JP5502080B2 - Epoxy resin composition, prepreg and cured products thereof - Google Patents

Description

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

  Epoxy resin compositions are generally cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., such as adhesives, paints, laminates, molding materials, casting materials, etc. It is used in a wide range of fields. In recent years, cured products of epoxy resins used in these fields have begun to be highly purified and have various properties such as flame retardancy, heat resistance, moisture resistance, toughness, low linear expansion coefficient, and low dielectric constant characteristics. There is a need for improvement.

In particular, in the electrical and electronic industry, which is a typical application of epoxy resin compositions, high-density mounting of semiconductors and high-density wiring of printed wiring boards have been promoted for the purpose of multi-function, high performance, and compactness. Progressing. However, high-density mounting and high-density wiring increase the heat generated from the inside of the semiconductor element and the printed wiring board, and may cause malfunction of the devices. Therefore, how to efficiently release generated heat to the outside is an important issue from the standpoint of energy efficiency and device design.
These heat countermeasures include various measures such as using a metal core substrate, constructing a structure that easily dissipates heat at the design stage, and densely filling high thermal conductive filler in the polymer material (epoxy resin) to be used. Has been made. However, since the thermal conductivity of the polymer material acting as a binder that connects the high thermal conductivity sites is low, the thermal conduction speed of the polymer material becomes the rate-determining, and efficient heat dissipation is not possible at present.

As a means for realizing high thermal conductivity of an epoxy resin, Patent Document 1 reports a method of introducing a mesogenic group into an epoxy resin structure. This document describes an epoxy resin having a biphenyl skeleton as an epoxy resin having a mesogenic group. In addition, as an epoxy resin other than the biphenyl skeleton, a phenyl benzoate type epoxy resin is described. However, since the epoxy resin needs to be produced by an epoxidation reaction by oxidation, there are difficulties in safety and cost, and it is practical. It can not be said.
Patent Documents 2 to 4 describe examples using an epoxy resin having a biphenyl skeleton, and Patent Document 3 describes a technique in which an inorganic filler having high thermal conductivity is used in combination. However, the thermal conductivity of the cured product obtained by the methods described in these documents is not at a level that satisfies the market demand, and a cured product having higher thermal conductivity using an epoxy resin that is available at a relatively low cost. There is a need for an epoxy resin composition that provides.

  Further, like the epoxy resin, the curing agent contained in the epoxy resin composition can be said to be an important factor for realizing high thermal conductivity. Conventionally, as a curing agent contained in an epoxy resin composition that the cured product has a high thermal conductivity, Patent Document 1 discloses 4,4′-diaminodiphenylbenzoate, 4,4′-diaminodiphenylmethane, References 2 and 3 report examples using amine-based curing agents such as 1,5-diaminonaphthalene. However, since these amine-based curing agents have a curing accelerating action, it is difficult to ensure a lifetime when preparing a cured product, and it is not preferable. On the other hand, in Patent Document 4, a phenol compound is used as a curing agent. In Patent Document 4, catechol novolak is specifically used, but the thermal conductivity of the cured product obtained by the method described in the same document is not at a level that satisfies the market demand, and has a higher thermal conductivity. Development of an epoxy resin composition that gives a cured product is desired.

Japanese Unexamined Patent Publication No. 11-323162 Japanese Unexamined Patent Publication No. 2004-2573 Japanese Unexamined Patent Publication No. 2006-63315 Japanese Unexamined Patent Publication No. 2003-137971

  The present invention has been made as a result of studies to solve such problems, and provides an epoxy resin composition whose cured product has high thermal conductivity.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides (1)
(A ′) epoxy resin,
(B) As a hardening | curing agent, following formula (1)-(5)

(In Formula (1), each R ₁ is independently present, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Or, it represents either a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, l represents the number of R ₁ , and is an integer of 0 to 4).

(In Formula (2), each R ₂ is independently present, and is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a carbon number. 1-15 substituted or unsubstituted alkylcarbonyl group, morpholinylcarbonyl group, C2-C10 substituted or unsubstituted alkyl ester group, C1-10 substituted or unsubstituted alkoxy group, phthalimide group Represents a piperonyl group or a hydroxyl group.)

(In Formula (3), each R ₃ independently represents a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 0 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, carbon, It represents any of a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. N represents the number of carbon atoms and represents an integer of 0, 1, or 2. m represents the number of R ₃ and satisfies the relationship of 0 ≦ m ≦ n + 2.

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

(In Formula (5), each R ₅ is independently present, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a carbon number. It represents either a substituted or unsubstituted alkoxy group of 1 to 10 or a hydroxyl group, and n is an integer of 1 to 10.)

