KR20140061371A - Epoxy resin mixture, epoxy resin composition, prepreg, and curing product of each - Google Patents

Abstract

The present invention provides an epoxy resin having a high thermal conductivity, a low viscosity and excellent workability. An epoxy resin composition comprising an epoxy resin (A) obtained by reacting a phenol compound (a) obtained by the reaction of a compound represented by the following formula (1) and a compound represented by the following formula (6) with epihalohydrin, An epoxy resin (B) obtained by further reacting the represented phenolic compound (b) with epihalohydrin and / or an epoxy resin obtained by reacting epihalohydrin with the phenol compound (c) represented by the following formula (8) The resin (C) is an epoxy resin.

Description

EPOXY RESIN MIXTURE, EPOXY RESIN COMPOSITION, PREPREG, AND CURING PRODUCT OF EACH), epoxy resin composition, prepreg,

The present invention relates to a novel epoxy resin mixture and an epoxy resin composition. And a cured product such as a prepreg formed by the epoxy resin composition.

The epoxy resin composition is generally used as a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance and electrical properties and is used in a wide range of fields such as adhesives, paints, laminated plates, molding materials and mold materials. In recent years, cured products of epoxy resins used in these fields are required to further improve various properties such as high purity, flame retardancy, heat resistance, moisture resistance, toughness, low linear expansion coefficient and low dielectric constant characteristics.

Particularly in the field of electric and electronic industry, which is a typical application of epoxy resin composition, high density packaging of semiconductors and high density wiring of printed wiring boards aiming at multifunctionalization, high performance and compactness are progressing. However, due to high density packaging or high density wiring, Heat generated from the inside of the printed wiring board increases, which may cause malfunction. Therefore, how to efficiently discharge the generated heat to the outside is an important issue in energy efficiency and device design. As a thermal countermeasure, various studies have been made, such as using a metal core substrate, knitting a structure that is easy to dissipate in the design stage, finely filling a high-temperature conduction filler in a polymer material (epoxy resin) to be used. However, since the thermal conductivity of the polymer material in the binder region connecting the high thermal conductivity region is low, the thermal conduction speed of the polymer material is low and the heat dissipation is not possible efficiently.

Patent Document 1 discloses that a mesogen group is introduced into a structure as means for realizing high thermal conductivity of an epoxy resin, and an epoxy resin having a biphenyl skeleton is described as an epoxy resin having a mesogen group. As the epoxy resin other than the biphenyl skeleton, a phenylbenzoate-type epoxy resin is described. However, since the epoxy resin needs to be produced by an epoxidation reaction by oxidation, it is said to be practically usable because it has difficulty in safety and cost I can not. Examples of using an epoxy resin having a biphenyl skeleton include Patent Documents 2 to 4, and in particular, Patent Document 3 describes a method of using an inorganic filler having a high thermal conductivity together. However, the thermal conductivity of the cured product obtained by the methods described in these documents is not a level satisfying market demand, and an epoxy resin composition which gives a cured product having a higher thermal conductivity using an epoxy resin which is relatively inexpensive is required have.

In addition, in order to obtain a cured product having a high thermal conductivity, properties required for an epoxy resin may be cited as well as those exhibiting high thermal conductivity when formed into a cured product. In addition, a low melt viscosity of the resin is also an important characteristic. Generally, a high-temperature conductive filler is difficult to overcome because its particle shape is not spherical in comparison with a general-purpose filler. Therefore, the workability is improved as the viscosity of the epoxy resin is lowered in the molten state. Therefore, in order to make the viscosity of the epoxy resin to a level required by the market, a low viscosity is strongly desired.

Japanese Patent Application Laid-Open No. 11-323162 Japanese Patent Application Laid-Open No. 2004-2573 Japanese Patent Application Laid-Open No. 2006-63315 Japanese Patent Application Laid-Open No. 2003-137971

An object of the present invention is to provide an epoxy resin mixture having a high thermal conductivity, a low viscosity and an excellent workability as a result of a study to solve such a problem.

The present inventors have conducted intensive studies in order to solve the above problems and have completed the present invention.

That is,

(1) at least one compound represented by the following formulas (1) to (5)

A phenol compound (a) containing an epoxy resin (A) obtained by reacting a phenol compound (a) obtained by a reaction of a compound represented by the following formula (6) with epihalohydrin, (C) obtained by reacting an epihalohydrin with an epoxy resin (B) obtained by further reacting an epihalohydrin with an epihalohydrin and / or a phenol compound (c) represented by the following formula (8) ≪ / RTI >

[In the formula (1), R ₁ independently represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or an alkoxy group having 1 to 10 carbon atoms . l is the number of R _1, is an integer of 1-4;

[In the formula (2), R ₂ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, an alkylester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, a morpholinylcarbonyl group, a phthalimide group, a piperonyl group or a hydroxyl group]

[In the formula (3), R ₃ independently represents a hydrogen atom, an alkylcarbonyl group having 0 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl ester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. n represents a carbon number and represents an integer of 0, 1, or 2; m represents the number of R < _{3 &} gt ;, and satisfies the relationship of 1 ≤ m ≤

[In the formula (4), R ₄ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group]

[In the formula (5), R ₅ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl ester group having 1 to 10 carbon atoms Or a hydroxyl group. And m is an integer of 1 to 10]

(6), R ₆ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a formyl group, an allyl group or an alkyl group having 1 to 10 carbon atoms Or an alkoxy group. k represents the number of R < ₆ > and is an integer of 1 to 4]

[In the formula (7), R ₇ , X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. k represents the number of R < ₇ > and represents an integer of 1 to 4]

[In the formula (8), R ₈ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. l represents the number of R ₈ , and represents an integer of 1 to 4; A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms and having a cyclic ring,

(2) A phenolic compound (b) and / or a phenolic compound (c), which contains the phenolic compound (a) described in the above (1) and is reacted with epihalohydrin By weight.

(3) In the above (2)

The sum of the proportions of the phenol compound (b) and the phenol compound (c) in the mixture of the phenol compounds (a) to (c) according to the above (1) before the reaction with the epihalohydrin is 1 to 30 mass% Wherein the epoxy resin mixture is obtained by reacting a mixture of phenolic compounds with epihalohydrin.

(4) An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing agent.

(5) In the above (4)

Wherein the epoxy resin composition comprises a phenol compound (a) as a curing agent in the epoxy resin mixture.

(6) In the above (4) or (5)

And an inorganic filler having a thermal conductivity of 20 W / m · K or more.

(7) The method according to any one of (4) to (6) above,

An epoxy resin composition characterized by being used for semiconductor sealing.

