TW201206894A - Diepoxy compound, process for preparation thereof, and compositions that contain the diepoxy compound - Google Patents

Abstract

A diepoxy compound represented by formula (1) [wherein R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom or C1-3 alkyl].

Description

201206894 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a diepoxy compound, a process for producing the same, and a composition containing the same. [Prior Art]

In Macromol. Chem. Phys. 1994, 195, 2307, the formula (A) is described:

A diepoxy compound (melting point: 24 ° C). J. Polym. Sci. Part A. Polym. Chem, 1 999, 3 7 ’ 419, recorded in equation (B):

A bis(epoxy compound) (melting point: 187 ° C). SUMMARY OF THE INVENTION The present invention provides [1] a diepoxide compound characterized by the formula (1)

R4 R. 201206894 (wherein R1, R2, R3 'R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); [2] a epoxide compound such as [1] , wherein the diepoxy compound represented by the formula (1) is a formula (Γ): R2, and a household 1.

R4 R5 (wherein R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); [3] as in [1] or [2] a diepoxide compound, wherein R1, R2, R3, R4, R5 and R6 are a hydrogen atom; [4] a compound of the formula (1): <, Rl〇

>=< R6 R4 R5 (wherein Ri, R2, r3, R4, 5 and 6 represent the same meaning as described above), and a method for producing a diepoxide compound, which is characterized by being contained in an inorganic base In the presence of the equation (2): R? R1

R4 R5 (wherein, R1, R2, R3, R4, 115 and R6 independently represent a hydrogen atom or 201206894 is a nominee of carbon number 1 to 3) represents a di-based compound and formula (3):

(In the formula, X1 represents a halogen atom) a reaction step of reacting an epihalohydrin; [5] The production method according to [4], wherein the dihydroxy compound represented by the formula (2) and the formula (3) are represented The reaction of the halohydrin is carried out in the presence of an inorganic test and a quaternary ammonium salt; [6] The process according to [5], wherein the dihydroxy compound represented by the formula (2) and the epihalohydrin represented by the formula (3) are used. The step of reacting comprises the following steps (i) and (Π): Step (i): a step, a step of mixing the dihydroxy compound represented by the formula (2) with the epihalohydrin and the quaternary ammonium salt represented by the formula (3) And (ii) a method of producing a mixture of the mixture of the steps (i) and the inorganic test. The method of any one of [4] to [6] wherein the inorganic base is an alkali metal hydroxide; The method of any one of [4] to [7] wherein R|, R2, R3, R4, R5 and R6 are a hydrogen atom; [9] a dihydroxy compound characterized by the formula (2):

R4 R5 (wherein, R1, R2, R3, R4, R5 and R0 each independently represent a hydrogen atom or 201206894 is an alkyl group having 1 to 3 carbon atoms) J袠不; [] a dihydroxy compound such as [9] The dihydroxy compound represented by the formula (2) is represented by the formula (2,):

°Ό, ',···〇-〇Η (2,) R and R each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). [11] The dihydroxy compound of [9] or [1] wherein r1, r2, R3, R4, R5 and R6 are a hydrogen atom. [12] One is to use equation (2):

(Expression in the formula) A method for producing a di-based compound, which is characterized by being contained in an acid

(wherein, R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) and a hydroxynaphthoic acid compound represented by the formula (?) -8 - 201206894

OH (7) represents a step of 4-hydroxy-1_(4-diphenyl)cyclohexyl reaction; [13] The production method of [12], wherein Ri'R2, ! ^3, :^4, R5 and R6 are a hydrogen atom; [I4] a composition characterized by containing the formula (1):

(wherein, R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) a diepoxide compound and a hardener; [15] as in [14] a composition, wherein R1, R2, R3, R4, R5 and R6 are a gas atom; [16] a composition according to [14] or [15], wherein the hardener is selected from the group consisting of an amine hardener, a phenol hardener and The hardener of at least one of the group of the anhydride hardeners: [17] the composition of [16], wherein the hardener is an amine hardener; [18] the composition of [17], wherein the amine hardens The agent is one selected from the group consisting of 4,4'-diamine diphenylmethane, 4,4'-diamine diphenylethane, 1,5-diamine naphthalene and p-phenylenediamine; [19] The composition of any one of [14] to [18], wherein the ruthenium contains alumina; -9-201206894 [20] the composition of [19], which contains two relative to formula (1) The oxidized salt is 75 parts by weight to 95 parts by weight, and the composition of [19] or [20], wherein the alumina is D50 (for the total of 100 parts by weight of the epoxy compound and the hardener and the alumina). Cumulative body 50% of the particle size) is an alumina crucible having a size of 2 μm or more and 1 μm or less, and an alumina crucible having a D50 of Ιμηι or more and ημηι or less and a mixture of alumina C having a D50 of Ο.ΟΙμπι or more and 5 μmη or less, and each of the alumina accounts for The ratio of the alumina crucible to the total of the alumina crucible and the alumina C is 1% by volume, the alumina A is 50 to 90% by volume, the alumina B is 5 to 40% by volume, and the alumina C is 1 to 1. [22] A cured product obtained by hardening a composition according to any one of [14] to [21]; [23] a prepreg characterized in that The composition according to any one of [14] to [21] is obtained by coating or immersing in a substrate, and then semi-hardening is carried out, [24] a cured product which is hardened as [19]~[2 The cured product obtained by the composition according to any one of the preceding claims, wherein the cured product contains alumina in a proportion of 50 to 80% by volume. BEST MODE FOR CARRYING OUT THE INVENTION The diepoxide compound of the present invention is of the formula (1):

R4 R5 -10- 201206894 (hereinafter, abbreviated as a diepoxy compound (1)) ° In the formula (1), r1, R2, R3, R4, R5 and R6 independently represent a hydrogen atom or a carbon number of 1 ~3 alkyl. The base of the carbon number of 1 to 3 is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and a methyl group is preferred. R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom or a methyl group, and R1, R2, R3, R4, r5 and R6 are preferably a hydrogen atom. The diepoxy compound (1) is of the formula ’1'): R 0

