Epoxy (meth) acrylate resin, curable resin composition, cured product, and article

Abstract

To provide an epoxy (meth)acrylate resin that can form a cured product having excellent elongation, adhesion and dielectric properties, a curable resin composition containing the epoxy methacrylate resin and a photopolymerization initiator, a cured product of the curable resin composition and an article having a coating layer composed of the cured product.SOLUTION: The present invention provides an epoxy (meth)acrylate resin containing an indan bisphenol type epoxy resin (A) having an indan skeleton represented by the general formula (1), and an unsaturated monobasic acid (B) as essential starting reactive materials.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an epoxy (meth) acrylate resin, a curable resin composition, a cured product, and an article.

Background Art

[0002] In recent years, curable resin compositions such as active energy ray curable compositions curable by active energy rays such as ultraviolet rays and thermosetting compositions curable by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical members. Among them, as the coating agent use, in general, it is required to be able to impart designability to the surface of various substrates, have excellent curability, and be able to form a coating film capable of preventing deterioration of the substrate surface. Furthermore, in recent years, materials having not only excellent heat resistance but also excellent dielectric properties of the obtained cured product have been demanded by the industrial world.

[0003] As a conventional active energy ray curable composition, a photosensitive resin composition containing an epoxy acrylate resin obtained by reacting an intermediate obtained by reacting a cresol novolak type epoxy resin, acrylic acid, and phthalic anhydride with tetrahydrophthalic anhydride is known (see, for example, Patent Document 1), but it does not satisfy the required properties that are increasingly demanded in terms of heat resistance, and also does not meet the current market requirements in terms of dielectric properties.

[0004] Therefore, there has been a demand for materials having excellent dielectric properties in addition to heat resistance.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide an epoxy (meth) acrylate resin, a curable resin composition, a cured product, and an article capable of forming a cured product having excellent elongation, adhesion, and dielectric properties.

Means for Solving the Problem

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an epoxy (meth) acrylate resin having a specific epoxy resin and an unsaturated monobasic acid as essential reaction raw materials, and have completed the present invention.

[0008] That is, the present invention relates to an epoxy (meth) acrylate resin, a curable resin composition, a cured product, and an article, characterized by using an epoxy resin (A) represented by the following general formula (1) and an unsaturated monobasic acid (B) as essential reaction raw materials.

[0009]

Chemical formula

Effects of the Invention

[0010] The epoxy (meth)acrylate resin of the present invention can form a cured product having excellent elongation, adhesion, and dielectric properties. Therefore, the curable resin composition containing the epoxy (meth)acrylate resin and a photopolymerization initiator can be suitably used as a coating agent or an adhesive. In the present invention, the "excellent dielectric properties" means a low dielectric constant and a low dielectric loss tangent.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0012] The epoxy (meth)acrylate resin of the present invention is characterized in that an epoxy resin (A) and an unsaturated monobasic acid (B) are used as essential reaction raw materials.

[0013] In the present invention, "(meth)acrylate" means acrylate and / or methacrylate. Also, "(meth)acryloyl" means acryloyl and / or methacryloyl. Further, "(meth)acrylic" means acrylic and / or methacrylic.

[0014] As the epoxy resin (A), the one represented by the following general formula (1) is used.

[0015]

Chemical formula

[0016] Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group and the like.

[0017] Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as phenyl group, alkoxyphenyl group, tolyl group, xylyl group, naphthyl group, alkoxynaphthyl group and the like.

[0018] It is preferable that Ra in the general formula (1) is any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. By being the alkyl group having 1 to 4 carbon atoms or the like, the planarity and crystallinity near the bisphenol group are reduced, the solvent solubility is improved, and a preferable embodiment in which a cured product can be obtained without impairing the reactivity of the bisphenol group is achieved.

[0019] It is preferable that q in the general formula (1) is 1 to 3, and more preferably 2. When q is 2, the influence of steric hindrance is small, which is a more preferable embodiment in the production (synthesis) of the epoxy resin (A).

[0020] In the general formula (), it is preferable that r is 0 and Rb is a hydrogen atom. Further, it is preferable that r is 1 to 3 and Rb is at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. In particular, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced during the formation of the indane skeleton in the epoxy resin (A), which is advantageous and a preferred embodiment for the production (synthesis) of the epoxy resin (A).

[0021] Examples of the method for producing the epoxy resin (A) include a method of epoxidizing a polyfunctional phenol resin.

[0022] The method of epoxidation is not particularly limited, and known techniques can be appropriately applied. For example, a method of reacting an indane bisphenol compound with epihalohydrin in the presence of a basic catalyst for epoxidation can be mentioned.

[0023] Examples of the indane bisphenol compound include a compound represented by the following general formula (2), a compound represented by the following general formula (5), and the like.

[0024]

Chemical formula

[0025] 〔In formula (2), each Rc is independently either a monovalent functional group represented by the following structural formula (3) or (4), and the ortho position of at least one Rc is a hydrogen atom. Further, each Rb independently represents an alkyl group, an alkyloxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and r represents an integer value of 0 to 3.〕

[0026]

Chemical formula

[0027]

Chem.

[0028]

Chem.

[0029] By reacting the compound of the general formula (2) and the compound of the general formula (5) in the presence of an acid catalyst, an indane bisphenol compound represented by the following general formula (6) can be obtained. In the following general formula (6), Ra, Rb, q, r, x and n are the same as those described above.

[0030]

Chem.