(8) A prepreg comprising the epoxy resin composition according to any one of (4) to (6) and a sheet-like fiber substrate.

(9) A cured product obtained by curing the epoxy resin composition according to any one of (4) to (7) or the prepreg according to (8).

(Effects of the Invention)

The epoxy resin mixture of the present invention is excellent in workability because it has a low melt viscosity and is excellent in heat conduction so that it is useful when it is used for various kinds of composite materials such as semiconductor sealing materials and prepregs, Do.

The epoxy resin mixture of the present invention is composed of a mixture containing the following epoxy resin (A) and further containing the following epoxy resin (B) and / or the following epoxy resin (C). First, phenolic compounds (a) to (c) which are precursors of the respective epoxy resins (A) to (C) will be described.

The phenol compound (a) is obtained by reacting at least one compound selected from the compounds represented by the following formulas (1) to (5) with a compound represented by the following formula (6).

Wherein R ₁ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, or an alkoxy group having 1 to 10 carbon atoms . l is the number of R _1, is an integer of 1-4;

In the formula (1), each of R _{1 s} independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms Do.

Specific examples of the compound represented by the formula (1) used for the reaction with the compound represented by the formula (6) to obtain the phenol compound (a) include 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4- Dihydroxyacetophenone, 3 ', 4'-dihydroxyacetophenone, 3', 5'-dihydroxyacetophenone, 2 ', 4'-dihydroxyacetophenone, Phenol, 2 ', 3', 4'-trihydroxyacetophenone, 2 ', 4', 6'-trihydroxyacetophenone monohydrate, 4'- Hydroxy-2'-methylacetophenone, 2'-hydroxy-5'-methylacetophenone, 4'-hydroxy-3'-methoxyacetophenone, , 4'-hydroxy-3'-nitroacetophenone, 4'-hydroxy-3 ', 5'-dimethoxyacetophenone, 4'-dimethoxy- -Hydroxy-3 ', 4'-dimethoxyacetophenone, 2'-hydroxy-4', 5'-dimethoxyacetophenone, Methyl acids, there may be mentioned 2 ', 3'-dihydroxy-4'-methoxy-acetophenone monohydrate. Hydroxy-3'-methoxyacetophenone, 4'-hydroxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethoxypolyethylacetophenone Acetophenone is preferred.

[In the formula (2), R ₂ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, an alkylester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, a morpholinylcarbonyl group, a phthalimide group, a piperonyl group or a hydroxyl group]

Specific examples of the compound represented by the formula (2) used for the reaction with the compound represented by the formula (6) to obtain the phenol compound (a) include acetone, 1,3-diphenyl-2-propanone, 2- Butanone, 1-phenyl-1,3-butanedione, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, acetylacetone, 2-hexanone, , Ethyl isobutyl ketone, 4-methyl-2-hexanone, 2,5-hexanedione, 1,6-diphenyl-1,6-hexanedione, 2-heptanone, 3- Heptanone, 2-methyl-4-heptanone, 5-methyl-3-heptanone, 6-methyl- Decanone, 3-decanone, 4-decanone, 5-methyl-2-octanone, Decanone, 2-undecaneone, 3-undecaneone, 4-undecaneone, 5-undecaneone, 6-undecaneone, Canon, 5-dodecanone, 6-dodecanone, 2-tetradecanone, 3-tetradecanone, Hexadecanone, 9-heptadecanone, 11-heneicosanic acid, 12-triclosanic acid, 14-pentadecanone, 4-methoxy-2-butanone, 4- (4-methoxyphenyl) -2-butanone, 4-methoxy- Methyl-2-pentanone, 4-methoxyphenylacetone, methoxyacetone, phenoxyacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, Butyl acetate, tert-butyl acetate, 3-pentyl acetoacetate, amyl acetoacetate, isoamyl acetoacetate, hexyl acetoacetate, heptyl acetoacetate, n-octyl acetoacetate, benzyl acetoacetate, dimethyl acetylsuccinate, dimethyl acetonylmalonic acid Diethyl, acetoacetic acid-2-methoxyethyl, acetoacetate Allyl, 4-sec-butoxy-2-butanone, benzyl butyl ketone, bisdimethoxyquercumine, 1,1-dimethoxy-3-butanone, 1,3-diacetoxyacetone, , 4- (4-hydroxyphenyl) -2-butanone, isoamylmethylketone, 4-hydroxy-2-butanone, Acetone, piperonylmethylketone, piperonyl acetone, phthalimide acetone, 4-isopropoxy-2-butanone, 4-isobutoxy-2-butanone, Acetylmorpholine, 1-acetyl-4-piperidone, and the like. Of these, acetone is preferable in view of high solvent solubility when epoxidized phenolic compounds are obtained and cured products of epoxy resin compositions exhibiting high thermal conductivity.

[In the formula (3), R ₃ independently represents a hydrogen atom, an alkylcarbonyl group having 0 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl ester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. n represents a carbon number and represents an integer of 0, 1, or 2; m represents the number of R < _{3 &} gt ;, and satisfies the relationship of 1 ≤ m ≤

In the formula (3), when R ₃ is a substituted or unsubstituted alkylcarbonyl group having 0 carbon atoms, the carbonyl structure of the cycloalkane constituting the main skeleton of the formula (3) For example, 1,3-cyclopentanedione.

Specific examples of the compound represented by the formula (3) used for the reaction with the compound represented by the formula (6) to obtain the phenol compound (a) include cyclopentanone, 3-phenylcyclopentanone, 2-acetylcyclopentanone , 1,3-cyclopentanedione, 2-methyl-1,3-cyclopentanedione, 2-ethyl-1,3-cyclopentanedione, cyclohexanone, 3-methylcyclohexanone, , 4-ethylcyclohexanone, 4-tert-butylcyclohexanone, 4-pentylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 3,3-dimethylcyclohexanone, 3,4 - dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 2-acetylcyclohexanone, 4-cyclohexanone carboxylic acid Ethyl, 1,4-cyclohexanedione monoethylene ketal, bicyclohexane-4,4'-dione monoethylene ketal, 1,4-cyclohexanedione mono-2,2-dimethyltrimethylene ketal, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 2-methyl-1,3-cyclohexanedione, 5-methyl-1,3-cyclohexanedione, dimedone, dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, 4,4'-bicyclohexanone, 2,2-bis -Oxocyclohexyl) propane, cycloheptanone, and the like. Among them, cyclopentanone, cyclohexanone, cycloheptanone, and 4-methylcyclohexanone are preferable because the solubility of the phenol compound obtained by epoxidation is high and the cured product of the epoxy resin composition exhibits high thermal conductivity. desirable.