R4 R (wherein, R1, R2 'R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) is preferably a stereoisomer. The diepoxy compound (1) is, for example, the formula (la) of the diepoxy compound (1) in which R1, r2, R3, R4, R5 and R6 are hydrogen atoms:

4-(4-(2,3-epoxypropoxy)phenyl)cyclohexyl=6-(2,3-epoxypropoxy)-2-naphthoate, Ia:

Stereo isomer (trans-4-(4-(2,3-epoxypropoxy)phenyl)cyclohexyl=6-(2,3-epoxypropoxy)-2-naphthalene Formate) is preferred. The melting point of the diepoxy compound (1) is lower than the melting point of the diepoxide compound represented by the above formula (A) or formula (b-11 - 201206894), so that the diepoxide compound can be melt-mixed at a lower temperature (1) ) It is hardened with a hardener and can be processed at low temperatures. The diepoxy compound (1) is present in the presence of an inorganic base and can be made by the formula (2):

R4 R5 (wherein, Ri, R2, r3, R4, and the same meaning as defined above) are represented by a base compound (hereinafter, abbreviated as compound (2)) and

(In the formula, X1 represents a halogen atom) The process of the reaction of an epihalohydrin (hereinafter referred to as epihalohydrin (3)) (hereinafter referred to as "step (I)) is produced. Compound (2) is of the formula (2 ’):

(In the formula, R1, R2, R3, R4, R5 and R6 are the same as defined above.) The stereoisomer is preferably represented. -12- 201206894 The best compound (2) is, for example, given by formula (2a):

〇H (2a) represents 4-(4-hydroxyphenyl)cyclohexyl=6-hydroxy-2-naphthoate, and formula (2a’):

The stereoisomer (trans-4-(4-hydroxyphenyl)cyclohexyl=6-hydroxy-2-naphthoate) is preferred. In the epihalohydrin (3), X1 is represented by a halogen atom, and a halogen atom is, for example, a chlorine atom and a bromine atom, and a chlorine atom is preferred. The epihalohydrin (3) is, for example, epichlorohydrin and epoxyindicarb, and epichlorohydrin is preferred. Two or more epihalohydrin (3) may be used in combination. The amount of the paradentol (3) used is generally 2 to 200 moles, preferably 5 to 150 moles, per mole of the compound (2). The inorganic base is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; and an alkali metal hydride such as sodium hydride or potassium hydride; The hydroxide is preferred, and sodium hydroxide and potassium hydroxide are preferred. It can be used in combination of two or more inorganic bases. The amount of the inorganic base to be used is usually 0.1 to 20 moles, preferably 0.5 to 10 moles, per mole of the compound (2). An inorganic base in the form of a solid such as a granule may be used. An alkali metal-13-201206894 hydroxide, an alkali metal carbonate or the like is used to stabilize the water in an aqueous solution having a concentration of about 1 to 60% by weight. The reaction of the compound (2) with the epihalohydrin (3) is preferably carried out in the presence of a quaternary ammonium salt. Here, the cranial finger includes an anion such as a chloride ion or a compound ion contained in a quaternary ammonium salt in which four hydrocarbon groups are bonded to a nitrogen atom. The inorganic base alkali metal hydroxide and the alkali metal carbon quaternary ammonium salt in the presence of the quaternary ammonium salt are, for example, tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, Benzyltriethyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, tetraethylammonium iodide, Tetrabutylammonium iodide, a quaternary ammonium halide such as a quaternary ammonium salt, a quaternary ammonium bromide is preferred, and benzyltrimethylammonium bromide is preferred. Two or more quaternary ammonium salts may be used in combination. The quaternary ammonium salt is used in the presence of a compound (2: 0.0001 to 1 mol, 0.001 to 0.5 mol, preferably the reaction of the compound (2) with epihalohydrin (3) or in the presence of a solvent. The solvent is, for example, propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, 3-pentanol, 2-hexanol, 3-hexanol '2-heptanol, 4 - decyl alcohol, 2-dodecanol, 3-methyl-2-butanol, alcohol, 3-methyl-2-pentanol, 5-methyl-2-hexanol, 4-alkali, In addition to the inorganic base, the salt of the quaternary ammonium salt is intended to be a salt of the quaternary ammonium salt, and the bromide ion and iodine are preferably subjected to the reaction acid salt. Ammonium chloride, tetrabutylammonium chloride, benzyl ammonium chloride , tetrabutylammonium bromide, tetramethyl iodide, tributylammonium iodide, tetrabutylammonium bromide and 1 mole, one can be used without solvent for methanol, ethanol, 1-, propylene glycol, 2 -penta-3-heptanol, 2-octanol 3,3-dimethyl-2-butyl-3-heptanol'2- 14- 201206894 methyl-2-propanol, 2-methyl-2-butanol , 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl Glycol-3-pentanol Alcohol solvent such as 3-ethyl-2,2-dimethyl-3-pentanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, methyl ethyl ketone , a ketone solvent such as methyl isobutyl ketone, N,N-dimethylformamide, ν, ν-dimethylacetamide, n-methylpyrrolidone, acetyl chloride, benzonitrile, dimethyl An inert polar solvent for a proton such as a chia code, and a diethyl ether 'ter t-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, anisole, etc. Ether solvent. Two or more solvents can be used in combination. When the reaction is carried out in the presence of a solvent, the solvent is used in an amount of usually 0.01 to 100 parts by weight, preferably 1 to 50 parts by weight, per part by weight of the compound (2). The reaction of the compound (2) with the epihalohydrin (3) can be carried out under normal pressure or under pressurized conditions or under reduced pressure. The reaction can be carried out under an inert atmosphere of nitrogen or argon. The reaction of the compound (2) with the epihalohydrin (3) is generally carried out by mixing the compound (2), the epihalohydrin (3), an inorganic base, and, if necessary, a quaternary ammonium salt and a solvent. The reaction temperature is generally -2 0 ° C to 150 ° C, -1 0 t to 1 2 0. (: The progress of the reaction can be confirmed by analyzing the amount of the compound (2) or the amount of the diepoxide compound (1) by a general analysis method such as liquid chromatography, until the second ring cannot be confirmed. It is preferred to carry out the reaction until the amount of the oxygen compound (1) is increased. The reaction time is usually from 1 to 15 〇 small -15 to 201206894. The step (I) contains the following steps (i) and (ii). Step (i): Step (ii) of mixing compound (2) with epihalohydrin (3) and quaternary ammonium salt: mixing the mixture obtained in step (i) with an inorganic base. Step (i) It can be carried out under normal pressure conditions or under pressurized conditions or under reduced pressure. Step (i) can be carried out under an inert atmosphere such as nitrogen and argon. Step (i) The reaction temperature is generally -1 0 ° C to 150 ° C, preferably 0 ° C to 120 ° C. The reaction time of step (i ) varies depending on the reaction temperature, but is generally 0.5 to 7 2 hours. The reaction mixture obtained in the step (i) may contain a diepoxy compound (1). Step (ii) It can be carried out under normal pressure conditions under pressure or under reduced pressure. Step (ii) can be carried out under an inert atmosphere such as nitrogen and argon. The reaction temperature of step (ii) The system is generally - 20 ° C to 12 (TC, -l ° ° C ~ 80 ° C is preferred. Step (ii) is until it is not possible to confirm the increase in the amount of formation of the diepoxide (1) is better Depending on the reaction temperature, the reaction time is generally 0.5 to 72 hours. After the end of step (ii), for example, the reaction mixture is mixed with water, and the solvent which is insoluble in water at the time of the period of 16.6 to 201206894 The liquid is obtained to obtain an organic layer containing the diepoxy compound (1). After the obtained organic layer is washed with, for example, water, the insoluble matter is removed by filtration if necessary, and the epoxy compound can be recovered by concentration. (1) The recovered diepoxy compound (1) can be further purified by a general purification method such as recrystallization. The insoluble solvent in water is, for example, dichloromethane, chloroform, chlorobenzene or dichlorobenzene. Halogenated hydrocarbon solvent, ethyl acetate, B An ester solvent such as butyl ester, an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene or mesitylene; and a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone. The amount of the diepoxy compound (1) is usually from 1 to 300 parts by weight, preferably from 10 to 200 parts by weight, based on 1 part by weight of the diepoxy compound (1). The diepoxy compound (1) is a compound (2) in the presence of a salt group. A compound represented by the formula (4) (wherein X2 is represented by a halogen atom) (hereinafter, abbreviated as the compound (4)) is reacted to obtain a formula (5) R; R1.

