TW201305272A - Epoxy resin mixture, epoxy resin composition, prepreg, and curing product of each - Google Patents

Abstract

The present invention provides an epoxy resin having a curing product that has a high thermal conductivity, and having a low viscosity and superior workability. The epoxy resin contains an epoxy resin (A) obtained by reacting epihalohydrin and a phenol compound (a) obtained by reacting the compounds represented by formula (1) and formula (6), and further contains: an epoxy resin (B) obtained by reacting epihalohydrin to the phenol compound (b) represented by formula (7); and/or an epoxy resin (C) obtained by reacting epihalohydrin and the phenol compound (c) represented by formula (8).

Description

Epoxy resin mixture, epoxy resin composition, prepreg and hardened material thereof

This invention relates to a novel epoxy resin mixture and epoxy resin composition. Further, it relates to a cured product of a prepreg or the like formed using an epoxy resin composition.

The epoxy resin composition is generally used as a cured product excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used in a wide range of fields such as an adhesive, a coating, a laminate, a molding material, and an injection molding material. . In recent years, various properties such as high purity, flame retardancy, heat resistance, moisture resistance, toughness, low linear expansion coefficient, and low dielectric constant characteristics are required for the cured epoxy resin used in these fields. Upgrade.

In particular, high-density packaging of semiconductors for high-density packaging, high-density wiring, and high-density wiring of printed circuits for the purpose of multi-functionalization, high-performance, and miniaturization are progressing in the field of electrical and electronic industries. However, the heat generated from the inside of the semiconductor element or the printed circuit board increases with high-density encapsulation or high-density wiring, which causes a malfunction. Therefore, in terms of energy efficiency or machine design, how to efficiently release the generated heat to the outside becomes an important issue. As a countermeasure against such heat, various methods such as assembling a metal core substrate, assembling a heat-dissipating structure at the design stage, or finely filling a high-heat-conductive filler for a polymer material (epoxy resin) to be used have been studied. However, the current state of the art is that a polymer material as a binder that connects a highly thermally conductive portion has a low thermal conductivity, so that the heat transfer rate of the polymer material is limited, and heat cannot be efficiently dissipated.

As a method for achieving high thermal conductivity of an epoxy resin, Patent Document 1 discloses that a mesogenic group is introduced into a structure, and in the same document, an epoxy resin having a liquid crystal priming group is described as having a biphenyl skeleton. Epoxy resin, etc. Further, as the epoxy resin other than the biphenyl skeleton, an epoxy resin of a phenyl benzoate type is described, but the epoxy resin must be produced by an epoxidation reaction caused by oxidation, and thus there is a problem in safety or cost. But can't say that it is practical. Patent Literatures 2 to 4 are examples in which an epoxy resin having a biphenyl skeleton is used. Patent Document 3 discloses a method in which an inorganic filler having a high thermal conductivity is used in combination. However, the thermal conductivity of the cured product obtained by the method described in the literature does not meet the level of market demand, and the industry requires an epoxy resin which can be obtained relatively inexpensively and which provides hardening with high thermal conductivity. Epoxy resin composition.

Further, in order to obtain a cured product having high thermal conductivity, it is needless to say that the properties of the epoxy resin are required, and high thermal conductivity is exhibited when the cured product is formed, and the low melt viscosity of the resin is also Important features. Generally, a highly thermally conductive filler is more difficult to fill a large amount of particles than a widely used filler. Therefore, when the epoxy resin is in a molten state, the lower the viscosity, the workability is improved. Therefore, in order to make the viscosity of the epoxy resin meet the market requirements, it is strongly desired to have a low viscosity.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 11-323162

Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-2573

Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-63315

Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-137971

The present invention has been made in order to solve such a problem, and provides an epoxy resin mixture having a high thermal conductivity and a low viscosity and excellent workability.

The present inventors have diligently studied to solve the above problems, and as a result, have completed the present invention.

In other words, the present invention relates to (1) an epoxy resin mixture containing one or more compounds represented by the following formulas (1) to (5) and reacting with a compound represented by the following formula (6); An epoxy resin (A) obtained by reacting a phenol compound (a) with an epihalohydrin; and further comprising a ring obtained by reacting a phenol compound (b) represented by the following formula (7) with an epihalohydrin An epoxy resin (C) obtained by reacting an oxy-resin (B) and/or a phenol compound (c) represented by the following formula (8) with an epihalohydrin:

(In the formula (1), R ₁ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or a carbon number of 1 to 10 Any one of the alkoxy groups. _l represents the number of R ₁ and is an integer from 1 to 4),

(In the formula (2), R ₂ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, An alkyl ester group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Any of morpholinylcarbonyl, oximeimine, piperonyl or hydroxyl groups,

(In the formula (3), R ₃ is independently present, and represents a hydrogen atom, an alkylcarbonyl group having a carbon number of 0 to 10, an alkyl group having a carbon number of 1 to 10, an aromatic group having a carbon number of 6 to 10, Any one of an alkyl 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 any one of 0, 1, and 2. m represents The number of R ₃ and satisfy the relationship of 1≦m≦n+2),

(In the formula (4), R ₄ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or Any of the hydroxyl groups),

(In the formula (5), R ₅ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Any one of an alkyl ester group having 1 to 10 carbon atoms or a hydroxyl group. Further, m is an integer of 1 to 10)

(In the formula (6), R ₆ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a methyl group, an allyl group. Any one of alkoxy groups having a carbon number of 1 to 10, k representing the number of R ₆ and an integer of 1 to 4),

(In the formula (7), R ₇ , X and Y are each independently present, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a hydroxyl group, or an alkoxy group having a carbon number of 1 to 10. Either k is the number of R ₇ and is an integer from 1 to 4)

(In the formula (8), R _{8 is} independently present and represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. l represents the number of R ₈ and is an integer from 1 to 4. A is a direct bond or an alkylene group having a carbon number of 5 to 10 having a ring; (2) an epoxy group as in the above item (1) a resin mixture obtained by reacting a phenol compound (a), a phenol compound mixture further containing a phenol compound (b) and/or a phenol compound (c) with an epihalohydrin; (3) a ring according to the above item (2) An oxy-resin mixture obtained by reacting a mixture of the phenol compounds (a) to (c) of the above item (1) before reacting with an epihalohydrin with an epihalohydrin, the phenol compounds (a) to (c) In the mixture, the mixture of the phenol compound (b) and the phenol compound (c) is 1 to 30% by mass of the phenol compound mixture; and (4) an epoxy resin composition containing the above item (1)~( (3) The epoxy resin composition according to any one of the preceding paragraphs (4), which comprises the phenol compound (a) as a hardener; (6) as in the preceding paragraph (4) or (5) an epoxy resin composition, which It is made of an inorganic filler containing a thermal conductivity of 20 W/m‧K or more.