[In the formula (4), R ₄ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group]

In formula (4), R ₄ independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted aryl group having 6 to 10 carbon atoms, an unsubstituted alkoxy group having 1 to 10 carbon atoms, .

Specific examples of the compound represented by the formula (4) used for the reaction with the compound represented by the formula (6) to obtain the phenol compound (a) include diacetyl, 2,3-pentanedione, 5-methyl-2,3-hexanedione, 2,3-heptanedione, and the like. Among them, diacetyl is preferable in view of high solubility of the solvent when the obtained phenol compound is epoxidized, and cured product of the epoxy resin composition shows high thermal conductivity.

[In the formula (5), R ₅ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl ester group having 1 to 10 carbon atoms , Or a hydroxyl group. And m is an integer of 1 to 10]

In the formula (5), R ₅ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group.

Specific examples of the compound represented by the formula (5) used for the reaction with the compound represented by the formula (6) to obtain the phenol compound (a) include ethyl diacetoacetate, 2,5-hexanedione, Ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-phenyl-2,4-pentanedione, ethyl 4-acetyl-5-oxohexanoate . Methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-methyl-2,4-pentanedione and the like are preferable because the solubility of the phenol compound obtained through epoxidation is high and the cured product of the epoxy resin composition exhibits high thermal conductivity. Pentanedione is preferred.

(6), R ₆ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a formyl group, an allyl group or an alkyl group having 1 to 10 carbon atoms Or an alkoxy group. k represents the number of R < ₆ > and is an integer of 1 to 4]

In the formula (6), R ₆ independently represents an alkoxy group having 1 to 3 carbon atoms.

Specific examples of the compound represented by the formula (6) used for the reaction with at least one compound selected from the compounds represented by the formulas (1) to (5) for obtaining the phenol compound (a) include 2-hydroxy Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 3,4-dihydroxy-benzaldehyde, 3,5-di-tert- butyl-4-hydroxybenzaldehyde, isobutyric acid, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-5-nitro-m-anisaldehyde, 2-hydroxy-5-methylisophthalaldehyde, 2-nitrobenzaldehyde, vanillin, o-vanillin, -Hydroxy-4-methoxybenzaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-5-methoxybenz 3-methoxysalicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, 3-ethoxysalicylaldehyde, 4-hydroxyisophthalaldehyde, 4- Dihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-tri Hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and the like. These may be used alone or in combination of two or more. It is preferable to use vanillin alone in view of the high solubility of the phenol compound obtained by epoxidation of the obtained phenol compound and high hardness of the cured product of the epoxy resin composition.

The phenol compound (a) is obtained by aldol condensation reaction of at least one compound represented by the formula (1) to (5) with a compound represented by the formula (6) under an acidic condition or a basic condition.

The compound represented by the formula (6) is used in an amount of 1.0 to 1.05 mol based on 1 mol of the compound represented by the formula (1), the compound 1 represented by the formula (2), the formula (3), the formula (4) It is preferable to use 2.0 to 3.15 moles based on the moles.

Examples of the acidic catalyst that can be used when the aldol condensation reaction is carried out under acidic conditions include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as toluenesulfonic acid, xylenesulfonic acid and oxalic acid. These may be used alone, or a plurality of types may be used in combination. The amount of the acidic catalyst to be used is preferably 0.01 to 1.0 mol, more preferably 0.2 to 0.5 mol, per 1 mol of the compound represented by the formula (6).

On the other hand, as the basic catalyst which can be used in the case of carrying out the aldol condensation reaction under basic conditions, metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, diethylamine, triethylamine, tributylamine, di Amine derivatives such as isobutylamine, pyridine and piperidine, and aminoalcohol derivatives such as dimethylaminoethyl alcohol and diethylaminoethyl alcohol. In the case of basic conditions, the basic catalyst exemplified above may be used singly or a plurality of types may be used in combination. The amount of the basic catalyst to be used is preferably 0.1 to 2.5 mol, more preferably 0.2 to 2.0 mol, per 1 mol of the compound represented by the formula (6).

In the reaction for obtaining the phenol compound (a), a solvent may be used if necessary. The solvent which can be used is not particularly limited as long as it has no reactivity with the compound represented by the formula (6) such as a ketone. In view of easily dissolving the compound represented by the formula (6) of the raw material, Is preferably used.

The reaction temperature is usually 10 to 90 占 폚, preferably 35 to 70 占 폚. The reaction time is usually from 0.5 to 10 hours, but there is no limit to the reactivity depending on the kind of the raw material compound. When the resin is withdrawn as a resin after the completion of the reaction, unreacted materials, solvents and the like are removed from the reaction solution under heating and decompression after washing with water or without washing with water. When the crystal is drawn out, the reaction solution is dropped into a large amount of water to precipitate crystals. When the reaction is carried out under basic conditions, the produced phenolic compound of the present invention can be dissolved in water, and thus precipitated as crystals under neutral to acidic conditions by adding hydrochloric acid or the like.

The phenol compound (b) is represented by the following formula (7).

Wherein R ₇ , X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. k represents the number of R < ₇ > and represents an integer of 1 to 4]

It is preferable that R ₇ , X and Y are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms from the viewpoint of maintaining a high thermal conductivity in the formula (7).

Examples of the phenol compound (b) include various bisphenols. BisP-A, BisP-A, UltriteP, DHBP, BisOC-F, BisP-B, BPP, BPA, BPE, Methylenebis-p-CR, TM-BPF, Bis-C, BisP-MIBK, Bis26X- Bis-BPT-A, and Ph-CC-AP (both manufactured by Honshu Kagaku Kogyo Co., Ltd.) And the like.

Of these, BPF and BPA are preferable from the viewpoint of maintaining a high thermal conductivity, and BPF is particularly preferable.

The phenol compound (c) is represented by the following formula (8).

Wherein each R ₈ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. l represents the number of R ₈ , and represents an integer of 1 to 4; A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms and having a cyclic ring,

Examples of the phenol compound (c) include cyclic aliphatic ketones and phenols corresponding respectively to biphenol and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol compounds of the biphenyl skeleton, And the like.

Specific examples of the compound include the following compounds.

BisP-CP, BisP-Z, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, and BisP-PZP are commercially available products. BisP-CPEDE (all manufactured by Honshu Kagaku Kogyo), and TCDBP (METROPORITAN EXIMCHEM XTD).

Next, the epoxy resin mixture of the present invention will be described.