[0031] In the indane skeleton (see the following general formula (7)), which is a characteristic of the indane bisphenol compound, the average number of repeating units n is 0.2 to 20, preferably 0.5 to 10, and more preferably 1 to 8 as the average number of repeating units n (average value), because a curable resin composition capable of forming a cured product excellent in elongation, adhesion and dielectric properties can be obtained.

[0032]

Chem.

[0033] Examples of the compound represented by the general formula (2) (hereinafter referred to as "compound (a)") include p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene, p- and m-bis(α-chloroisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene, or a mixture thereof. Further, nuclear alkyl group substituents of these compounds, such as diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, can also be used, and furthermore, nuclear halogen substituents, such as chlorodiisopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene, can also be used.

[0034] In addition, 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-bis(α-hydroxyisopropyl)benzenethiol, 2,5-diisopropenylbenzenethiol, 2,{\displaystyle 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, {\displaystyle 2}-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis(α-hydroxyisopropyl)benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene, 5-cyclohexyl-1,Examples thereof include 3 - diisopropenylbenzene, 5 - cyclohexyl - 1,3 - bis(α - hydroxyisopropyl)benzene, etc.

[0035] Note that the substituents contained in the compound (a) are not particularly limited, and the above - exemplified compounds can be used. However, in the case of substituents with a large steric hindrance, compared with substituents with a small steric hindrance, stacking of the resulting indane bisphenol compounds is less likely to occur, and crystallization of the indane bisphenol compounds is less likely to occur. That is, the solvent solubility of the indane bisphenol compounds is improved, which is a preferred embodiment.

[0036] Examples of the compound represented by the general formula (5) (hereinafter referred to as "compound (b)") include phenol or its derivatives, such as cresols like o-cresol, m-cresol, p-cresol; phenol; xylenols like 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols like o-ethylphenol, m-ethylphenol, p-ethylphenol; butylphenols like isopropylphenol, butylphenol, p-t-butylphenol; alkylphenols like p-pentylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol; halogenated phenols like fluorophenol, chlorophenol, bromophenol, iodophenol; monosubstituted phenols like p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol; condensed polycyclic phenols like 1-naphthol, 2-naphthol; polyphenols like resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, etc. These phenols or their derivatives may be used alone or in combination of two or more. Among them, for example, it is a more preferred embodiment to use a compound in which two of the ortho-position and para-position with respect to the phenolic hydroxyl group, such as 2,6-xylenol or 2,4-xylenol, are alkyl-substituted. However, if the steric hindrance is too large, there is also a concern that the reactivity in the synthesis of the indane bisphenol compound may be inhibited. Therefore, for example, it is preferable to use compound (b) having an alkyl group with 1 to 4 carbon atoms.

[0037] Examples of the method for producing the indane bisphenol compound represented by the general formula (6) include, for example, charging the compound (a) and the compound (b) such that the molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a)) is preferably 0.1 to 10, more preferably 0.2 to 8, and reacting them in the presence of an acid catalyst to obtain an indane bisphenol compound having an indane skeleton.

[0038] 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 resin; and heteropolyhydrochloric acid. These acid catalysts can be used alone or in combination of two or more. Further, since they can be easily removed by neutralization with a base and washing with water after the reaction, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid (among which p-toluenesulfonic acid) which are homogeneous catalysts are preferred.

[0039]

[0040] The reaction temperature in the production of the indan bisphenol compound represented by the general formula (6) may usually be in the range of 50 to 300°C. However, in order to suppress the formation of isomeric structures, avoid side reactions such as thermal decomposition, and obtain a high-purity indan bisphenol compound, 80 to 200°C is preferred.

[0041]

[0042] ​​In the method for producing the indane bisphenol compound, since phenol or its derivative also serves as a solvent, it is not necessarily required to use other solvents, but it is also possible to use a solvent. For example, in the case of a reaction system that also serves as a dehydration reaction, specifically, when reacting a compound having an α-hydroxypropyl group as a raw material, an azeotropic dehydration-capable solvent such as toluene, xylene, or chlorobenzene is used, and after completing the dehydration reaction, the solvent is distilled off, and then a method of performing the reaction within the above reaction temperature range may be adopted.

[0043] Examples of the organic solvent used for synthesizing the indane bisphenol compound include ketone compounds such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ether compounds such as dioxane and tetrahydrofuran; ester compounds such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, and xylene, etc. These may be used alone or in combination.

[0044] As the hydroxyl equivalent of the indane bisphenol compound, since a curable resin composition capable of forming a cured product excellent in elongation, adhesion, and dielectric properties can be obtained, 100 to 1000 g / equivalent is preferable, and 150 to 800 g / equivalent is more preferable. The hydroxyl equivalent of the indane bisphenol compound refers to the value calculated by the neutralization titration method based on JIS K 0070 (1992).

[0045] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, etc. These may be used alone or in combination. Among them, epichlorohydrin is preferable because it is easily available industrially.

[0046] Examples of the basic catalyst include amine compounds such as 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, tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium 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-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organometallic compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. Further, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. These basic catalysts can be used alone or in combination of two or more. In particular, alkali metal hydroxides are preferred because of their excellent catalytic activity in the epoxy resin synthesis reaction, and examples include sodium hydroxide and potassium hydroxide.In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in a solid form.