A phenol compound obtained by reaction of one or more of the compounds represented by formula (II) with hydroxybenzaldehyde, and (c) an inorganic filler having a thermal conductivity of 20 W / m · K or more,
An epoxy resin composition comprising
(2)
(A) an epoxy resin obtained by further reacting an epihalohydrin with the phenol compound described in (1) above;
(B ′) a curing agent, and (c) an inorganic filler having a thermal conductivity of 20 W / m · K or more,
An epoxy resin composition comprising
(3)
(A) the epoxy resin according to item (2),
(B) the phenolic compound according to item (1), and (c) an inorganic filler having a thermal conductivity of 20 W / m · K or more,
An epoxy resin composition comprising
(4)
The epoxy resin composition according to any one of (1) to (3), which is used for semiconductor sealing applications,
(5)
A prepreg comprising the epoxy resin composition according to any one of (1) to (3) and a sheet-like fiber base material,
(6)
A cured product obtained by curing the epoxy resin composition according to any one of (1) to (4) or the prepreg according to (5);
About.

  The epoxy resin composition of the present invention is useful when used in various composite materials including semiconductor encapsulating materials and prepregs, adhesives, paints and the like because the cured product is excellent in heat conduction.

  The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler (hereinafter referred to as “component (c)”) having a thermal conductivity of 20 W / m · K or more. As a curing agent, a phenol compound (hereinafter referred to as “component (b)”) obtained by reaction of one or more compounds represented by the following formulas (1) to (5) with hydroxybenzaldehydes, and / or Alternatively, the epoxy resin contains an epoxy compound (hereinafter referred to as “component (a)”) obtained by further reacting epihalohydrin with the component (b).

  First, (b) component which the epoxy resin composition of this invention contains as a hardening | curing agent is demonstrated. The component (b) is a phenol compound obtained by a reaction between one or more compounds represented by the following formulas (1) to (5) and hydroxybenzaldehydes.

(In Formula (1), each R ₁ is independently present, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Or, it represents either a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, l represents the number of R ₁ , and is an integer of 0 to 4).

(In Formula (2), each R ₂ is independently present, and is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a carbon number. 1-15 substituted or unsubstituted alkylcarbonyl group, morpholinylcarbonyl group, C2-C10 substituted or unsubstituted alkyl ester group, C1-10 substituted or unsubstituted alkoxy group, phthalimide group Represents a piperonyl group or a hydroxyl group.)

  In the formula (2), the substituent is preferably at least one selected from the group consisting of a carbonyl group, an ester group, an alkenyl group, a phenyl group, an alkoxy group, an ether group, a phthalimide group, and a piperonyl group.

(In Formula (3), each R ₃ independently represents a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 0 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, carbon, Either a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkyl ester group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. N represents the number of carbon atoms and represents an integer of 0, 1, or 2. m represents the number of R ₃ and satisfies the relationship of 0 ≦ m ≦ n + 2.

In the formula, when R ₃ is a substituted or unsubstituted alkylcarbonyl group having 0 carbon atoms, a carbonyl structure containing a carbon atom constituting a cycloalkane which is the main skeleton of the general formula (3) is used. For example, 1,3-cyclopentanedione and the like can be mentioned.
In the formula (3), the substituent is preferably an ether group.

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

(In Formula (5), each R ₅ is independently present, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a carbon number. It represents either a substituted or unsubstituted alkoxy group of 1 to 10 or a hydroxyl group, and n is an integer of 1 to 10.)

  Specific examples of the compound represented by the formula (1) used for the reaction with hydroxybenzaldehydes to obtain the component (b) include o-, m- and p-hydroxyacetophenone. Of these, p-hydroxyacetophenone is preferred because the cured product of the epoxy resin composition exhibits high thermal conductivity.

  Specific examples of the compound represented by the formula (2) used for the reaction with the hydroxybenzaldehydes to obtain the component (b) include 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 Nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 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-tetradecanone, 3-tetradecanone, 8-pentadecanone, 10-nonadecanone, 7-tridecanone, 2- Pentadecanone, 3-hexadecanone, 9-heptadecanone, 11-heneicosanone, 12-tricosanone, 14-heptacosanone, 16-hentriacontanone, 18-pentatriacontanone, 4-ethoxy-2-butanone, 4- (4-methoxy Phenyl) -2-butanone, 4 Methoxy-4-methyl-2-pentanone, 4-methoxyphenylacetone, methoxyacetone, phenoxyacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, sec-butyl acetoacetate, acetoacetic acid tert-butyl, 3-pentyl acetoacetate, amyl acetoacetate, isoamyl acetoacetate, hexyl acetoacetate, heptyl acetoacetate, n-octyl acetoacetate, benzyl acetoacetate, dimethyl acetylsuccinate, dimethyl acetonylmalonate, acetonylmalon Diethyl acetate, ethyl 4-acetyl-5-oxohexanoate, acetoacetate-2-methoxyethyl, allyl acetoacetate, 4-sec-butoxy-2-butanone, benzylbutylketone, bisdemethoxycurcumin, 1, 1-dimethoxy-3-butanone, 1,3-diacetoxyacetone, 4-hydroxyphenylacetone, 4- (4-hydroxyphenyl) -2-butanone, isoamylmethylketone, 4-hydroxy-2-butanone, 5-hexene 2-one, acetonylacetone, 3,4-dimethoxyphenylacetone, piperonylmethylketone, piperonylacetone, phthalimidoacetone, 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 the formula (3) used for the reaction with hydroxybenzaldehydes to obtain the component (b) include cyclopentanone, 3-phenylcyclopentanone, 1,3-cyclopentanedione. , 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-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, ethyl 4-cyclohexanonecarboxylate, 1,4-cyclohexanedione monoe Renketaru, bicyclohexane-4,4 '- dione monoethylene ketal, 1,3-cyclohexanedione, 1,4-cyclohexanedione, dimedone, 4,4' - bicyclohexanone, cycloheptanone, and the like.

