TW201105699A - Epoxy resin composition, prepreg and cured products thereof - Google Patents

Abstract

Disclosed is an epoxy resin composition from which a cured product having a high heat resistance and a high heat transfer rate can be obtained. Specifically disclosed is an epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler having a heat transfer rate of 20 W/mK or more, which contains, as said curing agent, a phenol compound obtained by reacting one or more compounds represented by formulae (1) to (5) with a hydroxybenzaldehyde, and/or, as said epoxy resin, an epoxy compound obtained by further reacting the aforesaid phenol compound with an epihalohydrin.

Description

201105699 VI. Description of the Invention: [Technical Field] The present invention relates to a novel epoxy resin composition and a prepreg obtained by using the above epoxy resin composition. Further, the present invention relates to a cured product obtained by hardening the above epoxy resin composition or prepreg. [Prior Art] The epoxy resin composition is generally used as a hardened material having excellent mechanical properties such as water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used for an adhesive, a coating, a laminate, a molding material, and an injection molding material. And so on. In recent years, the hardened materials of epoxy resins used in these fields are required to be characterized by high purity, such as flame retardancy, heat resistance, money resistance, strong bouncing property, low linear expansion ratio, and low dielectric constant property. And so on, the advancement of each feature. In particular, the high-density packaging or printed circuit board of semiconductors for the purpose of multi-function, high-performance, and miniaturization in the field of electrical and electronic industries, which represent the '11 applications of the 裒 树 月 月 旨Density cabling is continually developing Ctc density ablation or high-density wiring, which increases the heat generated from the inside of a semiconductor: a printed circuit board, which may cause a malfunction of the machine j. It is also an important issue to how to efficiently release the generated heat to the outside. As a countermeasure against such problems caused by heat, the industry has studied various methods such as enamel metal core substrates, assembly of heat-conductive fillers that are easy to dissipate at the design stage, and the like. Since the thermal conductivity of the polymer material which is a binder which connects the high heat conductive portion 2〇1105699 is low, the heat transfer rate of the polymer material becomes a speed limit, and heat cannot be efficiently dissipated. As a method for realizing high thermal conductivity of an epoxy resin, a method for introducing a liquid crystal primordium into an epoxy resin structure is reported in the patent document yi, and is described in the literature as an epoxy resin having a liquid crystal primordium. There is an epoxy resin having a skeleton, etc. In addition, as an epoxy resin other than a biphenyl skeleton, a phenyl benzoate type epoxy resin is described, but the epoxy resin must utilize an epoxidation reaction caused by oxidation. In order to manufacture, there is a problem in terms of safety and cost, and it cannot be said that it has practicality. Further, in Patent Documents 2 to 4, an example in which a biphenyl skeleton: an epoxy resin is used is described, in Patent Document 3 A method of using an inorganic filler having a thermal conductivity in combination is described. However, the thermal conductivity of the cured product obtained by the method described in the literature is not to satisfy the market demand = level, and the f-boundary is used. An epoxy resin composition capable of providing a cured product having a higher thermal conductivity than an epoxy resin obtained by a low-cost one. Further, it is considered that the epoxy resin composition is the same as the epoxy resin. The hardener contained therein is also an important factor for achieving high thermal conductivity. Previously, as a hardener which emphasizes a cured product and an epoxy resin composition having high thermal conductivity, it is reported in the patent document 使用 4, Examples of amine-based curing agents such as 4,-diaminodibenzoate benzoquinone 4'4-monoaminodiphenylmethane, and patents 2 and 3 report the use of an amine such as hydrazine or 5-diaminonaphthalene. However, since these amine-based hardeners have a hardening-promoting action, it is difficult to ensure a service life in the case of producing a cured product, and it cannot be said that it is preferable. On the other hand, in Patent Document 4, phenol is used. The compound is used as a hardener. In Patent Document 4 201105699, the phthalic acid varnish is specifically used in the 5th embodiment, but the thermal conductivity of the cured product obtained by the method described in the literature does not satisfy the market demand. In the prior art, it is desired to provide an epoxy resin composition having a cured material having a higher thermal conductivity. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. Japanese special opening 2〇〇6 633 15 SUMMARY OF THE INVENTION The present invention has been made to solve such a problem, and as a result, an epoxy resin composition having a high thermal conductivity of a cured product is provided. The present inventors have made an effort to solve the above problems, and have completed the present invention. The present invention relates to the following: (1) An epoxy resin composition comprising the following components: 0') epoxy resin, (b) a compound which is obtained by reacting a compound of the following formulas (1) to (5) as a curing agent with a base benzophenone, 0

6 201105699 (In the formula (1), R丨 exists independently, 砉_ & a non-wind atom, a substituted or unsubstituted alkyl group of a broken age A 1 to 10, and a carbon number of 6 to 10 Any one of a substituted or unsubstituted aryl group, a thiol group, or a carbon number, a cyclist or an unsubstituted alkoxy group of 1 to 10; * 〇~4 integer), and horse (2) (in the formula (2), 'R2 exist independently, and the table π is not a halogen atom, and the substituted or unsubstituted alkyl group having a carbon number of 1 to 20 is broken. A substituted or unsubstituted aromatic group having a number of 6 to 10, a carbon number of 1 to 丨5 < a substituted or unsubstituted alkyl group, a fluorenyl group, and a carbon number of 2~ Ιπ ·ν , substituted or unsubstituted alkyl group, carbon number A 1~ίο "substituted or unsubstituted oxo, phthalimido, sunflower or hydroxyl Either ^ II ΗWh (3) mm (in the formula (3), R3 is independently present, and represents a hydrogen atom, a substituted or unsubstituted burnt base, carbon having a carbon number of 〇~ίο The number ι ~ι〇 is replaced or Substituted alkyl group, substituted or unsubstituted aryl group having 6 to 10 carbon atoms, substituted or unsubstituted alkyl ester having 2 to 1 carbon number, 7 201105699 Any one of the bases 1 and 2 is an integer of 2, and the base or carbon number is 1 to 10, either substituted or unsubstituted. η represents the carbon number, and represents 〇, m represents the number of R3, and satisfies + Η

Ο 0 (4) Η (In formula (4), I exist independently, 矣 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 6 to 10, the unsubstituted or unsubstituted aromatic group, the carbon number of 1 to 、, ^ any of the alkoxy groups or the hydroxyl group),