The epoxy resin mixture of the present invention is obtained by epoxidation by reacting each of the phenolic compounds described above with epihalohydrin. Further, in the case of epoxidation, epihalohydrin may be previously reacted with each of the phenol compounds (a) to (c) to obtain epoxy resins (A) to (C), and the respective epoxy resins may be mixed. The method of reacting epihalohydrin with each phenol compound is not particularly limited as long as it is a known method. Specific examples thereof include those described in JP-A-05-155978 and JP-A-2008-179739 The described method can be used.

From the viewpoint of production, however, it is preferable to react the mixture of phenol compounds (a) to (c) with epihalohydrin to obtain an epoxy resin mixture. By the above-described production method, an epoxy resin (A) - (C) mixture can be obtained, and an epoxy resin in which the skeleton of some of the phenol compounds (a) - (c) is linked with a ring-opening glycidyl group.

As the epoxy resin mixture of the present invention, a phenol compound obtained by a reaction between a compound represented by the formula (6) and a compound represented by the formula (3) in that a cured product exhibiting a low melt viscosity and a high thermal conductivity is obtained (A) which is an epoxy resin of the epoxy resin (a) and further contains an epoxy resin (B) and / or an epoxy resin (C).

Hereinafter, a method for obtaining an epoxy resin mixture by reacting a mixture of phenolic compounds (a) to (c) with epihalohydrin will be described.

The sum of the amounts of the phenol compound (b) and the phenol compound (c) in the total amount of the phenol compounds (a) to (c) is preferably 1 to 30 mass%, more preferably 5 to 30 mass%. When the ratio of the sum of the amounts of the phenol compound (b) and the phenol compound (c) is 30 mass% or less, the thermal conductivity is not lowered, and when it is 1 mass% or more, the viscosity is not increased, It is preferable because there is no work.

As the epihalohydrin, epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, epibromohydrin and the like can be used in the reaction for obtaining the epoxy resin contained in the epoxy resin mixture of the present invention But epichlorohydrin which is industrially easily available is preferable. The amount of the epihalohydrin to be used is generally 2 to 20 mol, preferably 2 to 15 mol, particularly preferably 2 to 6.5 mol based on 1 mol of the hydroxyl group of the phenol compound. The epoxy resin is obtained by adding a phenol compound and an epihalohydrin in the presence of an alkali metal oxide, and then epoxidizing the resulting 1,2-halohydrin ether group by ring closure. At this time, by using epihalohydrin in an amount significantly smaller than usual as described above, the molecular weight of the epoxy resin can be increased and the molecular weight distribution can be widened. The resulting epoxy resin is a resinous material having a relatively low softening point and is drawn out from the system to exhibit excellent solvent solubility.

Examples of alkali metal hydroxides that can be used in the epoxidation reaction include sodium hydroxide and potassium hydroxide. These solids may be used as is, or an aqueous solution thereof may be used. In the case of using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water is removed from the mixture of water and epihalohydrin continuously distilled under reduced pressure or normal pressure, Or a method of continuously returning the hydrin only into the reaction system. The amount of the alkali metal hydroxide to be used is generally 0.9 to 3.0 mol, preferably 1.0 to 2.5 mol, more preferably 1.0 to 2.0 mol, particularly preferably 1.0 to 1.3 mol, based on 1 mol of the hydroxyl group of the phenol compound.

Further, the inventors of the present invention have found that by using sodium hydroxide in flake form in the epoxidation reaction, it becomes possible to remarkably reduce the amount of halogen contained in the epoxy resin obtained by using sodium hydroxide as an aqueous solution. This halogen is derived from epihalohydrin, and the more the epoxy resin is incorporated, the lower the thermal conductivity of the cured product. Further, it is preferable that this flaky sodium hydroxide is dividedly added into the reaction system. It is possible to prevent the reaction temperature from sharply decreasing by performing the addition in a divided manner, thereby making it possible to prevent the formation of impurity 1,3-halohydrin and halomethylene forms, and to form a cured product having a higher thermal conductivity .

In order to accelerate the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt to be used is generally 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol compound of the present invention.

Further, it is preferable to carry out the reaction by adding an aprotic polar solvent such as an alcohol such as methanol, ethanol or isopropyl alcohol or an alcohol such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran or dioxane for epoxidation. Among them, alcohols or dimethylsulfoxide are preferable. When an alcohol is used, an epoxy resin can be obtained in a high yield. On the other hand, when dimethyl sulfoxide is used, the amount of halogen in the epoxy resin can be further reduced.

When the alcohols are used, the amount thereof is usually 2 to 50% by mass, preferably 4 to 35% by mass with respect to the amount of epihalohydrin to be used. When an aprotic polar solvent is used, it is usually 5 to 100% by mass, preferably 10 to 80% by mass based on the amount of epihalohydrin used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.

After completion of the reaction, the epihalohydrin, the solvent, and the like are removed from the reaction solution after the reaction is washed with water or without heating and under reduced pressure. In order to further reduce the amount of halogen contained in the obtained epoxy resin, the recovered epoxy resin mixture of the present invention is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added So that the ring-closing can be ensured. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol compound of the present invention. The reaction temperature is usually from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.

After the completion of the reaction, the resulting salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain an epoxy resin mixture of the present invention. When the epoxy resin mixture of the present invention precipitates as crystals, the crystals of the epoxy resin mixture may be filtered after dissolving salts produced in a large amount of water.

As described above, the total halogen content of the epoxy resin mixture of the present invention obtained by using flaky sodium hydroxide is usually 1800 ppm or less, preferably 1600 ppm or less, and more preferably 700 ppm or less. Too much of the total halogen content adversely affects the electrical reliability of the cured product, and since the cured product remains at the ends of uncrosslinked molecules, the orientation of the molecules during the cured melt state does not progress, leading to a decrease in thermal conductivity.

The epoxy equivalent of the epoxy resin mixture of the present invention is 350 g / eq. In view of obtaining a low viscosity epoxy resin mixture. And particularly preferably 300 g / eq. Or less. The epoxy equivalent of the epoxy resin mixture of the present invention represents the average value of the epoxy equivalents of the respective epoxy resins contained in the obtained epoxy resin mixture.

Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention contains the epoxy resin mixture of the present invention as an essential component.

In the epoxy resin composition of the present invention, the epoxy resin mixture of the present invention can be used in combination with other epoxy resins.

