KR20120030049A - Epoxy resin composition, prepreg and cured products thereof - Google Patents

Abstract

The objective of this invention is providing the epoxy resin composition from which the hardened | cured material which has heat resistance and high thermal conductivity is obtained.
The epoxy resin composition which concerns on this invention is an epoxy resin composition which consists of an epoxy resin, a hardening | curing agent, and the inorganic filler of 20 W / m * K or more of thermal conductivity, and is a 1 type of compound represented by predetermined formula (1)-(5) as a hardening | curing agent. It contains the epoxy compound obtained by making epihalohydrin further react with the said phenol compound as a phenol compound and / or an epoxy resin obtained by reaction of the above and hydroxybenzaldehyde.

Description

Epoxy resin composition, prepreg and hardened | cured material thereof {EPOXY RESIN COMPOSITION, PREPREG AND CURED PRODUCTS THEREOF}

The present invention relates to a novel epoxy resin composition and a prepreg obtained by using the epoxy resin composition. Moreover, this invention relates to the hardened | cured material formed by hardening | curing the said epoxy resin composition or a prepreg.

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

In particular, in the electric and electronic industries, which are typical applications of epoxy resin compositions, high-density packaging of semiconductors and high-density wiring of printed wiring boards for the purpose of multifunction, high performance, and compactness have been advanced. However, high-density mounting or high-density wiring can increase the heat generated from the inside of a semiconductor element or a printed wiring board, which may cause malfunction of devices. Therefore, how to efficiently discharge the generated heat to the outside has become an important problem in terms of energy efficiency and device design.

As these tropical measures, various studies have been made, such as using a metal core substrate, making a structure which is easy to dissipate heat at the design stage, or finely filling a high thermal conductive filler into the polymer material (epoxy resin) to be used. However, since the thermal conductivity of the polymer material in the binder region connecting the high thermally conductive portions is low, the thermal conductivity speed of the polymer material becomes the rate rate and it is not possible to provide efficient heat dissipation.

As a means of realizing high thermal conductivity of an epoxy resin, Patent Literature 1 reports a method of introducing a mesogen group into an epoxy resin structure. The document describes an epoxy resin having a biphenyl skeleton as an epoxy resin having a mesogenic group. As epoxy resins other than the biphenyl skeleton, phenylbenzoate-type epoxy resins are described. However, since the epoxy resins need to be produced by epoxidation reactions by oxidation, they are difficult and practical in terms of safety and cost. Can not say.

Moreover, patent document 2-4 describes the example using the epoxy resin which has a biphenyl frame | skeleton, and patent document 3 describes the method of using together the inorganic filler which has high thermal conductivity especially. However, the thermal conductivity of the cured product obtained by the methods described in these documents is not at a level satisfying market demands, and an epoxy resin composition is required that provides a cured product having a higher thermal conductivity using an epoxy resin that is relatively inexpensive. have.

Moreover, the hardening | curing agent contained in an epoxy resin composition like an epoxy resin is said to be an important factor which implements high thermal conductivity. Conventionally, as a hardening | curing agent contained in the epoxy resin composition which the hardened | cured material has a high thermal conductivity, patent document 1 has 4,4'- diamino diphenyl benzoate, 4,4'- diamino diphenylmethane, and patent document 2 And 3, the example using the amine-type hardeners, such as 1, 5- diamino naphthalene, is reported. However, since these amine hardening | curing agents have a hardening acceleration | action action, it is difficult to ensure the life time at the time of producing hardened | cured material, and it cannot be said that it is preferable. On the other hand, in patent document 4, a phenolic compound is used as a hardening | curing agent. Although the catechol novolak is specifically used in patent document 4, the thermal conductivity of the hardened | cured material obtained by the method of the said document also does not satisfy the market demand, but the epoxy resin composition which provides the hardened | cured material which has higher thermal conductivity is provided. Development is required.

(Prior art technical literature)

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

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

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

Patent Document 4: Japanese Unexamined Patent Publication No. 2003-137971

This invention is made | formed as a result of examination in order to solve such a problem, and provides the epoxy resin composition which the hardened | cured material has high thermal conductivity.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention as a result of earnestly researching in order to solve the said subject.

That is, the present invention

(One)

(a ') epoxy resin,

(b) Phenolic compound obtained by reaction of 1 or more types of compound represented by following formula (1)-(5) with hydroxybenzaldehyde as a hardening | curing agent, and

(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher.

(In formula (1), R <_1> exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a hydroxyl group, or C1-C10. Any one of substituted or unsubstituted alkoxy groups, l represents the number of R ₁ , and is an integer of 0 to 4.

(In Formula (2), R <_2> is respectively independently present, and a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C15 substitution, or Unsubstituted alkylcarbonyl group, morpholinylcarbonyl group, substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, phthalimide group, piperonyl group or hydroxyl group Indicates one.)

(In Formula (3), R <_3> respectively exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkylcarbonyl group, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substitution, or N represents an unsubstituted aryl group, a substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxy group or hydroxyl group having 1 to 10 carbon atoms, n represents carbon number, and 0, 1, An integer of any one of 2. m represents the number of R ₃ and satisfies the relationship of 0 ≦ m ≦ n + 2.)

(In formula (4), R <_4> respectively exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or Or an unsubstituted alkoxy group or hydroxyl group.)

(In formula (5), R <_5> exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or Any of an unsubstituted alkoxy group or a hydroxyl group is shown, and n is an integer of 1-10.)

(2)

(a) an epoxy resin obtained by further reacting epihalohydrin with the phenolic compound according to the above (1),

(b ') a curing agent, and

(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher.

(3)

(a) the epoxy resin as described in said (2),

(b) the phenolic compound according to the above (1), and

(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher.

(4)

The epoxy resin composition in any one of said (1)-(3) used for semiconductor sealing use.