(In the formula (5), 'Rs are independently present, and the substituted non-hydrogen atom, the substituted or unsubstituted alkyl group having a carbon number of -20, and the substituted or unsubstituted carbon number of 6 to 1 are. Any one of an aromatic group and a carbon number of a substituted or unsubstituted alkoxy group or a hydroxyl group, wherein 11 is an integer), and (c) a thermal conductivity of 20 W/mK or more Inorganic filler. (2) An epoxy resin composition comprising the following components: (a) an epoxy resin obtained by reacting a phenol compound of the above item (1) with an epoxy fluoropropene 8 201105699 (epihalohydrin), b') hardener, and (4) inorganic filler having a thermal conductivity of 2 〇 w/mK or more. (3) An epoxy resin composition containing the following components: (a) the epoxy resin of the above item (2), (b) the expectation compound of the item (1), and (c) the thermal conductivity An inorganic filler material of 20 w/mK or more; (4) an epoxy resin composition according to any one of the items (1) to (3) above, which is used for semiconductor sealing purposes; ' ' (5) - a type of prepreg, The epoxy resin composition according to any one of the above items (1) to (3), and a sheet-like fibrous base material. (6) A hardened material obtained by curing the epoxy resin composition of any one of the above items (1) to (4) or the prepreg of the above item (5). Since the epoxy resin composition of the present invention is excellent in heat conductivity of the cured product, it is useful in the case of various composite materials, adhesives, paints and the like typified by semiconductor sealing materials and prepregs. [Embodiment] The epoxy resin composition of the present invention contains an epoxy resin, a curing agent, and an epoxy resin having a thermal conductivity of 20 W/mK or more (hereinafter referred to as "(〇刀)"). a phenol compound obtained by reacting one or more of the compounds represented by the following formulas (1) to (5) with a hydroxybenzaldehyde as a curing agent (hereinafter referred to as "(b) component) ") and/or an epoxy compound obtained by reacting the component (b) with epoxidized propane as an epoxy resin (hereinafter referred to as "(a) component"). 201105699 First, the epoxy of the present invention The component (b) which is a curing agent contained in the resin composition is described. The component (b) is obtained by reacting one or more compounds represented by the following formulas (1) to (5) with a hydroxybenzaldehyde. Phenol compound 0

(Ri)i (In the formula (1), the heart independently represents a substituted or unsubstituted alkyl group having a carbon number of ～10, a carbon number of 6 to 1 〇 or an unsubstituted aroma. The group, the hydroxyl group, or the carbon number is 丨~1〇 or any of the unsubstituted oxy groups. 1 represents the number of 1-4. Substituted substituted and 0 (2) ± (in the formula (2), R 2 is independently present, and 矣-& represents a substituted or unsubstituted alkane having a carbon number of i -20 a substituted or unsubstituted aromatic group having a carbon number of 6 to 1 Å, a substituted or unsubstituted alkylcarbonyl group, a porphyrinylcarbonyl group having a carbon number of 1 to ls, a carbon number of 2~ 1Λ ^ 2丨〇 substituted or unsubstituted alkyl ketone, followed by 1 to 10 substituted or unsubstituted burned 10 201105699 oxy, o-benzonitrile, geranyl or Any of the bases). In the formula (2), the above substituent is preferably selected from the group consisting of a carbonyl 'ester group, an alkenyl group, a phenyl group, an alkoxy group, an ether group, an o-benzidine group, and a sunflower group. At least one.

(3) (In the formula (3), R3 is independently present, and represents a hydrogen atom, a substituted or unsubstituted alkyl group having a carbon number of 〇10, a substituted carbon number of 丨~1〇 or An unsubstituted alkyl group, a substituted or unsubstituted aryl group having a carbon number of 6 to 10, a substituted or unsubstituted alkyl aryl group having a carbon number of 2 to 10, a substituted carbon number A WO or Unsubstituted alkoxy or any of the radicals. n represents a carbon number and represents any integer of 〇, 2. m represents the number of R3 and satisfies the relationship of 〇SmSn+2) 〇 _ R3 "(4) The case where the R is substituted or unsubstituted by the syllabic record" is a carbonyl structure in which a carbon atom constituting the cycloalkane of the general formula is formed, for example, 1 or the like. In the above (3), the above substituent is preferably an ether group.

'eight double two 1' carbon number 6 to 10 substituted 1 〇 substituted or unsubstituted (in the formula (4) 'R4 independently existed ~20 substituted or unsubstituted alkyl or not A substituted aromatic group having a carbon number of 1 to an alkoxy group or a trans group).