Specific examples of other epoxy resins include phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene and dihydroxynaphthalene) and various aldehydes (formaldehyde, Polycondensation products of aromatic compounds such as xylene and formaldehyde and phenols such as aldehydes, alkyl aldehydes, benzaldehydes, alkyl substituted benzaldehydes, hydroxybenzaldehydes, naphthalaldehydes, glutaraldehyde, phthalaldehyde, crotonaldehyde and cinnamaldehyde) , Polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenyl Biphenyl, butadiene and isoprene), phenols and ketones (acetone, methyl ethyl ketone, Polycondensates of phenols and aromatic dimethols (such as benzene dimethanol and biphenyl dimethanol), phenols and aromatic dichloromethyls (such as?,? '- dichloro Xylene and bischloromethylbiphenyl), polycondensates of phenols with aromatic bisalkoxymethyls (such as bismethoxymethylbenzene, bismethoxymethylbiphenyl and bisphenoxymethylbiphenyl), bisphenols and bisphenols Glycidyl ether epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin and the like can be cited as examples of the polycondensate of various aldehydes and glycidylated alcohols and the like. The epoxy resin used is not limited thereto. These may be used alone or in combination of two or more.

When another epoxy resin is used in combination, the proportion of the epoxy resin mixture of the present invention in the total epoxy resin component in the epoxy resin composition of the present invention is preferably 30 mass% or more, more preferably 40 mass% or more, and more preferably 70 mass% , And particularly preferably 100 mass% (when no other epoxy resin is used). However, when the epoxy resin mixture of the present invention is used as a modifier for the epoxy resin composition, it is added in a proportion of 1 to 30% by mass in the whole epoxy resin.

Examples of the curing agent contained in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds and phenol compounds. Specific examples of the other curing agents are shown in (a) to (e) below.

(a) Amine compound The diamine compound diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, etc.

(b) An acid anhydride compound The acid anhydride-based compound is a compound selected from the group consisting of phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride Etc

(c) amide compound dicyandiamide, or polyamide resin synthesized from dimer of linolenic acid and ethylenediamine

(d) Phenolic compounds The polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpenediphenol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3, 5 '-tetramethyl- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (Such as phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, and dihydroxynaphthalene) and aldehydes such as 1,2- (Such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde and furfural), ketones (such as p-hydroxyacetophenone and o-hydroxyacetophenone) Phenanthrene and tricyclopentadiene), phenol resins obtained by condensation of the phenols with substituted biphenyls (4,4'-bis (chlorine (Methoxymethyl) -1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis (chloromethyl) benzene, 1 , 4-bis (methoxymethyl) benzene and 1,4-bis (hydroxymethyl) benzene), etc., phenol resins and / or modified products of the phenol resins, tetrabromobisphenol A and halogenated phenols such as brominated phenol resin

(e) other imidazoles, BF ₃ ^- amine complex, a guanidine derivative

Of these curing agents, amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalene diamine, and condensation products of catechol with condensation products of aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls A phenol compound (a) which is a precursor of the epoxy resin (A), which is one component of the present invention, besides the curing agent having a structure in which hydrogen groups are adjacent is preferable because it contributes to the arrangement of the epoxy resin.

The amount of the curing agent to be used in the epoxy resin composition of the present invention is preferably 0.8 to 1.2 equivalents, more preferably 0.95 to 1.05, per one equivalent of the epoxy group of the epoxy resin.

The epoxy resin composition of the present invention can impart an excellent thermal conductivity to the cured product by containing an inorganic filler having an excellent thermal conductivity as required.

The inorganic filler contained in the epoxy resin composition of the present invention is added for the purpose of imparting a higher thermal conductivity to the cured product of the epoxy resin composition. When the thermal conductivity of the inorganic filler itself is too low, the combination of the epoxy resin and the curing agent There is a possibility that the high thermal conductivity obtained by the above method may be damaged. Therefore, the inorganic filler contained in the epoxy resin composition of the present invention preferably has a high thermal conductivity, and is usually at least 20 W / m · K, preferably at least 30 W / m · K, more preferably at least 50 W / m · K There is no restriction if it has a conductivity. The thermal conductivity referred to herein is a value measured according to ASTM E1530. Specific examples of the inorganic filler having such properties include inorganic fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina and magnesium oxide, fibrous fillers such as synthetic fibers and ceramics fibers , Coloring agents and the like. The shape of these inorganic fillers may be any of powder (bulk, spherical), short fiber, long fiber and the like, but in the case of a flat plate, the thermal conductivity of the cured product is higher due to the lamination effect of the inorganic filler itself and the heat radiation property of the cured product is further improved desirable.

The amount of the inorganic filler to be used in the epoxy resin composition of the present invention is usually 2 to 1000 parts by mass based on 100 parts by mass of the resin component in the epoxy resin composition. However, in order to increase the thermal conductivity as much as possible, It is preferable to increase the amount of the inorganic filler to be used as far as possible without causing any trouble to the handling of the inorganic filler. These inorganic fillers may be used alone or in combination of two or more.

It is also possible to use a filler having a thermal conductivity of 20 W / m · K or less in combination with an inorganic filler having a thermal conductivity of 20 W / m · K or more as long as the thermal conductivity of the filler as a whole can be maintained at 20 W / m · K or more. For the purposes of the present invention to obtain a cured product with a high thermal conductivity, the use of a filler having a thermal conductivity of less than 20 W / m · K should be limited to a minimum. There is no particular limitation on the type and shape of the filler that can be used in combination.

When the epoxy resin composition of the present invention is used for semiconductor encapsulation, the epoxy resin composition preferably has a heat conductivity of 20 W / m · K or more in a proportion of 75 to 93 mass% in the epoxy resin composition in terms of heat resistance, moisture resistance, mechanical properties, It is preferable to use an inorganic filler. In this case, the remainder is an epoxy resin component, a curing agent component, and other additives that are added according to need, and other inorganic fillers that can be used together as an additive, and a curing accelerator described later.

The epoxy resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, 2- Aminomethyl) phenol, triethylenediamine, triethanolamine and tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, diphenylphosphine and tributylphosphine Tetraphenylboronate and tetraphenylphosphonium ethyltriphenylborate; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium-ethyltriphenylborate; and organic compounds such as 2-ethyl-4- Methyl imidazole tetraphenyl borate, and tetramhenyl boron salts such as N-methyl morpholine tetraphenyl borate. The curing accelerator is used in an amount of 0.01 to 15 parts by mass based on 100 parts by mass of the epoxy resin.

Various additives such as a silane coupling agent, a releasing agent and a pigment, various thermosetting resins and various thermoplastic resins can be added to the epoxy resin composition of the present invention, if necessary. Specific examples of the thermosetting resin and the thermoplastic resin include a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a cyanato resin, an isocyanato compound, a benzoxazine compound, a vinylbenzyl ether compound, a polybutadiene and a modified product thereof, Modified resins of rhenitrile copolymers, indene resins, fluororesins, silicone resins, polyetherimides, polyether sulfone, polyphenylene ether, polyacetal, polystyrene, polyethylene, dicyclopentadiene resins and the like. The thermosetting resin or thermoplastic resin is used in an amount of not less than 60% by mass in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components described above, and preferable applications thereof include a semiconductor sealing material and a printed wiring board.