(5)

The prepreg which consists of an epoxy resin composition as described in any one of said (1)-(3), and a sheet-like fiber base material.

(6)

It is related with the hardened | cured material formed by hardening | curing the epoxy resin composition in any one of said (1)-(4), or the prepreg as described in said (5).

(Effects of the Invention)

Since the hardened | cured material is excellent in thermal conductivity, the epoxy resin composition of this invention is useful when it uses for various composite materials, such as a semiconductor sealing material and a prepreg, an adhesive agent, coating material, etc.

The epoxy resin composition of this invention is an epoxy resin composition which contains an epoxy resin, a hardening | curing agent, and an inorganic filler (Hereinafter, it describes as "(c) component") of 20 W / m * K or more of heat conductivity, As a hardening | curing agent, it is a following formula (1) Phenolic compound (henceforth "(b) component") obtained by reaction of 1 or more types of compound represented by (5), and hydroxybenzaldehyde, and / or an epoxy resin as said (b) component It contains the epoxy compound (henceforth "a component") obtained by making epihalohydrin further react.

First, the component (b) which the epoxy resin composition of this invention contains as a hardening | curing agent is demonstrated. (b) A component is a phenol compound obtained by reaction of 1 or more types of compound represented by following formula (1)-(5), and hydroxybenzaldehyde.

(In formula (1), R <_1> exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a hydroxyl group, or a C1-C10 group. Any one of a substituted or unsubstituted alkoxy group, l represents the number of R ₁ , and is an integer of 0-4.)

(In Formula (2), R <_2> respectively exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C15 substitution, or Unsubstituted alkylcarbonyl group, morpholinylcarbonyl group, substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, phthalimide group, piperonyl group or hydroxyl group Indicates one.)

In Formula (2), it is preferable that the said substituent is at least 1 sort (s) chosen from the group which consists of a carbonyl group, ester group, alkenyl group, phenyl group, alkoxy group, ether group, phthalimide group, and piperonyl group.

(In Formula (3), R <_3> respectively exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkylcarbonyl group, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substitution, or N represents an unsubstituted aryl group, a substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxy group or hydroxyl group having 1 to 10 carbon atoms, n represents carbon number, and 0, 1, Represents an integer of any one of 2. m represents the number of R ₃ and satisfies the relationship of 0 ≦ m ≦ n + 2.)

In addition, in the formula, when R <_3> is a C0 substituted or unsubstituted alkylcarbonyl group, the carbonyl structure which comprises the carbon atom which comprises cycloalkane which is a main skeleton of General formula (3) shows, for example, 1 , 3-cyclopentanedione, and the like.

In Formula (3), it is preferable that the said substituent is an ether group.

(In formula (4), R <_4> respectively exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or Or an unsubstituted alkoxy group or hydroxyl group.)

(In formula (5), R <_5> exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or Any of an unsubstituted alkoxy group or a hydroxyl group is shown, and n is an integer of 1-10.)

In order to obtain (b) component, o-, m-, and p-hydroxy acetophenone are mentioned as a specific example of the compound represented by Formula (1) used for reaction with hydroxybenzaldehyde. Among these, p-hydroxyacetophenone is preferable because the hardened | cured material of an epoxy resin composition shows high thermal conductivity.

In order to obtain the component (b), specific examples of the compound represented by formula (2) used in the reaction with hydroxybenzaldehyde are acetone, 1,3-diphenyl-2-propanone, 2-butanone, 1- Phenyl-1,3-butanedione, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, isoamyl methyl ketone, ethyl isobutyl ketone, 4- Methyl-2-hexanone, 1,6-diphenyl-1,6-hexanedione, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-4-heptanone, 5-methyl-3 -Heptanone, 6-methyl-2-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2- Nonanon, 3-nonanon, 4-nonanon, 5-nonanon, 2-decanone, 3-decanone, 4-decanone, 5-decanone, 2-undecanone, 3-undecanone, 4- Undecanone, 5-undecanone, 6-undecanone, 2-methyl-4-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 6-dodecanone, 2-tetra Decanone, 3-tetradecanone, 8-pentadecanone, 10-nonadecanone, 7-trideca , 2-pentadecanone, 3-hexadecanone, 9-heptadecanone, 11-heneicosanone, 12-tricosanone, 14-heptacosanone, 16-gentriacontanone, 18-pentatricontanone , 4-ethoxy-2-butanone, 4- (4-methoxyphenyl) -2-butanone, 4-methoxy-4-methyl-2-pentanone, 4-methoxyphenylacetone, methoxyacetone , Phenoxyacetone, methyl acetoacetic acid, acetoacetic acid ethyl, acetoacetic acid propyl, acetoacetic acid butyl, acetoacetic acid isobutyl, acetoacetic acid sec-butyl, acetoacetic acid tert-butyl, acetoacetic acid 3-pentyl, acetoacetic acid amyl, acetoacetic acid Isoamyl, acetoacetic acid hexyl, acetoacetic acid heptyl, acetoacetic acid n-octyl, acetoacetic acid benzyl, acetylsuccinic acid dimethyl, acetonylmaronic acid dimethyl, acetonylmaronic acid diethyl, 4-acetyl-5-oxohexanoate, aceto 2-methoxyethyl acetate, acetoacetic acid allyl, 4-sec- Methoxy-2-butanone, benzylbutyl ketone, bisdimethoxycurcumin, 1,1-dimethoxy-3-butanone, 1,3-diacetoxyacetone, 4-hydroxyphenylacetone, 4- (4-hydride Hydroxyphenyl) -2-butanone, isoamylmethylketone, 4-hydroxy-2-butanone, 5-hexen-2-one, acetonylacetone, 3,4-dimethoxyphenylacetone, piperonylmethylketone , Piperonyl acetone, phthalimide acetone, 4-isopropoxy-2-butanone, 4-isobutoxy-2-butanone, acetoxy-2-propanone, N-acetoacetylmorpholine, 1-acetyl -4-piperidone and the like.

