may be on any ring of the benzene ring present in one molecule; and the numbers of substituents in one molecule are p and q.

[0129] The compound having a phenolic hydroxyl group may also be, for example, a reaction product obtained by using, as essential reaction raw materials, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5): Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule.

[0130] [ka]

[0131] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3 represents 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 i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group. In formula (x-5), Y represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and j is an integer of 1 to 4.

[0132] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0133] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

[0134] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a curable resin composition that can form a cured product having excellent heat resistance and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

[0135] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0136] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0137] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0138] 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 may also use a basic catalyst or an acidic catalyst, if necessary.

[0139] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0140] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0141] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0142] Examples of the ester 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 unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

[0143] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as compounds having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more types.

[0144] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties. The alkylene oxide may be used alone or in combination of two or more.

[0145] 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 having excellent heat resistance and dielectric properties. The alkylene carbonate may be used alone or in combination of two or more.

[0146] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0147] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0148] 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 may also use a basic catalyst or an acidic catalyst, if necessary.

[0149] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0150] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0151] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0152] Furthermore, various (meth)acrylate monomers can also be used as the resin (C) having a polymerizable unsaturated group.

[0153] Examples of the (meth)acrylate monomer include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; aromatic 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, and phenylphenoxyethyl (meth)acrylate. Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propanediol, etc. Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

[0154] In addition to the above, the (meth)acrylate monomer may also be a (meth)acrylate monomer having a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

[0155] Examples of the phenol compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

[0156] Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. These cyclic carbonate compounds can be used alone or in combination of two or more.

[0157] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran, etc. These cyclic ether compounds can be used alone or in combination of two or more.

[0158] As the unsaturated monocarboxylic acid, the same unsaturated monobasic acids as those exemplified above can be used.

[0159] The amount of the resin (C) having a polymerizable unsaturated group used is preferably such that the mass ratio of the solid contents of the curable resin (A) to the resin (C) having a polymerizable unsaturated group [(A) / (C)] is 5 / 95 to 95 / 5, and more preferably 10 / 90 to 90 / 10, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0160] Furthermore, the curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as needed.

[0161] Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

[0162] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0163] Examples of the polybasic acid 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]heptacarboxylic acid. 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, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic 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.

[0164] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0165] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more.

[0166] Examples of the amide compounds include dicyandiamide, polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more.

[0167] Examples of the azo compounds include azobisisobutyronitrile.

[0168] Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, alkyl peroxycarbonate, etc. These organic peroxides can be used alone or in combination of two or more.

[0169] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. Examples of suitable polyols include polyester polyols obtained by co-condensation of the above polyol monomers with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

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

[0171] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0172] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0173] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,3-diphenyl-4-phenylenediamine), and methyl-p-benzoquinone.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination.

[0174] As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0175] 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.

[0176] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0177] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0178] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0179] Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0180] 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.

[0181] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

[0182] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0183] The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0184] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0185] The integrated light quantity of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 and more preferably 0.5 to 10 kJ / m 2 . When the integrated light quantity is within the above range, it is preferable because generation or suppression of uncured portions can be prevented.

[0186] Note that the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

[0187] In addition, since the cured product of the present invention has excellent heat resistance and dielectric properties, for example, in semiconductor device applications, it can be suitably used as a solder resist, an interlayer insulating material, a package material, an underfill material, a package adhesive layer for circuit elements, etc., and as an adhesive layer between an integrated circuit element and a circuit board. Also, in thin display applications typified by LCD and OELD, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer, etc. Among these, it can be particularly suitably used for solder resist applications.

[0188] The article of the present invention has a coating film made of the above cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, interior and exterior automotive materials, OA equipment, etc., semiconductor devices, display devices, imaging devices, etc.

Examples

[0189] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below.

[0190] <GPC measurement (evaluation of number average molecular weight and average number of repeating units)> Measurements were performed using the following measuring equipment and conditions, and a GPC chart was obtained for the curable resin having an indane skeleton obtained by the synthesis method shown below. From the results of the GPC chart, the average number of repeating units n contributing to the indane skeleton in the curable resin having an indane skeleton was calculated based on the number-average molecular weight (Mn) of the curable resin having an indane skeleton. 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 the average number of repeating units n was calculated. Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution (50 μl) containing 1.0 mass % of the curable resin having an indane skeleton obtained in the synthesis example, calculated as solid content, was filtered through a microfilter.

[0191] (Synthesis Example 1: Production of curable resin (A1) having an indane skeleton) A flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 48.9 parts by mass of 2,6-dimethylphenol, 272.0 parts by mass of α,α'-dihydroxy-1,3-diisopropylbenzene, 280 parts by mass of xylene, and 70 parts by mass of activated clay, and the mixture was heated to 120°C with stirring. The temperature was then raised to 210°C while removing the distillate using a Dean-Stark tube, and the mixture was allowed to react for 3 hours. The mixture was then cooled to 140°C, and 146.6 parts by mass of 2,6-dimethylphenol was added. The mixture was then heated to 220°C and allowed to react for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300 parts by mass of toluene, filtered to remove the activated clay, and the solvent and low-molecular-weight substances such as unreacted materials were distilled off under reduced pressure, yielding 365.3 parts by mass of intermediate phenol compound (b1). The hydroxyl group equivalent (phenol equivalent) of the resulting intermediate phenol compound (a1) was 299 g / equivalent.