A compound represented by R4 R5 (wherein R1, R2, R3, R4, R5 and R6 are the same as defined above) (hereinafter, abbreviated as compound (5)), a compound obtained by containing -17-201206894 (5) It can also be produced by the method of the step of oxidizing the oxidizing agent. In the compound (4), X2 represents a halogen atom, and a halogen atom is, for example, a chlorine atom and a bromine atom. The compound (4) is, for example, allyl chloride and allyl bromide. Two or more compounds (4) may be used in combination. The compound (4) is used in an amount of usually 2 to 200 moles, preferably 2 to 100 moles, per mole of the compound (2). The salt base may be an inorganic base or may be an organic salt base, and the inorganic base is preferably an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, and sodium carbonate or potassium carbonate. Alkali metal carbonate. An organic salt base such as pyridine. Among them, an alkali metal carbonate is preferred, and sodium carbonate and potassium carbonate are preferred. It is also possible to use two or more kinds of base groups in combination. When an inorganic base is used, it is used in an amount of usually 2 to 10 moles based on 1 mole of the compound (2). When an organic salt group is used, it is used in an amount of usually 2 mol or more relative to the compound (2) 1 mol. When the organic salt group of the liquid is used under the reaction conditions, a large excess of the organic salt group serving as a solvent can be used. The reaction of the compound (2) with the compound (4) is preferably carried out in a solvent. The solvent is, for example, the same as the solvent used for the reaction of the above compound (2) with the epihalohydrin (3). Further, as described above, when an organic salt group of a liquid under the reaction conditions is used, the organic salt group can be used as a solvent. -18 - 201206894 The reaction of the compound (2) with the compound (4) is generally carried out by mixing into the compound (2), the compound (4), a salt group and, if necessary, a solvent, but the order of mixing is not limited. The reaction system may be carried out under normal pressure or under pressure, or may be carried out under reduced pressure. Further, the reaction can be carried out under an inert gas atmosphere such as nitrogen gas or argon gas. The reaction temperature is generally -20 ° C to 120 ° C, and -10 ° C to 1 〇 (TC is preferred. The progress of the reaction can be confirmed by a general analytical method such as liquid chromatography until the compound cannot be confirmed (5) It is preferred to carry out the reaction until the amount of production is increased. The reaction mixture containing the obtained compound (5) is usually directly or after being washed with water, and mixed with an oxidizing agent to carry out a reaction between the compound (5) and an oxidizing agent. An oxidizing agent for converting a carbon-carbon double bond into an epoxy group, specifically, a peracid such as m-chloroperoxybenzoic acid, etc. The oxidizing agent is used in an amount relative to the compound (5) 1 mol. Generally, it is 2 to 20 moles. The reaction of the compound (5) with an oxidizing agent can be carried out under normal pressure conditions or under pressure, or under reduced pressure. It can be used in nitrogen and argon. The reaction is carried out in an inert gas atmosphere, and the reaction temperature is usually -2 0 ° C to 120 ° C, preferably -10 ° C to 100 ° C. The reaction can be carried out by a general analysis such as liquid chromatography. Method confirmed until the epoxy compound could not be confirmed (Ο The reaction is preferably carried out until the amount of the reaction is increased. The reaction time is usually from 5 to 72 hours. After completion of the reaction, the diepoxy compound (1) can be recovered by, for example, concentrating the reaction mixture. The residual oxidizing agent -19-201206894 is decomposed and then concentrated. The recovered diepoxy compound (1) can be further purified by a general purification method such as recrystallization. The compound (2) is in the presence of an acid. By making equation (6):