Examples of the compound represented by formula (3) used in the reaction with hydroxybenzaldehyde in order to obtain the component (b) include cyclopentanone, 3-phenylcyclopentanone, 1,3-cyclopentanedione and cyclohexanone. , 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 4-tert-butylcyclohexanone, 4-pentylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone Paddy, 3,3-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 4 -Cyclohexanone carboxylic acid ethyl, 1,4-cyclohexanedione monoethylene ketal, bicyclohexane-4,4'-dione monoethylene ketal, 1,3-cyclohexanedione, 1,4-cyclohexanedione, Dimedone, 4,4'-bicyclohexanone, cycloheptanone, etc. are mentioned.

Examples of the compound represented by formula (4) used in the reaction with hydroxybenzaldehyde in order to obtain the component (b) include diacetyl, 2,3-pentanedione, 3,4-hexanedione and 5-methyl-2. , 3-hexanedione, 2,3-heptanedione and the like.

To obtain the component (b), specific examples of the compound represented by formula (5) used in the reaction with hydroxybenzaldehydes include acetylacetone, diacetoacetic acid ethyl, 2,5-hexanedione, 3-methyl-2, 4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-phenyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, and the like. Listed.

To obtain the component (b), examples of the hydroxybenzaldehydes used in the reaction with one or more of the compounds represented by the formulas (1) to (5) include, for example, o-, m- and p-hydroxybenzaldehyde. And the like. These may use only 1 type or may use 2 or more types together. Among these, since the hardened | cured material of an epoxy resin composition shows especially high thermal conductivity, it is preferable to use p-hydroxybenzaldehyde independently.

(b) A component is obtained by the aldehyde condensation reaction of 1 or more types of compound represented by Formula (1)-(5), and under acidic conditions or basic conditions, and hydroxybenzaldehyde.

As for hydroxybenzaldehyde, it is preferable to use 1.0-1.05 mol with respect to 1 mol of compounds represented by Formula (1), and 2.0-3.15 mol with respect to 1 mol of compounds represented by Formula (2)-Formula (5), respectively. .

When the aldehyde condensation 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, organic acids such as toluenesulfonic acid, xylenesulfonic acid and oxalic acid. These may be used independently and may use multiple types together. The usage-amount of an acidic catalyst is 0.01-1.0 mol with respect to 1 mol of hydroxy benzaldehydes, Preferably it is 0.2-0.5 mol.

On the other hand, when performing an aldehyde condensation reaction under basic conditions, as a basic catalyst which can be used, metal hydroxides, such as sodium hydroxide and potassium hydroxide, alkali metal carbonates, such as potassium carbonate and sodium carbonate, diethylamine, triethylamine, tributylamine Amine derivatives such as diisobutylamine, pyridine and piperidine, and amino alcohol derivatives such as dimethylaminoethyl alcohol and diethylaminoethyl alcohol. In the case of basic conditions, the above-mentioned basic catalyst may be used independently, and multiple types may be used together. The usage-amount of a basic catalyst is 0.1-2.5 mol with respect to 1 mol of hydroxy benzaldehydes, Preferably it is 0.2-2.0 mol.

In reaction which obtains (b) component, you may use a solvent as needed. The solvent that can be used is not particularly limited as long as it has a reactivity with hydroxybenzaldehyde, such as ketones. However, alcohol is preferably used as a solvent in view of easily dissolving hydroxybenzaldehyde of a raw material. .

The reaction temperature is usually 10 to 90 ° C, preferably 35 to 70 ° C. Although reaction time is 0.5 to 10 hours normally, since there is a difference in reactivity by the kind of raw material compound, it is not limited only to this. When the reaction product is taken out as a resin after completion of the reaction, unreacted substances, solvents, and the like are removed from the reaction liquid under reduced pressure after washing with water or without washing with water. In the case of withdrawing the crystal, the crystal is precipitated by dropping the reaction liquid into a large amount of water. When the reaction is carried out under basic conditions, the resulting component (b) may be dissolved in water. Thus, hydrochloric acid is added to precipitate as a crystal under neutral and acidic conditions.

Next, the (a) component which the epoxy resin composition of this invention contains as an epoxy resin is demonstrated.

(A) component which the epoxy resin composition of this invention contains is obtained by making the (b) component obtained by the said method, and epihalohydrin react and epoxidize. In addition, at the time of epoxidation, you may use only one type of (b) component, or may use 2 or more types together. Moreover, you may use together phenolic compounds other than (b) component to (b) component.

As a phenolic compound other than (b) component which can be used together, if it is a phenolic compound normally used as a raw material of an epoxy resin, it can use without a restriction | limiting, but since the effect of this invention that hardened | cured material has high thermal conductivity may be impaired. It is preferable that the usage-amount of the phenol compound which can be used together is very small, and it is especially preferable to use only (b) component.

Especially as the (a) component, since the hardened | cured material which has high thermal conductivity is obtained, the epoxide obtained by using (b) component obtained by reaction of hydroxy benzaldehyde and the compound represented by Formula (3) is preferable.

In the reaction for obtaining the component (a), epichlorohydrin, α-methyl epichlorohydrin, β-methyl epichlorohydrin, epibromohydrin and the like can be used as epihalohydrin. Epichlorohydrin is readily available. The usage-amount of epihalohydrin is 2-20 mol normally with respect to 1 mol of hydroxyl groups of (b) component, Preferably it is 4-15 mol.

Examples of alkali metal hydroxides that can be used for the epoxidation reaction include sodium hydroxide and potassium hydroxide, and these may use solids as they are or may use an aqueous solution thereof. In the case of using an aqueous solution, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water is separated from the mixed solution of water and epihalohydrin continuously discharged under reduced pressure or normal pressure, The method of returning only epihalohydrin only in a reaction system may be sufficient. The use amount of alkali metal hydroxide is 0.9-3.0 mol normally with respect to 1 mol of hydroxyl groups of (b) component, Preferably it is 1.0-2.5 mol, More preferably, it is 1.1-2.0 mol.