[0047] Examples of the reaction between the indane bisphenol compound and the epihalohydrin include adding 1 to 10 moles of the epihalohydrin per 1 mole of the hydroxyl group contained in the indane bisphenol compound, and further adding 0.9 to 2 moles of a basic catalyst all at once or gradually per 1 mole of the hydroxyl group of the indane bisphenol compound, and reacting at a temperature of 20 to 120°C for 0.5 to 10 hours. This basic catalyst may be solid or its aqueous solution may be used. When using an aqueous solution, it is added continuously, and water and epihalohydrin are continuously distilled off from the reaction mixture under reduced pressure or normal pressure, and further separated to remove water and continuously return the epihalohydrin to the reaction mixture.

[0048] In addition, by using an organic solvent in combination during the epoxidation reaction, the reaction rate in the synthesis of the epoxy resin can be increased. Such organic solvents are not particularly limited. For example, hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirit; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol, and propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These organic solvents can be used alone or in combination of two or more kinds.

[0049] In addition, commercially available products can also be used as the organic solvent. Examples of such commercially available products include "No. 1 Spindle Oil", "No. 3 Solvent", "No. 4 Solvent", "No. 5 Solvent", "No. 6 Solvent", "Naphthol H", "Alkene 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7" manufactured by ENEOS Corporation; "Daiya Doll 13", "Diare 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol", "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Super Sol LA35", "Super Sol LA38" manufactured by Idemitsu Kosan Co., Ltd.; "Exxon D80", "Exxon D110", "Exxon D120", "Exxon D130", "Exxon D160", "Exxon D100K", "Exxon D120K", "Exxon D130K", "Exxon D280", "Exxon D300", "Exxon D320" manufactured by ExxonMobil Chemical Company; etc. The above organic solvent can be used alone or in combination of two or more. Also, in this embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.

[0050] Also, the organic solvent and water may be used in combination. At this time, the usage ratio of water in the mixed solvent is preferably in the range of 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the mixed solvent.

[0051] In the case where the basic catalyst used during the epoxidation reaction is an aqueous solution, the water content contained in the aqueous solution shall not be included in what is defined as the water in the mixed solvent.

[0052] When industrially producing the indan bisphenol type epoxy resin, in the first batch of epoxy resin production, all of the epihalohydrin used in the charge is new, but in the batches after the first batch, it is preferable to use a combination of the epihalohydrin recovered from the crude reaction product and the new epihalohydrin corresponding to the amount consumed and lost in the reaction.

[0053] After completion of the above epoxidation reaction, the reaction product is washed with water, and then unreacted epihalohydrin and the organic solvent used in combination are distilled off under heating and reduced pressure. Further, in order to further reduce the hydrolyzable halogen in the obtained indane bisphenol type epoxy resin, the indane bisphenol type epoxy resin is 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 is added to further conduct the reaction. At this time, for the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present. When using a phase transfer catalyst, the amount thereof used is preferably in the range of 0.1 to 3% by mass based on the indane bisphenol type epoxy resin used. After completion of the reaction, the generated salt is removed by filtration or washing with water, etc., and the organic solvent is distilled off under heating and reduced pressure, whereby an indane bisphenol type epoxy resin having a low content of hydrolyzable chlorine can be obtained.

[0054] After completion of the reaction, the reaction product is washed with water, and then unreacted epihalohydrin and the organic solvent used in combination are distilled off under heating and reduced pressure. Further, in order to further reduce the hydrolyzable halogen in the obtained indane bisphenol type epoxy resin, the indane bisphenol type epoxy resin is 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 is added to further conduct the reaction. At this time, for the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present. When using a phase transfer catalyst, the amount thereof used is preferably such that it is in the ratio of 0.1 to 3 parts by mass per 100 parts by mass of the indane bisphenol type epoxy resin used. After completion of the reaction, the generated salt is removed by filtration or washing with water, etc., and the organic solvent is distilled off under heating and reduced pressure, whereby the target indane bisphenol type epoxy resin can be obtained.

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

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

[0057] Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Acid halides and esterified products of the unsaturated monobasic acid can also be used. Further, compounds represented by the following general formula (8) and the like can also be used.

[0058]

Chemical formula

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

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

[0061]

Chemical formula

[0062] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, and the like. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

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

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

[0065] The molecular weight of the compound represented by the general formula (3) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

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

[0067] Since a cured product having excellent elongation, adhesion, and dielectric properties can be formed, the amount of the unsaturated monobasic acid (B) used is preferably in the range such that the acid group of the unsaturated monobasic acid (B) is 0.2 to 0.8 mol per 1 mol of the epoxy group of the epoxy resin (A).

[0068] The epoxy (meth)acrylate resin of the present invention can also use other compounds other than the epoxy resin (A) and the unsaturated monobasic acid (B) as raw materials, if necessary.

[0069] Examples of the other compounds include unsaturated monobasic acid anhydrides and the like.

[0070] Examples of the unsaturated monobasic acid anhydride include acrylic anhydride and methacrylic anhydride. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more.

[0071] The total mass ratio of the epoxy resin (A) and the unsaturated monobasic acid (B) in the raw materials (solid content) of the epoxy (meth)acrylate resin of the present invention is preferably 60% by mass or more because an epoxy (meth)acrylate resin capable of forming a cured product having excellent elongation, adhesion, and dielectric properties can be obtained.

[0072] The method for producing the epoxy (meth)acrylate resin of the present invention is not particularly limited, and it may be produced by any method. For example, a method of reacting all of the reaction raw materials containing the epoxy resin (A) and the unsaturated monobasic acid (B) at once in the presence of an acidic catalyst or a basic catalyst in a temperature range of 70 to 140°C is preferred.