(wherein, R1, R2, R3, R4, R5 and R6 represent the same meaning as described above) a hydroxynaphthoic acid compound (hereinafter, abbreviated as hydroxynaphthoic acid (6)

It can be produced by reacting 4-hydroxy-1-(4-hydroxyphenyl)cyclohexane (hereinafter, abbreviated as cyclohexane (7)). Hydroxynaphthoic acid (6) is, for example, 6-hydroxy-2-naphthoic acid. Cyclohexane (7) is a trans form represented by formula (7'): OH (7') h〇-〇... (trans-4-hydroxy-1-(4-hydroxyphenyl)cyclohexyl) It is better. The amount of cyclohexyl (7) used is relative to that of p-naphthoic acid (6) 1 mol. Generally, it is 1 to 30 moles, and 1 to 15 moles is preferably an acid such as sulfuric acid and P-toluenesulfonic acid. The amount used is generally 0.00 to 2 or more acids relative to the base -20-201206894 naphthoic acid (6) 1 mole. Preferably, the hydroxynaphthoic acid (6) and cyclohexane (7) are carried out. The solvent is, for example, a hexane, a heptane hydrocarbon solvent, or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene or dichlorobenzene. The solvent hydroxynaphthoic acid (6) is preferably 焉100 parts by weight, based on 1 part by weight. In general, hydroxynaphthoic acid (6) is mixed with cyclohexane i by mixing hydroxynaphthoic acid (6) and cyclohexane (7), and the order of mixing is not limited. The reaction system may be carried out under pressurized conditions, or may be in an inert atmosphere such as nitrogen and argon; the reaction temperature is generally 50 to 2 50 ° C, 60, and the time is based on the reaction. The difference in temperature is generally the progress of the hydrazine reaction to form water, but it is preferred to carry out the reaction while removing the generated water by the generated water. After completion of the reaction, the crystal of the compound (2) can be recovered by, for example, obtaining the reverse. Next, a description will be given of a compound containing a diepoxy compound (hereinafter referred to as a composition X). The composition X may contain two or more kinds of bicyclone, and the composition X may contain two or more kinds of curing agents. The composition X is in addition to the diepoxy compound (1) - 0.3 mol. The combinable reaction is in the presence of a solvent, an aliphatic benzene such as octane, a mesitylene, and a chlorine are used in an amount of 1 to 200 by weight. The reaction of 5 parts, 5:7) is carried out by using an acid and, if necessary, a solvent under reduced pressure under normal pressure. Minhang. -20 (TC is preferred. Reaction. 5 to 7 2 hours. Along with the removal of the reaction system, the mixture is filtered) and the composition of the hardener 1 compound (1). In addition to the hardener, it can be contained in -21 - 201206894. It is easy to prepare, and the composition is preferably a solvent. The solvent is a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, N, N-dimethylformamide, dimethyl amide. Examples include an inert polar solvent such as an inert polar solvent such as N-methylpyrrolidone or a butyl acetate, and an alcohol solvent such as propylene glycol monomethyl ether. The ketone solvent and an inert polar solvent for protons are oxime, methyl. Isobutyl ketone and N,N-dimethylformamide are preferred. Even if the solvent is removed by a solution obtained by dissolving the diepoxy compound (1) of the present invention and a hardener in a solvent, there is a tendency to obtain a uniform mixture. Further, even if the solvent is removed by mixing the mixture of the diepoxy compound (1) and the curing agent with alumina and a solvent described later, there is a tendency to obtain a uniform mixture. The hardener may have at least one functional group which can undergo a hardening reaction with the epoxy group in the diepoxy compound (1), or may exhibit a catalytic action in the hardening reaction of the diepoxy compound (1). Specifically, for example, the functional group is an amine-based amine curing agent, the functional group is a hydroxyl group-based phenol curing agent, and the functional group is an acid anhydride curing agent represented by -C0-0-C0- and a curing catalyst. An amine hardener, a phenol hardener and a hardening catalyst are preferred, and an amine hardener is preferred. The amine hardener is a carbon number of 2 to 2 such as ethylenediamine, trimethylamine, tetramethylammonium, hexamethylenediamine, diethylidenetriamine, and triamethylenetetramine. 0 aliphatic polyvalent amine, p-xylene diamine, m-xylene diamine, 1,5-diamino naphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diamine diphenylmethane , 4,4'-diylamine diphenylethane, 4,4,-diaminodiphenylpropane, 4,4,-diamine diphenyl ether, 1,1 bis (4-amino group Phenyl)cyclohexane, -22- 201206894 4,4'-diaminodiphenylanthracene, aromatic polyvalent amine such as bis("aminophenyl"phenylmethane, 4,4,-diamine An alicyclic polyvalent amine such as dicyclohexane, i,3-bis(aminomethyl)cyclohexane, or dicyanodiamine, wherein an aromatic polyvalent amine and dicyanodiamine The base is preferably 4,4,-diaminodiphenylmethane '4,4'-diamine diphenylethane' oxime, 5·diaminonaphthalene, p-phenylenediamine and dicyandiamide Preferably, the phenolic hardener is, for example, a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenyl structure, etc.), a naphthol aralkyl resin, and a poly Styrene resin. Phenolic resin is a resol type phenol resin such as aniline modified resol resin, dimethyl ether resol resin, phenol novolac resin, cresol aldehyde varnish resin, and third butyl phenol. A phenolic varnish type phenol resin such as a novolac resin or a nonylphenol novolak resin, and a special phenol resin such as a dicyclopentadiene-modified phenol resin, a modified phenol resin, and a trisphenol methane epoxy resin. The styrene resin is, for example, poly(p-oxystyrene). The acid anhydride hardener is, for example, maleic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, cis-4 -cyclohexene-1, 2 -Dicarboxylic anhydride and 5-(2,5-dioxotetrahydrofuranyl)_3_methyl-3_cyclohexene-12-dicarboxylic anhydride oxime-hardening catalyst such as 2-methylimidazole, 2-ethyl -4-methylimidazole, 2-heptadecylimidazole and benzyldimethylamine. The amount of the hardener used may be appropriately selected depending on the type thereof. When an amine hardener and a phenol hardener are used, the hardener is used. The total number of moles of the functional group which can be obtained by hardening the epoxy group with respect to the bicyclic oxidation (1) In the case of the epoxy group 1 Mo, it is preferred to use a hardener of 〇.5 to 1.5 mol, 0.9 to 1.1 -23-201206894. The composition X is in addition to the diepoxide compound (η). In addition to the hardener and the solvent, it may contain other properties as long as it does not cause a decrease in properties (for example, solubility, heat resistance, thermal conductivity, etc.) required for the cured product obtained by curing the composition X. Compounds having other epoxy groups, such as bisphenol oxime epoxy compounds, o-cresol epoxy compounds, bisphenol diglycidyl ether, 4,4'-bis (3,4) - epoxybuten-1-yloxy)phenyl benzoate, naphthalene diglycidyl ether and alpha-methylheptaphthalene-4,4'-diglycidyl ether. Further, the composition X may contain various additives in addition to the diepoxy compound (1), the curing agent, and the solvent. The additive is a hardening accelerator such as triphenylphosphine, 1,8-azabicyclo[5.4.0]-7-undecene, 2-phenylimidazole or the like; r-glycidoxypropyltrimethoxy a coupling agent such as decane or the like; a coloring agent such as carbon black; a low stress component such as a fluorene oil or a cerium rubber; a releasing agent for a natural wax, a synthetic hydrazine, a higher fatty acid or a metal salt thereof, a paraffin wax or the like; an antioxidant; Melt-crushed cerium oxide powder, molten spherical cerium oxide powder, crystalline cerium oxide powder, secondary condensed cerium oxide powder, etc.; α-alumina or transitional alumina (r-alumina, 0) - Alumina, 5-aluminum oxide, etc.; titanium dioxide: aluminum hydroxide; talc; clay; mica; and glass fiber. The composition X may contain an additive which does not cause a decrease in the desired properties (for example, a melting point, etc.) of the cured product obtained by hardening the composition X, and the composition X is cured by the composition X. From the viewpoint of the thermal conductivity of the cured product -24 to 201206894, it is preferred to contain alumina. The composition lanthanum is preferably a composition containing a diepoxy compound (1), a hardener, and alumina, and it is preferable that the composition X contains a solvent as described above in view of ease of preparation. When the composition X contains alumina, the content of the alumina is generally 75 parts by weight to 95 parts by weight of the 83 parts by weight based on 100 parts by weight of the total of the diepoxy compound (1) and the hardener and alumina. Preferably, parts to 90 parts by weight are preferred. The composition containing 75 parts by weight or more of the aluminum oxide compound (1) and the total amount of the hardener and the aluminum oxide is increased by the hardening of the composition. The thermal conductivity of the cured product tends to be 95 parts by weight or less, and the composition tends to be easily formed. Alumina-based granular alumina is preferable, and when the particle diameter of the cumulative volume of the fine particle side of the weight-accumulated particle size distribution is 50% (the average particle diameter measured by the laser diffraction method) is D50, D50 is 2 μm or more and ΙΟΟμιη The following aluminas A and D50 are preferably alumina having a thickness of Ιμπι or more and ΙΟμιη or less and alumina having a mixture of D50 of 氧化铝.ΟΙμηη and 5 μm or less of alumina C. Further, each alumina accounts for 100% by volume of the total of alumina crucible and alumina crucible and alumina C, alumina A is 50 to 90% by volume, alumina B is 5 to 40% by volume, and alumina C is 1 ~30% by volume is preferred. Such an alumina system can be prepared by appropriately mixing and modulating alumina having various average particle diameters which are commercially available. Further, the content ratio of the alumina contained in the cured product is preferably from 50 to 80% by volume, more preferably from 60 to 74% by volume, based on 100% by volume of the cured product. A method of hardening a composition obtained by hardening a crucible to heat a composition X to a specific temperature; heating and melting to inject into a mold, further adding the mold; melting the composition X, and melting the resultant a method of hardening an object into a mold; partially hardening the composition X, pulverizing the compound, filling the obtained powder into a mold, and melting the final product; and dissolving the composition X in a necessary manner The mixture is partially hardened, the solution obtained by casting is dried, and the like, and the solvent is removed, and if necessary, a specific time is applied by a press. Further, if necessary, the composition X is diluted with a solvent, and after coating the substrate, the obtained substrate is heated, and the substrate compound (1) is semi-cured to produce a prepreg. The prepreg of the layer can be used for pressing and heating by a press or the like, and can be used for the substrate of the prepreg such as woven or non-woven fabric of glass fiber, carbon fiber, or organic matter such as polyester or It is not woven. The cured product obtained by hardening the composition X is heat-transferred. The hardenability obtained by hardening the composition X containing alumina is more excellent. [Embodiment] The method is, for example, a method in which a portion of a mold obtained by heat-forming a preheated portion of the composition X is hardened, and the plurality of layers are heated by a drying or immersing in a solvent. The fiber-free woven fabric of the laminated board fiber or the like is excellent in the conductivity of the material. -26-201206894 EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. [Reference Example 1]