/y'卞, substituted or unsubstituted alkyl group having a carbon number of 1 to 20, taken or unsubstituted aryl group having a carbon number of 6 to 1 Å, carbon number & 丨~1() Any one of a substituted or unsubstituted alkoxy group or a hydroxyl group. Further, η is an integer of 1 to 10). In order to obtain the component (8), specific examples of the compound represented by the formula (1) used in the reaction with the group of the group of the formula (B) include an o-based group, a m-phenyl- acetophenone, and a ruthenium group. B_. Among these, in the case where the cured product of the epoxy resin composition exhibits high thermal conductivity, p-phenylacetophenone is preferred. For the specific example of the compound represented by the formula (7) used in the reaction with the sulfonyl group, it is known that: acetone, "3•二笨基基丙_, 2_ Ding net, 1 stupid 10-butanedione, 2-pentanone, 3-pentanone, 4_ 12 201105699 methyl-2-pentanone, 2-hexanone, 3-hexanone, isoamyl decyl ketone , ethyl isobutyl ketone, 4-methyl-2-hexanone, diphenyl d, 6-hexane di-, 2-heptanone, 3-heptanone, 4-heptanthene, 2-methyl_4 _heptanone, 5•mercapto_3_heptan_, 6-methyl-2·heptanone, 2,6·didecyl-4-heptanone, 2-octanone, 3-octanone, 4-octyl Keto. 5-mercapto-2-octanone, 2-nonanone, 3-fluorenone, 4-fluorenone, 5-fluorenone, 2-fluorenone, 3-ketone, 4-oxime, 5· Anthrone, 2_undecone, 3·11醐, 4_undecone, % undecane, 6-undecone, 2-methyl-4-indolone, 2_dodecanone, Hong Dodecanone, 4-unde-, 5-dodecanone, 6-dodecanoate, 2-tetradecanone, % tetradecanone, 8·pentadecanone, 1〇_nonadecanone, 7-tridecanone , 25 鲷, 36 ketone, heptadectone, 11 · 21 ketone, 12 - docosatrione, 14 • hexadecanone, oxime ketone, 18-35 , 4-ethoxy-2-butanone, 4-(4-methoxyphenyl)-2·butanone, 4-methoxy-4-4-2-pentanone, 4-methoxybenzene Propionate, methoxypropene, phenoxyacetone, methyl acetate, ethyl acetate, acetoacetate, butyl acetate, isobutyl acetate, acetonitrile Dibutyl ester, butyl phthalate, butyl acetate, amyl acetate, amyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, heptyl acetate N-octyl acetate, benzyl acetate, dinonyl acetyl succinate, diacetone acetonate, diethyl acetonate, diethyl acetoxy-5-oxohexanoate Ester, acetamidineacetic acid _2 methoxyethyl ester, allyl acetate acetate, 4-second butoxy-2-butanone, benzyl butyl ketone, bis-demethoxycurcumin, 1, 1-Dimethoxy-3-butanone, anthracene, 3-diethoxypropoxy-, 4-hydroxyphenylacetone, 4-(4-hydroxyphenyl)_2-butanone, isoamylmethyl ketone , hydroxy-2-butanone, 5-hexene-2-one, acetonylacetone, sulfonate, ketone methyl ketone , 曰 基 基 丙酮, 邻 曱 = = 13 201105699 Aminoacetone, 4-isopropoxy-2-butanone, 4-isobutoxy-2-butanone, ethoxylated -2- Propylene, N-acetonitrile, hydrazine, 1-ethyl fluorenyl-4,0 ketone, etc. In order to obtain the component (b), the formula used in the reaction with hydroxybenzaldehyde (3) Examples of the compound shown are: cyclopentanone, 3-phenylcyclopentanone, 1,3-cyclopentadione, cyclohexyl, 3-methylcyclohexanone, .4-methyl Cyclohexanone, 4-ethylcyclohexanone, 4-tert-butylcyclohexanone, 4-pentylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 3,3- Dimethylcyclohexanone, 3,4-didecylcyclohexyl, 3,5-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3,3,5-trimethylcyclo Hexanone, ethyl 4-cyclohexanone decanoate, 1,4-cyclohexanedione monoethylene ketal, dicyclohexane-4,4,-dione monoethylene ketal '1,3-cyclohexane Ketone, 1,4-cyclohexanedione, hametiketone, 4,4,-dicyclohexanone, cycloheptanone, and the like. In order to obtain the compound represented by the formula (4) used for the reaction with the hydroxybenzaldehyde, the component (b) is exemplified by 2,3-butanedione and 2,3-pentanedione. 3,4-hexanedione, 5-methyl-2,3-hexanedione, 2,3-heptanedione, and the like. Specific examples of the compound represented by the formula (5) used for the reaction of the component (b) with the hydroxybenzaldehyde include acetamidineacetone, ethyl acetate, and 2,5- Adipone, 3-methyl-2,4-pentanedione, 3·ethyl·2, heart pentosone, 3-butyl-2,4-pentanedione. 3-phenyl-2,4 - Pentanedione, 3-butyl-2, 4-pentanedione, and the like. One of the compounds shown is, for example, an ortho-hydroxy group. These may be made only of the epoxy resin composition, preferably used alone to obtain the component (b), as the hydroxybenzaldehyde used in the reaction with the formulae (1) to (5), benzoic acid. And m-hydroxybenzaldehyde and p-hydroxybenzoquinone may be used in combination of two or more kinds. The hardened materials of these materials exhibit a particularly high thermal conductivity. 201105699 For the base benzophenone. - (b) Tr is obtained by an aldol reaction of the formula (1) to (5) oxime with a hydroxybenzaldehyde, under acidic conditions τ or an experimental condition τ. For the compound 1 of the formula (1), it is preferred that the horse is 1.0 ^ 1 〇s gan γ γ. ^ ^ 5 mol, as shown in the formula (2) to the formula (5) The compound j is preferably used in an amount of 2.0 to 3.15 moles. When the alcohol condensation reaction is carried out under acidic conditions, examples of the acid medium which can be used include organic acids such as hydrochloric acid, sulfuric acid, and nitric acid, such as toluene-nonylbenzene acid and oxalic acid. These can be used alone or in combination with a plurality of ° acidic catalysts in an amount of from 0.1 to U moles, preferably from 0.2 to 0.5 moles, relative to the benzene. On the other hand, when the aldol reaction is carried out under alkaline conditions, the test|±catalyst' is a metal such as sodium hydroxide or potassium hydroxide: an alkali metal such as potassium carbonate or sodium carbonate. An amine-derived hydrazine such as diethylamine, amine-butylamine, diisobutylamine, pyridine or piperidine, and an amino alcohol such as monomethylaminoethanol and diethylaminoethanol. In the case of an alkaline condition, the above-mentioned bases = catalysts may be used alone or in combination. The amount of the test catalyst used is a lighter class = ear is (Μ~2·5 mole, preferably 0.2~20 moles. This can be used in the reaction of ^, if necessary, a solvent can also be used. The mixture is not particularly limited as long as it has reactivity with a hydroxybenzaldehyde such as a ketone, but it is preferred to use an alcohol as a raw material for dissolving the hydroxybenzaldehyde as a raw material. Solvent. 15 201105699 The reaction 'nucleus is usually 10 to 90 ° C, preferably 35 to 7 (TC. The reaction time is usually 05 to 1 Λ, * i ϋ hours, but the reaction varies depending on the type of the raw material compound' Therefore, it is not limited to 〇·5~10 hours. After the reaction is completed, 乍 is a tree & when it is taken out, 'the reaction product is washed with water or not washed with water, heated under reduced pressure, and the reaction solution is unreacted from the reaction liquid. Or a solvent or the like. When the form of the yang is removed, the reaction is carried out by adding the reaction liquid droplets to a large amount of water to carry out the reaction under the conditions of the test, and the resulting (b) is formed into a knife. It is also possible to dissolve in water, so hydrochloric acid or the like is added to form a neutral _ acidic condition. It is precipitated as a crystal. The component (a) which is an epoxy resin contained in the epoxy resin composition of the present invention will be described. The component 0) contained in the epoxy resin composition of the present invention is utilized. The component (b) obtained by the above method is reacted with epoxidized propane and epoxidized, and in the case of epoxidation, only one (8) component may be used, or two or more kinds may be used in combination. In the b) component, a phenol compound other than the component (8) may be used in combination. The phenol compound other than the component (b) which can be used in combination may be used without particular limitation as long as it is a phenol compound which is usually used as a raw material of the epoxy resin. However, since the effect of the present invention in which the cured product has a high thermal conductivity is impaired, it is preferred that the amount of the phenol compound which can be used in combination is extremely small, and it is particularly preferable to use only the component (b). In the case of obtaining a cured product having a particularly high thermal conductivity, it is preferred to use a ring obtained by reacting the component (b) obtained by the reaction of a hydroxybenzaldehyde with a compound represented by the formula (3). Oxide. 16 2 01105699 In the reaction of obtaining the component (4), it can be used as the epoxy acrylonitrile. The gas, the alcohol, the methyl alcohol, the alcohol, etc., are preferably industrially easy to obtain.相对 翕 氧 卤 院 之 之 1 1 1 1 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫Sodium oxide, hydrazine hydroxide, etc. 