[0073] The reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) can also be carried out in an organic solvent if necessary.

[0074] As the basic catalyst, the same ones as those exemplified as the basic catalyst above can be used, and the basic catalyst can be used alone or in combination of two or more.

[0075] The amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, more preferably in the range of 0.05 to 0.8 part by mass, based on 100 parts by mass in total of the epoxy resin (A) and the unsaturated monobasic acid (B) because an epoxy (meth)acrylate resin capable of forming a cured product having excellent elongation, adhesion, and dielectric properties can be obtained.

[0076] As the organic solvent, the same ones as those exemplified as the organic solvent above can be used, and the organic solvent can be used alone or in combination of two or more.

[0077] The epoxy (meth) acrylate resin of the present invention can be used as a curable resin composition by adding a photoinitiator.

[0078] Examples of the photoinitiator include photo radical 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-diphenylethane-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, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and the like.

[0079] Examples of commercially available products of the other photoinitiators 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", "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), etc. These photoinitiators can be used alone or in combination of two or more.

[0080] The addition amount of the photoinitiator is preferably used in the range of 0.5 to 20% by mass in the curable resin composition, for example.

[0081] The curable resin composition of the present invention may contain resin components other than the epoxy (meth)acrylate resin of the present invention described above (hereinafter sometimes referred to as "other resin components"). Examples of the other resin components include epoxy resins, resins having polymerizable unsaturated groups, various (meth)acrylate monomers, etc.

[0082] 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, oxazolidone type epoxy resins, etc. These epoxy resins can be used alone or in combination of two or more.

[0083] 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, bisphenol S type epoxy resin, etc.

[0084] 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, hydrogenated bisphenol S type epoxy resin, etc.

[0085] Examples of the biphenyl type epoxy resin include 4,4'-biphenyl type epoxy resin, 2,2'-biphenyl type epoxy resin, tetramethyl-4,4'-biphenyl type epoxy resin, tetramethyl-2,2'-biphenyl type epoxy resin, etc.

[0086] 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, hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.

[0087] Examples of the resin having a polymerizable unsaturated group include any resin having a polymerizable unsaturated group in the resin, and examples thereof include an epoxy resin having a polymerizable unsaturated group, a urethane resin having a polymerizable unsaturated group, an acrylic resin having a polymerizable unsaturated group, an amideimide resin having a polymerizable unsaturated group, an acrylamide resin having a polymerizable unsaturated group, an ester resin having a polymerizable unsaturated group, and the like.

[0088] 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 a urethane group-containing epoxy (meth)acrylate resin 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.

[0089] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resin can be used alone or in combination of two or more.

[0090] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

[0091] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, and the like.

[0092] Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. Further, as the aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure.

[0093] In the present invention, the alicyclic polybasic acid anhydride is defined as one in which an acid anhydride group is bonded to an alicyclic structure, regardless of the presence or absence of an aromatic ring in other structural sites. Examples of the alicyclic polybasic acid anhydride include acid anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, etc.

[0094] 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, benzophenonetetracarboxylic acid, etc.

[0095] These polybasic acid anhydrides can be used alone or in combination of two or more.

[0096] 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; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like thereof. These polyisocyanate compounds can be used alone or in combination of two or more thereof.

[0097] [Chemical formula] [In formula (9), R 1 is each independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 2 is 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.]

[0098] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. In addition, (poly)oxyalkylene-modified products obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the above-mentioned (meth)acrylate compounds having various hydroxyl groups, and lactone-modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned (meth)acrylate compounds having various hydroxyl groups can also be used. These (meth)acrylate compounds having a hydroxyl group can be used alone or in combination of two or more.

[0099] The method for producing the epoxy resin having a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the epoxy resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0100] As the organic solvent, the same solvents as those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0101] As the basic catalyst, the same catalysts as those exemplified as the above basic catalysts can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0102] 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.

[0103] As the polyisocyanate compound, the same compounds as those exemplified as the above polyisocyanate compounds can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

[0104] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the above (meth)acrylate compounds having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

[0105] Examples of the polyol compound 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 products obtained by introducing (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains and other (poly)oxyalkylene chains into the molecular structures of the various polyol compounds; lactone modified products obtained by introducing (poly)lactone structures into the molecular structures of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. The polyol compound can be used alone or in combination of two or more kinds.

[0106] As the polybasic acid anhydride, the same ones as those exemplified as the above polybasic acid anhydrides can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0107] The method for producing the urethane resin having a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the urethane resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0108] As the organic solvent, the same ones as those exemplified as the above organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0109] As the basic catalyst, the same ones as those exemplified as the above basic catalysts can be used, and the basic catalyst can be used alone or in combination of two or more.

[0110] Examples of the acrylic resin having a polymerizable unsaturated group include reaction products obtained by introducing a (meth)acryloyl group by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups into an acrylic resin intermediate obtained by polymerizing 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 as an essential component, and those obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product as necessary.

[0111] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, a compound having another polymerizable unsaturated group. Examples of the compound having another polymerizable unsaturated group 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; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These can be used alone or in combination of two or more.

[0112] The above-mentioned (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 from the perspective of reactivity, it is preferably the following combination. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable 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 preferable 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 preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more.

[0113] As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0114] The method for producing the acrylic resin having a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the acrylic resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0115] As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

[0116] As the basic catalyst, the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0117] 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, a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, 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. Note that the compound having a reactive functional group may or may not have a (meth)acryloyl group.

