TW201809059A - Composition, curing agent, prepreg and laminated board - Google Patents

Abstract

The invention relates to a composition, a curing agent, a prepreg, and a laminated board. The invention provides a curing agent composition which can improve the solubleness of an epoxy resin curing agent having excellent dielectric property, has balanced characteristics, and can improve the dielectric property and the adhesive strength, and an epoxy resin composition using the same. The epoxy resin curing agent composition is acquired by dissolving a bisphenol compound (A) represented by the following formula (1) and having an alicyclic structure and a phenol compound (B) represented by the following formula (2) in an organic solvent (c) selecting from non-aromatic solvents, wherein the mass ratio of the bisphenol compound (A) and the phenol compound (B) is (A) : (B)=5:95-95:5.

Description

Composition, hardened material, prepreg and laminated board

The present invention relates to an epoxy resin hardener composition that provides a hardened product with low dielectric properties and excellent adhesion, and an epoxy resin composition containing the hardener composition and an epoxy resin, and a cured product thereof.

Significant progress has been made in electrical and electronic equipment. In particular, printed wiring boards in data communication equipment perform large-capacity and high-speed processing of data. Therefore, requirements for improving dielectric properties such as low dielectric constant and low dielectric loss tangent are increasing. In addition, the wiring of metal foil is used to guarantee the adhesion by roughening. However, due to the necessity of high-speed processing in recent years, there is a tendency to suppress the roughening. Therefore, the problem of securing the adhesion has also become apparent.

As a method for improving the dielectric properties of epoxy resins, as shown in the Clausius-Mossotti equation, a decrease in the molar polarizability and an increase in the molar volume are effective. As an epoxy resin hardener to which the effect by an increase in the molar volume is applied, Patent Document 1 discloses a dicyclopentadiene / phenol resin. Then, the improvement of dielectric properties is also high, and compounds of various skeletons are being studied.

As a method for improving the dielectric properties, the present inventors focused on a bisphenol compound having an aliphatic ring as a linking group as a curing agent. However, this compound lacks solvent solubility when used in printed wiring board applications, and there is a problem that a sufficient concentration of a hardener solution (varnish) cannot be obtained.

Patent Document 2 discloses the use of a bisphenol compound such as bisphenol trimethylcyclohexylene as an epoxy resin raw material. Further, it is also disclosed that it can be used as a hardener for epoxy resins, but this is only a possibility, and there are no examples of concrete use as a hardener. Of course, there is no description about dielectric properties or solvent solubility.

On the other hand, the use of styrene-modified novolak resins as a hardener is disclosed in Patent Documents 3 to 4. However, although this hardener is excellent in heat resistance, dielectric properties, and the like, it has a problem in terms of adhesion. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2015-535865 [Patent Literature 2] Japanese Patent Publication No. 2-229181 [Patent Literature 3] Japanese Patent Publication No. 2010-235819 [Patent Literature 4] Japanese Patent Special Publication No. 2012-57079

[Problems to be Solved by the Invention] Although the present inventors have found that a bisphenol compound having an aliphatic ring as a linking group exhibits good dielectric properties as a hardener, they understand that its solvent solubility is poor and there is a problem that a sufficient concentration cannot be obtained. Problems with hardener solution. An object of the present invention is to provide an epoxy resin hardener composition that not only improves the solvent solubility of the hardener, but also improves the balance of characteristics such as dielectric properties and adhesion. Another object is to provide an epoxy resin composition that can easily obtain a prepreg useful as a printed wiring board application having excellent dielectric properties. [Means for solving problems]

That is, this invention is an epoxy resin hardener composition characterized by including the bisphenol compound (A) represented by following General formula (1), and the phenol compound (A) represented by following General formula (2). B) Dissolved in an organic solvent (C) selected from a non-aromatic solvent, and the mass ratio of the bisphenol compound (A) to the phenol compound (B) is (A): (B) = 5:95 ~ 95: 5. [Chemical 1] (Wherein R ¹ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon number An aralkyl group of 7 to 20 and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group of 1 to 20 carbon atoms, an alicyclic hydrocarbon group of 3 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 20 carbon atoms, and carbon number An aralkyl group of 7 to 20 or a halogenated alkyl group of 1 to 20 carbons, at least one of the ² m R ² is a group other than a hydrogen atom, and m is an integer of 3 to 9) [Chem. 2] (Wherein R ³ independently represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a substituent represented by the following general formula (3), k represents a number from 1 to 20, and p represents 0.1 to 2.5 Number) (Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁷ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and q represents an integer of 0 to 5)

A preferred aspect of the present invention is that the epoxy resin hardener composition satisfies any one or more of the following conditions: the total amount (A + B) of the bisphenol compound (A) and the phenol compound (B) and the non-aromatic system The mass ratio of the solvent (C) is (A + B): (C) = 45: 55 ～ 85: 15; the non-aromatic solvent (C) is a ketone solvent or a glycol solvent; the viscosity of the solution at 25 ° C It is in the range of 15 mPa · s to 5000 mPa · s; or it further contains a hardening accelerator (D).

In addition, the present invention is an epoxy resin composition, characterized in that an epoxy resin (E) is blended in the epoxy resin hardener composition.

The epoxy resin composition preferably has a phenolic hydroxyl group in the memory in a range of 0.2 mol to 1.5 mol with respect to 1 mol of the epoxy group of the epoxy resin (E).

In addition, the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition.

In addition, the present invention is a prepreg obtained by impregnating the epoxy resin composition into a substrate.

In addition, the present invention is an epoxy resin laminated board characterized by using the epoxy resin composition.

In addition, the present invention is an epoxy laminated board, which is characterized by using the prepreg. [Effect of the invention]

The epoxy resin hardener composition of the present invention is useful as a printed wiring board application because the solvent solubility is improved and impregnation in glass cloth is facilitated. In addition, a prepreg, a cured product, or a laminated board obtained by blending an epoxy resin composition with an epoxy resin in the epoxy resin hardener composition not only improves heat resistance and dielectric properties, but also improves It achieves an improvement in adhesion and is useful as a circuit board material with excellent balance of characteristics that cannot be obtained by itself.