In a reaction vessel equipped with a distillation apparatus, 7.0 g of 6-hydroxy-2-naphthoic acid and trans-4-hydroxy-1-(4-hydroxyphenyl)cyclohexane were added at room temperature (about 25 ° C). L〇.〇g, p-toluenesulfonate 〇.71g and xylene 80g. The resulting mixture was stirred under reflux for 7 hours and 30 minutes. At this time, the water which is generated along with the reaction is removed from the reaction vessel by the distillation apparatus, and the water which is generated in response to the reaction is removed. The resulting reaction mixture was cooled to room temperature. The solid which precipitated was filtered, and the solid was washed with methanol (200 mL), and then dried under reduced pressure for 5 hours to obtain a compound represented by the formula (2-1) (hereinafter, abbreviated as the compound (2-1)). White crystals 2.79 g. The crystal was analyzed by liquid chromatography, and the area percentage of the peak of the compound (2-1) equivalent to the chromatograph was calculated to be 96.9%. The content of the compound (2-1) in the crystal was assumed to be 96.9 wt%, and the yield of the compound (2-1) based on 6-hydroxy-2-naphthoic acid was 20%. W-NMR spectroscopy data (5: ppm, dimethyl subcode-d6) -27- 201206894 10.18 ( s, lH) , 9.14 ( s, lH) , 8_47 ( s, lH) , 7.98 ( d, lH) , 7.86(d,lH) - 7.76 ( d, 1H ) - 7.16 ( m,2H ) > 7.03 ( d,2H ) > 6.67 ( d,2H ) > 4.95 ( m, 1 H ) > 1.23-2.55 (c, 9H) [Example 1]