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

  Specific examples of the compound represented by the formula (5) used for the reaction with the hydroxybenzaldehydes in order to obtain the component (b) include acetylacetone, ethyl diacetoacetate, 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 , Etc.

  In order to obtain the component (b), 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. Can be mentioned. These may use only 1 type or may use 2 or more types together. Of these, it is preferable to use p-hydroxybenzaldehyde alone because the cured product of the epoxy resin composition exhibits particularly high thermal conductivity.

The component (b) is obtained by an aldol condensation reaction between one or more of the compounds represented by formulas (1) to (5) and hydroxybenzaldehyde under acidic conditions or basic conditions.
Hydroxybenzaldehyde is 1.0 to 1.05 mol relative to 1 mol of the compound represented by formula (1), and 2.0 mol relative to 1 mol of the compound represented by formula (2) to formula (5). It is preferred to use ˜3.15 moles respectively.

  When the aldol condensation reaction is performed 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 of a plurality of types. 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 the aldol condensation reaction is performed under basic conditions, usable basic catalysts include metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, diethylamine, Examples include amine derivatives such as triethylamine, tributylamine, diisobutylamine, pyridine and piperidine, and amino alcohol derivatives such as dimethylaminoethyl alcohol and diethylaminoethyl alcohol. Also in the case of basic conditions, the basic catalysts listed above may be used alone, or a plurality of types may be used in combination. 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 the reaction to obtain the component (b), a solvent may be used as necessary. The solvent that can be used is not particularly limited as long as it does not have reactivity with hydroxybenzaldehydes such as ketones, but alcohols are used as solvents in terms of easily dissolving the raw hydroxybenzaldehydes. Is preferred.

  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 with the kind of raw material compound, it is not this limitation. When taking out as a resin after completion | finish of reaction, an unreacted substance, a solvent, etc. are removed from a reaction liquid under heating and pressure reduction, after washing | cleaning a reaction substance without water washing. When taking out with a crystal | crystallization, a crystal | crystallization is deposited by dripping a reaction liquid in a lot of water. When the reaction is carried out under basic conditions, the produced component (b) may be dissolved in water, so that it is precipitated as crystals under neutral to acidic conditions by adding hydrochloric acid or the like.

Next, (a) component which the epoxy resin composition of this invention contains as an epoxy resin is demonstrated.
The component (a) contained in the epoxy resin composition of the present invention is obtained by reacting the component (b) obtained by the above method with epihalohydrin and epoxidizing it. In the case of epoxidation, only one type of component (b) may be used or two or more types may be used in combination. Further, a phenol compound other than the component (b) may be used in combination with the component (b).
The phenol compound other than the component (b) that can be used in combination can be used without particular limitation as long as it is a phenol compound that is usually used as a raw material for epoxy resins, but the effect of the present invention that the cured product has high thermal conductivity. Therefore, the amount of the phenol compound that can be used in combination is preferably as small as possible, and it is particularly preferable to use only the component (b).
As the component (a), a cured product having a particularly high thermal conductivity is obtained, and therefore, it is obtained using the component (b) obtained by the reaction of hydroxybenzaldehydes with the compound represented by the formula (3). Epoxidized products are preferred.

  In the reaction for obtaining the component (a), epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, but epichlorohydrin which is easily available industrially is preferable. 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 the alkali metal hydroxide that can be used for the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like, and these may be used as they are, or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and separated from a mixture of water and epihalohydrin distilled continuously under reduced pressure or normal pressure. Alternatively, water may be removed and only the epihalohydrin is continuously returned to the reaction system. The amount of alkali metal hydroxide used is usually 0.9 to 3.0 mol, preferably 1.0 to 2.5 mol, more preferably 1.1 to 2 mol per mol of the hydroxyl group of component (b). 0.0 mole.

  In order to accelerate the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mol of the hydroxyl group of component (b).