Hereinafter, embodiments of the present invention will be described in detail. The epoxy resin hardener composition of the present invention is obtained by dissolving a bisphenol compound (A) and a phenol compound (B) in a solvent.

The bisphenol compound (A) is represented by the general formula (1). In the formula, the position of the hydroxyl group may be any of the ortho, para, or meta positions with respect to the carbon atom bonded to the cycloalkylene group, but is preferably ortho or para, and more preferably para.

R ^{1 is} independently selected from a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms In the group consisting of aralkyl groups, in order to respond to the environment, when forming a halogen-free substrate, it is preferable to use a substituent other than a halogen atom, and a large substituent is preferable from the viewpoint of dielectric properties. However, although it also depends on the substitution position, the reactivity of the phenolic hydroxyl group is reduced due to the steric hindrance of a large substituent group, and it may not be able to harden smoothly, and the characteristics may be deteriorated. Therefore, it is necessary to pay attention to the selection. The substitution position of R ¹ with respect to the carbon atom bonded to the cycloalkylene group may be any of the ortho, para, and meta positions. Moreover, it is preferably ortho with respect to a hydroxyl group. All or two to three R ¹ are preferably a hydrogen atom.

R ^{2 is} independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. In the group consisting of haloalkyl groups having 1 to 20 carbon atoms, at least one is a group (substituent) other than a hydrogen atom. That is, although 2 m of R ² are present, at least one, preferably one to four, of R ² is the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, or haloalkyl group. In the case of forming a halogen-free substrate, other than the halogenated alkyl group, a large molecular structure is preferable from the viewpoint of dielectric properties. When R ² is a substituent other than hydrogen, the substitution position may be any position, but it is preferably a carbon atom close to the 1-position of the cycloalkylene group. In this position, there is little effect on the reactivity of the phenolic hydroxyl group, and rigidification of the skeleton is caused by steric hindrance, which may contribute to improvement of heat resistance. m is an integer of 3 to 9, preferably 4 to 7, and more preferably 4 to 5.

Among R ¹ and R ² , the aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, and hexyl. The alicyclic hydrocarbon group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 5 to 8 carbon atoms, and examples thereof include a cyclohexyl group and the like. The aromatic hydrocarbon group having 6 to 20 carbon atoms or the aralkyl group having 7 to 20 carbon atoms is preferably an aryl group having 6 to 13 carbon atoms or an aralkyl group having 7 to 14 carbon atoms, and examples thereof include phenyl, tolyl, ortho Xylyl, naphthyl, benzyl, phenethyl, 1-phenylethyl and the like. The halogenated alkyl group having 1 to 20 carbon atoms in R ² is preferably a halogenated alkyl group having 1 to 4 carbon atoms, and examples thereof include a brominated methyl group and the like. Examples of the halogen in R ¹ include fluorine, chlorine, and bromine. R ¹ and R ² are groups (substituents) other than a hydrogen atom, and when there are a plurality of the groups in the molecule, these substituents may be the same as or different from each other. From the viewpoint of ease of acquisition and physical properties of the cured product, a more preferred substituent is a methyl group or a phenyl group.

Specific examples of the bisphenol compound (A) include, but are not limited to, the phenol compounds shown below.

[Chemical 4]

These exemplified phenol compounds are also available as commercial products, and examples thereof include BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP-IPZ, BisP-nBZ, BisOEP-2HBP (above, trade names, manufactured by Honshu Chemical Industry Co., Ltd.) and the like.

Although the bisphenol compound (A) provides an epoxy resin composition or cured product with good characteristics, it is necessary to prepare an epoxy resin composition that is dissolved in a solvent when it is used as a prepreg for a printed wiring board. For this reason, it is necessary to dissolve the bisphenol compound (A) stably in a solvent. However, the bisphenol compound (A) can be dissolved only under limited conditions because of its high crystallinity. Therefore, it can be seen that problems occur in the steps described later.

The limited condition that the solvent can be dissolved means that the amount of the bisphenol compound (A) that can be dissolved is very small. When the glass cloth is impregnated and solvent-dried, the epoxy resin composition becomes low-viscosity and the resin component changes. less. In addition, the amount of dissolution can also be increased by heating, but there are new concerns about crystal precipitation caused by temperature reduction during storage or preparation, and preservation of the epoxy resin composition caused by preparation at high temperatures. Issues such as stability.

The present inventors have conducted intensive studies on this subject, and as a result, have found that by mixing the phenol compound (B) represented by the general formula (2), the solubility of the solvent can be improved, and it can be stably stored and managed at room temperature. An epoxy resin composition obtained by blending an epoxy resin therein is also a good one.

As the phenol compound (B) represented by the general formula (2), those known in Patent Document 3 or Patent Document 4 can be used.

In the general formula (2), R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group, a tert-butyl group, or a phenyl group, and more preferably a hydrogen atom or a methyl group. R ⁴ represents a substituent represented by the general formula (3). k is preferably a number of 1 to 20 in terms of the number of repetitions, and its average value (number average) is 1 to 20, preferably 1.5 or more, more preferably 1.7 to 10, particularly preferably 2.0 to 5.0, and even more preferably 2.2 to 4.0. In addition, p represents a number of 0.1 to 2.5 as an average value (quantity average), preferably 0.5 to 2.0, and more preferably 1.0 to 1.5.

In the general formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably one of R ⁵ and R ⁶ is a hydrogen atom. And the other is methyl. R ⁷ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, preferably a methyl group, a tert-butyl group, or a phenyl group, and more preferably a methyl group. q represents an integer of 0 to 5, and is preferably 0 or 1. Specific examples of the substituent represented by the general formula (3) include benzyl, methylbenzyl, ethylbenzyl, isopropylbenzyl, tert-butylbenzyl, cyclohexylbenzyl, and phenylbenzyl , Dimethylbenzyl, 1-phenylethyl, 1-tolylethyl, 1-xylylethyl, α-cumyl (2-phenylpropane-2-yl), 2-tolylpropane 2-yl, 2-xylylpropane-2-yl, and the like.