[0118] The amide-imide resin may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoints 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 preferably one having an acid anhydride group, and more preferably one having both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g as measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened. On the other hand, the measured value under conditions where the acid anhydride group is ring-opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.

[0119] Examples of the amide-imide resin include those obtained using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

[0120] As the polyisocyanate compound, the same compounds as those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

[0121] As the polybasic acid anhydride, the same ones as those exemplified as the above polybasic acid anhydride can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0122] In addition, the amide imide resin can, if necessary, be used in combination with a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride.

[0123] As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. 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-dicarboxylic acid, 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, benzophenonetetracarboxylic acid, etc. can be mentioned. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile and having a carboxyl group in its molecule can also be used. These polybasic acids can be used alone or in combination of two or more.

[0124] As the (meth)acrylate compound having a hydroxyl group, the same ones as those exemplified as the above (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more.

[0125] 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; mono(meth)acrylated products 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.

[0126] The method for producing the amide-imide resin having a polymerizable unsaturated group is not particularly limited, and any method can be used. In the production of the amide-imide resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0127] As the organic solvent, those similar to those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0128] As the basic catalyst, those similar to those exemplified as the above-mentioned basic catalysts can be used, and the basic catalyst can be used alone or in combination of two or more.

[0129] 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 an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

[0130] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified as the compound (a1) having a phenolic hydroxyl group described above can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more.

[0131] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product excellent in elongation, adhesion and dielectric properties can be obtained. The alkylene oxide can be used alone or in combination of two or more.

[0132] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product excellent in elongation, adhesion and dielectric properties can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

[0133] 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 and the like. The N-alkoxyalkyl (meth) acrylamide compound can be used alone or in combination of two or more.

[0134] As the polybasic acid anhydride, the same compounds as those exemplified as the polybasic acid anhydride described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0135] As the unsaturated monobasic acid, those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more kinds.

[0136] The method for producing the acrylamide resin having a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the acrylamide resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

[0137] As the organic solvent, those similar to those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more kinds.

[0138] As the basic catalyst, those similar to those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0139] As the acidic catalyst, those similar to those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more kinds.

[0140] 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 an alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

[0141] As the compound having a phenolic hydroxyl group, those similar to those exemplified as the above-mentioned compound 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 kinds.

[0142] As the alkylene oxide, the same ones as those exemplified as the above-mentioned alkylene oxide can be used. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product excellent in elongation, adhesion, and dielectric properties can be obtained. The alkylene oxide can be used alone or in combination of two or more.

[0143] As the alkylene carbonate, the same ones as those exemplified as the above-mentioned alkylene carbonate can be used. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product excellent in elongation, adhesion, and dielectric properties can be obtained. The alkylene carbonate can be used alone or in combination of two or more.

[0144] As the unsaturated monobasic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

[0145] As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.

[0146] The method for producing the ester resin having a polymerizable unsaturated group is not particularly limited, and it may be produced by any method. In the production of the ester resin having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

[0147] As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

[0148] As the basic catalyst, the same catalysts as those exemplified as the above-mentioned basic catalysts can be used, and the basic catalyst can be used alone or in combination of two or more kinds.

[0149] As the acidic catalyst, the same catalysts as those exemplified as the above-mentioned acidic catalysts can be used, and the acidic catalyst can be used alone or in combination of two or more kinds.

[0150] The usage amount of the resin having the polymerizable unsaturated group is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the (meth)acrylate resin of the present invention.

[0151] As for the various (meth)acrylate monomers, there is no particular limitation as long as they have a (meth)acryloyl group. For example, 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, octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate; aromatic mono(meth)acrylate compounds such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. 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 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 various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate;alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate, 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 is introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate; (poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; aliphatic poly(meth)acrylate compounds having four or more functional groups such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate; four or more functional group-containing (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 is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; four or more functional group-containing lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds;(Meth)acrylate compounds having a hydroxyl group such as 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, ditrimethylolpropane tri(meth)acrylate, etc.; (Poly)oxyalkylene modified products in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, etc. is introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; Lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; (Meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc.; (Meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, etc., and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylate products of diglycidyl ether compounds of polyhydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. These various (meth)acrylate monomers can be used alone or in combination of two or more.;

[0152] In addition, the curable resin composition of the present invention may contain various additives such as a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

[0153] The curing accelerator promotes the curing reaction. Examples thereof include phosphorus compounds, amine compounds, imidazole, metal organic salts, Lewis acids, amine complex salts, etc. These curing accelerators can be used alone or in combination of two or more. In addition, the addition amount of the curing accelerator is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.

[0154] 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; benzotriazoles such as 2-(2'-xanthene carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole; benzophenones such as 2-xanthene carboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

[0155] Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone; and melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.(3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, etc. amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl = bis[3-(dodecylthio)propionate], ditridecan-1-yl = 3,3'-sulfanediyldipropanoate and other thioether compounds, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitroso benzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitron dimethylamine, p-nitron-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, dinitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfonic acid sodium salt, 2-nitroso-1-naphthol-4-sulfonic acid sodium salt, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, ester of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphite compounds such as undecane, tris(nonylphenyl) phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylene tetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S’)zinc, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S’)nickel, 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, sulfur compounds such as dilauryl thiodipropionate, distearyl 3,3’-thiodipropionate, etc. These polymerization inhibitors can be used alone or in combination of two or more.

[0156] As the antioxidant, the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant can be used alone or in combination of two or more.