(7) The epoxy resin composition according to any one of the above items (4) to (6) for use in semiconductor packaging; (8) a prepreg, which is the former item (4) to (6) An epoxy resin composition and a sheet-like fibrous substrate; (9) a cured product obtained from the epoxy resin composition according to any one of the above items (4) to (7), or the foregoing item (8) The prepreg is hardened.

The epoxy resin mixture of the present invention is excellent in workability due to low melt viscosity, and further excellent in heat conductivity of the cured product, and thus can be used as various composite materials, adhesives, paints, and the like represented by semiconductor packaging materials and prepregs. .

The epoxy resin mixture of the present invention comprises a mixture of the following epoxy resin (A) further comprising the following epoxy resin (B) and/or the following epoxy resin (C). First, the epoxy resin (A) to (C) precursor phenol compounds (a) to (c) will be described separately.

The phenol compound (a) is obtained by reacting one or more compounds represented by the following formulas (1) to (5) with a compound represented by the following formula (6).

(In the formula (1), R ₁ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or a carbon number of 1 to 10 Any one of the alkoxy groups. _l represents the number of R ₁ and is an integer from 1 to 4.

The R ₁ groups in the formula (1) are each independently present, and are preferably 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, particularly preferably a hydrogen atom or carbon. The number is 1 to 3 alkoxy groups.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (1) which can be used for the reaction with the compound represented by the formula (6) include 2-hydroxyacetophenone and 3-hydroxyphenylethyl. Ketone, 4-hydroxyacetophenone, 2',4'-dihydroxyacetophenone, 2',5'-dihydroxyacetophenone, 3',4'-dihydroxyacetophenone, 3', 5' -Dihydroxyacetophenone, 2',3',4'-trihydroxyacetophenone, 2',4',6'-trihydroxyacetophenone-hydrate, 4'-hydroxy-3'-methyl Acetophenone, 4'-hydroxy-2'-methylacetophenone, 2'-hydroxy-5'-methylacetophenone, 4'-hydroxy-3'-methoxyacetophenone, 2'- Hydroxy-4'-methoxyacetophenone, 4'-hydroxy-3'-nitroacetophenone, 4'-hydroxy-3',5'-dimethoxyacetophenone, 4', 6' -dimethoxy-2'-hydroxyacetophenone, 2'-hydroxy-3',4'- Dimethoxyacetophenone, 2'-hydroxy-4',5'-dimethoxyacetophenone, 5-acetylsalicylic acid methyl ester, 2', 3'- Dihydroxy-4'-methoxyacetophenone hydrate. Among these, in view of high solvent solubility in the epoxidation of the obtained phenol compound, and the cured product of the epoxy resin composition exhibits high thermal conductivity, 4'-hydroxy-3'-methoxy is preferred. Acetophenone, 4'-hydroxyacetophenone.

(In the formula (2), R ₂ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, An alkyl ester group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Any of a morphylcarbonyl group, a quinone imine group, a sunflower group or a hydroxyl group. )

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (2) which can be used for the reaction with the compound represented by the formula (6) include acetone and 1,3-diphenyl-2- Acetone, 2-butanone, 1-phenyl-1,3-butanedione, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, acetamidine acetone, 2-hexanone, 3 -hexanone, isoamyl methyl ketone, ethyl isobutyl ketone, 4-methyl-2-hexanone, 2,5-hexanedione, 1,6-diphenyl-1 ,6-hexanedione, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-4-heptanone, 5-methyl-3-heptanone, 6-methyl-2-heptan Ketone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2-nonanone, 3-fluorenone, 4-nonanone, 5-fluorenone, 2-nonanone, 3-fluorenone, 4-nonanone, 5-nonanone, 2-undecone, 3-undecone, 4-undecone, 5- Undecane, 6-undecone, 2-methyl-4-undecone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 6-dodecanone , 2-tetradecanone, 3-tetradecanone, 8-pentadecanone, 10-nodecanone, 7-tridecanone, 2-pentadecanone, 3-hexadecanone, 9-heptadecanone, 11 -hexadecanone, 12-docostrione, 14-hexadecanone 16-31-one, 18-trimethyl ketone, 4-ethoxy-2-butanone, 4-(4-methoxyphenyl)-2-butanone, 4-methoxy-4- Methyl-2-pentanone, 4-methoxyphenylacetone, methoxyacetone, phenoxyacetone, methyl acetoxyacetate, ethyl acetate, propyl acetate, butyl acetate , isobutyl acetoacetate, second butyl acetate, tert-butyl acetate, 3-pentyl acetate, amyl acetate, isoamyl acetate, acetamidine Hexyl acetate, heptyl acetate, n-octyl acetate, benzyl acetate, dimethyl acetyl succinate, dimethyl acetonate, diethyl acetonate , 2-methoxyethyl acetate, allyl acetate, 4-second butoxy-2-butanone, benzylbutyl ketone, bis-demethoxycurcumin, 1,1 -dimethoxy-3-butanone, 1,3-diethoxypropenylacetone, 4-hydroxyphenylacetone, 4-(4-hydroxyphenyl)-2-butanone, isoamylmethyl ketone , 4-hydroxy-2-butanone, 5-hexen-2-one, acetonylacetone, 3,4-dimethoxyphenylacetone, sunflower-based methyl ketone, sunflower-based acetone, o- Dimethyl acyl imino propanone, 4-isopropoxy-2-butanone, 4-isobutoxy-2-butanone, 2-propanone acetyl group, N- acetyl acetyl group Porphyrin, 1-ethenyl-4-piperidone and the like. Among these, acetone is preferred in view of high solvent solubility in epoxidation of the obtained phenol compound and high heat conductivity of the cured product of the epoxy resin composition.

(In the formula (3), R ₃ is independently present, and represents a hydrogen atom, an alkylcarbonyl group having a carbon number of 0 to 10, an alkyl group having a carbon number of 1 to 10, an aromatic group having a carbon number of 6 to 10, Any one of an alkyl 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 any one of 0, 1, and 2. m represents The number of R ₃ and satisfies the relationship of 1≦m≦n+2.)