Specific examples of the phenol compound (B) include, for example, a resin obtained by adding an aromatic modifier to a phenol novolac resin, or a phenol substituted with an aralkyl group, and others as necessary. Phenol is a resin made of novolac together with formaldehyde. Examples of the aralkyl-substituted phenol include styrenated phenol and cumylphenol. Examples of preferred forms when using formaldehyde for the reaction include formalin aqueous solution, p-formaldehyde, and trioxane. Examples of the aromatic modifier include styrenes or benzylating agents. The styrenes may contain a small amount of unsaturated bond-containing components such as α-methylstyrene, divinylbenzene, indene, benzofuran, benzothiophene, indole, and vinylnaphthalene as impurities. Examples of benzylating agents include benzyl chloride, benzyl bromide, benzyl iodide, methyl benzyl chloride, ethyl benzyl chloride, isopropyl benzyl chloride, tert-butyl benzyl chloride, and cyclohexyl benzyl chloride. , Phenylbenzyl chloride, methylbenzyl chloride, α, α-dimethylbenzyl chloride, etc., benzyl methyl ether, methyl benzyl methyl ether, ethyl benzyl methyl ether, benzyl ethyl Ether, benzylpropyl ether, benzylbutyl ether, etc., benzyl alcohol, methyl benzyl alcohol, ethyl benzyl alcohol, propyl benzyl alcohol, butyl benzyl alcohol, cyclohexyl benzyl alcohol, Phenylbenzyl alcohol, methylbenzyl alcohol, dimethylbenzyl alcohol, and the like.

By setting the blending ratio (mass ratio) of the bisphenol compound (A) and the phenol compound (B) to a range of (A) :( B) = 5: 95 to 95: 5, it is possible to stably dissolve in a solvent at a high concentration. in. From the viewpoint of solubility, it is sufficient if it is the above-mentioned blending ratio, but in the case of reducing the dielectric loss tangent, it is preferable to use a plurality of phenol compounds (B), and preferably (A): (B) = 60 : 40 to 5: 95. In addition, in the case of improving the adhesive force, it is preferable to use a plurality of bisphenol compounds (A), and more preferably (A) :( B) = 40: 60 to 95: 5.

The solvent used in the epoxy resin hardener composition of the present invention is a non-aromatic solvent, and preferably a non-aromatic polar solvent. Examples of non-aromatic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclopentanone, and cyclohexanone; or ethylene glycol, propylene glycol, and butanediol. Diols such as diethylene glycol, diethylene glycol, or methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethyl cellosolve, methoxypropanol, ethoxypropanol, methylcarbitol Glycol ethers such as alcohol, butyl carbitol, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or cellosolve acetate, methyl cellosolve acetate, methoxypropyl Glycol esters such as methyl acetate, ethyl carbitol acetate, or N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Isoamidine, or alcohols such as methanol, ethanol, isopropanol, butanol, or ethers such as diethyl ether, tetrahydrofuran, or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and diethylene glycol Esters such as ethyl esters, or lactones such as γ-butyrolactone, fluorenes such as dimethylsulfinium, or ureas such as tetramethylurea, or dichloromethane, 1,2-dichloroethane Halogenated hydrocarbons such as 1,4-dichlorobutane, or nitriles such as acetonitrile, etc., but Limited thereto, it may be one, and can also be used more. The boiling point of these non-aromatic solvents is preferably 30 ° C to 230 ° C, more preferably 50 ° C to 200 ° C, particularly preferably 65 ° C to 180 ° C, and particularly preferably 75 ° C to 160 ° C. Regarding the selection of the solvent, in addition to solubility, it is important to have a boiling point or evaporation rate that can be removed by heating when making a prepreg, and can be selected according to the process temperature. Among these non-aromatic solvents, ketone solvents (C1) and glycol solvents (C2) are preferred, and methyl ethyl ketone, cyclopentanone, and methoxypropanol are particularly preferred from the viewpoint of evaporability or boiling point. Preferred. The glycol-based solvent (C2) includes all glycols, glycol ethers, and glycol esters.

Regarding the amount of the solvent, it is important to dissolve the resin component so as not to impede the impregnating viscosity in the glass cloth when the prepreg is made, and to maintain a necessary amount of the resin component when the prepreg is formed. In addition, it is preferably as small as possible due to the energy that needs to be removed during transportation, storage, or prepreg formation. The solubility of the bisphenol compound (A) is greatly improved by using the phenol compound (B) in combination. Therefore, the amount of the solvent in the epoxy resin hardener composition is preferably such that the solution viscosity at 25 ° C is 15 mPa · s to 5000 mPa · The range of s. If the solution viscosity is too high, the impregnation property in the base glass cloth tends to decrease. The viscosity of the solution varies with the type or amount of the solvent, and also changes with the molecular weight or viscosity of the phenol compound (B), so it must be adjusted. Therefore, the mass ratio of the total amount (A + B) of the bisphenol compound (A) and the phenol compound (B) to the non-aromatic solvent (C) is preferably (A + B): (C) = 45: 55 ～ 85:15, more preferably 50:50 to 80:20, particularly preferably 55:45 to 75:25, and particularly preferably 60:35 to 70:30. In the case of only the bisphenol compound (A), if the resin component (non-volatile content) is 45% or more, crystals are precipitated, but by forming a mixture of the bisphenol compound (A) and the phenol compound (B), even if it is not volatile, The component is 45% or more, and more preferably 50% or more, and crystals do not precipitate. The epoxy resin hardener composition of the present invention is preferably a solution (varnish-like) dissolved in the solvent. More preferred is a homogeneous solution.

The epoxy resin hardener composition may contain a hardening accelerator (D). As the hardening accelerator, a general hardening accelerator used in a phenol hardening system can be used, and specific examples include imidazole-based, phosphine-based, amine-based, 1,8-diazabicyclo [5.4.0] 11-7 -Ene (1,8-diazabicyclo [5.4.0] undec-7-ene, DBU), etc., but it is not limited thereto.