'These solids can be used directly, or an aqueous solution can be used. In the case of using an aqueous solution, 'the method can also be as follows: the aqueous solution of the alkali metal hydroxide is continuously added Into the reaction system, and by continuously separating the water from the mixture of water and epoxy propylene by distilling under reduced pressure or under normal pressure, and only returning the epoxide propane continuously Into the reaction system. The amount of metal hydroxide used is generally 〇~3Q mol, preferably 〜2·5 mol, more preferably 丨丨~厶^) Mo. In order to promote the epoxidation reaction, a tetra-ammonium salt such as tetramethyl gasification, tetramethylammonium bromide or trimethylbenzylammonium vaporate is preferably added as a catalyst. The amount of the quaternary ammonium salt used is usually 〇1 to 15 g' with respect to the hydroxy oxime of the component (b), preferably 〇.2 to 1 〇 g. Further, in the case of epoxidation, in terms of reaction progress, it is preferred to add an alcohol such as decyl alcohol, ethanol or isopropanol, dimercaptosulfone, dimercaptosulfoxide, tetranitrofuran, dioxane, etc. The reaction is carried out by an aprotic polar solvent or the like. In the case of using the above alcohols, the amount thereof is usually from 2 to 50% by mass, preferably from 4 to 20% by mass, based on the amount of the epoxy group, and is also used in the use of an aprotic polar solvent. In the case of the epihalohydrin, the amount is usually from 5 to 100% by mass, preferably from 1 to 8 Å by mass. . 17 201105699 The reaction temperature is usually 30 to 90 ° C. Preferably, it is 35 to 8 (TC. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction is finished, the reaction is washed or not. The water is washed, and the epoxy propylene oxide, the solvent, and the like are removed from the reaction liquid under heating and reduced pressure. Further, in order to further reduce the amount of the hydrolyzable γ element contained in the component (a), the recovered (a) may be used. The component is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of sodium hydroxide or potassium hydroxide is added to the metal hydroxide to carry out the reaction. By performing the above operation, the ring opening can be surely performed. In the case where the amount of the alkali metal hydroxide is usually 0.01 to 0.3 mol, preferably 0.05 to 2 mol, relative to the hydroxy oxime of the component (b). The reaction/dish degree is usually 50 to 120 C. The reaction time is usually ο" to 2 hours. After the completion of the reaction, the salt formed is removed by filtration, washing with water, etc., and the solvent is distilled off under reduced pressure under heating to obtain the component (a). When the component is precipitated as crystal, it may be The salt formed is dissolved in a large amount of water, and the crystal of the component (a) is filtered. The epoxy resin composition of the present invention is described below. The epoxy resin composition of the present invention contains an epoxy resin and a hardener. An inorganic filler having a rate of 2 G and containing at least one of the component (a) as the epoxy resin and the component (b) as the curing agent as an essential component. In the epoxy resin composition of the present invention, The (4) component of the epoxy resin may be used singly or in combination with other epoxy resins (hereinafter referred to as "components"). Specific examples of the (a,) component include bisphenols (bisphenol a, double) Phenol 18 201105699 F, bisphenol S, biphenol, bisphenol ad and bisphenol i, etc.) or phenols (phenol, substituted benzene, aromatic substituted phenyl, naphthol, trans-substituted Naphthalene, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene, etc.) and various acids (ruthenium, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted, basal formic acid) ·Naphthoic acid, pentane, benzophenone, crotonaldehyde a polycondensate of cinnamaldehyde or the like, an aromatic compound such as xylene, a polycondensate of formaldehyde and a polycondensate of an age, an age class, and various dilute compounds (dicyclopentadiene, decene, vinylcyclohexene, Polycondensates, phenols and the like of butadiene, vinyl-ene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene and isoprene Polycondensates of ketones (acetone, methyl ethyl ketone, decyl isobutyl ketone, acetophenone and dibenzophenone), phenols and aromatic sterols (benzene dimethanol and biphenyl dioxime) Polycondensates of alcohols, etc., polycondensates of phenols and aromatic di-gas methyls U, a, di-dioxene and di-n-decylbiphenyl, phenols and aromatic bis-alkoxymethyl a polycondensate of a class of (dimethoxymercaptobenzoic acid fluorenylbiphenyl and bisphenoxymethylbiphenyl), a polycondensate of a bisphenol and various aldehydes, and a glycidation of an alcohol or the like Glycidol (4), epoxy resin, alicyclic epoxy resin, glycidylamine-based oxy-oxygen resin, glycidol-based epoxy resin, etc. Often the epoxy resin used is not limited thereto and the like. These may be used alone or in combination of two or more. In the case where the component (U) is used in combination, the proportion of the component (4) in the epoxy resin of the present invention is preferably more than 3% by mass or more. 4% by mass or more and more preferably quality. ,. The above is particularly preferably 100% by mass (when the (a,) component is not used in combination). In the case of using (4) 19 201105699, all of the ring-shaped knives are added as a modifier of the epoxy resin composition in an amount of 1 to 3 % by mass in the oxygen resin. The epoxy resin composition of the present invention may be used as a component of the hardener (b), or may be used in combination with other hardeners. Examples of other curing agents (hereinafter referred to as "(b') component)" contained in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, a brewing amine compound, and (4) a compound [will Specific examples of the components (10) are shown in the following (a) to (a) amine compounds. 〇diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and (b) an acid anhydride compound, phthalic anhydride, trimellitic anhydride, tetrasuccinic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, mercaptoic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid anhydride, etc. (c) guanamine compound from dicyanodiamine or linolenic oil Polyamide resin synthesized by acid dimer and ethylenediamine (d) phenolic compound polyphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, bismuth, 4, 4 ,-dihydroxybiphenyl, 2,2'-dihydroxyl stupid, 3,3',5,5·-tetramethyl-(ij,-biphenyl)·4·4′·diol, p-benzene Diphenol, resorcinol, naphthalenediol, Tris-Phenylphenyl)decane and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; by phenols (Example 20 201105699 such as phenol, alkyl phenol, naphthalene) Phenols, alkyl-substituted naphthols, dihydroxybenzenes, and dihydroxynaphthalenes, etc.) with aldehydes (furfural, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones ( a phenol resin obtained by condensation of p-hydroxyacetophenone and o-hydroxyacetophenone or the like (dicyclopentadiene, tricyclopentadiene, etc.); by using the above phenols and substituted biphenyls Classes (4,4,-bis(gasmethyl)-1,1,-biphenyl and 4,4,-bis(methoxymethyl)-1,1,·biphenyl, etc.) or substituted benzene Phenol obtained by polycondensation of a base such as 1,4-bis(methylmethyl)benzene, i,4-bis(methoxymethyl)benzene, and 1,4-bis(fluorenyl)benzene Resin; the above-mentioned genus and/or the above-mentioned oxime resin modification; tetrabromobiguanide A and brominated age resin and other functionalizations (e) other imidazoles, BF:j-amine complexes, anthracene derivatives Among these (b,) components, preferred is diaminodiphenylmethane, two An amine compound such as a diphenyl sulfone or a naphthalene diamine, and a condensate of catechol with an aldehyde, a ketone, a diene, a substituted biphenyl or a substituted phenyl group, etc. The component has a structure in which the active hydrogen groups are adjacent to each other, whereby the epoxy resin is well aligned. For example, in the case of a condensate with o-diphenol, the hydroxyl groups reacted by thermal hardening are in the ortho position to each other, thus: In another aspect, if (4) the hydrogen groups of the reaction are hardened by nitrogen atoms, the Q groups are also polymerized in parallel in this case. The (b') component can be used alone. In the case of using the (b,) component in combination, the proportion of the component (8) in the hardener component of the present hair composition is preferably more than or equal to, and more preferably, more preferably. It is 30 mass% or more, 20 mass / 〇, and more preferably 7 〇f 4 21 201105699 is preferably 100% by mass (when the component (b,) is not used together). In the epoxy resin composition of the present invention, the amount of all the hardeners comprising the component (b) is preferably from 0.5 to 2.0 equivalents, more preferably from 6 to 15 equivalents per equivalent of the epoxy resin of the epoxy resin. equivalent. The epoxy resin composition of the present invention is preferably a component of the component (b) which is used as the (4) component of the epoxy resin and (4) by mass% of the material hardener. The inorganic filler contained in the epoxy resin composition of the present invention is added for the