[0157] Moreover, as commercially available products of the polymerization inhibitor and the antioxidant, for example, "Q-1300", "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S", "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd., etc. can be mentioned.

[0158] As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0159] As the inorganic filler, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. can be mentioned.

[0160] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0161] Examples of the inorganic pigment include, for example, white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, ultramarine blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0162] Examples of the white pigment include, for example, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc.

[0163] Examples of the organic pigment include, for example, quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, quinophthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, azo pigment, etc. These organic pigments can be used alone or in combination of two or more.

[0164] Examples of the flame retardant include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as amide phosphates; phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and organic phosphorus compounds such as derivatives obtained by reacting the same 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 glasses. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

[0165] 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 radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, it may be irradiated in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

[0166] As the ultraviolet light source, an ultraviolet lamp is generally used from the viewpoints of practicality and economy. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, an LED, etc. are mentioned.

[0167] 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 the generation of uncured portions can be prevented or suppressed.

[0168] Note that the irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

[0169] In addition, since the cured product of the present invention is excellent in elongation, adhesion, and dielectric properties, for example, in semiconductor device applications, solder resist, interlayer insulating material, package material, underfill material, package adhesive layer such as circuit elements, and integrated circuit elements It can be suitably used as an adhesive layer between the circuit board. Further, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. in thin display applications typified by LCD and OELD. Among these, it can be particularly suitably used for solder resist applications.

[0170] The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, interior and exterior automotive materials, and OA equipment, as well as semiconductor devices, display devices, and imaging devices.

Examples

[0171] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below. <Evaluation of GPC measurement)> Measurements were performed using the following measuring equipment and conditions, and GPC charts (FIGS. 1 and 2) were obtained for the indane bisphenol compound (1) and indane bisphenol-type epoxy resin (A-1) obtained in the following Synthesis Examples. From the results of the GPC charts, the average number of repeating units (n) contributing to the indane skeleton in the indane bisphenol compound was calculated based on the number-average molecular weight (Mn) of the indane bisphenol compound. (Note that the average number of repeating units (n) of the indane bisphenol-type epoxy resin is the same as the average number of repeating units (n) of the indane bisphenol compound.) Specifically, for compounds where n is 0 to 4, the theoretical molecular weight and each measured molecular weight in GPC were plotted on a scatter diagram, an approximation line was drawn, and the number-average molecular weight (Mn) was determined from the point on the line indicated by the measured value (Mn(1)), and n was calculated. Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution containing 1.0% by mass (in terms of solid content) of the indan bisphenol compound (1) obtained in the synthesis example shown below and the indan bisphenol type epoxy resin (A-1), filtered through a microfilter (50 μl).

[0172] <Softening point> Measurement method: In accordance with JIS K7234 (ring and ball method), the softening point (°C) of the indan bisphenol type epoxy resin obtained in the synthesis example shown below was measured.

[0173] (Synthesis example 1: Synthesis of indan bisphenol compound (1)) Into a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet, 244 parts by mass of 2,6-xylenol, 388 parts by mass of m-bis(α-hydroxyisopropyl)benzene, 633 parts by mass of toluene, and 19 parts by mass of paratoluenesulfonic acid monohydrate were charged while blowing nitrogen gas, and the mixture was heated. During the process, the water generated by the reaction was removed using the Dean-Stark apparatus, and the temperature was raised to 120 °C and held for 10 hours. After cooling the reaction solution, it was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. After removing the catalyst residue by washing with water, the volatile components were distilled off by heating and reduced pressure to obtain the indan bisphenol compound (1). The average number of repeating units n of the obtained indan bisphenol compound (1) was 1.50, and the hydroxyl equivalent was 342 g / equivalent. The GPC chart (Figure 1) of the obtained indan bisphenol compound (1) is shown.

[0174]

Chemical formula

[0175] (Synthesis Example 2: Synthesis of indane bisphenol type epoxy resin (A-1)) A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas. 342 parts by mass of the indane bisphenol compound (1) obtained in Synthesis Example 1 (hydroxyl equivalent: 342 g / equivalent), 370 parts by mass of epichlorohydrin, and 27 parts by mass of n-butanol were charged and dissolved. After heating to 50°C, 220 parts by mass of a 20% aqueous sodium hydroxide solution was added over 3 hours, and the mixture was further reacted at 50°C for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 800 parts by mass of methyl isobutyl ketone and 120 parts by mass of n-butanol were added and dissolved. To this solution, 15 parts by mass of a 10 wt% aqueous sodium hydroxide solution was added, and the mixture was reacted at 80°C for 2 hours. The mixture was then washed with water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain indane bisphenol-type epoxy resin (A-1). The softening point of the obtained indane bisphenol-type epoxy resin (A-1) was 73°C, the epoxy equivalent was 419 g / equivalent, and the average number of repeating units n was the same as that of indane bisphenol compound (1). The GPC chart of the obtained indane bisphenol-type epoxy resin (A-1) is shown in Figure 2.

[0176] [ka] ····(A-1)

[0177] (Synthesis Example 3: Production of phenolic resin (r1)) Into a flask equipped with a stirrer, a cooling tube, and a nitrogen inlet, while blowing nitrogen gas, 360 parts by mass of α-naphthol, 586 parts by mass of toluene, and 377 parts by mass of bis(chloromethyl)biphenyl were charged and heated to 80°C. 245 parts by mass of a 49% aqueous sodium hydroxide solution was added dropwise thereto over 1 hour, and then heated to 90°C and held for 11 hours. It was neutralized with 85% phosphoric acid until the pH became neutral, the stirring was stopped, and the lower layer was withdrawn. 15 parts by mass of p-toluenesulfonic acid was added, and it was heated to 180°C over 2 hours while distilling off the volatile components, then neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral, and the pressure was reduced while maintaining the internal temperature to distill off the volatile components, obtaining a phenol resin (r1). The hydroxyl equivalent was 272 g / equivalent.