In the reaction vessel equipped with the cooling device, 1.50 g of the compound (2-1) obtained in the above [Reference Example 1], tetrabutylammonium bromide ruthenium ruthenium 68 g > epichlorohydrin 16 g and 2- were added at room temperature. Methyl-2-propanol 10.4 g. After the resulting mixture was stirred at 70 ° C for 6 hours, 0.34 g of tetrabutylammonium bromide was added, followed by stirring for 8 hours. After the resulting mixture was cooled to 13 ° C, 3.50 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at 13 ° C for 2 hours and then cooled to 〇 ° C. To the obtained reaction mixture, 25 mL of ion-exchanged water was added, and 75 mL of chloroform was further added thereto at room temperature, followed by liquid separation. After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to give a crude product. To the obtained crude product, toluene and 2-propanol were added. The resulting mixture was warmed to 70 ° C, stirred at the same temperature for 1 hour, cooled to room temperature, and allowed to stand overnight at -28-201206894. The precipitated solid was recovered by filtration of solid, washed with 2-propanol and dried to give white crystals (yield: 2.21. To the obtained crystals, toluene and 2-propanol were added. The resulting mixture was warmed to 70 ° C, stirred at the same temperature for 1 hour, cooled to room temperature, and allowed to stand overnight. The precipitated solid is recovered by filtration, washed with 2-propanol, and dried to obtain a diepoxy compound represented by the formula (i-1) (hereinafter, abbreviated as a diepoxy compound (1_1)). White crystals 1.1 6 g. The crystal was analyzed by liquid chromatography, and the area percentage of the peak corresponding to the diepoxy compound (1-1) of the obtained chromatograph was calculated to be 91.8%. When the content of the diepoxy compound (1-1) in the crystal is assumed to be 9 1 - 8 wt%, the yield of the diepoxy compound (1-1) based on the compound (2 _ 1 ) is 55%. The temperature of 162 ° C. h-NMR spectral data ((5 _· ppm, CDCh) 8.53 ( s,lH ) > 8.05 ( dd, 1Η ) , 7.87 ( d,lH) , 7.75 (

d,lH) > 7.07-7.3 5 ( c,4H ) ,6.88 ( d,2H) > 5.09 ( m, 1H ), 4.39 ( dd,lH) , 4.20 ( dd,lH) ' 4.08 ( m,lH ), 3.96 ( m, 1 H ) « 3.44 ( m,lH ) , 3.35 ( m,lH ) ,2.89-3.01 (c,2H) ' 2.70-2.88 ( c,2H ) ,2.55 ( m,lH) > 2.18-2.38 (c,2H) ' 1-89-2.12 (c,2H) , 1.50-1.82 ( c,4H) [Example 2] -29- 201206894 ο