purpose of imparting a higher thermal conductivity to the cured product of the epoxy resin composition. When the thermal conductivity of the inorganic filler itself is too low, The high thermal conductivity obtained by the combination of epoxy resin and hardener is impaired. Therefore, as the inorganic filler contained in the epoxy resin composition of the invention, the higher the thermal conductivity, the more preferable, and it is usually 2 〇 κ or more, preferably more than 250 w/mK, more preferably 5 〇. There is no limit to the thermal conductivity above w/m κ. Further, the thermal conductivity referred to herein means a value measured by the method according to ASTM E153G. Specific examples of the inorganic filler having such characteristics include inorganic boron fillers such as boron nitride, aluminum nitride, tantalum nitride, tantalum carbide, oxidized words, tungsten carbide, aluminum oxide, and magnesium oxide. Fiber fillers such as fibers and ceramic fibers, I-color agents, etc.: The shape of these non-filled materials may be any of powder (block, spherical), monofilament, filament, etc., especially if it is a flat plate. In the case of the inorganic filler, the thermal conductivity of the cured product is higher and the heat dissipation property of the cured product is further improved by the lamination effect of the inorganic filler itself. The amount of the inorganic filler used in the epoxy resin composition of the present invention is 22 201105699. The resin component in the epoxy resin composition is usually 2 to \000 parts by mass, preferably 4 Å. 1 part by mass, but in order to increase the thermal conductivity as much as possible, it is preferred to increase the inorganic filler as much as possible within a range that does not cause an obstacle to the use of the epoxy resin composition of the present invention in a specific use. Usage amount. These inorganic fillers may be used alone or in combination of two or more. In addition, if the thermal conductivity of the entire filler material can be maintained in the range of 20 W /mK or more, the thermal conductivity of the inorganic filler having a thermal conductivity of 2 Å or more can be used in combination with a thermal conductivity of 2 〇 W / / m. A filler of κ or less, but for the purpose of the present invention in which a cured product having a high thermal conductivity is obtained as much as possible, the use of a filler having a thermal conductivity of 20 W/mK α should be limited to a minimum. The kind or shape of the filler which can be used in combination is not particularly limited. When the epoxy resin composition of the present invention is used for semiconductor sealing applications and prepreg applications, it is preferably an epoxy resin in terms of heat resistance, moisture resistance, mechanical properties and the like of the cured product. An inorganic filler having a thermal conductivity of 2 〇 w/mK or more is used in the composition in an amount of from 6 〇 to 93% by mass. In this case, the residue is an epoxy resin component, a hardener component, and other additives added as needed, and as an additive, another inorganic filler which can be used in combination, or a hardening accelerator which will be described later. In the epoxy resin composition of the present invention, as long as it contains at least one of the component (4) as the epoxy resin and the component (8) as the curing agent, it is possible to remove the material (4), even if the oxygen is cut. The resin (not particularly limited, but preferably, for example, the component (8)), the component of the component (8) and the component (C), or the component (4) and the curing agent are not particularly limited, but 23 201105699 is preferably, for example, the above ( b, the components of the components (c) and (c) are similar to the components comprising the components (3) and (b) and (c), and the cured product also has excellent thermal conductivity. A hardening accelerator may also be contained in the epoxy resin composition of the present invention. As a hardening accelerator which can be used, for example, a 2-based base taste can be mentioned. Imidazoles such as 2-ethylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, 2-(didecylaminodecyl)phenol, triethylenediamine, triethanolamine and hydrazine , a metal compound such as a tribasic amine such as benzodiazepine (5,4,fluorenyl)undecene-7, an organic phosphine such as triphenylphosphine, diphenylphosphine or tributylphosphine, and a compound such as tin octylate. Tetrasubstituted squamous-tetrasubstituted borate such as tetraphenyl sulphate tetraphenyl boron I salt and tetraphenyl sulphate ethyl triphenyl sulphate, 2-ethyl-4-mercaptoimidazole-tetraphenylboronic acid a tetraphenylboron salt such as a salt or a N-mercaptoporphyrin tetrasyl borate. The hardening accelerator is used in an amount of 0.01 to 15 parts by mass, based on 100 parts by mass of the epoxy resin. In the epoxy resin composition of the present invention, various compounding agents such as a decane coupling agent, a releasing agent, and a pigment, and various thermosetting resins and various thermoplastic resins may be added as the thermosetting resin and the thermoplastic resin. Examples thereof include a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a cyanate resin, an isocyanate compound, a benzofluorene D compound, a vinyl benzyl ether compound, a polybutadiene, and The modified substance, the modified product of acrylonitrile copolymer, oxime resin, fluororesin, oxime resin, polyether oximine, polyether oxime, polyether ether, polyacetal, polystyrene, polyethylene, dicyclopentane Dilute resin, etc. The thermosetting resin or the thermoplastic resin is used in an amount of 60% by mass or less based on the epoxy resin composition of the present invention. The epoxy resin composition of the present invention can be used as a preferred printed circuit board or the like by arranging the semiconductor sealing material or mixing them uniformly by using the above-mentioned respective components 24 201105699. The epoxy resin composition of September can be easily made into a cured product by the same method as the previously known method. The formation of the cured product of the present invention can be carried out, for example, by using an extruder, a kneader or a roll, etc., an epoxy resin, a hardener, and an inorganic filler having a thermal conductivity of 20 W/mK or more. The required hardening accelerator, compounding agent, various thermosetting tree stalks or various thermoplastic resins are sufficiently mixed until uniformity is obtained to obtain an epoxy resin composition, which is then subjected to melt casting, transfer molding, and injection molding. The epoxy resin composition is formed by a method such as compression molding or the like, and then added to < 2 to 1 〇+ above the melting point thereof. 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. Further, the epoxy resin composition of the present invention may be formed into a varnish containing a solvent. The varnish may be, for example, a mixture of an epoxy resin, a hardener, an inorganic filler having a thermal conductivity of 20 W/m.1 C or more, and other components as needed, and anthracene, xylene, acetone, mercaptoethyl. Ketone, mercaptoisobutyl ketone, % hexanone, cyclopentanone, N, N, dimethyl decyl decylamine, N, N,-dimercaptoacetamide, monomethyl argon, N-曱基. An alcohol ether such as ethylene ketone, ethylene glycol dioxime ether, ethylene glycol diethyl ether, dipropylene glycol dioxime ether, dipropylene glycol diethyl ether, diethyl ether monoterpene ether, diethylene glycol diethyl ether, etc. Ester, butyl acetate, thiol cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monoterpene ether acetate, pentanoic acid Esters such as alkyl esters, dialkyl succinates, dialkyl adipates, 25 201105699 cyclic esters such as r-butyrolactone, petroleum ether, petroleum brain, hydrogenated petroleum brain and Shiyue b solvent It is obtained by mixing an organic solvent such as a petroleum solvent such as oil. The amount of the emulsifier is usually 10 to 95% by mass, preferably 15 to 85% by mass based on the total varnish. 〇 The varnish obtained as described above is impregnated with glass fiber, carbon fiber, poly ray fiber, polyamide fiber, and oxidized. The prepreg of the present invention can be obtained by removing the solvent by heating and removing the varnish into a semi-hardened state after the sheet-like fibrous base material such as aluminum fiber or paper. In addition, the term "semi-hardened state" as used herein means a state in which a part of the epoxy group which is a reactive functional group remains unreacted. The prepreg can be hot pressed to obtain a cured product. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the synthesis examples, examples, and comparative examples, parts represent parts by mass. Further, the epoxy equivalent, the melting point and the thermal conductivity were measured under the following conditions. • Epoxy equivalents were measured by the method described in JIS K-7236, in units of g / eq · 〇 • Melting point