Further, in the formula (3), when the R ₃ is a substituted or unsubstituted alkylcarbonyl group having a carbon number of 0, it means a carbonyl group containing a carbon atom constituting the cycloalkane of the main skeleton of the formula (3). The structure may, for example, be 1,3-cyclopentanedione or the like.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (3) which can be used for the reaction with the compound represented by the formula (6) include cyclopentanone and 3-phenylcyclopentanone. 2-Ethylcyclopentanone, 1,3-cyclopentanedione, 2-methyl-1,3-cyclopentadione, 2-ethyl-1,3-cyclopentadione, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 4-tert-butylcyclohexanone, 4-pentylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 3,3-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 4,4-dimethylcyclohexane Ketone, 3,3,5-trimethylcyclohexanone, 2-ethenylcyclohexanone, ethyl 4-cyclohexanoneate, 1,4-cyclohexane 1,4-cyclohexanedione monoethylene ketal, dicyclohexane-4,4'-dione monoethylene ketal, 1,4-cyclohexanedione mono-2,2-dimethyl extension Propylene ketal, 2-ethylindolyl-5,5-dimethyl-1,3-cyclohexanedione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-ring Adipone, 2-methyl-1,3-cyclohexanedione, 5-methyl-1.3-cyclohexanedione, dimedone, 1,4-cyclohexanedione-2,5- Dimethyl dicarboxylate, 4,4'-dicyclohexanone, 2,2-bis(4-oxocyclohexyl)propane, cycloheptanone, and the like. Among these, in view of high solvent solubility in the epoxidation of the obtained phenol compound and high heat conductivity of the cured product of the epoxy resin composition, cyclopentanone, cyclohexanone, and cycloglycan are preferred. Ketone, 4-methylcyclohexanone.

(In the formula (4), R ₄ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or Any of the hydroxyl groups.)

The R ₄ groups in the formula (4) are each independently present, and are preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted aryl group having 6 to 10 carbon atoms, and a carbon number. It is an unsubstituted alkoxy group or a hydroxyl group of 1 to 10.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (4) which can be used for the reaction with the compound represented by the formula (6) include 2,3-butanedione and 2,3-. Pentanedione, 3,4-hexanedione, 5-methyl-2,3-hexyl Diketone, 2,3-heptanedione, and the like. Among these, 2,3-butanedione is preferable in terms of high solvent solubility in the epoxidation of the obtained phenol compound and high heat conductivity of the cured product of the epoxy resin composition.

(In the formula (5), R ₅ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Any one of an alkyl ester group having 1 to 10 carbon atoms or a hydroxyl group. Further, m is an integer of 1 to 10.

The R ₅ group in the formula (5) is independently present, and is preferably 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.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (5) which can be used for the reaction with the compound represented by the formula (6) include ethyl acetate and 2,5-hexane. Diketone, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-phenyl-2,4 - Pentanedione, ethyl 4-ethenyl-5-oxohexanoate, and the like. Among these, in view of high solvent solubility in the epoxidation of the obtained phenol compound, and the cured product of the epoxy resin composition exhibits high thermal conductivity, 3-methyl-2,4-pentyl is preferred. Diketone, 3-ethyl-2,4-pentanedione.

(In the formula (6), R ₆ is independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a methyl group, an allyl group. Any one of a group or alkoxy group having a carbon number of 1 to 10. k represents the number of R ₆ and is an integer of 1 to 4.

The R ₆ groups in the formula (6) are each independently present, and are preferably an alkoxy group having 1 to 3 carbon atoms.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (6) which can be used for the reaction with one or more selected from the compounds represented by the formulae (1) to (5) include: Hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzene Formaldehyde, syringaldehyde, 3,5-di-tris-butyl-4-hydroxybenzaldehyde, isovanillin, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzene Formaldehyde, 3,4-dihydroxy-5-nitrobenzaldehyde, vanillin, o-vanillin, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-5-nitro-meta-anisaldehyde (2-hydroxy -5-nitro-m-anisaldehyde), 2-hydroxy-5-methylisofurfural, 2-hydroxy-4-methoxybenzaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-5-A Oxybenzaldehyde, 5-nitrovanal aldehyde, 5 -allyl-3-methoxysalicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, 3-B Oxalalaldehyde, 4-hydroxyisobutyraldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2, 3,4-Trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and the like. These may be used alone or in combination of two or more. Among these, in view of high solvent solubility in the epoxidation of the obtained phenol compound and high heat conductivity of the cured product of the epoxy resin composition, vanillin is preferably used alone.

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

The compound represented by the formula (6) is preferably 1.0 to 1.05 mol per mol of the compound 1 represented by the formula (1), and is relative to the formula (2), the formula (3), the formula (4), and The compound 1 shown in the formula (5) is preferably used in an amount of 2.0 to 3.15 moles.

When the aldol reaction is carried out under acidic conditions, examples of the acidic catalyst that can be used 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 in combination. The amount of the acid catalyst to be used is preferably 0.01 to 1.0 mol, more preferably 0.2 to 0.5 mol, based on the compound 1 of the formula (6).

On the other hand, when the aldol reaction is carried out under alkaline conditions, examples of the basic catalyst that can be used include metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as potassium carbonate and sodium carbonate. Metal salt, diethylamine, An amine derivative such as triethylamine, tributylamine, diisobutylamine, pyridine or piperidine, and an amino alcohol derivative such as dimethylaminoethanol and diethylaminoethanol. In the case of alkaline conditions, the above-mentioned alkaline catalysts may be used singly or in combination. The amount of the basic catalyst used is preferably from 0.1 to 2.5 mol, more preferably from 0.2 to 2.0 mol, based on the compound 1 of the formula (6).

In the reaction for obtaining the phenol compound (a), a solvent may also be used as needed. The solvent which can be used is not particularly limited as long as it has reactivity with the compound represented by the formula (6), and it is easy to dissolve the raw material of the compound represented by the formula (6). In general, it is preferred to use an alcohol as a solvent.

The reaction temperature is usually from 10 to 90 ° C, preferably from 35 to 70 ° C. The reaction time is usually 0.5 to 10 hours, but the reactivity varies depending on the kind of the raw material compound, and thus is not limited thereto. After the completion of the reaction, when the resin is taken out as a resin, the reaction product is washed with water or not, and an unreacted product, a solvent or the like is removed from the reaction liquid under heating and reduced pressure. In the case of taking out in the form of crystals, crystals are precipitated by adding the reaction droplets to a large amount of water. When the reaction is carried out under alkaline conditions, since the produced phenol compound of the present invention may be dissolved in water, hydrochloric acid or the like is added to form a neutral to acidic condition, which is precipitated by crystallization.

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

(wherein R ₇ , X and Y are each independently present, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms; k is the number of R ₇ and is an integer from 1 to 4.)

In the formula (7), R ₇ , X and Y are each independently present in terms of maintaining high thermal conductivity, and are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Various bisphenols are mentioned as a phenol compound (b). Specifically, BPF, BPA, BPE, Methylenebis-p-CR, TM-BPF, Bis-C, BisP-MIBK, Bis26X-A, BisP-AP, BisOPP-A, UltratriP, DHBP, BisOC- F, BisP-B, BisP-IBTD, Bis-BA, BisP-IOTD, BisOIPP-A, BisP-DED, BisOSBP-A, BisOTBP-A, Bis2M6B-IBTD, BisOCHP-A, Ph-CC-AP (any All are manufactured by the state chemical industry) and so on.

Among these, in terms of maintaining high thermal conductivity, BPF and BPA are preferable, and BPF is particularly preferable.