(1-1) In a reaction vessel equipped with a cooling device, 15.0 g of the compound (2-1), 4.0 g of tetrabutylammonium bromide, and I53 g of epihalohydrin were added at room temperature. Further, when the compound (2-1) is analyzed by liquid chromatography, and the area percentage of the peak corresponding to the compound (2-1) of the obtained chromatograph is calculated to be 96.8%, the content of the compound (2-1) to be used is determined. The amount is assumed to be 96.8 wt%. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to 18 t. To the obtained mixture, 3 3 · 1 g of a 15 % by weight aqueous sodium hydroxide solution was slowly added. After the resulting mixture was stirred at 18 ° C for 4 hours, it was cooled to 0 ° C to give a reaction mixture, and 25 mL of ion-exchanged water was added thereto, and 75 mL of chloroform was added thereto at room temperature, followed by liquid separation. After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to give 23.4 g of crude product [1]. Into a reaction vessel equipped with a cooling device, 22.3 g of a crude product [1], 4.0 g of tetrabutylammonium bromide, 644 g of chloroform and 175 g of 2-methyl-2-propanol were added at room temperature. After the resulting mixture was cooled to 18 ° C, 30.9 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at 18 ° C for 2 hours and then cooled to 〇 ° C. To the obtained mixture, after adding 8 mL of ion-exchanged water, it was subjected to a solution of -30-201206894. The obtained organic layer was washed three times with ion-exchanged water, and then removed by filtration. The obtained filtrate was concentrated to give a crude product. To the obtained crude product [2], toluene and 2-propanol were added, and the mixture was heated to 70 ° C and stirred at the same temperature for 1 hour. The ί mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was washed with 2-propanol, and dried to give a white crystal (15 g) containing bis. The crystal was analyzed by liquid chromatography, and the area ratio of the peak of the obtained chromatograph 二 to the epoxy compound (1-1) was calculated to be 9 5.2%. [Example 3] 20 parts by weight of a mixed epoxy compound (1-1) and 21 parts by weight of 4,4'-diaminediphenylmethane (Wako Pure Chemical Industries Co., Ltd.) Solvent N,N-dimethylformammine, ί liquid composition. The obtained composition was concentrated by a centrifugal concentrating device to obtain a powdery composition of 3. The obtained powdery composition was filled in an alumina pan. The alumina disk having the composition was heated by a differential scanning calorimeter (DSC Q2000 manufactured by LYCO Co., Ltd.) to obtain a cured product (ϊ: heated in a nitrogen atmosphere at 140 ° C, after 20 minutes, heating To !/ °C 'and then heat at 200 °C for 30 minutes). The hardened product will be given a cold name. (:.: lysate [2 ί, I will filter it back to the sputum (;; when it is equivalent to ί化剂J to make a solution to dissolve 1 evenly fill a funeral instrument! The strip is divided into 1 80 1 To 20 -31 - 201206894 When heated to 1 40 °C, the observation indicates the heat generated by the hardening reaction of the diepoxide compound (1-1) and the hardener. The differential scanning calorimeter (heating rate: 2〇°) c / min, measured temperature range: room temperature ~ 200 °c), when measuring the glass transition point of the cured product is 166 ° C. [Example 4] In Example 3, except that 1,5-diamine naphthalene was used. (Wako Pure Chemical Industries Co., Ltd.) 17 parts by weight of the substituted 4,4'-diamine diphenylmethane 21 parts by weight, the same as in Example 3, to obtain a solution-like composition. The composition was concentrated by a centrifugal concentrating device to obtain a uniform powdery composition. The obtained powdery composition was heated as in Example 3 to obtain a cured product. When heated to l4 ° C, the observation revealed that The heat of the curing reaction of the epoxy compound (1-1) with the hardener. As measured in Example 3 At the glass transition point of the cured product, the glass transition point was 1 3 9 r. [Example 5] In addition to the use of cis-4 -cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) 32 weight In place of 2 parts by weight of 4,4'-diamine diphenylcarbamate in Example 3, 2 - 8 parts by weight of 2-phenylimidazole as a hardening accelerator was further used, and the remainder was as in Example 3. This was carried out to obtain a solution-like composition, and the obtained solution-like composition was concentrated by a centrifugal concentrating device to obtain a uniform powdery composition. -32-201206894 The powder obtained by heating as in Example 3 The composition obtained a cured product. When heated to 1 40 ° C, the observation showed that the epoxide compound (1-i) and the hardener reacted with heat generation. The glass transition point of the cured product was 1 0 6 °C. [Example 6] Except that 5-(2,5-dioxotetrahydrofuranyl)_3•methyl_3_cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) was used. 28 parts by weight of 21 parts by weight of 4,4'-diamine diphenylmethane in the substitution example 3, further used The composition of the solution was obtained as in Example 3 except that it was 2.6 parts by weight of the 2-phenylimidazole of the hardening accelerator. The obtained solution was obtained by concentration in a centrifugal concentration apparatus to obtain a uniform powder. A composition obtained by heating the obtained powdery composition as in Example 3 to obtain a cured product. When heated to 140 ° C, the point 'observed to cause the diepoxide compound (1 -1 ) and the hardener The heat of the hardening reaction. The glass transition point of the hardened material was 128 °C. [Example 7] In place of 87 parts by weight of the phenol novolak resin curing agent "MEH-785 1 H" (manufactured by Mingwa Kasei Co., Ltd.), 21 parts by weight of 4,4,-diamine diphenylmethane in the substitution example 3 was used. Further, in the same manner as in Example 3, except that 4 parts by weight of triphenylphosphine as a curing accelerator was used, a solution-like composition was obtained. The obtained solution-like composition was concentrated in a centrifugal concentration set -33 - 201206894 to obtain a homogeneous powdery composition. The obtained powdery composition was heated as in Example 3 to obtain a cured product. When heated to a temperature of 1 40 ° C, observation revealed heat generation which caused a hardening reaction of the diepoxide compound ( 1 -1 ) with the hardener. The glass transition point of the hardened material is 1 1 2 °C. [Example 8] In addition to using 10 parts by weight of dicyanamide (manufactured by Wako Pure Chemical Industries, Ltd.) in place of 21 parts by weight of 4,4'-diaminediphenylmethane in Example 3, it was further used as a hardening. Except for 2.2 parts by weight of 2-phenylimidazole of the accelerator, the remainder was carried out as in Example 3 to obtain a solution-like composition. The obtained solution in the form of a solution was concentrated by a centrifugal concentrating device to obtain a homogeneous powdery composition. The obtained powdery composition was heated as in Example 3 to obtain a cured product. At the time of heating to 1 40 ° C, observation revealed heat generation which caused a hardening reaction of the diepoxide compound (1 -1 ) with the hardener. The glass transition point of the hardened material is 1 6 8 °C. [Example 9] 17 parts by weight of a 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a hardening agent, and an alumina powder, 100 parts by weight of a diepoxy compound (1 -1 ) 1 076 parts by weight (a-alumina powder manufactured by Sumitomo Chemical Co., Ltd.; alumina powder Α1 and average particle diameter (D50) by an average particle diameter (D50) of 18 μηι as determined by laser diffraction method -34- 201206894 is a weight ratio of alumina powder B1 of 3μιηη to alumina powder C1 of average particle diameter (D50) of 0.4 μm (alumina powder Α 1 / alumina powder Β 1 / alumina powder C1 ) = 796 / 1 5 1 / 1 29, volume ratio (alumina powder Α 1 / alumina powder Β 1 / alumina powder C1) = 74/14/12 by mixing) and, as solvent, methyl isobutyl ketone 430 weight The composition was prepared by mixing 12 parts by weight with hydrazine and dimethyl carbamide. The prepared composition was applied to a polyethylene terephthalate (PET) film at a thickness of 400 μm by a coater. The PET film coated with the composition was dried at room temperature for 1 hour, and then dried at 150 ° C for 3 minutes, and then the PET film was peeled off to obtain a sheet. The obtained sheet was sandwiched between aluminum foil having a thickness of 40 μm and vacuum-formed (pressing conditions: vacuum degree lkPa, pressing pressure 6 MPa, pressing temperature 1 50 ° C, time 20 minutes). The temperature was raised to 180 ° C in 40 minutes, and vacuum press forming was carried out. The aluminum foil was peeled off to obtain a flaky cured product having a thickness of 351 μm. The Xenon Flash analyzer nanoflash LFA447 model manufactured by NETZSCH was used to measure the thermal conductivity of the carbide as l〇.7W/(m.K). The density of the alumina powder is obtained by hardening the cured product containing the diepoxy compound (1-1) and the 1,5-diaminonaphthalene, which does not contain the alumina powder, to a density of 1.2 g / cm 3 When the content ratio of the alumina powder in the obtained cured product was calculated to be 3.97 g/cm3, the content of the alumina powder in the cured product was 74% by volume. [Example 1 0] -35-201206894 100 parts by weight of a mixed epoxy compound (1-1) and 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent 17 A solution in the form of a solution was prepared in an amount of 430 parts by weight of methyl isobutyl ketone as a solvent and 70 parts by weight of N,N-dimethylformamide. The obtained composition was impregnated into a glass fiber woven fabric having a thickness of 0.2 mm, and dried by heating to obtain a prepreg. The obtained prepreg was superposed on four sheets, and formed at a temperature of 175 ° C and a pressure of 4 MPa by press molding for 90 minutes to obtain a laminate. Industrial Applicability The epoxide compound of the present invention has a low melting point, so that it is easy to obtain, and the cured product obtained by curing the composition containing the epoxy compound has high thermal conductivity. -36-