EXSTAR6000 test sample manufactured by Seiko Instruments Inc. 2 mg~5 mg Heating rate ι 〇. 〇/min • The thermal conductivity is measured by the method according to ASTM E1530. • The hydroxyl equivalent of 26 201105699 is measured according to the method described in JIS 00·0070, and the unit is / eq· 〇 Synthesis Example 1 is equipped with a stirrer, a reflux cooling tube, The flask of the stirring apparatus was charged with 136 parts of p-hydroxyacetone, 124 parts of p-hydroxybenzaldehyde and 3 parts of ethanol' and dissolved. After 51.0 parts of 97% sulfuric acid was added thereto and the temperature was raised to 6 Torr <t, and the reaction was carried out at this temperature for 8 hours, the reaction liquid was poured into 2 parts of water to be crystallized. After filtration and crystallization, water washing was carried out twice with 6 parts of water, followed by vacuum drying to obtain 2200 parts of a reddish brown crystalline ruthenium compound 1. The melting point of the obtained crystal was 203 as determined by DSC. (Comparative Example 2) A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was charged with 29 parts of acetone, 124 g of p-hydroxybenzaldehyde, and 3 parts of ethanol, and dissolved therein. 80 parts of 50% hydrogen was added thereto. After the sodium oxide aqueous solution was heated, the temperature was raised to 45. (The reaction was carried out at this temperature for 1 to 20 hours, and then the reaction solution was poured into 8 mL of 1 N 5 hydrochloric acid to be crystallized. After filtration and crystallization, 6 〇 was used. The water was washed twice with water, and then vacuum dried to obtain 210 parts of the yellow crystal compound 2. The melting point of the obtained crystal was determined by DSC to be 1 〇 1. Synthesis Example 3 was equipped with a stirrer and a reflux cooling tube. The flask of the stirring device was charged with 49 parts of cyclohexanone, 124 parts of p-hydroxybenzaldehyde and 250 parts of ethanol, and dissolved. 25 parts of 37% hydrochloric acid was added thereto, and the temperature was raised to 60 ° C, and the reaction was carried out at this temperature. After 10 hours, the reaction solution was poured into 1 part of water to be crystallized. After filtration and crystallization, it was washed twice with 800 parts of water, and then dried in a vacuum of 27 201105699 to obtain 21 parts of a yellow crystalline phenol compound. 3. Obtained The melting point of the obtained crystal was determined by DSC to be 289. (: Synthesis Example 4: Nitrogen flushing was carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and the force obtained by the synthesis example i was obtained. Phenol compound 92511 epoch alcohol, 139 parts of dimercapto ytterbium (DMs 〇), after the temperature drop to 45 ° C and dissolved, after 7G minutes, add 4 〇 tablets of sodium hydroxide The reaction was carried out for 15 hours at 45 t, and then the temperature was raised to 70 ° C for 3 〇 minutes. After the completion of the reaction, a solvent such as a surface alcohol was left at 7 (TC) under reduced pressure. The solution was poured into 1500 parts of water to precipitate crystals. After filtration and crystallization, it was washed with 曰 甲醇 methanol, and vacuum-dried 7 times, thereby obtaining 166 parts of epoxy resin! The epoxy equivalent of the resin was 2 〇〇g/eq' 'melting point was determined by DSC to be 1〇8〇c. Synthesis Example 5 Nitrogen flushing was performed on one side of a flask equipped with a sandpaper mixer, a reflux cooling tube, and a mixing device... Surface addition force σ 133 parts of the oxime compound obtained in Synthesis Example 2 2, 925 parts of surface gas alcohol, 139 parts of DMS hydrazine, heated to Μ f under the mixing and dissolution, after 7G minutes of stepwise addition of 4G tablets of sodium hydroxide, 'maintaining price for h5 hours reaction, its (4) After the reaction is completed, the thief is allowed to react for 30 minutes. After the reaction is completed, 800 parts of excess solvent such as surface gas alcohol is sprayed off using a rotary evaporator, and the residue is poured into the water to precipitate crystals. The mixture was washed with _ methanol, and then vacuum dried at 7 〇t, thereby obtaining the epoxy resin 2 of 201105699. The obtained ring entangled β γ γ oxy oxy oxy oxychloride was 220 g / Eq., the melting point was determined to be 1 1 7 °c by DSC. Synthesis Example 6 Nitrogen rinsing was carried out in a flask equipped with a search machine, a reflux cooling tube, and a dropping device, and the phenolation obtained in Synthesis Example 3 was added by σ 153. 3, 925 parts of epichlorohydrin, 139 parts of Dms 〇, heated to 45 c under stirring, and dissolved, after adding 4 ounces of sodium hydroxide in steps of 90 minutes, 'maintain 45 ° C for 1.5 The reaction was carried out for an hour and then the temperature was raised to 70. (: The reaction was carried out for 30 minutes. After the completion of the reaction, 800 parts of excess solvent such as surface gas alcohol was distilled off under reduced pressure using a rotary evaporator at 7 Torr. The residue was poured into 1500 parts of water to precipitate crystals. After filtration and crystallization, it was washed with 6 parts of methanol, and then vacuum dried at 70 ° C, thereby obtaining 99 parts of epoxy resin 3. The epoxy equivalent of the obtained epoxy resin was 219 g/eq. The melting point was determined by DSC to be 145 ° C. Examples 1 to 3 and Comparative Examples 1 to 3 Various components were blended in the proportions (parts) of Table 1, after kneading by a mixing roll and subsequent tableting A resin molded body is prepared by transfer molding. Then, the resin molded body is heated at 160 ° C for 2 hours and further heated at 180 ° C for 8 hours, thereby obtaining the epoxy resin composition of the present invention and The cured product of the resin composition was compared. The results obtained by measuring the thermal conductivity of the cured product are shown in Table 1. 29 201105699 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition of the formulation n, · Epoxy resin 1 100 Epoxy resin 2 100 Epoxy Resin 3 100 100 Epoxy Resin 4 100 100 Hardener 20 18 18 23 18 23 Inorganic Filler 1 274 270 270 281 Inorganic Filler 2 157 154 154 161 Inorganic Filler 3 298 311 Physical Thermal Conductivity of Hardened ( W/mK) 3.9 3.9 4.0 3.5 0.68 0.62 Epoxy Resin 4: A biphenyl type epoxy resin containing an epoxy resin represented by the following formulas (6) and (7), etc. (trade name: YL-6) 12 1H Japan Epoxy Resins manufactures an epoxy equivalent of 175 g/eq.)