In order to promote the epoxidation reaction, it is preferable to add quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of (b) component, Preferably it is 0.2-10 g.

In addition, it is preferable in the progress of reaction to carry out reaction by adding alcohols, such as methanol, ethanol, and isopropyl alcohol, an aprotic polar solvent, such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, etc. at the time of epoxidation.

When using the said alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 mass%. In addition, when using an aprotic polar solvent, it is 5-100 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 mass%.

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 reaction product is removed from the reaction solution under reduced pressure by heating with or without washing with water. Furthermore, in order to further reduce the amount of hydrolyzable halogen contained in (a) component, collect | recovered (a) component is melt | dissolved in solvents, such as toluene and methyl isobutyl ketone, and alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are carried out. You may react by adding aqueous solution. By performing such an operation, the closing ring can be assured. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of (b) component, Preferably it is 0.05-0.2 mol. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and (a) component is obtained by further distilling a solvent off under heating pressure reduction. In addition, when (a) component precipitates as a crystal | crystallization, after melt | dissolving the salt produced | generated in a large amount of water, you may collect and collect the crystal | crystallization of (a) component.

Hereinafter, it describes about the epoxy resin composition of this invention.

The epoxy resin composition of this invention contains an epoxy resin, a hardening | curing agent, and inorganic filler of 20 W / m * K or more of heat conductivity, and also contains at least any one of (a) component as an epoxy resin and (b) component as a hardening | curing agent as an essential component. do.

In the epoxy resin composition of this invention, (a) component which is an epoxy resin can be used individually or in combination with another epoxy resin (henceforth "a component").

Specific examples of the component (a ') include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, bisphenol I, etc.) and phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Hydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaraldehyde, phthalaldehyde , Polycondensates of crotonaldehyde and cinnamic aldehyde), aromatic compounds such as xylene, polycondensates of formaldehyde and phenols, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornenadi N, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbipe , Polycondensates of butadiene and isoprene), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone), phenols and aromatic dimethanols (benzenedimethanol and biphenyldiphenyl) Polycondensates of methanol, etc., polycondensates of phenols and aromatic dichloromethyls (such as α, α'-dichloroxylene and bischloromethylbiphenyl), phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxy Glycidyl ether epoxy resins glycidylated with polycondensates of methyl biphenyl and bisphenoxymethyl biphenyl, bisphenols and various aldehydes, and alcohols, alicyclic epoxy resins and glycidyls Although an amine epoxy resin, glycidyl ester epoxy resin, etc. are mentioned, It is not limited to these if it is an epoxy resin normally used. These may use only one type or may use 2 or more types together.

When using together (a ') component, 30 mass% or more is preferable, as for the ratio of (a) component to all the epoxy resin components in the epoxy resin composition of this invention, 40 mass% or more is more preferable, 70 mass% The above is more preferable, Especially preferably, it is 100 mass% (when not using (a ') component together). However, when using (a) component as a modifier of an epoxy resin composition, it adds in the ratio used as 1-30 mass% in all the epoxy resins.

In the epoxy resin composition of this invention, (b) component which is a hardening | curing agent can be used individually or in combination with another hardening | curing agent.

As another hardening | curing agent (henceforth "(b ') component") which the epoxy resin composition of this invention contains, an amine type compound, an acid anhydride type compound, an amide type compound, a phenol type compound, etc. are mentioned, for example. Specific examples of these (b ') components are shown in the following (a) to (e).

(a) Amine compound

Diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine and naphthalenediamine, etc.

(b) acid anhydride compounds

Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylnasic acid anhydride, hexahydro phthalic anhydride and methylhexahydro phthalic anhydride, etc.

(c) Amide Compound

Polyamide resins synthesized from dimers of dicyandiamide or linolenic acid and ethylenediamine

(d) phenolic compounds

Polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpenediphenol, 4,4'- dihydroxy biphenyl, 2,2'- dihydroxy biphenyl, 3,3 ', 5,5 '-Tetramethyl- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane and 1,1,2,2- Tetrakis (4-hydroxyphenyl) ethane and the like); Phenols (e.g. phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene and dihydroxynaphthalene, etc.) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Phenol resins obtained by condensation of benzaldehyde, furfural and the like), ketones (such as p-hydroxy acetophenone and o-hydroxyacetophenone, and the like) or dienes (such as dicyclopentadiene and tricyclopentadiene); The phenols and substituted biphenyls (4,4'-bis (chloromethyl) -1,1'-biphenyl and 4,4'-bis (methoxymethyl) -1,1'-biphenyl, etc.) or substituted Phenolic resin obtained by polycondensation with phenyl (1, 4-bis (chloromethyl) benzene, 1, 4-bis (methoxymethyl) benzene, 1, 4-bis (hydroxymethyl) benzene, etc.); Modified products of the phenols and / or the phenol resins; Halogenated phenols such as tetrabromobisphenol A and brominated phenol resins

(e) other imidazoles, BF ₃ -amine complexes, guanidine derivatives

Among these (b ') components, amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalenediamine, and catechols with aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls Condensates and the like are preferred. This is because these components have a structure in which active hydrogen groups are adjacent to each other, whereby an epoxy resin is favorably arranged. For example, in the case of a condensate with catechol, since the hydroxyl groups reacted by thermosetting are in the ortho position, they are polymerized so as to be parallel to each other. On the other hand, in an amine, since the hydrogen groups reacting at the time of thermosetting are lined up in parallel via a nitrogen atom, it superposes | polymerizes also in parallel.

(b ') A component may be used independently and may use multiple together.