The epoxy resin composition of the present invention can be easily made into the cured product by the same method as conventionally known. For example, an epoxy resin, an essential component of the epoxy resin composition of the present invention, a curing agent, an inorganic filler having a thermal conductivity of 20 W / m · K or more, and, if necessary, a curing accelerator, a compounding agent, various thermosetting resins, The epoxy resin composition of the present invention obtained by sufficiently mixing the epoxy resin composition of the present invention with an extruder, a kneader, a roll or the like until it becomes homogeneous is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, By heating for 2 to 10 hours, a cured product of the epoxy resin composition of the present invention can be obtained. The epoxy resin composition of the present invention can be used for semiconductor encapsulation by sealing a semiconductor element mounted on a lead frame or the like by the above-described method.

The epoxy resin composition of the present invention may also be a varnish containing a solvent. The varnish may contain at least an epoxy resin mixture according to the present invention, and if necessary, a mixture containing other components such as an inorganic filler having a thermal conductivity of 20 W / m · K or more is dissolved in toluene, xylene, acetone, methyl ethyl ketone , N, N'-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether, acetyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve Sorb acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, It can be obtained by mixing with an organic solvent such as esters such as dialkyldialkyl or adipic acid dialkyl, cyclic esters such as? -Butyrolactone, petroleum ether such as petroleum ether, petroleum naphtha, petroleum naphtha with addition of water and solvent naphtha Can be obtained. The amount of the solvent is generally 10 to 95% by mass, preferably 15 to 85% by mass, based on the entire varnish.

After the varnish obtained as described above is impregnated into a fiber base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, the solvent is removed by heating, and the epoxy resin composition The prepreg of the present invention can be obtained. As used herein, the term " semi-cured state " means a state in which an epoxy group, which is a reactive functional group, remains partially unreacted. The prepreg can be hot-pressed to obtain a cured product.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In Synthetic Examples, Examples and Comparative Examples, parts means parts by mass.

The epoxy equivalent, ICI viscosity and thermal conductivity were measured under the following conditions.

· Epoxy equivalent

Measured by the method described in JIS K-7236, and the unit is g / eq.

· Melt viscosity

Melting viscosity measured by cone plate method at 150 ° C

Measuring instrument: Cone plate (ICI) High temperature viscometer

(Produced by RESEACH EQUIPMENT (LONDON) LTD.)

· Thermal Conductivity

It is measured by the method according to ASTM E1530, and the unit is W / mK.

Synthesis Example 1

136 parts of 4'-hydroxyacetophenone, 152 parts of vanillin and 200 parts of ethanol were added and dissolved in a flask equipped with a stirrer, a reflux condenser and an agitator. After adding 20 parts of 97 mass% sulfuric acid to the mixture, the mixture was heated to 60 ° C, reacted at this temperature for 10 hours, and then 1200 parts of water was poured into the reaction liquid to precipitate crystals. The crystals were filtered, washed twice with 600 parts of water, and then vacuum dried to obtain 256 parts of phenol compound 1 as a yellow crystal. The endothermic peak temperature determined by DSC measurement of the obtained crystal was 233 ° C.

Synthesis Example 2

166 parts of 4'-hydroxy-3'-methoxyacetophenone, 122 parts of 4-hydroxybenzaldehyde and 200 parts of ethanol were added and dissolved in a flask equipped with a stirrer, a reflux condenser and a stirrer. After adding 20 parts of 97% sulfuric acid to the mixture, the mixture was heated to 50 ° C and reacted at this temperature for 10 hours. The reaction mixture was poured into 1200 parts of water to precipitate crystals. The crystals were filtered off, washed twice with 600 parts of water, and then vacuum dried to obtain 285 parts of phenol compound 2 as a brownish crystal. The endothermic peak temperature determined by DSC measurement of the obtained crystal was 193 ° C.

Synthesis Example 3

56 parts of 4-methylcyclohexanone, 152 parts of vanillin and 150 parts of ethanol were added and dissolved in a flask equipped with a stirrer, a reflux condenser and an agitator. After adding 10 parts of 97% by mass sulfuric acid, the temperature was raised to 50 ° C, and after 10 hours of reaction at this temperature, 25 parts of sodium tripolyphosphate was added and stirred for 30 minutes. Thereafter, 500 parts of methyl isobutyl ketone (MIBK) was added, and the mixture was rinsed twice with 200 parts of water. Thereafter, the solvent was distilled off with an evaporator to obtain 304 parts of semi-solid phenol compound 3.

Synthesis Example 4

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 29 parts of acetone, 152 parts of vanillin and 300 parts of ethanol to dissolve. 80 parts of a 50% aqueous solution of sodium hydroxide was added thereto, and the temperature was raised to 45 ° C. After 120 hours of reaction at this temperature, the reaction solution was poured into 800 mL of 1.5N hydrochloric acid to precipitate crystals. The crystals were filtered, washed twice with 600 parts of water, and then vacuum-dried to obtain 165 parts of phenol compound 4 as yellow crystals. The melting point of the obtained crystal was found to be 201 占 폚 by DSC measurement.

Example 1

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 80 parts of the phenol compound 1 obtained in Synthesis Example 1, 20 parts of 4,4'-biphenol, 300 parts of epichlorohydrin, (Hereinafter referred to as " DMSO ") was added, and the mixture was heated to 70 deg. C with stirring to dissolve. 33 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by reaction for 2.5 hours at 70 deg. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 290 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 9 parts of a 30% sodium hydroxide aqueous solution was added thereto under stirring. The mixture was reacted for 1 hour, washed with water until the washing water became neutral, And then methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 130 parts of the epoxy resin mixture 1. The epoxy equivalent of the obtained epoxy resin mixture was 200 g / eq. The melt viscosity was 0.03 Pa · s.