  In addition, during the epoxidation, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using the said alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-20 mass%. Moreover, 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 washed with water or without washing with water, and the epihalohydrin, the solvent and the like are removed from the reaction solution under heating and reduced pressure. In order to further reduce the amount of hydrolyzable halogen contained in the component (a), the recovered component (a) is dissolved in a solvent such as toluene and methyl isobutyl ketone, and sodium hydroxide, potassium hydroxide, etc. You may react by adding the aqueous solution of an alkali metal hydroxide. By performing such an operation, the ring closure can be ensured. In this case, the usage-amount of an 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. 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 produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain component (a). In addition, when the component (a) is precipitated as crystals, the crystals of the component (a) may be filtered out after dissolving a salt generated in a large amount of water.

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, and an inorganic filler having a thermal conductivity of 20 W / m · K or more, and (a) component as an epoxy resin and (b) as a curing agent. At least one of the components is contained as an essential component.

  In the epoxy resin composition of the present invention, the component (a) which is an epoxy resin can be used alone or in combination with another epoxy resin (hereinafter referred to as “component (a ′)”).

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, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc. ), Polycondensates of xylene and other aromatic compounds with formaldehyde Polyphenols and phenols, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polycondensates, phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.) Polycondensates, phenols and aromatic dichloromethyls (such as α, α'-dichloroxylene and bischloromethylbiphenyl), phenols and aromatic bisalkoxymethyls ( Polycondensates with smethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and glycidyl ether epoxy resins and alicyclic epoxies obtained by glycidylation of alcohols, etc. Resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, and the like can be mentioned, but are not limited thereto as long as they are usually used epoxy resins. These may be used alone or in combination of two or more.
When the component (a ′) is used in combination, the proportion of the component (a) in the total epoxy resin component in the epoxy resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and 70% by mass. The above is more preferable, and particularly preferable is 100% by mass (when the component (a ′) is not used in combination). 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 the present invention, the component (b), which is a curing agent, can be used alone or in combination with other curing agents.
Examples of other curing agents (hereinafter referred to as “component (b ′)”) contained in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. It is done. Specific examples of these components (b ′) are shown in the following (a) to (e).
(A) Amine-based compounds Diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, etc. (b) Acid anhydride-based compounds Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride , Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. (c) Amide compounds Dicyandiamide or linolenic acid dimer and ethylenediamine Polyamide resin, etc.

(D) Phenol compounds Polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 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 (eg, phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene and dihydroxynaphthalene) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydro) Phenolic resins obtained by condensation with xybenzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones (p-hydroxyacetophenone, o-hydroxyacetophenone, etc.), or dienes (dicyclopentadiene, tricyclopentadiene, etc.); Phenols and substituted biphenyls (such as 4,4′-bis (chloromethyl) -1,1′-biphenyl and 4,4′-bis (methoxymethyl) -1,1′-biphenyl), or substituted phenyls ( Phenol resins obtained by polycondensation with 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene and the like; Or a modified product of the phenol resin; Lumpur A and halogenated phenols such as brominated phenol resin (e) Other imidazoles, BF 3 _- amine complex, guanidine derivatives

Among these components (b ′), amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalenediamine, and condensates of catechol and aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls are preferable. . This is because these components have a structure in which active hydrogen groups are adjacent to each other, whereby the epoxy resin is well arranged. For example, in the case of a condensate with catechol, since the hydroxyl groups that react by thermosetting are in the ortho positions, they are polymerized so as to be arranged in parallel. On the other hand, in the case of amines, hydrogen groups that react during thermosetting are arranged in parallel via nitrogen atoms, and in this case, polymerization is performed so that they are also arranged in parallel.
Component (b ′) may be used alone or in combination.
When the component (b ′) is used in combination, the proportion of the component (b) in the total curing agent component in the epoxy resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 70% by mass. The above is more preferable, and particularly preferable is 100% by mass (when the component (b ′) is not used in combination).
In the epoxy resin composition of the present invention, the use amount of the total curing agent including the component (b) is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins, and 0.6 to 1 .5 equivalents are particularly preferred.
As the epoxy resin composition of the present invention, it is most preferable to use 100% by mass of component (a) as an epoxy resin and 100% by mass of component (b) as a curing agent.