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

(In the formula, R ₈ is independently present and represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. The number of R ₈ and an integer of 1 to 4. A is a direct bond or an alkylene group having a ring of 5 to 10 carbon atoms)

The A site of the phenol compound (c) is a biphenyl skeleton directly bonded to a biphenyl skeleton or a 3,3',5,5'-tetramethyl-4,4'-biphenol compound, and each of them may be mentioned. a phenolic compound formed by reacting a cyclic aliphatic ketone with a phenol.

Specifically, a compound as shown below can be mentioned.

The above phenol compound is commercially available, and examples thereof include BisP-CP, BisP-Z, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, and Bis26X-IPZ. , BisP-TCD, BisOC-CDE, Bis26X-CDE, BisP-CHEP, BisP-COCT, BisP-CPeDE (any one is manufactured by the state chemical industry), TCDBP (METROPORITAN EXIMCHEM XTD) and the like.

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

The epoxy resin mixture of the present invention is obtained by reacting each of the above phenol compounds with an epihalohydrin and epoxidizing. Further, in the epoxidation, each of the phenol compounds (a) to (c) is previously reacted with an epoxy halopropane to obtain epoxy resins (A) to (C), and the respective epoxy resins may be mixed. The method of reacting the respective phenolic compounds with the epihalohydrin is not particularly limited as long as it is known, and specific examples thereof can be used, for example, those described in JP-A-2005-179978 and JP-A-2008-179739. method.

However, in terms of production, it is preferred to react a mixture of the phenol compounds (a) to (c) with an epihalohydrin to obtain an epoxy resin mixture. By the production method, a mixture of the epoxy resins (A) to (C) can be obtained, and further, an epoxy group-bonded epoxy having a skeleton of a part of each of the phenol compounds (a) to (c) can be produced. Resin.

As the epoxy resin mixture of the present invention, in the case of a cured product which exhibits a low melt viscosity and has a high thermal conductivity, it is preferred to contain a compound represented by the formula (6) and a compound represented by the formula (3). The epoxide of the phenol compound (a) obtained by the reaction of the compound, that is, the epoxy resin (A), further contains a mixture of the epoxy resin (B) and/or the epoxy resin (C).

Hereinafter, a method of reacting a mixture of the phenol compounds (a) to (c) with an epihalohydrin to obtain an epoxy resin mixture will be described.

The sum of the amounts of the phenol compound (b) and the phenol compound (c) is 1 to 30% by mass, and more preferably 5 to 30% by mass based on the total amount of the phenol compounds (a) to (c). When the ratio of the amount of the phenol compound (b) and the phenol compound (c) is 30% by mass or less, the thermal conductivity does not become low, and if it is 1% by mass or more, the viscosity is viscous. The degree does not become high, and the adhesion to the metal does not decrease, but is preferable.

In the reaction of the epoxy resin contained in the epoxy resin mixture of the present invention, as the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin can be used. And epibromohydrin, etc., preferably epichlorohydrin which is industrially easily available. The amount of the epihalohydrin used is usually 2 to 20 moles, preferably 2 to 15 moles, and particularly preferably 2 to 6.5 moles, relative to the hydroxyl group of the phenol compound. The epoxy resin is obtained in the presence of an alkali metal oxide by reacting a phenol compound with an epihalohydrin, and then subjecting the formed 1,2-halopropane ether group to ring-opening to epoxidation. . At this time, the epihalohydrin is used in a smaller amount than usual, whereby the molecular weight of the epoxy resin is increased and the molecular weight distribution is wide. As a result, the obtained epoxy resin was taken out from the system with a resin having a lower softening point, and exhibited excellent solvent solubility.

Examples of the alkali metal hydroxide which can be used in the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like, and these may be used as they are, or an aqueous solution of these may be used. In the case of using an aqueous solution, it may be a method in which an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epoxy halogen are continuously distilled off from the reduced pressure or under normal pressure. The mixture of propane is separated to remove water, and only the epihalohydrin is continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.9 to 3.0 moles, preferably 1.0 to 2.5 moles, more preferably 1.0 to 2.0 moles, and particularly preferably 1.0 to 1.3 moles, relative to the hydroxyl group of the phenol compound. ear.

Further, the present inventors have found that the epoxidation reaction, particularly by using a sodium hydroxide in the form of a sheet, is more remarkable than the use of sodium hydroxide in an aqueous solution. Reduce the amount of halogen contained in the epoxy resin obtained. This halogen is derived from an epoxy halopropane, and the more the epoxy resin is mixed, the lower the thermal conductivity of the cured product. Further, this sheet-like sodium hydroxide is preferably added in portions to the reaction system. By performing the divided addition, the sudden decrease in the reaction temperature can be prevented, and thereby the formation of the impurity 1,3-halopropane or halomethylene can be prevented, and the hardening with higher thermal conductivity can be formed. Things.

In order to promote the epoxidation reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is preferably used as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on the hydroxyl group of the phenol compound.

Further, in the case of epoxidation, in terms of reaction progress, it is preferred to add an alcohol such as methanol, ethanol or isopropanol, dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran or the like. The reaction is carried out by an aprotic polar solvent such as an alkane. Among these, an alcohol or dimethyl fluorene is preferred. In the case of using an alcohol, the epoxy resin can be obtained with high efficiency. On the other hand, in the case of using dimethyl fluorene, the amount of halogen in the epoxy resin can be further reduced.

In the case of using the above alcohols, the amount thereof to be used is usually 2 to 50% by mass, preferably 4 to 35% by mass based on the amount of the epihalohydrin. Moreover, when an aprotic polar solvent is used, the amount to be used with respect to the epihalohydrin is usually 5 to 100% by mass, preferably 10 to 80% by mass.

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

After completion of the reaction, the reactant is washed with water or not, and the epihalohydrin or solvent is removed from the reaction solution under heating and reduced pressure. Again, for Further, the amount of halogen contained in the epoxy resin is further reduced, and the recovered epoxy resin mixture may be dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added. The aqueous solution is used for the reaction, and the ring closure can be surely performed. 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 the hydroxyl group of the phenol compound of the present invention. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the salt formed is removed by filtration, washing with water, or the like, and the solvent is distilled off under reduced pressure under heating to obtain an epoxy resin mixture of the present invention. Further, when the epoxy resin mixture of the present invention is crystallized, the crystals of the epoxy resin mixture may be removed by filtration after dissolving the produced salt in a large amount of water.

The total halogen amount of the epoxy resin mixture of the present invention obtained by using the sheet-like sodium hydroxide as described above is usually 1800 ppm or less, preferably 1600 ppm or less, more preferably 700 ppm or less. If the total amount of halogen is too large, the electrical reliability of the cured product may be adversely affected, and in terms of the remaining uncrosslinked end, the intermolecular alignment in the molten state at the time of hardening may not proceed. Thermal conductivity is reduced.