[0178] (Synthesis Example 4: Production of Epoxy Resin (A-2)) Into a flask equipped with a thermometer, a cooling tube, and a stirrer, while purging with nitrogen gas, 272 parts by mass of the phenol resin (r1) obtained in Synthesis Example 3, 740 parts by mass of epichlorohydrin, and 53 parts by mass of n-butanol were charged and dissolved. After raising the temperature to 50°C, 220 parts by mass of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then reacted at 50°C for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 600 parts by mass of methyl isobutyl ketone and 100 parts by mass of n-butanol were added and dissolved. Further, 15 parts by mass of a 10 wt% aqueous sodium hydroxide solution was added to this solution and reacted at 80°C for 2 hours, and then washed with water repeatedly until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through a fine filtration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (A-2). The softening point of the obtained epoxy resin (A-2) was 100°C, and the epoxy equivalent was 325 g / equivalent.

[0179] (Example 1: Production of Epoxy Acrylate Resin (1)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 114 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indane bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 36 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 °C for 20 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain the target epoxy acrylate resin (1). The non-volatile content of this epoxy acrylate resin (1) was 80% by mass, and the epoxy equivalent of the solid content was 932 g / equivalent. Also, the molar ratio of the acid groups of acrylic acid to 1 mol of the epoxy groups of the indane bisphenol type epoxy resin (A-1) was 0.5 mol.

[0180] (Example 2: Production of epoxy acrylate resin (2)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 119 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indane bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 18 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 °C for 12 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain the target epoxy acrylate resin (2). The non-volatile content of this epoxy acrylate resin (2) was 80% by mass, and the epoxy equivalent of the solid content was 297 g / equivalent. Also, the molar ratio of the acid groups of acrylic acid to 1 mol of the epoxy groups of the indane bisphenol type epoxy resin (A-1) was 0.25 mol.

[0181] (Example 3: Production of epoxy acrylate resin (3)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 117.5 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indan bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 10.8 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C for 3 hours to obtain the target epoxy acrylate resin (3). The non-volatile content of this epoxy acrylate resin (3) was 80% by mass, and the epoxy equivalent of the solid content was 253 g / equivalent. Also, the molar number of the acid groups of acrylic acid with respect to 1 mol of the epoxy groups of the indan bisphenol type epoxy resin (A-1) was 0.15 mol.

[0182] (Example 4: Production of epoxy acrylate resin (4)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 118.3 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indan bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 54 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 15 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 1.4 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C for 3 hours to obtain the target epoxy acrylate resin (4). The non-volatile content of this epoxy acrylate resin (4) was 80% by mass, and the epoxy equivalent of the solid content was 1015 g / equivalent. Also, the molar number of the acid groups of acrylic acid with respect to 1 mol of the epoxy groups of the indan bisphenol type epoxy resin (A-1) was 0.75 mol.

[0183] (Example 5: Production of epoxy acrylate resin (5)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 160 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indan bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 54 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 °C for 18 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 1.4 parts by mass of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain the target epoxy acrylate resin (5). The non-volatile content of this epoxy acrylate resin (5) was 75% by mass, and the epoxy equivalent of the solid content was 1756 g / equivalent. Also, the molar ratio of the acid groups of acrylic acid to 1 mol of the epoxy groups of the indan bisphenol type epoxy resin (A-1) was 0.85 mol.

[0184] (Example 6: Production of epoxy acrylate resin (6)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 210.4 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indan bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.3 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 2.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 °C for 12 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, the target epoxy acrylate resin (6) was obtained. The non-volatile content of this epoxy acrylate resin (6) was 70% by mass, and the epoxy equivalent of the solid content was 10940 g / equivalent. Also, the molar ratio of the acid groups of acrylic acid to 1 mol of the epoxy groups of the indan bisphenol type epoxy resin (A-1) was 1.0 mol.

[0185] (Example 7: Production of epoxy methacrylate resin (1)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 115.5 parts by mass of methyl isobutyl ketone and 419 parts by mass of the indan bisphenol type epoxy resin (A-1) obtained in Synthesis Example 2 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 43 parts by mass of methacrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 20 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C for 3 hours to obtain the target epoxy methacrylate resin (1). The non-volatile content of this epoxy methacrylate resin (1) was 80% by mass, and the epoxy equivalent of the solid content was 936 g / equivalent. Also, the molar number of the acid groups of methacrylic acid with respect to 1 mol of the epoxy groups of the indan bisphenol type epoxy resin (A-1) was 0.5 mol.

[0186] (Comparative Example 1: Production of Epoxy Acrylate Resin (R1)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 90.3 parts by mass of methyl isobutyl ketone and 325 parts by mass of the epoxy resin (A-2) obtained in Synthesis Example 4 were charged. After adding 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 36 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 20 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C for 3 hours to obtain the epoxy acrylate resin (R1). The non-volatile content of this epoxy acrylate resin (R1) was 80% by mass, and the epoxy equivalent of the solid content was 753 g / equivalent.