Hardener 1:1, 5-naphthalenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., amine equivalent weight 40 g/eq.) Inorganic filler 1: spherical alumina (trade name: DAW-100, electrical and chemical industry, thermal conductivity) 38 W/m_K) Inorganic filler 2: Boron nitride (trade name: SGP Electrochemical Industry, thermal conductivity 60 W/m'K) Inorganic filler 3: Fused cerium oxide (trade name: MSR2212 Longsen 30 201105699 Manufacturing 'thermal conductivity 1.38 W/mK> Example 4 100 parts of the epoxy resin 3 obtained in Synthesis Example 6 was added to 1000 parts of dimethylformamide, and further dissolved at 7 〇〇c. , return to room temperature.

18 parts of 1,5-naphthalenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., having an amine equivalent of 4 〇g/eq) dissolved in 48 parts of dimethyl decylamine at 7 ° C, and returned to the chamber. temperature. The above epoxy resin solution and the hardener solution are mixed and stirred by a homomixer of a stirring airfoil to form a uniform varnish, and further 224 parts (50 parts by volume relative to 100 parts by volume of the resin solid component) are added to the inorganic filler (trade name) The epoxy resin composition of the present invention is prepared by mixing and stirring 100 g of a thermal conductivity of 60 W / m 'K) and 100 parts of dimethylformamide. The varnish of the epoxy resin composition was impregnated with a glass fiber woven fabric (trade name: 7628/AS890AW manufactured by Asahi-Schwebel) having a thickness of 22 mm, and dried to obtain a prepreg. Four sheets of the above prepreg were superposed on the copper foil disposed on both sides thereof, and then heated and pressed at a temperature of 4 MPa for 9 minutes to be integrated, thereby obtaining a thickness of 〇.8峨. Laminated board. The thermal conductivity of the laminated board was measured and found to be "w / ιη · Κ:. Comparative Example 4 The epoxy resin 3 in Example 4 was changed to the amount of the epoxy resin material, and the 1,5-naphthalene was used. A laminate was obtained by the same operation procedure as in Example * except that the amount of the diamine was changed to 23 parts, and the inorganic filler t was changed to 234 parts. The thermal conductivity of the laminate was measured and found to be 31. 201105699 3.6 W/m. K. Example 5 Various components were prepared in the proportions (parts) of Table 2, thoroughly mixed, directly loaded into a mold, and pressure-molded at 175 ° C to thereby prepare a resin molded body. The resin molded body was heated at 160 ° C for 2 hours, and further heated at 18 ° C for 8 hours to obtain a cured product of the epoxy resin composition of the present invention. The thermal conductivity of the cured product was measured. The results are shown in Table 2. Examples 6 to 8 and Comparative Examples 5 to 7 Various components were blended in the proportions (parts) of Table 2, and were formed by transfer molding after kneading by a mixing roll and subsequent tableting. To prepare a resin molded body. Then, the resin molded body was heated at 160 ° C for 2 hours, and further The epoxy resin composition of the present invention and the cured resin composition of the present invention were obtained by heating at 180 ° C for 8 hours. The results of measuring the thermal conductivity of these cured materials are shown in Table 2. Furthermore, Table 2 Epoxy Resin 3, Hardener 1, and Inorganic Fillers 1 and 2 are the same as those in Examples 1 to 3. [Table 2] Example 5 Example 6 Example 7 Example 8 Comparative Example 5 Comparative Example 7 Composition of the formulation - - 100 ring gas wax 3 100 100 ring resin 5 100 100 100 100 Hardening layer 1 15 Hardening layer 2 69 56 Hardening layer 3 47 38 Hardening #1 4 "26 21 Inorganic filler 1 387 357 336 288 316 277 263 Inorganic bismuth material 2 220 203 191 164 180 158 150 Hardening promotion 刽 1 1 1 1 1 1 Physical thermal conductivity of hardened material iW/nrK) 4.2 ΊΤ 3.7 3.7 3.3 3.4 Ί7 32 201105699 Epoxy 5 : Epoxy resin represented by the following formula (8) (trade name NC-3000 Nippon Chemical Co., Ltd. has an epoxy equivalent of 276 g/call)