The blending amount of the hardening accelerator (D) may be appropriately selected according to the purpose of use, but it is used in an amount of 0.02 to 15 parts by mass based on 100 parts by mass of the total of the bisphenol compound (A) and the phenol compound (B). . It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and particularly preferably 0.5 to 5 parts by mass. By using a hardening accelerator, the hardening temperature can be reduced or the hardening time can be shortened.

The epoxy resin (E) is blended in the epoxy resin hardener composition to obtain an epoxy resin composition. The usable epoxy resin (E) is not particularly limited, and it is a conventionally used epoxy resin, and a polyfunctional epoxy resin containing two or more epoxy groups is preferred. Specific examples include, but are not limited to, polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more epoxy resins of the same system may be used in combination, and epoxy resins of different systems may be used in combination.

Specific examples of the polyglycidyl ether compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, biphenol type epoxy resin, and hydroquinone type. Epoxy resin, bisphenol fluorene type epoxy resin, naphthalene glycol type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, m-phenylene Phenolic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alkyl novolac epoxy resin, aromatic modified phenol novolac epoxy resin, bisphenol novolac ring Oxygen resin, naphthol novolac epoxy resin, β-naphthol aralkyl epoxy resin, naphthyl glycol aralkyl epoxy resin, α-naphthol aralkyl epoxy resin, biphenyl Aralkylphenol epoxy resin, trihydroxyphenylmethane epoxy resin, tetrahydroxyphenylethane epoxy resin, dicyclopentadiene epoxy resin, alkylene glycol epoxy resin, The aliphatic cyclic epoxy resin and the like are not limited to these.

Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resin, m-xylylenediamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, Isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, aminophenol type epoxy resin, etc. are not limited to these.

Specific examples of the polyglycidyl ester compound include, but are not limited to, dimer acid epoxy resin, hexahydrophthalic acid epoxy resin, trimellitic acid epoxy resin, and the like.

Examples of the alicyclic epoxy compound include, but are not limited to, aliphatic cyclic epoxy resins such as Celloxide 2021 (manufactured by Daicel Chemical Industry Co., Ltd.).

Specific examples of other modified epoxy resins include urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy-modified polybutadiene rubber derivatives, and carboxyl-terminated butyronitrile (Carboxyl-terminated butyronitrile, CTBN) modified epoxy resin, polyvinyl aromatic hydrocarbon polyoxides (eg, divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resin, etc. But it is not limited to these.

In particular, for the purpose of lowering the dielectric constant, the epoxy resin (E) is preferably an epoxy resin containing an aliphatic substituent. For the purpose of further improving heat resistance, a polyfunctional phenol novolac is preferred. The varnish-type epoxy resin and cresol novolac-type epoxy resin are preferably bisphenol A-type epoxy resin and bisphenol F-type epoxy resin for the purpose of reducing viscosity, but they are not limited to these.

In the epoxy resin composition of the present invention, a curing agent other than the bisphenol compound (A) and the phenol compound (B) may be used in combination as long as the physical properties are not impaired. The curing agent that can be used in combination is not particularly limited, and it is not particularly limited if the epoxy resin is to be cured. A phenol-based curing agent, acid anhydride-based curing agent, amine-based curing agent, or hydrazine-based curing agent other than those described above can be used. Agents, active ester-based hardeners, phosphorus-containing hardeners and other hardeners for epoxy resins. These hardeners may be used alone, or two or more hardeners of the same system may be used in combination, and hardeners of different systems may be used in combination. The range in which the epoxy resin composition does not impair physical properties refers to a mixture of a bisphenol compound (A) and a phenol compound (B) with respect to 100 parts by mass of the epoxy resin composition containing other hardeners. The amount of the bisphenol compound (A) is 5 parts by mass or more, preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.

Examples of the phenol-based hardener include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolac resin, and naphthol -A phenol co-condensation novolak resin, a naphthol-cresol co-condensation novolak resin, a biphenyl-modified phenol resin, a biphenyl-modified naphthol resin, and an aminotriazine-modified phenol resin, but it is not limited to these.

In addition, a benzoxazine compound that is ring-opened to a phenol compound by heating can also be used as a hardener. Specific examples include benzoxazine compounds such as bisphenol A type, bisphenol F type, and bisphenol S type, but are not limited thereto.

Specific examples of the acid anhydride-based hardener include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and phthalic acid. Acid anhydride, trimellitic anhydride, hydrogenated trimellitic anhydride, methylnadic anhydride, succinic anhydride, maleic anhydride, etc., or 4,4'-oxydiphthalic anhydride, 4,4'-di Phthalic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like, but it is not limited to these.

Examples of the amine-based hardener include 2,4,6-tris (dimethylaminomethyl) phenol, dimer diamine, dicyandiamine and derivatives thereof, or acids such as dimer acids and Polyamine-based condensates such as polyamines and other amine-based compounds are not limited thereto.

Specific examples of the hydrazine-based hardener include, but are not limited to, dihydrazide adipate, dihydrazide isophthalate, dihydrazide sebacate, and dihydrazide dodecanedioate.

Examples of the active ester-based hardener include a reaction product of a polyfunctional phenol compound and an aromatic carboxylic acid as described in Japanese Patent No. 5152445, and Epiclon HPC-8000-65T (Dicson ( (DIC) Co., Ltd.), etc., but not limited to these.