The inorganic filler contained in the epoxy resin composition of the present invention is added for the purpose of imparting higher thermal conductivity to the cured product of the epoxy resin composition, and the thermal conductivity of the inorganic filler itself is too low. In some cases, the high thermal conductivity obtained by the combination of the epoxy resin and the curing agent may be impaired. Therefore, as the inorganic filler contained in the epoxy resin composition of the present invention, the one having higher thermal conductivity is preferable, usually 20 W / m · K or more, preferably 30 W / m · K or more, more preferably 50 W / m. -There is no restriction as long as it has a thermal conductivity of K or higher. In addition, heat conductivity here is the value measured by the method based on ASTM E1530. Specific examples of inorganic fillers having such characteristics include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, magnesium oxide, synthetic fibers, Examples thereof include fibrous fillers such as ceramic fibers, and coloring agents. The shape of these inorganic fillers may be any of powder (bulk shape, spherical shape), single fiber, long fiber, etc. However, in particular, if it is a flat plate, the cured product is cured by the lamination effect of the inorganic filler itself. This is preferable because the thermal conductivity becomes higher and the heat dissipation of the cured product is further improved.
Although the usage-amount of the inorganic filler in the epoxy resin composition of this invention is 2-1000 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 is heat conduction. In order to increase the rate as much as possible, it is preferable to increase the amount of the inorganic filler as much as possible within a range that does not hinder the handling of the epoxy resin composition of the present invention in a specific application. These inorganic fillers may be used alone or in combination of two or more.

  Further, if the thermal conductivity of the entire filler can be maintained at 20 W / m · K or more, the thermal conductivity of the inorganic filler with 20 W / m · K or more is 20 W / m · K or less. However, in order to obtain a cured product having as high a thermal conductivity as possible, the use of a filler having a thermal conductivity of 20 W / m · K or less is minimal. Should be kept on. There is no particular limitation on the type and shape of the filler that can be used in combination.

  When the epoxy resin composition of the present invention is used for semiconductor sealing applications and prepreg applications, it is 60 to 93 in the epoxy resin composition from the viewpoint of heat resistance, moisture resistance, mechanical properties, etc. of the cured product. It is preferable to use an inorganic filler having a thermal conductivity of 20 W / m · K or more in a proportion of mass%. In this case, the balance is an epoxy resin component, a curing agent component, and other additives that are added as necessary. Examples of the additive include other inorganic fillers that can be used in combination and a curing accelerator that will be described later.

  The epoxy resin composition of the present invention may contain at least one of the component (a) as an epoxy resin and the component (b) as a curing agent as an essential component. An epoxy resin (not particularly limited, for example, the component (a ′) is preferred) and a component (b) and a component (c), or a component (a) and a curing agent (not particularly limited, Even if it is a composition containing said (b ') component and (c) component, the hardened | cured material is the same as the composition containing (a) component, (b) component, and (c) component. Excellent thermal conductivity.

  The epoxy resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Tertiary amines such as triethanolamine and 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium ethyltriphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and N Such as tetraphenyl boron salts such methylmorpholine tetraphenylborate and the like. 0.01-15 mass parts is used for a hardening accelerator as needed with respect to 100 mass parts of epoxy resins.

  If necessary, various compounding agents such as a silane coupling agent, a release agent and a pigment, various thermosetting resins, various thermoplastic resins, and the like can be added to the epoxy resin composition of the present invention. Specific examples of thermosetting resins and thermoplastic resins include vinyl ester resins, unsaturated polyester resins, maleimide resins, cyanate resins, isocyanate compounds, benzoxazine compounds, vinyl benzyl ether compounds, polybutadiene and its modified products, and acrylonitrile. Examples include modified polymers, indene resins, fluororesins, silicone resins, polyetherimides, polyethersulfones, polyphenylene ethers, polyacetals, polystyrenes, polyethylenes, and dicyclopentadiene resins. The thermosetting resin or thermoplastic resin is used in an amount occupying 60% by mass or less in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components, and preferred applications thereof include semiconductor encapsulants and printed wiring boards.
The epoxy resin composition of the present invention can be easily made into a cured product by the same method as conventionally known. Formation of the cured product of the present invention includes, for example, an epoxy resin, a curing agent, an inorganic filler having a thermal conductivity of 20 W / m · K or more, and, if necessary, a curing accelerator, a compounding agent, various thermosetting resins, and various heat. After thoroughly mixing a plastic resin or the like with an extruder, kneader, or roll until it becomes uniform to obtain an epoxy resin composition, the epoxy resin composition is melt-cast, transfer molding, injection molding It can be carried out by molding by the method or compression molding method and then heating for 2 to 10 hours above its melting point. When the epoxy resin composition of the present invention is used for semiconductor sealing applications, the semiconductor element mounted on a lead frame or the like may be sealed by the above method.

Moreover, the epoxy resin composition of this invention can also be made into the varnish containing a solvent. The varnish includes, for example, a mixture containing an epoxy resin, a curing agent, an inorganic filler having a thermal conductivity of 20 W / m · K or more, and other components as 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 dimethyl ether, dipropylene glycol diethyl Glycol ethers such as ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cello Rub acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, esters such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum ether, petroleum naphtha, hydrogenated petroleum It can be obtained by mixing with an organic solvent such as a petroleum solvent such as naphtha and solvent naphtha. The amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass with respect to the whole varnish.
The varnish obtained as described above is impregnated into a sheet-like fiber 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 half-finished. By setting it to a cured state, the prepreg of the present invention can be obtained. Here, the “semi-cured state” means a state in which an epoxy group which is a reactive functional group partially remains unreacted. The prepreg can be hot press molded to obtain a cured product.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the synthesis examples, examples, and comparative examples, “part” means “part by mass”. The epoxy equivalent, melting point, and thermal conductivity were measured under the following conditions.
-Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is.
Melting point Seiko Instruments Inc. EXSTAR6000 made
Measurement sample 2 mg to 5 mg Temperature rising rate 10 ° C./min.
-Thermal conductivity Measured by a method based on ASTM E1530-Hydroxyl equivalent Measured by a method based on the method described in JIS K-0070, and the unit is g / eq. It is.