2: phenol compound 3 obtained by Synthesis Example 3 (hydroxyl equivalent: 153%/eq.) Name: Η·1, Minghe Chemical Co., Ltd. Manufactured having a hydroxyl equivalent of 10 〇5 g/eq) Hardener 3: Formula (9) Phenolic novolac resin shown (commodity

Hardener 4: a catechol novolac resin represented by the following formula (1〇) (hydroxyl equivalent weight: 59 g/eq., softening point i〇4〇c)

Hardening accelerator: Triphenylphosphine (manufactured by Behind Chemical Industry Co., Ltd.) Example 9 100 parts of epoxy resin 5 (NC_3〇〇〇) and 56 parts of the phenol compound 3 obtained in Synthesis Example 3 were dissolved in 1 70 at 70 ° C. After mashing in dimethylformamide, it was returned to room temperature. 33 201105699 One part was dissolved in 48 parts of dimethylformamide at 7 °C and dissolved in 48 parts of dimethylformamide at room temperature. The homogenizer of the stirring airfoil is used to mix and mix the above epoxy resin solution and the hardening accelerator solution to form a uniform varnish, and further 296 parts (relative to the solid content of the resin HM) are added in a volume of 5 parts by volume. An inorganic filler (trade name: manufactured by SGP Electrochemical Industry, thermal conductivity: 6〇w, K), and 100 parts of dimercaptoamine amine are mixed and dropped to prepare the epoxy resin composition of the present invention. . The varnish of the epoxy resin composition was impregnated into a glass fiber woven fabric (trade name: 7628/AS89() AW Asahi_Schwebei) having a thickness of 〇 2 mm, and dried by heating to obtain a prepreg. Four sheets of the above prepreg were overlapped with the copper disposed on both sides thereof, and then subjected to heat and pressure molding at a temperature of 175 t '4 Mpa for 90 minutes to obtain a thickness of 〇·8 mm. Laminated board. The thermal conductivity of the laminate was measured and found to be 4 $ w / m. κ. Comparative Example 8 The 56 parts of the phenol compound 3 in Example 9 was changed to 29 parts of the singular varnish resin represented by the formula (9), and the amount of the inorganic filler was changed to 245 parts, and other examples were carried out. The laminated sheet was obtained in the same operation sequence as in Example 9. The thermal conductivity of the laminate was measured and found to be 3 9 w/m. Comparative Example 9 The 56 parts of the phenol compound 3 in Example 9 was changed to 38 parts of the phthalic phenol varnish resin represented by the formula (1). The amount of the inorganic filler was changed to 262 parts 'other than' to obtain 34 201105699 laminate by the same operation sequence as in Example 9. The thermal conductivity of the laminate was measured and found to be 4 丨 w/m K . Comparative Example 1 _ Resolved to room temperature after dissolving _ part of Epoxy Resin 5 (NC_3000) in 1 part of dimethylformamide. After dissolving 15 parts of M-clayed diamine as a hardener in 48 parts of dimethylformamide at 70 ° C, the mixture was returned to room temperature, and the homogenous mixer of the airfoil was mixed and stirred to dissolve the above epoxy resin solution. The sizing agent is prepared into a uniform varnish, and further 224 parts (50 parts by volume relative to the solid content of the resin) is added to the inorganic filler (trade name: SGp Electric Chemical Industry, thermal conductivity: 60 W/ mK), and 1 part of dimethyl ketone were mixed and mixed to prepare an epoxy resin composition of a comparative example. The laminate was obtained by carrying out the subsequent steps in the same operation sequence as in the embodiment 9. The thermal conductivity of the laminate was measured and found to be 4 4 claws. From the above results, it was confirmed that the cured product of the epoxy resin composition of the present invention has 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 and electronic parts, laminates (printed circuit boards, etc.), and the like. The present invention has been described in detail with reference to the specific embodiments thereof, and various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the invention. Furthermore, 'this application is based on the patent application of the patent application dated December 21, 2009 (Japanese Patent Special Purpose 2〇〇9 2887〇6) and the 2nd June 9th Japanese patents (Japanese Patent Application No. 2009-136455), and the entire contents of which are incorporated by reference. In addition, all references cited herein are incorporated herein by reference. r Zhao and so on in electrical, electronic • Cheng:: material:: sealing materials are extremely useful. "A wide range of agents, optical materials, etc. [Simple description of the diagram] None [Main component symbol description] None 36

Claims (1)

201105699 VII. Patent application scope: 1. An epoxy resin composition containing the following components: (a') epoxy resin; (b) as a hardener by the following formulas (1) to (5) The phenolic compound obtained by reacting one or more kinds with hydroxybenzaldehyde is shown, 0 of 0 Ri (in the formula (1), 1^ are independently present, and represent a hydrogen atom, a substituted or unsubstituted alkyl group of 〜1 〇, an aromatic group having a carbon number of 6 to k, or an unsubstituted aryl group. Any one of a substituted or unsubstituted alkoxy group having a carbon number of 1 to 1; a substituted 不 之 不 不 不 不 丨 2 2 2 (2) R2xV2 Η Η Η Η (In the formula (2), R2 is independently present, 矣_ a non-hydrogen atom of -20 or a substituted or unsubstituted alkyl group, a 峻 number, a carbon number or an unsubstituted The aromatic group and the carbon number of 1~ls '~10 are substituted by the alkylcarbonyl group of the substituted earth, the quinone carbonyl group, the carbon number is 2~~未爱37 201105699 Substituted alkyl ester group, carbon number is 1 oxy, phthalimido, hydrazine 〜10 of the substituted or unsubstituted alkane to any of the lysine base or the hydroxyl group), (3) (in the formula (3), 'R3 is independently present, indicating that the hydrogen material has a carbon number of 〇~10 a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkyl group having a carbon number of 丨~1〇, a substituted or unsubstituted aromatic group having a carbon number of 6 to 1 Å, and a carbon number Is a substituted or unsubstituted alkyl ester group of 2 to fluorene, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or a hydroxyl group; η represents a carbon number, and represents Any one of 〇, 丨, 2, 1 m represents the number of R3, and satisfies the relationship of 〇smsn+2), Η Ο 〇 (4) (In the formula (4), the ruler 4 has independently a substituted or unsubstituted alkyl group of -20, a substituted or unsubstituted aryl group having a carbon number of 6 to 〇, and a carbon number of Any one of 1 to 10 substituted or unsubstituted alkoxy or hydroxyl groups), 38 201105699 (In the formula (5), 1 is independently present, and represents an atom, a substituted or unsubstituted alkyl group of carbon -20, a salicy or unsubstituted aryl group having a carbon number of 6 to 1 Å, carbon Any one of the substituted or unsubstituted alkoxy groups or hydroxyl groups of the number of (1); in addition, 4 (1); and ' (0) an inorganic filler having a thermal conductivity of 20 W/mK or more. An epoxy resin composition comprising the following components: (a) an epoxy resin obtained by reacting a phenolic compound of the first application of the patent range with epithrohydrin, (b' a hardener; and (〇) an inorganic filler having a thermal conductivity of 20 W/m or more. 3. The % oxygen resin composition' is composed of the following components: (a) The ring of claim 2 (b) a compound of the first paragraph of the patent application scope; and (c) an inorganic filler having a thermal conductivity of 20 w/mK or more. 4 'As claimed in any of claims 1 to 3 of the patent scope The epoxy resin composition of the item 'is used for semiconductor sealing purposes. 5, - a type of prepreg, which is claimed in any one of claims 1 to 3. The epoxy resin composition and the sheet-like fibrous base material are composed of the epoxy resin composition of the prepreg hardened epoxy resin according to any one of claims 1 to 4 of claim 31. The object or the scope of the patent application is made. VIII. Schema: No 40