The ratio of the epoxy resin and the hardener in the epoxy resin composition is preferably 1 mole to the epoxy group of the epoxy resin, and the phenolic hydroxyl group is 0.2 to 1.5 moles. When a curing agent other than a phenolic curing agent is used in combination as the curing agent, the active hydrogen group of the curing agent is preferably 0.2 mol to 1.5 mol relative to 1 mol of the epoxy group of the epoxy resin. Regardless of whether the ratio of the phenolic hydroxyl group or the active hydrogen group of the hardener is lower or higher than the above range, there is a concern that hardening becomes incomplete and good hardened physical properties cannot be obtained. A preferred range is 0.3 to 1.5 mol, a more preferred range is 0.5 to 1.5 mol, and a particularly preferred range is 0.8 to 1.2 mol. From another viewpoint, the total of the phenolic hydroxyl groups of the bisphenol compound (A) and the phenol compound (B) is preferably 0.8 mol to 1.2 mol relative to 1 mol of the epoxy group of the epoxy resin (E). It is more preferably 0.9 mol to 1.1 mol, and particularly preferably 0.95 mol to 1.05 mol. When the hardening agent other than the bisphenol compound (A) and the phenol compound (B) is used in the epoxy resin composition, it is preferable to add the optimal blending amount of the epoxy resin or hardening agent to be used later. the amount. For example, when a phenol-based hardener, an amine-based hardener, or an active ester-based hardener is used in combination, it is preferable to mix an active hydrogen group of approximately equal moles with respect to the epoxy group, and when an acid anhydride-based hardener is used in combination, An acid anhydride group of 0.5 mol to 1.2 mol, preferably 0.6 mol to 1.0 mol is preferably blended with respect to 1 mol of the epoxy group.

The active hydrogen group refers to a functional group containing an active hydrogen reactive with an epoxy group (a functional group containing a potential active hydrogen that generates active hydrogen by hydrolysis or the like, or a function exhibiting an equivalent hardening effect) Group), specifically, an acid anhydride group, a carboxyl group, an amine group, or a phenolic hydroxyl group. In addition, as for the active hydrogen group, a carboxyl group (-COOH) or a phenolic hydroxyl group (-OH) was calculated as 1 mole, and an amine group (-NH ₂ ) was calculated as 2 moles. When the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the hardener used can be determined by reacting a single epoxy resin with a known epoxy equivalent such as phenyl glycidyl ether and a hardener with an unknown active hydrogen equivalent, and measuring the amount of the single epoxy resin consumed. Of active hydrogen equivalent.

Fillers (fillers) can also be blended in the epoxy resin composition. Specific examples include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, Inorganic fillers such as clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, or carbon fiber, glass fiber, alumina fiber , Silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramide fiber, ceramic fiber and other fibrous fillers, or fine particle rubber. Among these fillers, those which do not decompose or dissolve with an oxidizing compound such as an aqueous solution of a permanganate used in the surface roughening treatment of the hardened material are preferred. Particularly, fused silica or crystalline silica is easily available. Fine particles are preferred. Moreover, when the compounding quantity of a filler is especially increased, it is preferable to use a fused silica. The fused silica may be either crushed or spherical. However, in order to increase the amount of fused silica and to suppress an increase in the melt viscosity of the molding material, it is more preferable to use spheres mainly. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the fineness distribution of the spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. The reason for generally using a filler includes the effect of improving the impact resistance of a hardened material, and the low linear expansion of the hardened material. Moreover, when metal hydroxides, such as aluminum hydroxide, boehmite, and magnesium hydroxide, are used, it functions as a flame retardant adjuvant, and has the effect of improving flame retardance. When used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

When the linear expansion of a hardened | cured material or flame retardance is considered, it is preferable that the compounding quantity of a filler is high. The solid content (non-volatile content) in the epoxy resin composition is preferably 1% to 90% by mass, more preferably 10% to 85% by mass, particularly preferably 40% to 80% by mass, and particularly preferably It is preferably 50% by mass to 70% by mass. When there are many compounding quantities, there exists a possibility that the adhesiveness required for a laminated board use may fall, and there exists a possibility that a hardened | cured material may become brittle and sufficient mechanical physical property may not be obtained. In addition, if the blending amount is small, there is a concern that the blending effect of the filler, such as improvement of the impact resistance of the cured product, does not occur.

The average particle diameter of the filler is preferably 0.05 μm to 1.5 μm, and more preferably 0.1 μm to 1 μm. When the average particle diameter of the filler is within this range, the fluidity of the epoxy resin composition is kept good. The average particle diameter can be measured with a fineness distribution measuring device.

In the epoxy resin composition, various conventionally known flame retardants can be used for the purpose of improving the flame retardancy of the obtained cured product. Examples of usable flame retardants include halogen-based flame retardants, phosphorus-based flame retardants (phosphorus compounds as flame retardants), nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, Organometallic salt-based flame retardants and the like. From the viewpoint of environment, a halogen-free flame retardant is preferred, and a phosphorus-based flame retardant is particularly preferred. These flame retardants are not subject to any restrictions in use. They can be used alone, or multiple flame retardants of the same system can be used. In addition, flame retardants of different systems can also be used in combination.

In the epoxy resin composition of the present invention, in addition to a hardening accelerator and a filler, if necessary, a thermoplastic resin or a thermosetting resin other than an epoxy resin, a silane coupling agent, an antioxidant, a release agent, Defoamer, emulsifier, thixotropy imparting agent, smoothing agent, pigment and other additives. Further, a reactive diluent or the like may be blended for viscosity adjustment.

In the epoxy resin composition of the present invention, a thermoplastic resin may be blended as necessary. It is effective especially when an epoxy resin composition is shape | molded in sheet form or film form. Examples of the thermoplastic resin include phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, acrylonitrile butadiene styrene (ABS) Resin, acrylonitrile styrene (AS) resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyfluorene Amine resins, thermoplastic polyimide resins, polyimide resins, polytetrafluoroethylene resins, polyether resins, imine resins, polyphenylene ether resins, modified polyphenylene ether resins, polyether resins, polyfluorene resins A resin, a polyetheretherketone resin, a polyphenylene sulfide resin, a polyvinyl formal resin, and the like are not limited thereto. In terms of compatibility with epoxy resins, phenoxy resins are preferred, and in terms of low dielectric properties, polyphenylene ether resins or modified polyphenylene ether resins are preferred.