The epoxy equivalent of the epoxy resin mixture of the present invention is preferably 350 g/eq. or less, particularly preferably 300 g/eq. or less, from the viewpoint of obtaining a low-viscosity epoxy resin mixture. Further, the epoxy equivalent of the epoxy resin mixture of the present invention is an average 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. this invention The epoxy resin composition 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 may be used in combination with other epoxy resins.

Specific examples of the other epoxy resin include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, and alkane). Substituted dihydroxybenzene and dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzenedialdehyde) Polycondensate of crotonaldehyde, crotonaldehyde, cinnamaldehyde, etc., polycondensate of aromatic compound such as xylene and formaldehyde, polycondensate of phenol, phenol and various diene compounds (dicyclopentadiene, terpene, vinyl Cyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene and isoprene Polycondensate of diene, etc., polycondensate of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanol Polycondensates of benzenes, phenols and aromatic dichloromethyls (α,α'-dichloroform) And polycondensates of bischloromethylbiphenyl, etc., phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl and bisphenoxymethyl linkage) a polycondensate of benzene or the like, a polycondensate of bisphenols and various aldehydes, and a glycidyl ether epoxy resin, an alicyclic epoxy resin, or a glycidylamine epoxy resin obtained by glycidylating an alcohol or the like. The glycidyl ester epoxy resin or the like is not limited thereto as long as it is a commonly used epoxy resin. These can be used only by one type. It is also possible to use two or more types together.

In the case where other epoxy resins are used in combination, the proportion of all the epoxy resin components in the epoxy resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass. % or more, more preferably 70% by mass or more, and particularly preferably 100% by mass (in the case where other epoxy resins are not used in combination). In the case where the epoxy resin mixture of the present invention is used as a modifier for the epoxy resin composition, it is added in a ratio of 1 to 30% in all the epoxy resins.

Examples of the curing agent contained in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. Specific examples of such curing agents are shown in the following (a) to (e).

(a) Amine compounds: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophorone diamine, naphthalene diamine, etc.

(b) An acid anhydride compound: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid Formic anhydride, nadic methyl anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

(c) a guanamine compound: a polyamide resin synthesized from a dimer of dicyanodiamine or linoleic acid and ethylenediamine

(d) Phenolic compounds: polyphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl , 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-4.4'-diol, p-phenylene Phenol, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc.; by phenols (eg phenol) , alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene and dihydroxy naphthalene, etc.) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde and a phenol resin obtained by condensation of a ketone (such as hydroxyacetophenone or o-hydroxyacetophenone) or a diene (dicyclopentadiene or tricyclopentadiene); And substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl Or the substituted phenyl group (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.) a phenol resin obtained by polycondensation; a modified substance of the above phenols and/or the above phenol resin; a halogenated phenol such as tetrabromobisphenol A or a brominated phenol resin

(e) Other imidazoles, BF ₃ -amine complexes, anthracene derivatives

Among these hardeners, in addition to amine compounds such as diaminodiphenylmethane, diaminodiphenylphosphonium and naphthalene diamine, and catechol and aldehydes, ketones, dienes, A phenolic compound (a) which is a precursor of the epoxy resin (A) of the component 1 of the present invention, in addition to a hardener having a structure in which an active hydrogen group is adjacent to each other, such as a condensate of a substituted biphenyl or a substituted phenyl group. It is preferred because the epoxy resin is well aligned.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably from 0.8 to 1.2 equivalents, particularly preferably from 0.95 to 1.05 equivalents, per equivalent of the epoxy group of the epoxy resin.

The epoxy resin composition of the present invention may contain an inorganic filler excellent in heat conductivity as needed, thereby imparting a high thermal conductivity superior to the cured product.

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, and when the thermal conductivity of the inorganic filler itself is too low, The high thermal conductivity obtained by the combination of epoxy resin and hardener is impaired. Therefore, as the inorganic filler contained in the epoxy resin composition of the present invention, the higher the thermal conductivity, the more preferable, as long as it is usually 20 W/m‧K or more, preferably 30 W/m‧K or more. More preferably, the thermal conductivity of 50 W/m ‧ or more is not limited. Further, the thermal conductivity as referred to herein means a value measured in accordance with the method of ASTM E1530. Specific examples of the inorganic filler having such characteristics include inorganic powders such as boron nitride, aluminum nitride, tantalum nitride, tantalum carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide. Filler, fibrous filler such as synthetic fiber or ceramic fiber, colorant, etc. The shape of the unfilled material may be any one of a powder (bulk, spherical), a monofilament, a filament, etc., and especially if it is a flat shape, it is made by the lamination effect of the inorganic filler itself. The heat conductivity of the cured product becomes higher, and the heat dissipation property of the cured product is further improved, which is preferable.

The amount of the inorganic filler 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, but in order to increase the thermal conductivity as much as possible, it is preferably The amount of the inorganic filler to be used is increased as much as possible within the range which does not cause any trouble in the use of the epoxy resin composition of the present invention in a specific use. These inorganic fillers may be used alone or in combination of two or more.

Moreover, if the thermal conductivity of the entire filler material can be maintained in the range of 20 W/m‧K or more, the thermal conductivity can be 20 W/m‧K or more. In the inorganic filler, a filler having a thermal conductivity of less than 20 W/m‧K is used in combination, but the thermal conductivity is less than 20 W/m‧K for the purpose of the present invention in which a cured product having a high thermal conductivity is obtained as much as possible. The use of fillers should be limited to a minimum. The kind or shape of the filler which can be used in combination is not particularly limited.

When the epoxy resin composition of the present invention is used for semiconductor packaging applications, it is preferably 75 to 93 in terms of heat resistance, moisture resistance, mechanical properties and the like of the cured product. The ratio of the mass% is an inorganic filler having a thermal conductivity of 20 W/m‧K or more. In this case, the residue is an epoxy resin component, a hardener component, and other additives which are added as needed, and as an additive, another inorganic filler which can be used together, or a hardening accelerator mentioned later.

The epoxy resin composition of the present invention may also contain a hardening 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, and 2-(dimethylidene). Aminomethyl)phenol, triethylenediamine, triethanolamine and 1,8-diazabicyclo(5,4,0)undecene-7 (1,8-diazabicyclo(5.4.0)-undecene- 7) tertiary amines, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, tetraphenylphosphonium-tetraphenylborate and tetraphenylphosphonium-B Tetrasubstituted fluorene-tetrasubstituted borate such as triphenylborate, 2-ethyl-4-methylimidazolium-tetraphenylborate and N-methyl A tetraphenylboron salt such as a porphyrin-tetraphenylborate. The hardening accelerator is used in an amount of 0.01 to 15 parts by mass, based on 100 parts by mass of the epoxy resin.