[0192] Next, 365.3 parts by mass of the resulting intermediate phenol compound (a1) and 700 parts by mass of toluene were placed in a flask equipped with a thermometer, a condenser, and a stirrer and stirred at approximately 85°C. Next, 29.9 parts by mass of dimethylaminopyridine was added, and once all solids appeared to have dissolved, 277.5 parts by mass of methacrylic anhydride was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued for an additional 3 hours at 85°C. The reaction solution was added dropwise over 1 hour to 4,000 parts by mass of methanol in a beaker that was vigorously stirred with a magnetic stirrer. The resulting precipitate was filtered under reduced pressure through a membrane filter and then dried to obtain a curable resin (A1) (average number of repeating units n = 1.6) having an indane skeleton of the following structural formula. The average number of repeating units n was calculated from the number average molecular weight (Mn) measured by GPC, the GPC chart of which is shown in Figure 1. The average number of repeating units n was calculated in the same manner for the other examples and comparative examples below.

[0193] [ka]

[0194] (Synthesis Example 2: Production of curable resin (A2) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the methacrylic anhydride in Synthesis Example 1 was changed to 227.0 parts by mass of acrylic anhydride, to obtain a curable resin (A2) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0195] [ka]

[0196] (Synthesis Example 3: Production of curable resin (A3) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 306.3 parts by mass of o-phenylphenol, to obtain a curable resin (A3) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0197] [ka]

[0198] (Synthesis Example 4: Production of curable resin (A4) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 317.3 parts by mass of 2-cyclohexylphenol, to obtain a curable resin (A4) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0199] [ka]

[0200] (Synthesis Example 5: Production of curable resin (A5) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 331.6 parts by mass of 2-benzylphenol, to obtain a curable resin (A5) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0201] [ka]

[0202] (Synthesis Example 6: Production of curable resin (A6) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 169.4 parts by mass of phenol, to obtain a curable resin (A6) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0203] [ka]

[0204] (Synthesis Example 7: Production of curable resin (A7) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 198.2 parts by mass of catechol and the amount of methacrylic anhydride added was changed to 555.0 parts by mass, to obtain a curable resin (A7) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0205] [ka]

[0206] (Synthesis Example 8: Production of curable resin (A8) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 was changed to 227.0 parts by mass of pyrogallol and the amount of methacrylic anhydride added was changed to 832.5 parts by mass, to obtain a curable resin (A8) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0207] [ka]

[0208] (Synthesis Example 9: Production of curable resin (A9) having an indane skeleton) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,6-dimethylphenol in Synthesis Example 1 above was changed to 259.5 parts by mass of 2-naphthol, to obtain a curable resin (A9) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0209] [ka]

[0210] (Synthesis Example 10: Production of curable resin (A10) having an indane skeleton) A flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 48.9 parts by weight of 2,6-dimethylphenol, 272.0 parts by weight of α,α'-dihydroxy-1,3-diisopropylbenzene, 280 parts by weight of xylene, and 70 parts by weight of activated clay, and the mixture was heated to 120°C with stirring. The temperature was then raised to 210°C while removing the distillate water using a Dean-Stark trap, and the mixture was allowed to react for 3 hours. The mixture was then cooled to 140°C, and 146.6 parts by weight of 2,6-dimethylphenol was added. The mixture was then heated to 220°C and allowed to react for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300 parts by weight of toluene, filtered to remove the activated clay, and distilled under reduced pressure to obtain 365.3 parts by weight of intermediate phenol compound (a10). The phenol equivalent was 299 g / equivalent.

[0211] Next, 365.3 parts by mass of the obtained intermediate phenol compound (a10), 0.184 parts by mass of 2,4-dinitrophenol (2,4-DNP), 23.5 parts by mass of tetrabutylammonium bromide (TBAB), 209 parts by mass of chloromethylstyrene, and 400 parts by mass of methyl ethyl ketone were added to a flask equipped with a thermometer, a condenser, and a stirrer, and the mixture was heated to 75°C while stirring. Next, 48% NaOH aqueous solution was added dropwise to the reaction vessel maintained at 75°C over 20 minutes. After the dropwise addition was completed, stirring was continued at 75°C for an additional 4 hours. After 4 hours, the mixture was cooled to room temperature, 100 parts by mass of toluene was added, and 10% HCl was added for neutralization. The aqueous phase was then separated by liquid separation and washed three times with water. The resulting organic phase was concentrated by distillation, and the product was reprecipitated by adding methanol. The precipitate was filtered and dried to obtain a curable resin (A10) (average number of repeating units n=1.6) having an indane skeleton of the following structural formula.