Examples of the other additives include thermosetting other than epoxy resins such as phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, diallyl phthalate resin, and thermosetting polyimide. Resins, or organic pigments such as quinacridone, azo, and phthalocyanine; or inorganic pigments such as titanium oxide, metal foil pigments, and rust preventive pigments; or hindered amine, benzotriazole, and diphenyl UV absorbers such as ketone, or hindered phenol-based, phosphorus-based, sulfur-based, hydrazine-based antioxidants, or silane-based, titanium-based coupling agents, or stearic acid, palmitic acid, zinc stearate, Mold release agents such as calcium stearate, additives such as leveling agents, rheology control agents, pigment dispersants, anti-sagging agents, defoamers, etc. The blending amount of these other additives is preferably in the range of 0.01% by mass to 20% by mass with respect to the solid content (nonvolatile content) in the epoxy resin composition.

In the epoxy resin composition of the present invention, a reactive diluent may be formulated as necessary. Examples of the reactive diluent include monofunctional glycidyl compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, resorcinol glycidyl ether, and neopentyl glycol glycidyl Polyfunctional glycidyl compounds such as ether, 1,6-hexanediol diglycidyl ether, polyfunctional glycidyl groups such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether The compounds are not limited to these.

The epoxy resin composition of the present invention can be impregnated into a fibrous reinforcing substrate to be used as a prepreg used in printed wiring boards and the like. The fibrous reinforcing substrate may be woven or non-woven fabrics of inorganic fibers such as glass, or polyester resins, organic resins such as polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyimide resins, but It is not limited to this. The method for producing a prepreg from an epoxy resin composition is not particularly limited. For example, since the epoxy resin composition of the present invention contains a solvent, it is preferably varnished. Therefore, it can be prepared by adjusting an organic solvent A resin varnish having an appropriate viscosity is obtained by impregnating the fibrous substrate with the resin varnish and then heating and drying the resin varnish to semi-harden (B-stage) the resin component. The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time is adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes. At this time, the mass ratio of the epoxy resin composition and the reinforcing substrate to be used is not particularly limited, and it is usually preferably adjusted so that the resin component in the prepreg becomes 20% by mass to 80% by mass. In addition, the epoxy resin composition in this case is preferably a homogeneous solution obtained by dissolving the whole, but particles or crystals may be present in the case of preparing a filler or a reinforcing substrate, and in this case, these are desirable. Evenly dispersed.

The epoxy resin composition of the present invention can be formed into a sheet or film shape and used as an adhesive layer of a laminated board. In this case, a conventionally well-known method can be used for sheeting or film formation. The method for manufacturing the adhesive sheet is not particularly limited, and can be obtained, for example, by applying on a supporting base film which is not dissolved in the resin varnish, using a reverse roll coater, a notch wheel coater, a die coater, or the like. The resin varnish-like epoxy resin composition was applied on a machine, and then the resin component was B-staged by heating and drying. In addition, if necessary, another supporting base film is laminated on the coating surface (adhesive layer) as a protective film and dried to obtain an adhesive sheet having protective films on both sides of the adhesive layer. Supporting base films include: metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicon film, and polyimide Among these films, a polyethylene terephthalate film having no defects such as breakage, excellent dimensional accuracy, and excellent cost is also preferred. In addition, a metal foil that is easy to be multilayered of a laminated board is preferred, and a copper foil is particularly preferred. The thickness of the supporting base film is not particularly limited, but it is preferably 10 μm to 150 μm, and more preferably 25 μm to 50 μm, because it has strength as a support and is less likely to cause lamination defects. The thickness of the protective film is not particularly limited, but is usually 5 μm to 50 μm. In addition, in order to easily peel the formed adhesive sheet, it is preferable to perform a surface treatment with a mold release agent in advance. The thickness of the coated resin varnish is preferably 5 μm to 200 μm, and more preferably 5 μm to 100 μm, based on the thickness after drying. The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time is adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes. The adhesive sheet obtained in this way usually becomes an insulating adhesive sheet, but conductive adhesive can also be obtained by mixing a conductive metal or metal-coated fine particles in an epoxy resin composition. sheet. In addition, the support base film is peeled after being laminated on a circuit board or after being heated and hardened to form an insulating layer. When the support base film is peeled after the adhesive sheet is heat-cured, adhesion of dust and the like in the curing step can be prevented.

A method for manufacturing a laminated board using the prepreg of the present invention or the insulating adhesive sheet will be described. For example, when a prepreg is used to form a laminate, one or more prepregs are laminated, metal foils are arranged on one or both sides to form a laminate, and the laminate is heated under pressure. The prepreg can be hardened and integrated to obtain a laminated board. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. As a condition for heating and pressing the laminate, it is only necessary to appropriately adjust the heating and pressing under the condition that the epoxy resin composition is hardened. However, if the pressing pressure is too low, the Air bubbles remain in the inside and the electrical characteristics may be deteriorated. Therefore, it is desirable to pressurize under conditions that satisfy moldability. The heating temperature is preferably 160 ° C to 250 ° C, and more preferably 170 ° C to 220 ° C. The pressing pressure is preferably 0.5 MPa to 10 Mpa, and more preferably 1 MPa to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. Furthermore, the single-layer laminated board obtained as described above can be used as an inner layer material to make a multilayer board. In this case, firstly, on the multilayer board, circuit formation is performed using an additive method or a subtractive method, etc., and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an internal layer. Layer. A prepreg or an insulating adhesive sheet is used to form an insulating layer on one or both sides of the circuit forming surface of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

When an insulating layer is formed using an insulating adhesive sheet, an insulating adhesive sheet is arranged on a circuit formation surface of a plurality of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is arranged between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Next, the laminated material is integrally molded by applying heat and pressure to form a cured product of the insulating adhesive sheet as an insulating layer, and a multilayered inner layer material is formed. Alternatively, the hardened material of the insulating adhesive sheet is used as an insulating layer to form an inner layer material and a metal foil as a conductive layer. Here, the metal foil may be the same as that used in a laminated board used as an inner layer material. The heating and press forming can be performed under the same conditions as the forming of the inner layer material.