In the epoxy resin composition of the present invention, various formulation agents such as a decane coupling agent, a release agent, and a pigment, various thermosetting resins, various thermoplastic resins, and the like may be added as needed. Specific examples of the thermosetting resin and the thermoplastic resin include a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a cyanate resin, an isocyanate compound, and benzo. Compound, vinyl benzyl ether compound, polybutadiene and modified substance thereof, modified product of acrylonitrile copolymer, oxime resin, fluororesin, oxime resin, polyether oximine, polyether oxime, polyphenylene ether, poly Acetal, polystyrene, polyethylene, dicyclopentadiene resin, and the like. The thermosetting resin or the thermoplastic resin is used in an amount of 60% by mass or less based on the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components, and as a preferred use thereof, a semiconductor package material, a printed circuit board or the like can be given.

The epoxy resin composition of the present invention can be easily made into a cured product by the same method as previously known. For example, a cured product of the epoxy resin composition of the present invention can be obtained by the following method: an epoxy resin, a hardener, and a thermal conductivity of 20 W/m‧K which are essential components of the epoxy resin composition of the present invention. The inorganic filler, the hardening accelerator, the compounding agent, various thermosetting resins, various thermoplastic resins, and the like, if necessary, are sufficiently mixed until necessary to obtain uniformity by using an extruder, a kneader, a roll, or the like. The epoxy resin composition of the invention is then molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further obtained by heating at a melting point or higher for 2 to 10 hours. The epoxy resin composition of the present invention can be used for semiconductor packaging applications by encapsulating a semiconductor element mounted on a lead frame or the like as described above.

Further, the epoxy resin composition of the present invention may be formed into a varnish containing a solvent. The varnish may be, for example, a mixture of other components including at least one epoxy resin mixture of the present invention, optionally containing an inorganic filler having a thermal conductivity of 20 W/m‧K or more, with toluene, xylene, acetone, and the like. Ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethyl hydrazine, Glycol ethers such as N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether (glycol ether), ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate (carbitol acetate), propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc., γ-butyrolactone (γ-butylolactone) The cyclic esters are obtained by mixing an organic solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent solvent such as solvent naphtha. The amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass based on the total amount of the varnish.

After immersing the varnish obtained as described above in a fiber substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, the solvent is removed by heating, and the epoxy resin of the present invention is composed. The article is in a semi-hardened state, whereby the prepreg of the present invention can be obtained. In addition, the "semi-hardened state" here means a state in which a part of the epoxy group of a reactive functional group remains unreacted. The prepreg can be hot pressed to obtain a cured product.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the synthesis examples, examples, and comparative examples, the parts are parts by mass.

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

‧Epoxy equivalent

The measurement was carried out by the method described in JIS K-7236, and the unit was g/eq.

‧melt viscosity

Melt viscosity by a cone plate method at 150 ° C

Measuring machine: cone and plate (ICI) high temperature viscometer

(Manufactured by RESEARCH EQUIPMENT (LONDON) LTD.)

‧Thermal conductivity

The measurement was carried out in accordance with the method of ASTM E1530 in units of W/m‧K.

Synthesis Example 1

A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was charged with 136 parts of 4'-hydroxyacetophenone, 152 parts of vanillin, and 200 parts of ethanol, and dissolved. After adding 20 parts of 97% by mass of sulfuric acid thereto, the temperature was raised to 60 ° C, and after reacting at this temperature for 10 hours, the reaction liquid was poured into 1200 parts of water to be crystallized. After filtration and crystallization, the mixture was washed twice with 600 parts of water, and then vacuum dried to obtain 256 parts of a yellow crystalline phenol compound 1. The crystallization peak obtained by DSC was 233 ° C.

Synthesis Example 2

In a flask equipped with a stirrer, a reflux cooling tube and a stirring device, 166 parts of 4'-hydroxy-3'-methoxyacetophenone and 122 parts of 4-hydroxybenzamide were charged. The aldehyde and 200 parts of ethanol were dissolved. After adding 20 parts of 97% sulfuric acid thereto, the temperature was raised to 50 ° C, and after reacting at this temperature for 10 hours, the reaction liquid was poured into 1200 parts of water to be crystallized. After filtration and crystallization, the mixture was washed twice with 600 parts of water, and then vacuum dried to obtain 285 parts of a brownish crystalline phenol compound 2. The crystallization peak obtained by DSC was 193 ° C.

Synthesis Example 3

A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was charged with 56 parts of 4-methylcyclohexanone, 152 parts of vanillin, and 150 parts of ethanol, and dissolved. After adding 10 parts of 97% by mass of sulfuric acid, the temperature was raised to 50 ° C, and after reacting at this temperature for 10 hours, 25 parts of sodium tripolyphosphate was added and stirred for 30 minutes. Thereafter, 500 parts of methyl isobutyl ketone (MIBK) was added, and then washed twice with 200 parts of water, and then the solvent was distilled off by an evaporator to obtain 304 parts of a semisolid phenol compound 3.

Synthesis Example 4

A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was charged with 29 parts of acetone, 152 parts of vanillin, and 300 parts of ethanol, and dissolved. After 80 parts of a 50% aqueous sodium hydroxide solution was added thereto, the temperature was raised to 45 ° C, and after reacting at this temperature for 120 hours, the reaction liquid was poured into 800 mL of 1.5 N hydrochloric acid to cause crystallization. After filtration and crystallization, the mixture was washed twice with 600 parts of water, and then vacuum dried to obtain 165 parts of a yellow crystalline phenol compound 4. The melting point of the obtained crystal was determined by DSC to be 201 °C.

Example 1

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device Under nitrogen purge, 80 parts of the phenol compound obtained in Synthesis Example 1, 1, 20 parts of 4,4'-biphenol, 300 parts of epichlorohydrin, and 75 parts of dimethylarsine (hereinafter DMSO) were added while stirring. The temperature was raised to 70 ° C and dissolved. After 33 parts of sodium hydroxide was added in portions over 90 minutes, the reaction was carried out 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 ° C using a rotary evaporator. The residue was dissolved in 290 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 9 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. The evaporator was distilled off under reduced pressure at 180 ° C to obtain methyl isobutyl ketone or the like, whereby 130 parts of the epoxy resin mixture 1 was obtained. The epoxy resin mixture obtained had an epoxy equivalent of 200 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 2

A nitrogen purge was carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and 80 parts of the phenol compound obtained in Synthesis Example 2, 20 parts of 4,4'-biphenol, 300 parts of epichlorohydrin, and 75 were added thereto. The DMSO was heated to 70 ° C with stirring and dissolved. After 33 parts of sodium hydroxide was added in portions over 90 minutes, the reaction was carried out 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 ° C using a rotary evaporator. The residue was dissolved in 290 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 9 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. The evaporator was distilled off under reduced pressure at 180 ° C to remove methyl isobutyl ketone or the like, thereby obtaining 130 parts of a ring. Oxygen 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