[0212] [ka]

[0213] (Synthesis Example 11: Production of Resin (C1) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 188 parts by mass of bisphenol A type epoxy resin (EPICLON 850-S manufactured by DIC Corporation, epoxy equivalent weight 188 g / equivalent), and 0.26 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.13 parts by mass of methoquinone as a thermal polymerization inhibitor were added. Thereafter, 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing in air, thereby obtaining a resin (C1) having a polymerizable unsaturated group.

[0214] (Synthesis Example 12: Production of Resin (C2) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (DIC Corporation's "EPICLON 850CRP," epoxy equivalent 173 g / equivalent). 0.21 parts by weight of dibutylhydroxytoluene as an antioxidant and 0.21 parts by weight of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by weight of acrylic acid and 0.21 parts by weight of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 10 hours while blowing air. After confirming that the acid value was 1 mg KOH / g or less, 0.21 parts by weight of oxalic acid was added and the mixture was stirred at 70 ° C for 3 hours to obtain a resin (C2) having polymerizable unsaturated groups. The epoxy equivalent of this resin (C2) having polymerizable unsaturated groups was 450 g / equivalent.

[0215] (Example 1: Preparation of curable resin composition (1)) The curable resin (A1) having an indane skeleton obtained in Synthesis Example 1 and a photopolymerization initiator (B1) ("Omnirad 907" manufactured by IGM; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) were mixed to obtain a curable resin composition, and then methyl ethyl ketone and 2-ethyl-4-methylimidazole were added in the parts by mass shown in Table 1 to obtain a curable resin composition (1). Note that the parts by mass of the curable resin in Table 1 refer to solid content values.

[0216] (Examples 2 to 13: Preparation of curable resin compositions (2) to (13)) Using the compositions and blendings shown in Table 1, curable resin compositions (2) to (11) were obtained in the same manner as in Example 1.

[0217] (Comparative Example 1: Preparation of curable resin composition (R3)) The resin (C1) having a polymerizable unsaturated group obtained in Synthesis Example 11 and a photopolymerization initiator (B1) ("Omnirad 907" manufactured by IGM; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) were mixed to obtain a curable resin composition, and then methyl ethyl ketone and 2-ethyl-4-methylimidazole were added in the parts by mass shown in Table 1 to obtain a curable resin composition (R1).

[0218] The curable resin compositions (1) to (11) and (R1) obtained in the above examples and comparative examples were evaluated as follows.

[0219] [Heat resistance evaluation method] The curable resin compositions obtained in each of the Examples and Comparative Examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied curable resin compositions to a copper foil to a thickness of 50 μm. 2 After irradiating the film with ultraviolet light, the film was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 35 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). Note that a higher glass transition temperature indicates better heat resistance.

[0220] [Method for measuring dielectric constant] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored for 24 hours in a room at 23°C and 50% humidity to prepare a test piece. The dielectric constant of the test piece at 1 GHz was measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. by the cavity resonance method.

[0221] [Method for measuring dielectric loss tangent] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0222] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (11) and (R1) obtained in the above examples and comparative examples.

[0223] [Table 1]

[0224] "Acrylate monomer" in Table 1 refers to bisphenol A EO-modified diacrylate ("Miramer M-240" manufactured by MIWON Co., Ltd.).

[0225] Examples 1 to 13 shown in Table 1 are examples of curable resin compositions using the curable resin composition of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance and dielectric properties.

[0226] On the other hand, Comparative Example 1 is an example of a curable resin composition that does not contain a curable resin having an indane skeleton. It was confirmed that the cured product of this curable resin composition had extremely insufficient heat resistance and also had insufficient dielectric properties, with a high dielectric constant.

Claims

1. A curable resin composition comprising a curable resin (A) having an indane skeleton represented by the following general formula (1) and a photopolymerization initiator (B): A curable resin composition, wherein X in general formula (1) is a (meth)acryloyl group. 【Chemistry 1】 [In formula (1), X represents a polymerizable unsaturated group. Ra and Rb each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms; j represents an integer of 1 to 3; k and l each independently represent an integer of 0 to 3; n represents the average number of repeating units and is a number of 0.5 to 20; and m is an integer of 0 to 2.]

2. 2. The curable resin composition according to claim 1, wherein the curable resin (A) has an indane skeleton represented by the following general formula (2): 【Chemistry 2】 [In formula (2), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and R1 and R2 are not both hydrogen atoms at the same time, and n represents the average number of repeating units and is a number from 0.5 to 20.]

3. 3. The curable resin composition according to claim 1, further comprising a resin (C) having a polymerizable unsaturated group.

4. The curable resin composition according to claim 3, wherein the mass ratio of the solid content of the curable resin (A) to the solid content of the resin (C) having a polymerizable unsaturated group [(A) / (C)] is in the range of 5 / 95 to 95 / 5.

5. A cured product of the curable resin composition according to any one of claims 1 to 4.

6. An article having a coating film made of the cured product according to claim 5.

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