In addition, when using the prepreg to form an insulating layer, one or more prepregs are laminated on the circuit formation surface of the inner layer material, and a metal foil is disposed on the outside to form a laminate. body. Then, the laminated body is integrally molded by applying heat and pressure, thereby forming a hardened material of the prepreg as an insulating layer, and forming a metal foil on the outside thereof as a conductive layer. Here, the metal foil may be the same as that used in a laminated board used as an inner layer board. The heating and press forming can be performed under the same conditions as the forming of the inner layer material. The printed wiring board can be formed by performing via formation or circuit formation on the surface of the multi-layer laminated board formed in the above-mentioned manner using an addition method or a subtractive method. In addition, by using the printed wiring board as an inner layer material and repeating the above steps, a multi-layered multilayer board can be formed.

In addition, in a case where the epoxy resin composition is coated on a laminated board to form an insulating layer, the epoxy resin composition is preferably applied at a thickness of 5 μm to the circuit forming surface of the outermost layer of the inner layer material. After a thickness of 100 μm, it is formed into a sheet shape by heating and drying at 100 ° C. to 200 ° C., preferably 150 ° C. to 200 ° C. for 1 minute to 120 minutes, preferably 30 minutes to 90 minutes. It is formed by a method commonly called a casting method. The thickness after drying is preferably 5 μm to 150 μm, and preferably 5 μm to 80 μm. In addition, in order to obtain a sufficient film thickness and to prevent uneven coating or streaks, the viscosity of the epoxy resin composition at 25 ° C is preferably in the range of 10 mPa · s to 40,000 mPa · s, and particularly preferably 200 mPa · s ～ 30000 mPa · s. A printed wiring board can be formed by performing via formation or circuit formation on the surface of the multilayer laminated board formed in the above-mentioned manner by using an addition method or a subtractive method. In addition, by using the printed wiring board as an inner layer material and repeating the above steps, a multilayer laminated board can be further formed. [Example]

The present invention will be specifically described with examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "part" means mass parts, and "%" means mass%. The measurement methods were measured by the following methods. An analysis method and a measurement method are shown below.

(1) Non-volatile content: According to JISK6910 standard (5.6 non-volatile content). Specifically, when the sample amount was set to 1 g, the test temperature was set to 150 ° C., and the test time was set to 1 hour, the solid content remaining after distilling off the solvent was regarded as a non-volatile component. (2) Solubility: It will be prepared at a predetermined ratio, and even if it is left to stand at room temperature for 1 week, it will not see the precipitation of crystals when it is impacted by stirring. It is indicated by "○". Or, crystals are precipitated within one week even if dissolved, and are represented by "×". (3) Solution viscosity: For the solution (varnish) after the solubility test, the viscosity at 25 ° C. was measured using an E-type viscometer. Specifically, an E-type viscosity meter (manufactured by Tokyo Toki Sangyo Co., Ltd., RE85H) was used, and cone No. 1 or No. 6 was used. The case where crystals and the like precipitate and cannot be measured is expressed as "NG". (4) Glass transition temperature: Measured at 20 ° C / min using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR6000DSC6200) in accordance with IPC-TM-6502.4.25.c. The DSC and Tgm (the intermediate temperature of the variation curve with respect to the wiring between the glass and rubber states) are displayed. (5) Dielectric constant and dielectric loss tangent: By using a material analyzer (manufactured by Agilent Technologies) in accordance with the IPC-TM-6502.5.5.9 standard, the capacity method is used to obtain The dielectric constant and the dielectric loss tangent were evaluated. (6) Peel strength and interlayer adhesion: measured in accordance with JISC6481. Interlayer adhesion is measured between the 7th layer and the 8th layer.

Synthesis Example 1 In a glass separable flask equipped with a stirring device, a thermometer, a nitrogen introduction device, a cooling tube, and a dropping device, 105 parts of a phenol novolac resin (phenolic hydroxyl equivalent (g / eq.) Was 105, The softening point was 130 ° C), 0.1 part of p-toluenesulfonic acid, and the temperature was raised to 150 ° C. While maintaining this temperature, 94 parts of styrene was added dropwise over 3 hours, and stirring was continued at this temperature for 1 hour. Then, it was dissolved in 500 parts of methyl isobutyl ketone (MIBK) and washed with water 5 times at 80 ° C. Then, MIBK was distilled off under reduced pressure, and then a styrene-modified phenol novolak resin (b-1) represented by the following formula (4) was obtained. The obtained phenolic hydroxyl equivalent of (b-1) was 199, the softening point was 110 ° C, and p (average value) in the formula (4) was 0.9.

[Chemical 5]

Synthesis Example 2 In the same apparatus as Synthesis Example 1, 105 parts of a phenol novolak resin (105 phenolic hydroxyl equivalent and a softening point of 67 ° C) and 0.13 parts of p-toluenesulfonic acid were added, and the temperature was raised to 150 ° C. While maintaining the temperature, 156 parts of styrene was added dropwise over 3 hours, and stirring was continued at the temperature for 1 hour. Then, the same treatment as in Synthesis Example 1 was performed to obtain a styrene-modified phenol novolac resin (b-2). The obtained phenolic hydroxyl equivalent of (b-2) was 261, the softening point was 75 ° C, and p was 1.5.