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was performed while adding 80 parts of the phenol compound obtained in Synthesis Example 3, 20 parts of 4,4'-biphenol, and 235 parts of epichlorohydrin, 59. The DMSO was heated to 45 ° C with stirring and dissolved, and 26 parts of plate-like sodium hydroxide was added in portions over 90 minutes, and then maintained at 45 ° C for 1.5 hours, and then heated to 70 ° C for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 ° C using a rotary evaporator. The residue was dissolved in 271 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 8 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. Evaporator was used to distill off methyl isobutyl ketone or the like under reduced pressure at 180 ° C, whereby 122 parts of the epoxy resin mixture 3 were obtained. The epoxy resin mixture obtained had an epoxy equivalent of 235 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 4

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was performed while adding 80 parts of the phenol compound obtained in Synthesis Example 4, 20 parts of 4,4'-biphenol, and 261 parts of epichlorohydrin, 65. The DMSO was heated to 45 ° C with stirring and dissolved. After 29 minutes of sodium hydroxide was added in portions over 90 minutes, the mixture was maintained at 45 ° C for 1.5 hours, and then heated to 70 ° C for 30 minutes. After the reaction is over, use a rotary evaporator An excess of epichlorohydrin or the like was distilled off under reduced pressure at 135 °C. The residue was dissolved in 279 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 8 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. Evaporator was used to distill off methyl isobutyl ketone or the like under reduced pressure at 180 ° C, whereby 126 parts of the epoxy resin mixture 4 was obtained. The epoxy resin mixture obtained had an epoxy equivalent of 220 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 5

90 parts of the phenol compound obtained in Synthesis Example 1, 10 parts of bisphenol F (BPF), 284 parts of epichlorohydrin, and 71 parts were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring apparatus while performing nitrogen purge. Dimethylhydrazine (hereinafter referred to as DMSO) was dissolved by heating to 70 ° C with stirring, and 32 parts of plate-like sodium hydroxide was added in portions over 90 minutes, and then maintained 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 ° C using a rotary evaporator. The residue was dissolved in 286 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 9 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. The evaporator was distilled off under reduced pressure at 180 ° C to give methyl isobutyl ketone or the like, whereby 128 parts of the epoxy resin mixture 5 were obtained. The epoxy resin mixture obtained had an epoxy equivalent of 204 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 6

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device Nitrogen was added, and 90 parts of the phenol compound obtained in Synthesis Example 2, 10 parts of BPF, 284 parts of epichlorohydrin, and 71 parts of DMSO were added thereto, and the mixture was heated to 70 ° C with stirring and dissolved, and separated in 90 minutes. After 32 parts of sheet-like sodium hydroxide were added in this order, the reaction was carried out 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 ° C using a rotary evaporator. The residue was dissolved in 286 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 9 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. The evaporator was distilled off under reduced pressure at 180 ° C to give methyl isobutyl ketone or the like, whereby 129 parts of the epoxy resin mixture 6 was obtained. The epoxy resin mixture obtained had an epoxy equivalent of 205 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 7

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was performed while adding 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 under stirring. The temperature was raised to 45 ° C and dissolved. After 24 minutes of sodium hydroxide was added in portions over 90 minutes, the temperature was maintained at 45 ° C for 1.5 hours, and then the temperature was raised to 70 ° C and the reaction was carried out for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 ° C using a rotary evaporator. The residue was dissolved in 264 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 7 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. Distillation of methyl isobutyl ketone under reduced pressure at 180 ° C Etc., thereby obtaining 119 parts of the epoxy resin mixture 7. The epoxy resin mixture obtained had an epoxy equivalent of 250 g/eq. and a melt viscosity of 0.03 Pa‧s.

Example 8

90 parts of the phenol compound obtained in Synthesis Example 4, 10 parts of BPF, 241 parts of epichlorohydrin, and 60 parts of DMSO were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring apparatus while stirring. The temperature was raised to 45 ° C and dissolved. After 27 parts of sodium hydroxide was added in portions over 90 minutes, the temperature was maintained at 45 ° C for 1.5 hours, and then the temperature was raised to 70 ° C and the reaction was carried out for 30 minutes. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 135 ° C using a rotary evaporator. The residue was dissolved in 273 parts of MIBK and washed with water to remove salts. After washing with water, the MIBK solution was heated to 70 ° C, and 7 parts of a 30% aqueous sodium hydroxide solution was added under stirring to carry out a reaction for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was rotated. The evaporator was distilled off under reduced pressure at 180 ° C to obtain methyl isobutyl ketone or the like, whereby 123 parts of the epoxy resin mixture 8 were obtained. The epoxy resin mixture obtained 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, 2

The components were blended in the proportions (parts) of Table 1, and the resin molded body was prepared by transfer molding after kneading and tableting by a mixing roll, and heated at 160 ° C for 2 hours and further heated at 180 ° C for 8 hours to obtain the present. The cured epoxy resin composition and the cured resin composition of the invention. The results of measuring the thermal conductivity of these cured materials are shown in Table 1.

Epoxy resin 9: Epoxy resin represented by the following formula (9) (trade name: NC-3000 Nippon Chemical Co., Ltd. epoxide equivalent: 276 g/eq.)

Epoxy resin 10: bisphenol type epoxy resin containing epoxy resin represented by the following formulas (10) and (11) (trade name: YL-6121H Japan Epoxy Resins, epoxy equivalent 175 g/eq) .)

Hardener 1: Phenol compound 1 obtained in Synthesis Example 1

Hardener 2: Phenol compound 2 obtained in Synthesis Example 2

Hardener 3: phenol compound 3 obtained in Synthesis Example 3

Hardener 4: phenolic compound 4 obtained in Synthesis Example 4

Hardener 5: a phenol novolac represented by the following formula (12) (trade name: H-1, manufactured by Minghe Chemical Co., Ltd., hydroxyl equivalent: 105 g/eq.)

Hardening accelerator: triphenylphosphine (manufactured by Beixing Chemical Industry)

Examples 25 to 40 and Comparative Examples 3 and 4

The components were prepared in a ratio of parts in Table 2, and kneaded and tableted by a mixing roll, and then a resin molded body was prepared by transfer molding, and heated at 160 ° C for 2 hours and further heated at 180 ° C for 8 hours to obtain the present. The cured epoxy resin composition and the cured resin composition of the invention. The results of measuring the thermal conductivity of these hardened materials are shown in Table 2.

Inorganic filler 1: spherical alumina (trade name: DAW-100 electrical and chemical industry manufacturing thermal conductivity 38 W / m ‧ K)

Inorganic filler 2: Boron nitride (trade name: SGP electrical and chemical industry manufacturing thermal conductivity 60 W/m‧K)

Example 41

After 100 parts of the epoxy resin mixture 1 obtained in Example 1 was dissolved in 1000 parts of dimethylformamide at 70 ° C, it was returned to room temperature. 20 parts of a hardener of 1,5-naphthalenediamine (manufactured by Tokyo Chemicals Co., Ltd., amine equivalent 40 g/eq.) was dissolved in 48 parts of dimethylformamide at 70 ° C, and returned to room temperature. The above epoxy resin solution and the hardener solution are mixed and stirred by a homomixer of a stirring airfoil to form a uniform varnish, and further 228 parts (50 parts by volume relative to 100 parts by volume of the resin solid component) of the inorganic filler are added (product Name: manufactured by SGP Electrochemical Industry, thermal conductivity: 60 W/m‧K), and 100 parts of dimethylformamide were mixed and stirred to prepare an epoxy resin composition of the present invention.