Example 2

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 80 parts of the phenol compound 2 obtained in Synthesis Example 2, 20 parts of 4,4'-biphenol, 300 parts of epichlorohydrin, and 75 parts of DMSO The mixture was heated to 70 ° C under stirring to dissolve, 33 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the mixture was reacted at 70 ° C for 2.5 hours. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 290 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 9 parts of a 30% sodium hydroxide aqueous solution was added under stirring. The mixture was reacted for 1 hour and washed with water until the wash water became neutral. Methyl isobutyl ketone and the like were distilled off under reduced pressure to obtain 130 parts of the epoxy resin mixture 2. The obtained epoxy resin mixture had an epoxy equivalent of 201 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 3

80 parts of phenol compound 3 obtained in Synthesis Example 3, 20 parts of 4,4'-biphenol, 235 parts of epichlorohydrin and 59 parts of DMSO were added to a flask equipped with a stirrer, a reflux condenser and a stirrer, 26 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the mixture was kept at 45 캜 for 1.5 hours, then heated to 70 캜 and reacted for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 271 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 8 parts of a 30% aqueous sodium hydroxide solution was added under stirring. The mixture was reacted for 1 hour and then washed with water until the wash water became neutral. The obtained solution was then filtered through a rotary evaporator Methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 122 parts of epoxy resin mixture 3. The obtained epoxy resin mixture had an epoxy equivalent of 235 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 4

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 80 parts of the phenol compound 4 obtained in Synthesis Example 4, 20 parts of 4,4'-biphenol, 261 parts of epichlorohydrin, and 65 parts of DMSO 29 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the mixture was kept at 45 캜 for 1.5 hours, then heated to 70 캜 and reacted for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 279 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 8 parts of a 30% aqueous sodium hydroxide solution was added under stirring. The mixture was reacted for 1 hour and then washed with water until the wash water became neutral. The obtained solution was then filtered through a rotary evaporator And then methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 126 parts of the epoxy resin mixture 4. The obtained epoxy resin mixture had an epoxy equivalent of 220 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 5

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 90 parts of phenol compound 1 obtained in Synthesis Example 1, 10 parts of bisphenol F (BPF), 284 parts of epichlorohydrin, dimethylsulfoxide , DMSO) was added, and the mixture was heated to 70 deg. C with stirring to dissolve. 32 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was continued at 70 deg. C for 2.5 hours. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 286 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 9 parts of a 30% sodium hydroxide aqueous solution was added under stirring. The mixture was reacted for 1 hour and washed with water until the wash water became neutral. And then methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 128 parts of the epoxy resin mixture 5. The obtained epoxy resin mixture had an epoxy equivalent of 204 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 6

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 90 parts of the phenol compound 2 obtained in Synthesis Example 2, 10 parts of BPF, 284 parts of epichlorohydrin, and 71 parts of DMSO while nitrogen purging was carried out. And 32 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by reaction at 70 DEG C for 2.5 hours. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 286 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 占 폚, and 9 parts of a 30% sodium hydroxide aqueous solution was added under stirring. The mixture was reacted for 1 hour and washed with water until the wash water became neutral. Methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 129 parts of an epoxy resin mixture 6. The obtained epoxy resin mixture had an epoxy equivalent of 205 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 7

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 90 parts of the phenol compound 3 obtained in Synthesis Example 3, 10 parts of BPF, 212 parts of epichlorohydrin and 53 parts of DMSO while nitrogen purging was carried out. And 24 parts of flaky sodium hydroxide was added in portions over 90 minutes. After that, the mixture was kept at 45 캜 for 1.5 hours, then heated to 70 캜 and reacted for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 264 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 DEG C, and 7 parts of a 30% sodium hydroxide aqueous solution was added under stirring. After the reaction was carried out for 1 hour, washing was carried out until the washing water became neutral, and the obtained solution was filtered using a rotary evaporator Methyl isobutyl ketone or the like was distilled off under reduced pressure to obtain 119 parts of an epoxy resin mixture 7. The obtained epoxy resin mixture had an epoxy equivalent of 250 g / eq. And a melt viscosity of 0.03 Pa · s.

Example 8

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 90 parts of the phenol compound 4 obtained in Synthesis Example 4, 10 parts of BPF, 241 parts of epichlorohydrin and 60 parts of DMSO while nitrogen purging was carried out. And 27 parts of flaky sodium hydroxide was added in portions over 90 minutes. After that, the mixture was kept at 45 캜 for 1.5 hours, then heated to 70 캜 and reacted for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 占 폚 using a rotary evaporator. The residue was dissolved in 273 parts of MIBK and then washed with water to remove the salt. After washing with water, the temperature of the MIBK solution was raised to 70 DEG C, and 7 parts of a 30% sodium hydroxide aqueous solution was added under stirring. After the reaction was carried out for 1 hour, washing was carried out until the washing water became neutral, and the obtained solution was filtered using a rotary evaporator Methyl isobutyl ketone and the like were distilled off under reduced pressure to obtain 123 parts of an epoxy resin mixture 8. The obtained epoxy resin mixture had an epoxy equivalent of 229 g / eq. And a melt viscosity of 0.03 Pa · s.

Examples 9 to 24 and Comparative Examples 1 and 2

The components were mixed in a ratio shown in Table 1, kneaded with a mixing roll, made into tablets, and then formed into a resin molding by transfer molding. The resulting mixture was further heated at 160 캜 for 2 hours and at 180 캜 for 8 hours to obtain an epoxy resin composition A cured product of the comparative resin composition was obtained. The results of measuring the thermal conductivity of these cured products are shown in Table 1.

Epoxy resin 9: An epoxy resin (trade name: NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g / eq.) Represented by the following formula (9)

Epoxy resin 10: A biphenyl type epoxy resin (trade name: YL-6121H, manufactured by Japan Epoxy Resin, epoxy equivalent: 175 g / eq.) Containing an equimolar amount of an epoxy resin represented by the following formulas (10)

Curing agent 1: The phenol compound 1 obtained in Synthesis Example 1

Curing agent 2: Phenol compound 2 obtained in Synthesis Example 2

Curing agent 3: Phenol compound 3 obtained in Synthesis Example 3

Curing agent 4: Phenol compound 4 obtained in Synthesis Example 4

Hardener 5: Phenol novolac (trade name: H-1, manufactured by Meiwa Chemical Co., Ltd., hydroxyl equivalent weight: 105 g / eq.) Represented by the following formula (12)

Curing accelerator: triphenylphosphine (manufactured by Hokko Kagaku Kogyo Co., Ltd.)

Examples 25 to 40 and Comparative Examples 3 and 4

The components were mixed in proportions (parts) shown in Table 2, kneaded with a mixing roll, made into tablets, and then formed into a resin molding by transfer molding. The resulting mixture was further heated at 160 캜 for 2 hours and at 180 캜 for 8 hours, A cured product of the comparative resin composition was obtained. The results of measuring the thermal conductivity of these cured products are shown in Table 2.