When using together (b ') a component, 20 mass% or more is preferable, as for the ratio of (b) component to all the hardening | curing agent components in the epoxy resin composition of this invention, 30 mass% or more is more preferable, 70 mass% or more More preferably, it is 100 mass% (when not using a component (b ') together) more preferably.

In the epoxy resin composition of this invention, 0.5-2.0 equivalent is preferable with respect to 1 equivalent of epoxy groups of all the epoxy resins, and, as for the usage-amount of all the hardening | curing agents containing (b) component, 0.6-1.5 equivalent is especially preferable.

As the epoxy resin composition of this invention, the case where 100 mass% of (a) component is used as an epoxy resin and 100 mass% of (b) component is used as a hardening agent is the most preferable.

The inorganic filler contained in the epoxy resin composition of the present invention is applied for the purpose of imparting 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, it is obtained by the combination of the epoxy resin and the curing agent. High thermal conductivity may be impaired. Therefore, as an inorganic filler which the epoxy resin composition of this invention contains, it is so preferable that thermal conductivity is high, and it is 20W / m * K or more normally, Preferably it is 30W / m * K or more, More preferably, it is 50W / m * K or more There is no restriction as long as In addition, the thermal conductivity here is the value measured by the method based on ASTME1530. Specific examples of the inorganic filler having such characteristics include inorganic fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, magnesium oxide, fibrous fillers such as synthetic fibers, ceramic fibers, Colorants and the like. The inorganic filler may be in the form of powder (lump shape, spherical shape), short fibers, or long fibers, but in particular, in the case of a flat plate, the thermal conductivity of the cured product becomes higher due to the lamination effect of the inorganic filler itself, It is preferable because it further improves.

Although the usage-amount of the inorganic filler in the epoxy resin composition of this invention is 2-100 mass parts normally with respect to 100 mass parts of resin components in an epoxy resin composition, Preferably it is 400-1000 mass parts, but in order to make thermal conductivity as high as possible It is preferable to increase the usage-amount of an inorganic filler as much as possible in the range which does not interfere with the handling etc. in the specific use of the epoxy resin composition of this invention. These inorganic fillers may use only 1 type, or may use two or more types together.

In addition, as long as the thermal conductivity of the filler as a whole can be maintained at 20 W / m-K or more, an inorganic filler having a thermal conductivity of 20 W / m-K or more may be used in combination with a filler having a thermal conductivity of 20 W / m-K or less. Since it is an object of the present invention to obtain a cured product having high thermal conductivity, use of a filler having a thermal conductivity of 20 W / m · K or less should be minimized. There is no restriction | limiting in particular in the kind and shape of the filler which can be used together.

When using the epoxy resin composition of this invention for a semiconductor sealing use, and when using it for a prepreg use, the ratio which occupies 60-93 mass% in an epoxy resin composition from the points of heat resistance, moisture resistance, and mechanical properties of hardened | cured material. It is preferable to use an inorganic filler having a thermal conductivity of 20 W / m · K or more. In this case, remainder is an additive added according to an epoxy resin component, a hardening | curing agent component, and other necessities, As an additive, it is another inorganic filler which can be used together, a hardening accelerator mentioned later, etc.

The epoxy resin composition of this invention should just contain at least one of (a) component as an epoxy resin, and (b) component as a hardening | curing agent as an essential component, and epoxy resin (it does not specifically limit in addition to embodiment mentioned above), For example, the composition containing the said (a ') component is preferable), (b) component, and (c) component, or (a) component and hardening | curing agent (It is not specifically limited, For example, said (b'). Even if it is a composition containing a component) and (c) component, the hardened | cured material has the outstanding thermal conductivity similarly to the composition containing (a) component, (b) component, and (c) component.

The epoxy resin composition of this invention can also contain a hardening accelerator. As a curing accelerator which can be used, for example, imidazoles, such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole, 2- ( Tertiary amines such as dimethylaminomethyl) phenol, triethylenediamine, triethanolamine and 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, diphenylphosphine and tributyl Organic phosphines such as phosphine, metal compounds such as octylic acid tin, tetra substituted phosphonium tetra substituted borates such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium ethyltriphenylborate, 2-ethyl-4 Tetraphenyl boron salts, such as -methylimidazole tetraphenyl borate and N-methylmorpholine tetraphenyl borate, etc. are mentioned. A hardening accelerator is used as needed for 0.01-15 mass parts with respect to 100 mass parts of epoxy resins.

Various compounding agents, such as a silane coupling agent, a mold release agent, and a pigment, various thermosetting resins, various thermoplastic resins, etc. can be added to the epoxy resin composition of this invention as needed. Specific examples of the thermosetting resin and the thermoplastic resin include vinyl ester resins, unsaturated polyester resins, maleimide resins, cyanate resins, isocyanate compounds, benzoxazine compounds, vinyl benzyl ether compounds, polybutadienes and modified substances thereof, and acrylonitrile copolymers. Modified compounds, indene resins, fluorine resins, silicone resins, polyether imides, polyether sulfones, polyphenylene ethers, polyacetals, polystyrenes, polyethylene, dicyclopentadiene resins, and the like. The amount which occupies 60 mass% or less in the epoxy resin composition of this invention is used for a thermosetting resin or a thermoplastic resin.

The epoxy resin composition of this invention is obtained by mixing each said component uniformly, As a preferable use, a semiconductor sealing material, a printed wiring board, etc. are mentioned.

The epoxy resin composition of this invention can be easily made into the hardened | cured material by the method similar to what is conventionally known. Formation of the cured product of the present invention is, for example, an epoxy resin, a curing agent and an inorganic filler having a thermal conductivity of 20 W / m? K or more, and a curing accelerator, a compounding agent, various thermosetting resins, various thermoplastic resins, etc. After mixing sufficiently until it becomes uniform using a roll etc. and obtaining an epoxy resin composition, the said epoxy resin composition is shape | molded by the molten casting method, the transfer molding method, the injection molding method, the compression molding method, etc., and it is 2 to 10 hours beyond the melting point then, It can carry out by heating. When using the epoxy resin composition of this invention for a semiconductor sealing use, what is necessary is just to seal the semiconductor element mounted in a lead frame etc. by said method.