Synthesis example 1
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 136 parts of p-hydroxyacetophenone, 124 parts of p-hydroxybenzaldehyde and 300 parts of ethanol were charged and dissolved. After 51.0 parts of 97% sulfuric acid was added thereto, the temperature was raised to 60 ° C., and after reaction at this temperature for 8 hours, the reaction solution was poured into 1200 parts of water for crystallization. The crystals were separated by filtration, washed twice with 600 parts of water, and then vacuum-dried to obtain 220 parts of phenol compound 1 as reddish brown crystals. The melting point of the obtained crystal was 203 ° C. by DSC measurement.

Synthesis example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 29 parts of acetone, 124 g of p-hydroxybenzaldehyde, and 300 parts of ethanol and dissolved. After adding 80 parts of 50% aqueous sodium hydroxide solution to this, the temperature was raised to 45 ° C., and after reacting at this temperature for 120 hours, the reaction solution was poured into 800 mL of 1.5N hydrochloric acid for crystallization. The crystals were separated by filtration, washed twice with 600 parts of water, and then vacuum-dried to obtain 210 parts of phenol compound 2 as yellow crystals. The melting point of the obtained crystal was 101 ° C. by DSC measurement.

Synthesis example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 49 parts of cyclohexanone, 124 parts of p-hydroxybenzaldehyde and 250 parts of ethanol and dissolved. After adding 25 parts of 37% hydrochloric acid to this, the temperature was raised to 60 ° C., and after reacting at this temperature for 10 hours, the reaction solution was poured into 1000 parts of water for crystallization. The crystals were separated by filtration, washed twice with 800 parts of water, and then vacuum-dried to obtain 210 parts of phenol compound 3 as yellow crystals. The melting point of the obtained crystal was 289 ° C. by DSC measurement.

Synthesis example 4
While purging a flask equipped with a stirrer, a reflux condenser, and a stirrer with nitrogen purge, add 120 parts of the phenol compound 1 obtained in Synthesis Example 1, 925 parts of epichlorohydrin, and 139 parts of dimethyl sulfoxide (DMSO). The solution was heated to 45 ° C., dissolved, and 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then kept at 45 ° C. for 1.5 hours, then heated to 70 ° C. and reacted for 30 minutes. I did it. After completion of the reaction, 800 parts of excess solvent such as epichlorohydrin was distilled off under reduced pressure at 70 ° C. using a rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. The crystals were filtered, washed with 600 parts of methanol, and then vacuum dried at 70 ° C. to obtain 166 parts of epoxy resin 1. The epoxy equivalent of the obtained epoxy resin is 200 g / eq. The melting point was 108 ° C. by DSC.

Synthesis example 5
While purging a flask equipped with a stirrer, a reflux condenser, and a stirrer with nitrogen purge, add 133 parts of phenol compound 2 obtained in Synthesis Example 2, 925 parts of epichlorohydrin, and 139 parts of DMSO, and rise to 45 ° C. with stirring. After warming, dissolving, and adding 40 parts of flaky sodium hydroxide over 90 minutes, the reaction was continued at 45 ° C for 1.5 hours, then heated to 70 ° C and reacted for 30 minutes. After completion of the reaction, 800 parts of excess solvent such as epichlorohydrin was distilled off under reduced pressure at 70 ° C. using a rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. The crystals were filtered, washed with 600 parts of methanol, and then vacuum dried at 70 ° C. to obtain 180 parts of epoxy resin 2. The epoxy equivalent of the obtained epoxy resin is 220 g / eq. The melting point was 117 ° C. by DSC.

Synthesis Example 6
While purging a flask equipped with a stirrer, a reflux condenser and a stirrer with nitrogen purge, add 153 parts of the phenol compound 3 obtained in Synthesis Example 3, 925 parts of epichlorohydrin, and 139 parts of DMSO, and stir to 45 ° C. The mixture was heated and dissolved, and 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was continued at 45 ° C. for 1.5 hours and then at 70 ° C. for 30 minutes. After completion of the reaction, 800 parts of excess solvent such as epichlorohydrin was distilled off under reduced pressure at 70 ° C. using a rotary evaporator. The residue was poured into 1500 parts of water to precipitate crystals. The crystals were filtered, washed with 600 parts of methanol, and then vacuum dried at 70 ° C. to obtain 199 parts of epoxy resin 3. The epoxy equivalent of the obtained epoxy resin is 219 g / eq. The melting point was 145 ° C. by DSC.