Inorganic filler 1: spherical alumina (trade name: DAW-100 manufactured by Denki Kagakukogyo Co., Ltd., thermal conductivity: 38 W / mK)

Inorganic filler 2: boron nitride (trade name: SGP manufactured by Denki Kagaku Kogyo Co., thermal conductivity 60 W / mK)

Example 41

100 parts of the epoxy resin mixture 1 obtained in Example 1 was dissolved in 1,000 parts of dimethylformamide at 70 占 폚 and then returned to room temperature. 20 parts of 1,5-naphthalenediamine (manufactured by Tokyo Kasei, amine equivalent: 40 g / eq.) As a curing agent was dissolved at 48 deg. C in dimethylformamide, and the temperature was returned to room temperature. The epoxy resin solution and the curing agent solution were mixed and stirred with a homogenizer of a stirring blade type to obtain a uniform varnish. 228 parts of an inorganic filler (trade name: SGP Denki Kagaku Kogyo Co., Ltd., thermal conductivity 60 W / m 占)) 50 parts by volume relative to 100 parts by volume) and 100 parts of dimethylformamide were further added and mixed and stirred to prepare an epoxy resin composition of the present invention.

The varnish of the epoxy resin composition was impregnated with a glass fiber woven fabric (trade name: 7628 / AS890AW, manufactured by Asahi Shovel) having a thickness of 0.2 mm and heated and dried to obtain a prepreg. Four prepregs and copper foils disposed on both sides of the prepregs were superimposed by heating and pressing at a temperature of 175 DEG C and a pressure of 4 MPa for 90 minutes to obtain a laminate having a thickness of 0.8 mm. The thermal conductivity of this laminate was measured to be 4.1 W / m · K.

Example 42

The same procedure as in Example 41 was repeated, except that the epoxy resin mixture 1 in Example 41 was changed to 100 parts of the epoxy resin mixture 3, the amount of 1,5-naphthalene diamine was changed to 17 parts, and the amount of the inorganic filler was changed to 222 parts To obtain a laminated board. The thermal conductivity of this laminate was measured to be 4.6 W / m · K.

Example 43

The procedure of the same procedure as that of Example 41 was repeated except that the epoxy resin mixture 1 of Example 41 was changed to 100 parts of the epoxy resin mixture 5, the amount of 1,5-naphthalene diamine was changed to 20 parts, and the amount of the inorganic filler was changed to 228 parts To obtain a laminated board. The thermal conductivity of this laminate was measured to be 4.1 W / m · K.

Example 44

The procedure of the same procedure as in Example 41 was repeated, except that the epoxy resin mixture 1 of Example 41 was changed to 100 parts of the epoxy resin mixture 7, the amount of 1,5-naphthalene diamine was changed to 16 parts, and the amount of the inorganic filler was changed to 222 parts To obtain a laminated board. The thermal conductivity of this laminate was measured to be 4.5 W / m · K.

Comparative Example 5

The procedure of Example 41 was repeated except that the epoxy resin mixture 1 of Example 41 was changed to 100 parts of epoxy resin 10 (YL-6121H), 23 parts of 1,5-naphthalene diamine and 234 parts of inorganic filler, To obtain a laminated board. The thermal conductivity of this laminate was measured to be 3.6 W / m · K.

From the above results, it was confirmed that the cured product of the epoxy resin composition containing the epoxy resin mixture of the present invention had excellent thermal conductivity. Therefore, the epoxy resin of the present invention is very useful when it is used in an insulating material for electric / electronic parts, a laminate (printed wiring board, etc.).

Although the present invention has been described in detail with reference to specific embodiments thereof, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2011-163830) filed on July 27, 2011, which is incorporated by reference in its entirety. Also, all references cited here are taken as a whole.

The cured product of the epoxy resin composition of the present invention has excellent thermal conductivity as compared with the conventional cured product of the epoxy resin, and is also excellent in solvent solubility. Therefore, it is very useful for a wide range of applications such as electric and electronic materials, molding materials, mold materials, laminated materials, paints, adhesives, resists and optical materials as sealing materials and prepregs.

Claims (9)

At least one compound represented by the following formulas (1) to (5)
A phenol compound (a) containing an epoxy resin (A) obtained by reacting a phenol compound (a) obtained by a reaction of a compound represented by the following formula (6) with epihalohydrin, (C) obtained by reacting epihalohydrin with an epoxy resin (B) obtained by further reacting an epihalohydrin with a phenol compound (b) and / or a phenol compound (c) By weight based on the weight of the epoxy resin.

[In the formula (1), R ₁ independently represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or an alkoxy group having 1 to 10 carbon atoms . l is the number of R _1, is an integer of 1-4;

[In the formula (2), R ₂ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, an alkylester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, a morpholinylcarbonyl group, a phthalimide group, a piperonyl group or a hydroxyl group]

[In the formula (3), R ₃ independently represents a hydrogen atom, an alkylcarbonyl group having 0 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl ester group having 2 to 10 carbon atoms , An alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. n represents a carbon number and represents an integer of 0, 1, or 2; m represents the number of R < _{3 &} gt ;, and satisfies the relationship of 1 ≤ m ≤

[In the formula (4), R ₄ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group]

[In the formula (5), R ₅ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl ester group having 1 to 10 carbon atoms Or a hydroxyl group. And m is an integer of 1 to 10]

(6), R ₆ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a formyl group, an allyl group or an alkyl group having 1 to 10 carbon atoms Or an alkoxy group. k represents the number of R < ₆ > and is an integer of 1 to 4]

[In the formula (7), R ₇ , X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. k represents the number of R < ₇ > and represents an integer of 1 to 4]

[In the formula (8), R ₈ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. l represents the number of R ₈ , and represents an integer of 1 to 4; A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms and having a cyclic ring, An epoxy resin obtained by reacting epihalohydrin with a phenol compound mixture containing the phenol compound (a) according to claim 1 and further containing a phenol compound (b) and / or a phenol compound (c) mixture. 3. The method of claim 2,
(B) and the phenol compound (c) in the mixture of the phenol compounds (a) to (c) according to claim 1 reacting with epihalohydrin in an amount of 1 to 30 mass% Is reacted with epihalohydrin to obtain a mixture of epoxy resins. An epoxy resin composition comprising the epoxy resin mixture according to any one of claims 1 to 3 and a curing agent. 5. The method of claim 4,
An epoxy resin composition comprising a phenol compound (a) as a curing agent in an epoxy resin composition. The method according to claim 4 or 5,
And an inorganic filler having a thermal conductivity of 20 W / m · K or more. 7. The method according to any one of claims 4 to 6,
An epoxy resin composition characterized by being used for semiconductor encapsulation. A prepreg characterized by comprising the epoxy resin composition according to any one of claims 4 to 6 and a sheet-like fiber base. A cured product obtained by curing the epoxy resin composition according to any one of claims 4 to 7 or the prepreg according to claim 8.