The varnish of the epoxy resin composition was impregnated into a glass fiber woven fabric (trade name: 7628/AS890AW Asahi-Schwebel) having a thickness of 0.2 mm, and dried by heating to obtain a prepreg. Four sheets of the prepreg were superposed on the copper foil disposed on both sides thereof, and then heated and pressed at a temperature of 175 ° C and a pressure of 4 MPa for 90 minutes to be integrated, thereby obtaining a laminate having a thickness of 0.8 mm. . The thermal conductivity of the laminate was measured and found to be 4.1 W/m‧K.

Example 42

Change the epoxy resin mixture 1 in Example 41 to 100 parts, respectively. The laminated board was obtained in the same operation procedure as in Example 41 except that the amount of the epoxy resin mixture 3,1,5-naphthalenediamine was changed to 17 parts, and the amount of the inorganic filler was changed to 222 parts. The thermal conductivity of the laminate was measured and found to be 4.6 W/m‧K.

Example 43

The epoxy resin mixture 1 in the example 41 was changed to 100 parts of the epoxy resin mixture, and the amount of the 1,5-naphthalenediamine was changed to 20 parts, and the amount of the inorganic filler was changed to 228 parts. In the same operation sequence as in Example 41, a laminate was obtained. The thermal conductivity of the laminate was measured and found to be 4.1 W/m‧K.

Example 44

The epoxy resin mixture 1 in Example 41 was changed to 100 parts of the epoxy resin mixture, and the amount of 1,5-naphthalenediamine was changed to 16 parts, and the amount of the inorganic filler was changed to 222 parts. In the same operation sequence as in Example 41, a laminate was obtained. The thermal conductivity of the laminate was measured and found to be 4.5 W/m‧K.

Comparative Example 5

The epoxy resin mixture 1 in Example 41 was changed to 100 parts of epoxy resin 10 (YL-6121H), the amount of 1,5-naphthalenediamine was changed to 23 parts, and the amount of inorganic filler was changed to 234 parts. Further, a laminate was obtained in the same operation sequence as in Example 41. The thermal conductivity of the laminate was measured and found 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 has excellent thermal conductivity. Therefore, this The epoxy resin of the invention is extremely useful for applications such as insulating materials for electric and electronic parts, laminated boards (printed circuit boards, etc.).

The present invention has been described in detail with reference to the specific embodiments thereof, and various modifications and changes can be made without departing from the spirit and scope of the invention.

In addition, the present application is based on Japanese Patent Application No. 2011-163830, filed on Jan. 27, 2011. Also, all of the reference frames cited herein are incorporated as a whole.

The cured product of the epoxy resin composition of the present invention has excellent thermal conductivity as compared with the cured product of the prior epoxy resin, and is also excellent in solvent solubility. Therefore, it is extremely useful as a packaging material and a prepreg which is equivalent to a wide range of applications such as electrical and electronic materials, molding materials, injection molding materials, laminated materials, coating materials, adhesives, photoresists, and optical materials.

Claims (9)

An epoxy resin mixture containing a phenol compound (a) and a ring obtained by reacting one or more compounds represented by the following formulas (1) to (5) with a compound represented by the following formula (6); An epoxy resin (A) obtained by reacting an oxyhalopropane; and further comprising an epoxy resin (B) obtained by reacting a phenol compound (b) represented by the following formula (7) with an epihalohydrin and/or The epoxy resin (C) obtained by reacting the phenol compound (c) represented by the formula (8) with an epihalohydrin: (In the formula (1), R _{1 is} independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or a carbon number of 1 to 10. Any of alkoxy groups; l represents the number of R ₁ and is an integer from 1 to 4), (In the formula (2), R _{2 is} independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkylcarbonyl group having 1 to 15 carbon atoms, and carbon. a number of 2 to 10 alkyl ester groups, a carbon number of 1 to 10 alkoxy groups, Any of a morphylcarbonyl group, a quinone imine group, a sunflower group or a hydroxyl group), (In the formula (3), R _{3 is} independently present, and represents a hydrogen atom, an alkylcarbonyl group having a carbon number of 0 to 10, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, and carbon. The number is an alkyl ester group of 2 to 10, an alkoxy group having a carbon number of 1 to 10, or a hydroxyl group; n represents a carbon number and represents any one of 0, 1, 2; m represents R ₃ , and satisfy the relationship of 1≦m≦n+2), (In the formula (4), R _{4 is} independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. Any of them), (In the formula (5), R _{5 is} independently present, and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and carbon. Any one of an alkyl ester group or a hydroxyl group of 1 to 10; and m is an integer of 1 to 10) (In the formula (6), R _{6 is} independently present, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, a decyl group, and an allyl group. Or any one of alkoxy groups having a carbon number of 1 to 10; 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 exist, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a hydroxyl group, or an alkoxy group having a carbon number of 1 to 10. Either k represents the number of R ₇ and is an integer from 1 to 4) (In the formula (8), R _{8 is} independently present, and represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms; l represents the number of R ₈ and is an integer from 1 to 4; A is a direct bond or an alkylene group having a ring of 5 to 10 carbon atoms). An epoxy resin mixture which is reacted with an epihalohydrin by a phenol compound mixture containing the phenol compound (a) and further containing the phenol compound (b) and/or the phenol compound (c) described in the first paragraph of the patent application. Got it. The epoxy resin mixture of claim 2, which is obtained by reacting a mixture of the phenol compounds (a) to (c) described in the first claim of the reaction with the epihalohydrin with the epihalohydrin. In the mixture of the phenol compounds (a) to (c), the sum of the proportions of the phenol compound (b) and the phenol compound (c) is 1 to 30% by mass. An epoxy resin composition comprising the epoxy resin mixture and the hardener according to any one of claims 1 to 3. An epoxy resin composition according to item 4 of the patent application, which comprises a phenol compound (a) as a curing agent. An epoxy resin composition according to claim 4 or 5, which comprises an inorganic filler having a thermal conductivity of 20 W/m‧K or more. The epoxy resin composition according to any one of claims 4 to 6 is for use in semiconductor packaging. A prepreg comprising the epoxy resin composition according to any one of claims 4 to 6 and a sheet-like fibrous substrate. A cured product obtained by hardening an epoxy resin composition according to any one of claims 4 to 7 or a prepreg according to item 8 of the patent application.