[0187] (Example 8: Preparation of Curable Resin Composition (1)) 100 parts by mass (80 parts by mass as solid content) of the epoxy acrylate resin (1) having a non-volatile content of 80% by mass obtained in Example 1, 20 parts by mass of an acrylate monomer, a photopolymerization initiator (5 parts by mass of "Omnirad 184D" manufactured by IGM Resins and 1.6 parts by mass of 2-ethyl-4-methylimidazole were mixed to obtain a curable resin composition (1).

[0188] (Examples 9 to 14: Preparation of curable resin compositions (2) to (7)) Except that the epoxy acrylate resins (2) to (6) and epoxy methacrylate resin (1) obtained in Examples 2 to 7 were used in the blending amounts shown in Table 1 instead of the epoxy acrylate resin (1) used in Example 8, curable resin compositions (2) to (7) were obtained in the same manner as in Example 8.

[0189] (Comparative Example 2: Preparation of curable resin composition (R1)) 100 parts by mass (80 parts by mass as solid content) of the acrylate resin (R1) with a nonvolatile content of 80% by mass obtained in Comparative Example 1, 20 parts by mass of an acrylate monomer, 5 parts by mass of a photopolymerization initiator ("Omnirad 184D" manufactured by IGM Resins), and 1.6 parts by mass of 2-ethyl-4-methylimidazole were mixed to obtain a curable resin composition (R1).

[0190] Using the curable resin compositions (1) to (7) and (R1) obtained in the above Examples and Comparative Examples, the following evaluations were conducted.

[0191] [Method for measuring elongation] The elongation was measured based on a tensile test. [Preparation of test piece 1] The curable resin compositions obtained in the Examples and Comparative Examples were applied onto a copper foil (electrolytic copper foil "F2-WS" 18 μm manufactured by Furukawa Electric Co., Ltd.) using a 50 μm applicator, irradiated with ultraviolet rays of 10 kJ / m 2 and then heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product).

[0192] [Tensile test] The test piece 1 was cut into a size of 10 mm × 80 mm, and a tensile test of the test piece 1 was conducted under the following measurement conditions using a precision universal testing machine Autograph "AG-IS" manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured.

[0193] Measurement conditions: temperature 23°C, humidity 50%, distance between scale lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm / min

[0194] [Evaluation method for adhesion] The evaluation of adhesion was carried out by measuring the peel strength. [Preparation of test piece 2] The curable resin composition obtained in the examples and comparative examples was applied onto a copper foil (manufactured by Furukawa Electric Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50-μm applicator, irradiated with ultraviolet rays of 10 kJ / m 2 and then heated at 160°C for 1 hour to obtain test piece 2.

[0195] [Measurement method for peel strength] The test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and the 90° peel strength was measured using a peel tester ("A&D tensilon" manufactured by A&D Company, Limited, peel speed 50 mm / min).

[0196] [Measurement method for dielectric constant] The curable resin composition obtained in each example and comparative example was applied onto a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80°C for 30 minutes. Then, after irradiating with ultraviolet rays of 10 kJ / m 2 a cured coating film was obtained by heating at 160°C for 1 hour. Then, the cured coating film was peeled from the glass substrate to obtain a cured product. Then, the one stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours was used as a test piece, and the dielectric constant of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[0197] [Measurement method for dielectric tangent] The curable resin composition obtained in each example and comparative example was applied onto a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80°C for 30 minutes. Then, after irradiating with ultraviolet rays of 10 kJ / m 2After irradiating with ultraviolet rays, it was heated at 160 °C for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Then, the one stored in a room at a temperature of 23 °C and a humidity of 50% for 24 hours was used as a test piece, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[0198] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (7) prepared in Examples 8 to 14 and the curable resin composition (R1) prepared in Comparative Example 2.

[0199]

Table 1

[0200] The description of the parts by mass of the epoxy acrylate resin and the epoxy methacrylate resin in Table 1 is the solid content value.

[0201] In addition, "acrylate monomer" in Table 1 indicates EO-modified diacrylate of bisphenol A ("Miramaer M240" manufactured by Miwon Specialty Chemical).

[0202] "Photoinitiator" in Table 1 indicates "Omnirad 184D" manufactured by IGM Resins.

[0203] Examples 8 to 14 shown in Table 1 are examples of curable resin compositions using the epoxy (meth) acrylate resin of the present invention. It was confirmed that the cured products of these curable resin compositions have excellent elongation, adhesion, and dielectric properties.

[0204] On the other hand, Comparative Example 2 shown in Table 1 is an example of a curable resin composition that does not use an indane bisphenol type epoxy resin having an indane skeleton represented by the general formula (1) as a raw material of the epoxy (meth) acrylate resin. It was confirmed that the cured product of this curable resin composition has insufficient elongation, adhesion, and dielectric properties.

Claims

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

2. The epoxy (meth)acrylate resin according to Claim 1, wherein the number of moles of the acid group of the unsaturated monobasic acid (B) is in the range of 0.2 to 0.8 with respect to 1 mole of the epoxy group of the epoxy resin (A).

3. The epoxy (meth)acrylate resin according to Claim 1 or 2, wherein the epoxy (meth)acrylate resin has an epoxy group and a (meth)acryloyl group.

4. A curable resin composition comprising the epoxy (meth)acrylate resin according to any one of Claims 1 to 3 and a photoinitiator.

5. The curable resin composition according to Claim 4, further comprising a (meth)acrylate monomer.

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

7. An article characterized by having a coating film comprising the cured product according to Claim 6.

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