JP5443993B2 - Epoxy resin, production method thereof, epoxy resin composition and cured product - Google Patents

Description

  The present invention relates to an epoxy resin that gives a cured product excellent in high thermal conductivity, low thermal expansion, high heat resistance, low hygroscopicity, gas barrier properties, etc., a method for producing the same, an epoxy resin composition using this epoxy resin, and its curing Related to things. The epoxy resin, the epoxy resin composition and the cured product are suitably used for insulating materials in the electric and electronic fields such as a heat dissipation board, a printed wiring board, and semiconductor sealing.

  In recent years, in electronic devices, high-density mounting of semiconductor packages, high integration and high speed of LSIs, etc. have been attempted, but measures to dissipate heat generated by this have become very important issues. . For heat dissipation measures, heat-conductive molded bodies made of heat-dissipating materials such as metals, ceramics, and polymer compositions are used for heat-dissipating members such as printed wiring boards, semiconductor packages, housings, heat pipes, heat-dissipating plates, and heat-diffusing plates Is being considered.

  Among these heat dissipation members, heat conductive epoxy resin cured products using epoxy resin are excellent in electrical insulation, mechanical properties, heat resistance, chemical resistance, adhesion, low density, etc. Widely used mainly in the electric and electronic fields as products, laminates, sealing materials, adhesives and the like.

  The epoxy resin composition constituting the thermally conductive epoxy resin cured product is known in which an epoxy resin is blended with a thermally conductive filler having high thermal conductivity, but obtained from a conventionally known epoxy resin. In the cured epoxy resin, the thermal conductivity is not sufficient.

  As an epoxy resin composition excellent in high thermal conductivity, one using an epoxy resin having a mesogenic structure is known. For example, Patent Literature 1 requires a biphenol type epoxy resin and a polyhydric phenol resin curing agent. An epoxy resin composition as a component is shown, and it is disclosed that it is excellent in stability and strength at high temperatures and can be used in a wide range of fields such as adhesion, casting, sealing, molding and lamination. Patent Document 2 discloses an epoxy compound having in its molecule two mesogenic structures connected by a bent chain. Patent Document 3 discloses an epoxy precursor having two mesogenic groups (biphenyl) connected by a bent chain. Furthermore, Patent Document 4 discloses a resin composition containing an epoxy compound having a mesogenic group.

Japanese Patent Laid-Open No. 7-90052 JP-A-9-118673 JP 2000-355565 A JP-A-11-323162 JP 2004-123847 A JP 2005-325231 A JP 2005-306955 A

  Since the epoxy compound having such a mesogenic structure and its precursor have a very high melting point, there is a problem that handling property is poor when a composition mixed with a curing agent or an inorganic filler is used. In addition, a cured product obtained from an epoxy compound having such a mesogenic structure has optical anisotropy, and thus liquid crystalline expression having a domain of several μm to several tens of μm has been confirmed. The crystal phase is not sufficiently formed. Therefore, a clear endothermic peak based on the melting point of the crystal phase is not observed even in the differential thermal analysis. In other words, the cured products obtained from the epoxy compounds having a mesogenic structure reported so far do not produce crystal phases sufficiently, and are sufficiently high in thermal conductivity, low thermal expansion, high heat resistance, low moisture absorption and gas barrier properties. The effect is not expressed. In addition, a cured product obtained from a conventionally known epoxy compound having a mesogenic structure has insufficient crystal growth, so that its heat resistance depends on the glass transition point and is high based on the melting point of the crystal phase. Heat resistance cannot be expected. Furthermore, many epoxy resins having a mesogenic structure have a high melting point per se, and there is a drawback in that the handling property such as adjustment and molding of the epoxy resin composition is inferior.

  In addition to the epoxy resin having high crystallinity, a resin composition using an aromatic polyester (Patent Document 5), or a resin composition in which a liquid crystal polymer such as an aromatic polyester is blended with a polyarylene sulfide resin. Although a thing is proposed, since liquid crystal polymers, such as aromatic polyester, are highly viscous, there exists a problem inferior to a moldability (patent documents 6, 7). In addition, there is a limit to compositing with inorganic fillers due to high viscosity.

  Therefore, the object of the present invention is to provide a heat-radiating substrate, a printed wiring board, a semiconductor encapsulating and the like that gives a resin cured product having high thermal conductivity, low thermal expansion, high heat resistance, low moisture absorption and gas barrier properties. An object of the present invention is to provide an epoxy resin suitably used for an insulating material and the like, a production method thereof, an epoxy resin composition using the epoxy resin, and a cured product thereof.