Examples 1-3 and Comparative Examples 1-3
Various components were blended in the proportions (parts) shown in Table 1, and after kneading with a mixing roll and subsequent tableting, a resin molded body was prepared by transfer molding. Next, the resin molded body was heated at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to obtain a cured product of the epoxy resin composition of the present invention and the comparative resin composition. The results of measuring the thermal conductivity of these cured products are shown in Table 1.

  Epoxy resin 4: Biphenyl type epoxy resin containing an equimolar amount of the epoxy resin represented by the following formulas (6) and (7) (trade name: YL-6121H made by Japan Epoxy Resin, epoxy equivalent of 175 g / eq.)

Curing agent 1: 1,5-naphthalenediamine (manufactured by Tokyo Chemical Industry, amine equivalent 40 g / eq.)
Inorganic filler 1: spherical alumina (trade name: DAW-100, manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 38 W / m · K)
Inorganic filler 2: Boron nitride (trade name: SGP, manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 60 W / m · K)
Inorganic filler 3: fused silica (trade name: MSR2212, made by Tatsumori, thermal conductivity 1.38 W / m · K)

Example 4
100 parts of the epoxy resin 3 obtained in Synthesis Example 6 was added to 1000 parts of dimethylformamide, and this was dissolved at 70 ° C., and then returned to room temperature.
In 48 parts of dimethylformamide, 18 parts of 1,5-naphthalenediamine (manufactured by Tokyo Chemical Industry, amine equivalent 40 g / eq.) As a curing agent was dissolved at 70 ° C., and then returned to room temperature. The above epoxy resin solution and the curing agent solution are mixed and stirred with a stirring blade type homomixer to make a uniform varnish, and further an inorganic filler (trade name: SGP, manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 60 W / m · K) 224 parts (50 parts by volume with respect to 100 parts by volume of resin solid content) and 100 parts of dimethylformamide were added and mixed and stirred to prepare the epoxy resin composition of the present invention.
The varnish of this epoxy resin composition was impregnated into a 0.2 mm thick glass fiber woven fabric (trade name: 7628 / AS890AW, manufactured by Asahi Schwer) and dried by heating to obtain a prepreg. After the four prepregs and the copper foils arranged on both sides thereof were superposed, they were integrated by heating and pressing for 90 minutes under the conditions of a temperature of 175 ° C. and a pressure of 4 MPa to obtain a laminate having a thickness of 0.8 mm. The thermal conductivity of the laminate was measured and found to be 4.8 W / m · K.

Comparative Example 4
Example 4 except that 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 inorganic filler was changed to 234 parts. A laminate was obtained by the same operation procedure as in No. 4. The heat conductivity of this laminate was measured and found to be 3.6 W / m · K.

Example 5
Various components were blended in the proportions (parts) shown in Table 2, mixed well, then directly put into a mold, and pressure molded at 175 ° C. to prepare a resin molded body. Subsequently, the cured product of the epoxy resin composition of the present invention was obtained by heating the resin molding at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. The results of measuring the thermal conductivity of the cured product are shown in Table 2.

Examples 6-8 and Comparative Examples 5-7
Various components were blended in the proportions (parts) shown in Table 2, and after kneading with a mixing roll and subsequent tableting, a resin molded body was prepared by transfer molding. Next, the resin molded body was heated at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to obtain a cured product of the epoxy resin composition of the present invention and the comparative resin composition. The results of measuring the thermal conductivity of these cured products are shown in Table 2. 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 the following formula (8) (trade name: NC-3000, Epoxy equivalent 276 g / eq. Manufactured by Nippon Kayaku)

Curing agent 2: Phenol compound 3 obtained by Synthesis Example 3 (hydroxy pray equivalent 153 g / eq.)
Curing agent 3: Phenol novolak resin represented by the following formula (9) (trade name: H-1, Meiwa Kasei's hydroxyl equivalent 105 g / eq.)