Moreover, the epoxy resin composition of this invention can also be used as the varnish containing a solvent. The varnish may be, for example, an epoxy resin, a curing agent and an inorganic filler having a thermal conductivity of 20 W / m? K or higher, and a mixture containing other components, if necessary, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, cyclopentanone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene Glycol ethers such as glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cello Solvate acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutaric acid, dialkyl succinate, adipic acid dial With esters, such as γ- butynyl it can be obtained by mixing with an organic solvent such as a petroleum solvent of cyclic esters, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, such as lactone. The quantity of a solvent is 10-95 mass% normally with respect to the whole varnish, Preferably it is 15-85 mass%.

The varnish obtained as described above is impregnated into a sheet-like fibrous base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and then the solvent is removed by heating, and the varnish is semi-hardened. By making it into the state, the prepreg of this invention can be obtained. In addition, the "semi-cured state" here means the state in which the epoxy group which is a reactive functional group remains partially unreacted. Hardened | cured material can be obtained by hot press molding the said prepreg.

(Example)

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In a synthesis example, an Example, and a comparative example, a part means a mass part. In addition, epoxy equivalent, melting | fusing point, and thermal conductivity were measured on condition of the following.

? Epoxy equivalent

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

? Melting point

Manufactured by Seiko Instruments Inc.EXSTAR6000

Measurement sample 2 mg-5 mg Temperature increase rate 10 degreeC / min.

Thermal conductivity

Measured according to ASTM E1530

Hydroxyl equivalent

It measures by the method based on the method of JISK-0070, and a unit is g / eq.

Synthesis Example 1

136 parts of p-hydroxyacetophenone, 124 parts of p-hydroxybenzaldehyde and 300 parts of ethanol were added to a flask equipped with a stirrer, a reflux condenser and a stirring device, and dissolved. After adding 51.0 parts of 97% sulfuric acid to this, it heated up to 60 degreeC, after reaction at this temperature for 8 hours, the reaction liquid was poured into 1200 parts of water, and it crystallized. The crystals were filtered off, washed twice with 600 parts of water, and then dried in vacuo to obtain 220 parts of phenol compounds 1 of reddish brown crystals. Melting | fusing point of the obtained crystal | crystallization was 203 degreeC by DSC measurement.

Synthesis Example 2

29 parts of acetone, 124 g of p-hydroxybenzaldehyde, and 300 parts of ethanol were added to the flask equipped with the stirrer, the reflux condenser, and the stirring apparatus, and dissolved. 80 parts of 50% sodium hydroxide aqueous solution was added to this, and it heated up to 45 degreeC, after reaction at this temperature for 120 hours, the reaction liquid was poured into 800 mL of 1.5N hydrochloric acid, and crystallized. The crystals were filtered off, washed twice with 600 parts of water, and then dried in vacuo to obtain 210 parts of yellow phenol compounds 2 as yellow crystals. Melting | fusing point of the obtained crystal | crystallization was 101 degreeC by DSC measurement.

Synthesis Example 3

49 parts of cyclohexanone, 124 parts of p-hydroxybenzaldehyde and 250 parts of ethanol were dissolved in a flask equipped with a stirrer, a reflux condenser and a stirring device. 25 parts of 37% hydrochloric acid was added to this, and it heated up to 60 degreeC, after reaction at this temperature for 10 hours, the reaction liquid was poured into 1000 parts of water, and it crystallized. The crystals were filtered off, washed twice with 800 parts of water, and then vacuum dried to obtain 210 parts of yellow phenol compounds 3 as yellow crystals. Melting | fusing point of the obtained crystal | crystallization was 289 degreeC by DSC measurement.

Synthesis Example 4

120 parts of phenolic compounds 1 obtained by the synthesis example 1, 925 parts of epichlorohydrin, and 139 parts of dimethyl sulfoxide (DMSO) were added, carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus, and stirring After heating up to 45 degreeC and melt | dissolving and dividingly adding 40 parts of flake shaped sodium hydroxide over 90 minutes, it heated up at 70 degreeC for 1.5 hours, and reacted for 30 minutes, remaining 45 degreeC. After completion | finish of reaction, 800 parts of solvents, such as excess epichlorohydrin, were distilled off under reduced pressure at 70 degreeC using the rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. After filtering the crystal | crystallization, 600 parts of methanol were wash | cleaned and 166 parts of epoxy resins 1 were obtained by vacuum-drying at 70 degreeC after that. The epoxy equivalent of the obtained epoxy resin was 200 g / eq., And melting | fusing point was 108 degreeC by DSC.

Synthesis Example 5

133 parts of phenolic compound 2 obtained by the synthesis example 2, 925 parts of epichlorohydrin, and 139 parts of DMSO were added, carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus, and it heated up to 45 degreeC under stirring. After melt | dissolving and dividingly adding 40 parts of flake shaped sodium hydroxide over 90 minutes, it heated up to 70 degreeC for 1.5 hours with 45 degreeC, and reaction was performed for 30 minutes. After completion | finish of reaction, 800 parts of solvents, such as excess epichlorohydrin, were distilled off under reduced pressure at 70 degreeC using the rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. After filtering the crystal | crystallization, it wash | cleaned with 600 parts of methanol, and 180 parts of epoxy resins 2 were obtained by vacuum-drying at 70 degreeC after that. The epoxy equivalent of the obtained epoxy resin was 220 g / eq., And melting | fusing point was 117 degreeC in DSC.