The description of the abbreviations used in an Example and a comparative example is as follows. (1) Bisphenol compound (A): BisP-TMC: 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., BisP-TMC, phenolic The hydroxyl equivalent is 155 and the melting point is 206 ° C.) (2) Phenol compound (B): (b-1): Phenol compound (b-2) obtained in Synthesis Example 1: Phenol compound (3) obtained in Synthesis Example 2 Other phenol compounds: PN: phenol novolac resin (manufactured by Showa Denko Corporation, BRG-557, phenolic hydroxyl equivalent is 105, softening point is 80 ° C) DCPD: dicyclopentadiene · phenol compound (Qunei (Manufactured by Chemical Co., Ltd., GDP9140, phenolic hydroxyl equivalent is 196, softening point is 130 ° C) (4) Solvents Ketone solvents (C1): methyl ethyl ketone (MEK), cyclopentanone (CP) glycols Solvent (C2): Methyl cellosolve (MC), methoxypropanol (PM) Aromatic solvents: toluene (TL) (5) Hardening accelerator (D): 2E4MZ: 2-ethyl-4- Methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2E4MZ) (6) Epoxy resin (E): TX-1466: Aminomethyl Ester modified epoxy resin (manufactured NSSC Chemical Co., TX-1466, an epoxy equivalent of 298, a softening point of 87 deg.] C)

Example 1 to Example 7 The bisphenol compound (A), the phenol compound (B), and the solvent were blended at the blending ratios (parts) shown in Table 1, and heated and stirred to dissolve as needed to obtain a predetermined nonvolatile component. Hardener composition (varnish). The results of the solubility and the dissolution viscosity are shown in Table 1.

Comparative Examples 1 to 9 Each component was formulated according to the blending ratios (parts) described in Tables 2 and 3, and heated and stirred as needed to dissolve, to obtain a hardener composition (varnish) having a predetermined nonvolatile content concentration. The results of solubility and solubility viscosity are shown in Tables 2 and 3.

[Table 1]

[Table 2]

[table 3]

As shown in Table 1, when the phenol compound (A) is blended with the phenol compound (B), the stability as a solution is improved, and handling with a high solid content becomes easy. On the other hand, as shown in the comparative example of Table 2, even if another phenol compound is used instead of the phenol compound (B), the solvent solubility of the bisphenol compound (A) is not improved. Even when the phenol compound (B) is blended in the bisphenol compound (A), in the case of an aromatic solvent such as toluene, the solubility required as a resin varnish becomes insufficient.

Example 8 and Comparative Example 10 to Comparative Example 14 An epoxy resin composition was prepared according to the formulation (solid content value) described in Table 4. The hardener composition was the hardener composition (varnish) obtained in Example 2, Comparative Example 1, Comparative Example 3, Comparative Example 7, Comparative Example 8, and Comparative Example 9. If necessary, it is diluted with a solvent, and the epoxy resin composition varnish is impregnated into a glass cloth (ISO7628 type, thickness 0.16 mm). The impregnated glass cloth was dried in a hot air loop oven at 150 ° C to obtain a prepreg. The obtained 8 pieces of prepreg were overlapped with copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness: 35 μm), and the temperature condition was 130 ° C × 15 minutes + 190 ° C × 80 minutes Under vacuum pressure of 2 MPa, a 1.6 mm thick laminated board was obtained. Table 4 shows the results of the copper foil peeling strength, interlayer adhesion, and glass transition temperature of the laminated board.

In addition, the obtained prepreg was pulverized, and a sieve was used to form a powdery prepreg powder having a 100-mesh pass rate. The obtained prepreg powder was added to a mold made of fluororesin, and subjected to a vacuum pressure of 2 MPa under a temperature condition of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes to obtain a 50 mm square × 2 mm thick Test strip. Table 4 shows the results of the dielectric constant and the dielectric loss tangent of the test piece.

[Table 4] [Industrial availability]

The epoxy resin hardener composition of the present invention is easy to handle, such as storage stability, and can be used as an epoxy resin hardener for an electronic circuit board excellent in heat resistance, adhesion, and dielectric properties.

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Claims (11)

An epoxy resin hardener composition comprising a bisphenol compound (A) represented by the following general formula (1) and a phenol compound (B) represented by the following general formula (2), wherein The organic solvent (C) in a non-aromatic solvent is used, and the mass ratio of the bisphenol compound (A) to the phenol compound (B) is (A): (B) = 5:95 to 95: 5, In the formula, R ¹ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 7 carbon atoms. Aralkyl of -20, R ² each independently represents a hydrogen atom, an aliphatic hydrocarbon group of 1 to 20 carbons, an alicyclic hydrocarbon group of 3 to 20 carbons, an aromatic hydrocarbon group of 6 to 20 carbons, and 7 carbons Aralkyl of 20 to 20 or haloalkyl of 1 to 20 carbons, at least one of 2m R ² is a group other than a hydrogen atom, and m is an integer of 3 to 9, In the formula, R ³ each independently represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a substituent represented by the following general formula (3), k represents a number from 1 to 20, and p represents a number from 0.1 to 2.5 , In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁷ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and q represents an integer of 0 to 5. The epoxy resin hardener composition according to item 1 of the patent application scope, wherein the total amount of the bisphenol compound (A) and the phenol compound (B) (A + B) and the mass of the non-aromatic solvent (C) The ratio is (A + B): (C) = 45: 55 ～ 85: 15. The epoxy resin hardener composition according to claim 1 or claim 2, wherein the non-aromatic solvent (C) is a ketone solvent or a glycol solvent. The epoxy resin hardener composition according to item 1 or item 2 of the patent application scope, wherein the solution viscosity at 25 ° C is in the range of 15 mPa · s to 5000 mPa · s. The epoxy resin hardener composition according to item 1 or 2 of the scope of the patent application, characterized in that it contains a hardening accelerator (D). An epoxy resin composition, which is prepared by blending an epoxy resin (E) in the epoxy resin hardener composition according to any one of claims 1 to 5 of the scope of patent application. The epoxy resin composition according to item 6 of the scope of application for a patent, wherein the phenolic hydroxyl group is present at 0.2 mol to 1.5 mol relative to 1 mol of the epoxy group of the epoxy resin (E). A hardened epoxy resin is obtained by hardening the epoxy resin composition according to item 6 or 7 of the scope of patent application. A prepreg is prepared by impregnating an epoxy resin composition according to item 6 or item 7 of a patent application in a substrate. An epoxy resin laminated board is characterized by using the epoxy resin composition according to item 6 or item 7 of the scope of patent application. An epoxy resin laminated board is characterized by using a prepreg as described in item 9 of the scope of patent application.