Claims (1)

201206894 VII. Patent application scope: i. A diepoxide compound characterized by formula (1): (wherein, R1, R2, r3, R, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). 2. For example, in the scope of claim 1, the epoxy compound of the first item, wherein the bis(epoxy compound represented by ◦ is of the formula (丨'): It is a stereoisomer represented by an alkyl group having 1 to 3 carbon atoms. 3. For the epoxy compound according to item 1 or item 2 of the patent application, wherein r1, R2, R3, R4, R5 and R6 are a hydrogen atom. 4. One way to use equation (1): (In the formula, Ri, R2 'R3, R4, Han 5, and 6 are the same meanings as described above), and a method for producing a diepoxide compound, which is characterized by being contained in the presence of an inorganic base-37-201206894, Let equation (2): (wherein, R1, R2, R3, R4, 5 and R6 independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) and a dihydroxy compound represented by the formula: (3) (wherein, the X1 system A reaction step indicating the reaction of an epihalohydrin represented by a halogen atom. 5. The production method according to the fourth aspect of the invention, wherein the reaction of the dihydroxy compound represented by the formula (2) with the epihalohydrin represented by the formula (3) is carried out in the presence of an inorganic base and a quaternary ammonium salt. 6. The method of claim 5, wherein the step of reacting the dihydroxy compound represented by the formula (2) with the epihalohydrin represented by the formula (3) comprises the following steps (i) and (ii): Step (i): a step of mixing the dihydroxy compound represented by the formula (2) with the epihalohydrin and the quaternary ammonium salt represented by the formula (3), the step (ii): mixing the mixture obtained in the step (i) with an inorganic base Step " 7. The manufacturing method as described in claim 4, wherein the inorganic base is an alkali metal hydroxide. 8. The manufacturing method of claim 4, wherein R1, R2, R3, R4, R5 and R6 is a hydrogen atom. -38 - 201206894 9. A dihydroxy compound characterized by the formula (2): OH (2) R4 R5 (wherein R1, R2, R3, R4, and R5 and an alkyl group which independently represents a hydrogen atom or a carbon number of 1 to 3) are represented. 10. The compound according to claim 9 bis, wherein the dihydroxy compound represented by the formula (2) is represented by the formula (2'): R4 R5 (wherein R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) is a stereoisomer. 11. The pharmaceutically acceptable compound according to claim 9 or claim 1, wherein R1, R2, R3, R4, 5 and R6 are a hydrogen atom. 1 2 .—A kind of formula (2): R4 R5 A method for producing a di-based compound, which is characterized by being contained in the presence of an acid, such that (6) -39 - 201206894 ΌΗ (6) R4 R5 (wherein R1, R2, R3, R4, and 6 are independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) and a hydroxynaphthoic acid compound represented by the formula (7) OH (7) represents the step of 4-hydroxy-1-(4 hydroxyphenyl)cyclohexane reaction. The manufacturing method of claim 12, wherein Ri, R2, R3, R4, R5 and R6 are a hydrogen atom. 14. A composition characterized by containing formula (1): R4 R5 (wherein R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) is a diepoxide compound and a curing agent. 1 5. The composition of claim 14 wherein R2, R3, R4, R5 and R6 are a hydrogen atom. 16. The composition of claim 14 or claim 15, wherein the curing agent is at least one selected from the group consisting of an amine hardener, a phenol hardener, and an acid anhydride hardener. 17. The composition of claim 16 wherein the hardener is -40 - 201206894 amine hardener. 1 8 . The composition of claim 17 wherein the amine hardener is selected from the group consisting of 4,4,-diamine diphenylmethane, 4,4,-diamine diphenylethane, 1,5 - one of a group of diamine naphthalenes and p-phenylenediamines. 19. The composition of claim 14 or the composition of item 15 wherein the bismuth contains tin oxide. 20. The composition of claim 19, wherein the aluminum oxide is 75 parts by weight based on 1 part by weight of the total of the diepoxide compound represented by the formula (1) and the hardener and alumina. 95 parts by weight. 2 1. The composition of claim 19, wherein the alumina is D50 (the cumulative volume of 50% of the particle size) is 2 μm or more and ΙΟΟμπι or less of the alumina crucible, and the D50 is Ιμπι or more ΙΟμιη or less of the alumina crucible And a mixture of D50 of 氧化铝.ΟΙμηι or more and 5 μm or less of alumina C, and each alumina accounts for 100 vol% of the total of alumina cerium and alumina cerium and alumina C, and alumina A is 50 to 90 vol%. The alumina B is 5 to 40% by volume, and the alumina C is 1 to 30% by volume. A hardened material obtained by hardening a composition according to any one of claims 1 to 2 of the patent application. A prepreg which is obtained by coating or immersing a composition according to any one of claims 14 to 21 to a substrate and then performing semi-hardening. A cured product obtained by hardening a composition according to any one of the above-mentioned items, wherein the cured product contains alumina in a proportion of 50 ~ 80% by volume. -41 - 201206894 IV. Designated representative map: (1) The representative representative of the case is: None. (2) Simple description of the symbol of the representative figure: None 201206894 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (1) -4-