Synthesis Example 6

153 parts of phenolic compound 3 obtained by the synthesis example 3, 925 parts of epichlorohydrin, and 139 parts of DMSO were added, carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus, and it heated up to 45 degreeC under stirring. After dissolving and dividingly adding 40 parts of flake sodium hydroxide over 90 minutes, it heated up at 70 degreeC for 1.5 hours with 45 degreeC, and reaction was performed for 30 minutes. After completion | finish of reaction, 800 parts of solvents, such as excess epichlorohydrin, were distilled off under reduced pressure at 70 degreeC using the rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. After filtering the crystal | crystallization, it wash | cleaned with 600 parts of methanol, and 199 parts of epoxy resins 3 were obtained by vacuum-drying at 70 degreeC after that. The epoxy equivalent of the obtained epoxy resin was 219g / eq., And melting | fusing point was 145 degreeC by DSC.

Examples 1 to 3 and Comparative Examples 1 to 3

Various components were mix | blended in the ratio (part) of Table 1, and the resin molding was prepared by transfer molding after kneading with a mixing roll and then tableting. Next, the cured product of the epoxy resin composition and the comparative resin composition of the present invention was obtained by heating the resin molded product at 160 ° C. for 2 hours and at 180 ° C. for 8 hours. Table 1 shows the results of measuring the thermal conductivity of these cured products.

Epoxy resin 4: Biphenyl type epoxy resin containing equimolar moieties of epoxy resin represented by following formula (6) and (7) (brand name: YL-6121H Japan Epoxy Resin Co., Ltd. Epoxy equivalent 175g / eq.)

Curing agent 1: 1,5-naphthalenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., amine equivalent 40g / eq.)

Inorganic filler 1: spherical alumina (brand name: DAW-100 DENKI KAGAKU KOGYO KABUSHIKI KAISHA, heat conductivity 38W / m? K)

Inorganic filler 2: Boron nitride (Brand name: SGP DENKI KAGAKU KOGYO KABUSHIKI KAISHA, Thermal conductivity 60W / m? K)

Inorganic filler 3: Fused silica (trade name: MSR2212 Yongsam manufactured, thermal conductivity of 1.38W / m? K)

Example 4

100 parts of epoxy resin 3 obtained in Synthesis Example 6 was added to 1000 parts of dimethylformamide, and after dissolving it at 70 ° C, the temperature was returned to room temperature.

After dissolving 18 parts of 1,5-naphthalenediamine (A Tokyo Chemical Industry Co., Ltd. make, amine equivalent of 40 g / eq.) Which is a hardening | curing agent in 48 parts of dimethylformamide, it returned to room temperature. 224 parts of said epoxy resin solution and hardening | curing agent solution are mixed and stirred by the stirring blade type homomixer, and it is made into a uniform varnish, and an inorganic filler (brand name: SGP DENKI KAGAKU KOGYO KABUSHIKI KAISHA, heat conductivity 60W / m? K) 50 volume part) and 100 parts of dimethylformamide were added with respect to 100 volume part of resin solid content, and it mixed and stirred, and prepared the epoxy resin composition of this invention.

The varnish of this epoxy resin composition was impregnated into the glass fiber woven fabric (brand name: 7628 / AS890AW Asahi Shovel make) of thickness 0.2mm, and it heat-dried and obtained the prepreg. After the four prepregs and the copper foil blended on both sides thereof were superposed, they were integrally heated and molded for 90 minutes under conditions of a temperature of 175 ° C and a pressure of 4 MPa to obtain a laminated plate having a thickness of 0.8 mm. It was 4.8 W / m * K when the heat conductivity of this laminated sheet was measured.

Comparative Example 4

The epoxy resin 3 in Example 4 was changed to 100 parts of epoxy resin 4 (YL-6121H), the amount of 1,5-naphthalenediamine was changed to 23 parts, and the amount of the inorganic filler was changed to 234 parts, respectively. The laminated board was obtained by the operation procedure. It was 3.6 W / m * K when the heat conductivity of this laminated sheet was measured.

Example 5

The various components were mix | blended in the ratio (part) of Table 2, and after mixing enough, it directly put in a frame and pressure-molded at 175 degreeC, and the resin molding was prepared. Next, the hardened | cured material of the epoxy resin composition of this invention was obtained by heating the said resin molded object further at 160 degreeC for 2 hours, and 180 degreeC for 8 hours. Table 2 shows the results of measuring the thermal conductivity of this cured product.

Examples 6-8 and Comparative Examples 5-7

Various components were mix | blended in the ratio (part) of Table 2, and the resin molding was prepared by transfer molding after kneading with a mixing roll and then tableting. Next, the cured product of the epoxy resin composition and the comparative resin composition of the present invention was obtained by further heating the resin molded article at 160 ° C. for 2 hours and at 180 ° C. for 8 hours. Table 2 shows the results of measuring the thermal conductivity of these cured products. In addition, the epoxy resin 3, the hardening | curing agent 1, and the inorganic fillers 1 and 2 in Table 2 are the same as what was used in Examples 1-3.

Epoxy resin 5: Epoxy resin represented by following formula (8) (brand name: NC-3000

Nippon Kayaku Co., Ltd. Epoxy Equivalent 276g / eq.)

Curing agent 2: Phenolic compound 3 obtained by the synthesis example 3 (hydroxyl equivalent 153g / eq.)

Curing agent 3: Phenolic novolak resin represented by following formula (9) (brand name: H-1, MEIWA PLASTIC INDUSTRIES, LTD.

Curing agent 4: Catechol novolak resin represented by following formula (10) (hydroxyl equivalent 59g / eq., Softening point 104 degreeC)

Curing accelerator: triphenylphosphine (manufactured by HOKKO CHEMICAL INDUSTRY CO., LTD.)

Example 9

After dissolving 100 parts of epoxy resin 5 (NC-3000) and 56 parts of phenolic compound 3 obtained by the synthesis example 3 at 70 degreeC at 1000 parts of dimethylformamide, it returned to room temperature.