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

  Curing accelerator: Triphenylphosphine (manufactured by Hokuko Chemical)

Example 9
In 1000 parts of dimethylformamide, 100 parts of epoxy resin 5 (NC-3000) and 56 parts of phenol compound 3 obtained in Synthesis Example 3 were dissolved at 70 ° C. and then returned to room temperature.
1 part of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) as a curing accelerator was dissolved in 48 parts of dimethylformamide at 70 ° C. and then returned to room temperature. The above epoxy resin solution and curing accelerator solution are mixed and stirred with a stirring blade type homomixer to obtain a uniform varnish, and further an inorganic filler (trade name: SGP, manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 60 W / m · K). ) 296 parts (50 parts by volume with respect to 100 parts by volume of resin solids) and 100 parts of dimethylformamide were added and mixed and stirred to prepare the epoxy resin composition of the present invention.
The varnish of this epoxy resin composition was impregnated into a 0.2 mm thick glass fiber woven fabric (trade name: 7628 / AS890AW, manufactured by Asahi Schwer) and dried by heating to obtain a prepreg. After the four prepregs and the copper foils arranged on both sides thereof were superposed, they were integrated by heating and pressing for 90 minutes under the conditions of a temperature of 175 ° C. and a pressure of 4 MPa to obtain a laminate having a thickness of 0.8 mm. The heat conductivity of this laminate was measured and found to be 4.5 W / m · K.

Comparative Example 8
Lamination was carried out in the same procedure as in Example 9, except that 56 parts of phenol compound 3 in Example 9 was changed to 29 parts of phenol novolac resin represented by formula (9) and the amount of inorganic filler was changed to 245 parts. I got a plate. The thermal conductivity of this laminate was measured and found to be 3.9 W / m · K.

Comparative Example 9
Lamination was carried out in the same procedure as in Example 9, except that 56 parts of phenol compound 3 in Example 9 was changed to 38 parts of catechol novolac resin represented by formula (10) and the amount of inorganic filler was changed to 262 parts. I got a plate. The thermal conductivity of this laminate was measured and found to be 4.1 W / m · K.

Comparative Example 10
After dissolving 100 parts of epoxy resin 5 (NC-3000) at 70 ° C. in 1000 parts of dimethylformamide, the temperature was returned to room temperature.
After dissolving 15 parts of 1,5-naphthalenediamine as a curing agent in 70 parts of dimethylformamide at 70 ° C., the temperature was returned to room temperature. The above epoxy resin solution and the curing agent solution are mixed and stirred with a stirring blade type homomixer to make a uniform varnish, and further an inorganic filler (trade name: SGP, manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 60 W / m · K) 224 parts (50 parts by volume with respect to 100 parts by volume of resin solids) and 100 parts of dimethylformamide were added and mixed and stirred to prepare an epoxy resin composition of a comparative example.
Subsequent steps obtained a laminate by the same operation procedure as in Example 9. The heat conductivity of this laminate was measured and found to be 4.4 W / m · K.

  From the above results, it was confirmed that the cured product of the epoxy resin composition of the present invention had excellent thermal conductivity. Therefore, the cured product of the epoxy resin composition of the present invention is extremely useful when used for insulating materials for electric / electronic parts, laminated boards (printed wiring boards, etc.) and the like.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2009-288706) filed on December 21, 2009 and a Japanese patent application (Japanese Patent Application No. 2009-136455) filed on June 5, 2009. Which is incorporated by reference in its entirety. Also, all references 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 a cured product of a conventional epoxy resin. Therefore, it is extremely useful for a wide range of applications such as an electric / electronic material, a molding material, a casting material, a laminated material, a paint, an adhesive, a resist, and an optical material as a sealing material and a prepreg.

Claims (6)

(A ′) epoxy resin,
(B) As a hardening | curing agent, following formula (1)-(3)

(In the formula (1), _{R 1} is present independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, the number of .l is _{R 1} representing one of the alkoxy group having 1 to 3 carbon atoms Represents an integer of 1 to 4.)

(Equation (2), R ₂ is present each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a alkoxy group having 1 to 3 carbon atoms.)

(In Formula (3), each R ₃ is independently present and represents any of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. N represents the number of carbon atoms; Represents an integer of 0, 1, or 2. m represents the number of R ₃ and satisfies the relationship of 1 ≦ m ≦ n + 2.
And a phenol compound obtained by a reaction with one or more of the compounds represented by formula (1) and a hydroxybenzaldehyde selected from o-, m- and p-hydroxybenzaldehyde , and (c) an inorganic packing having a thermal conductivity of 20 W / m · K or more. Material,
An epoxy resin composition for a polymer material that serves as a binder to connect high heat conduction sites containing the selenium. (A) an epoxy resin obtained by further reacting an epihalohydrin with the phenol compound according to claim 1;
(B ′) a curing agent, and (c) an inorganic filler having a thermal conductivity of 20 W / m · K or more,
An epoxy resin composition for a polymer material that serves as a binder to connect high heat conduction sites containing the selenium . (A) the epoxy resin according to claim 2,
(B) the phenol compound according to claim 1, and (c) an inorganic filler having a thermal conductivity of 20 W / m · K or more,
An epoxy resin composition for a polymer material that serves as a binder to connect high heat conduction sites containing the selenium .   The epoxy resin composition as described in any one of Claims 1-3 used for a semiconductor sealing use.   A prepreg comprising the epoxy resin composition according to any one of claims 1 to 3 and a sheet-like fiber base material.   Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-4, or the prepreg of Claim 5.