One part of triphenylphosphine (manufactured by HOKKO CHEMICAL INDUSTRY CO., LTD.), A curing accelerator, was dissolved at 70 ° C after 48 parts of dimethylformamide, and then returned to room temperature. 296 parts of said epoxy resin solution and hardening accelerator solution were mixed and stirred by the stirring blade type homomixer to make a uniform varnish, and also an inorganic filler (brand name: SGP DENKI KAGAKU KOGYO KABUSHIKI KAISHA, heat conductivity 60W / m? K) (50 vol. Parts to 100 vol. Of resin solid content) and 100 parts of dimethylformamide were added, followed by mixing and stirring to prepare the epoxy resin composition of the present invention.

The varnish of this epoxy resin composition was impregnated into the glass fiber woven fabric (brand name: 7628 / AS890AW Asahi Shovel make) of thickness 0.2mm, and it heat-dried and obtained the prepreg. After stacking the four prepregs and the copper foil blended on both sides thereof, the mixture was heated and molded for 90 minutes under the condition of a temperature of 175 ° C and a pressure of 4 MPa to obtain a laminated plate having a thickness of 0.8 mm. It was 4.5 W / m * K when the heat conductivity of this laminated sheet was measured.

Comparative Example 8

56 parts of phenol compounds 3 in Example 9 were prepared in 29 parts of the phenol novolac resin represented by the formula (9), except that the amount of the inorganic filler was changed to 245 parts, respectively. Got it. It was 3.9 W / m * K when the heat conductivity of this laminated sheet was measured.

Comparative Example 9

56 parts of phenolic compounds 3 in Example 9 were laminated by 38 parts of catechol novolak resin represented by Formula (10) except having changed the quantity of the inorganic filler into 262 parts, respectively, by the operation procedure similar to Example 9 Got. It was 4.1 W / m * K when the heat conductivity of this laminated sheet was measured.

Comparative Example 10

After dissolving 100 parts of epoxy resin 5 (NC-3000) at 1000 degreeC in 1000 parts of dimethylformamide, it returned to room temperature.

After dissolving 15 parts of 1, 5- naphthalenediamine which is a hardening | curing agent at 70 degreeC at 48 parts of dimethylformamide, it returned to room temperature. 224 parts of the above-mentioned epoxy resin solution and hardener solution were mixed and stirred with a homomixer of a stirring blade type to make a uniform varnish, and an inorganic filler (brand name: SGP DENKI KAGAKU KOGYO KABUSHIKI KAISHA, manufactured with thermal conductivity 60 W / m? K). 50 volume part) and 100 parts of dimethylformamide were added with respect to 100 volume part of resin solid content, and it mixed and stirred, and prepared the epoxy resin composition of the comparative example.

The subsequent process obtained the laminated board by the same operation procedure as Example 9. It was 4.4 W / m * K when the heat conductivity of this laminated sheet was measured.

From the above result, it was confirmed that the hardened | cured material of the epoxy resin composition of this invention has the outstanding thermal conductivity. Therefore, the hardened | cured material of the epoxy resin composition of this invention is very useful when used for the insulation material for electrical and electronic components, a laminated board (printed wiring board, etc.).

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

Moreover, this application is based on the Japanese patent application (patent application 2009-288706) filed on December 21, 2009 and the Japanese patent application (patent application 2009-136455) filed on June 5, 2009, The whole is incorporated by reference. Also, all references cited herein are incorporated in their entirety.

(Industrial availability)

The hardened | cured material of the epoxy resin composition of this invention has the outstanding thermal conductivity compared with the hardened | cured material of the conventional epoxy resin. 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, optical materials, and the like as sealing materials and prepregs.

Claims (6)

(a ') epoxy resin,
(b) Phenolic compound obtained by reaction of 1 or more types of compound represented by following formula (1)-(5) with hydroxybenzaldehyde as a hardening | curing agent, and
(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher.

[(In formula (1), R <_1> exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a hydroxyl group, or a C1-C ?.). Any one of ten substituted or unsubstituted alkoxy groups, l represents the number of R ₁ , and is an integer of 0 to 4;

[In Formula (2), R <_2> exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C15 substitution, or Unsubstituted alkylcarbonyl group, morpholinylcarbonyl group, substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, phthalimide group, piperonyl group or hydroxyl group Represents one]

[In Formula (3), R <_3> respectively exists independently, and is a hydrogen atom, a C1-C10 substituted or unsubstituted alkylcarbonyl group, a C1-C10 substituted or unsubstituted alkyl group, a C6-C10 substitution, or An unsubstituted aryl group, a C2-C10 substituted or unsubstituted alkylester group, a C1-C10 substituted or unsubstituted alkoxy group, or a hydroxyl group is shown. n represents a carbon number and represents the integer of any one of 0, 1, 2. m represents the number of R ₃ and satisfies the relationship of 0≤m≤n + 2]

[In Formula (4), R <_4> exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or Any one of an unsubstituted alkoxy group or hydroxyl group]

[In Formula (5), R <_5> respectively exists independently, and is a hydrogen atom, a C1-C20 substituted or unsubstituted alkyl group, a C6-C10 substituted or unsubstituted aryl group, a C1-C10 substitution, or The unsubstituted alkoxy group or hydroxyl group is shown. And n is an integer of 1 to 10] (a) an epoxy resin obtained by further reacting epihalohydrin with the phenolic compound according to claim 1,
(b ') a curing agent, and
(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher. (a) the epoxy resin according to claim 2,
(b) the phenolic compound according to claim 1, and
(c) An epoxy resin composition comprising an inorganic filler having a thermal conductivity of 20 W / m · K or higher. The method according to any one of claims 1 to 3,
An epoxy resin composition, which is used for semiconductor sealing applications. The prepreg which consists of the epoxy resin composition of any one of Claims 1-3, and a sheet-like fiber base material. Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 1-4, or the prepreg of Claim 5.