That is, the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent, wherein an epoxy resin represented by the following general formula (1) is blended as an epoxy resin component, and 4,4′-dihydroxy as a curing agent. Diphenylmethane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxybiphenyl, hydroquinone, 1,5-naphthalenediol, 2,6-naphthalenediol and reaction products of these bifunctional phenols with epichlorohydrin, these bifunctional phenols A differential scanning calorific value characterized by blending at least one phenolic curing agent selected from the group consisting of phenolic resins represented by the following general formula (2): In the analysis, it has an endothermic peak based on the melting point from 100 ° C to 300 ° C. Relates to an epoxy resin composition for heat absorption amount in terms of the resin component to obtain a crystalline epoxy resin cured product is 5 J / g or more. This epoxy resin can be obtained by reacting a phenolic resin represented by the following general formula (2) with epichlorohydrin. In the general formulas (1) and (2), A independently represents a non-mesogenic divalent aromatic group which may have a substituent, and l independently represents an integer of 3 to 30. , M independently represents a number from 0.1 to 15, and n represents a number from 0 to 15. However, the above non-mesogenic divalent aromatic groups are phenylene group, naphthylene group, anthracene group, diphenylmethane group, 1,1-diphenylethane group, 1,1,1-methyldiphenylethane group, diphenylether group, diphenyl. It is at least one group selected from the group consisting of sulfide groups, diphenyl sulfoxide groups, diphenyl sulfone groups, and diphenyl ketone groups. This non-mesogenic divalent aromatic group may have a substituent.

（但し、Ａは置換基を有していてもよい非メソゲン系の２価の芳香族基を示し、ｌは３から３０の整数を示し、ｍは０．１から１５の数を示し、ｎは０から１５の数を示す）

(However, A represents a non-mesogenic divalent aromatic group which may have a substituent, l represents an integer of 3 to 30, m represents a number of 0.1 to 15, n Indicates a number from 0 to 15)

（但し、Ａ、ｌ及びｍは一般式（１）と同じ意味を有する）

(However, A, l and m have the same meaning as in general formula (1))

  The non-mesogenic divalent aromatic group is preferably an aromatic group selected from a phenylene group, a naphthylene group, a diphenyl ether group, a diphenyl sulfide group, or a diphenylmethane group. Further, in the general formula (1), m may be an epoxy resin having an integer of 1 to 15.

（但し、Ａは置換基を有していてもよい非メソゲン系の２価の芳香族基を示し、ｌは３から３０の整数を示し、ＸはＯＨと縮合反応する基を示す）Moreover, this invention relates to the manufacturing method of the epoxy resin characterized by making the phenolic resin and epichlorohydrin represented by the said General formula (2) react. Here, as the phenolic resin represented by the general formula (2), a method obtained by reacting a bisphenol compound represented by the following general formula (3) and a condensing agent represented by the general formula (4) is suitable. .

(However, A represents a non-mesogenic divalent aromatic group which may have a substituent, l represents an integer of 3 to 30, and X represents a group that undergoes a condensation reaction with OH)

  Furthermore, this invention is an epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, Comprising: Said epoxy resin was mix | blended as an epoxy resin component, It is an epoxy resin composition characterized by the above-mentioned. An inorganic filler can be blended in the epoxy resin composition. Moreover, this invention is a hardened | cured material obtained by hardening this epoxy resin composition. This cured product preferably has an endothermic peak based on the melting point from 100 ° C. to 300 ° C. in the differential scanning calorimetry, and the endothermic amount converted to a resin component is 5 J / g or more. Moreover, it is preferable that hardened | cured material is what combined the inorganic filler and heat conductivity is 3 W / m * K or more.

First, the epoxy resin of this invention is demonstrated.

  The epoxy resin of the present invention is represented by the above general formula (1), wherein A is a non-mesogenic divalent aromatic group which may have a substituent. A mesogen is a divalent organic group having a rigid structure necessary for molecules to exhibit liquid crystallinity, and examples of the liquid crystalline substance include compounds described in the following documents. Liquid Crystals in Tablen II, D.D. Demus et al Eds. VEB Deutscher Verlag fur Grundstoffindustrie, Leipzig, 1984. Examples thereof include phenylbenzoate, biphenyl, stilbene, diazobenzene, aniline benzylidene, and derivatives thereof, and aromatic compounds that do not have these structures are non-mesogens.

Preferred non-mesogenic divalent aromatic groups include phenylene group, naphthylene group, anthracene group, diphenylmethane group, 1,1-diphenylethane group, 1,1,1-methyldiphenylethane group, diphenyl ether group, diphenyl. Examples thereof include a sulfide group, a diphenyl sulfoxide group, a diphenyl sulfone group, and a diphenyl ketone group. Here, the anthracene group means a group formed by removing two hydrogens from anthracene, such as a diphenylmethane group, a 1,1-diphenylethane group, a 1,1,1-methyldiphenylethane group, a diphenyl ether group, a diphenyl sulfide group, a diphenyl. sulfoxide group, diphenyl sulfone group, diphenyl ketone group refers to a group represented by -Ph-X-Ph-, Ph is a phenylene group, X is _{CH 2, C 2 H 4,} C 3 H 6, O , S, SO, SO ₂ or CO. Preferably, it is a group represented by a phenylene group, a naphthylene group, or —Ph—Y—Ph— (wherein Ph is a phenylene group and Y is CH ₂ , O, or S).

  The divalent aromatic group may have a substituent, and preferable substituents include hydrocarbon groups such as methyl group, ethyl group, allyl group, propargyl group, phenyl group and benzyl group, methoxy group, and ethoxy group. , Alkoxy groups such as allyloxy group and phenoxy group, and halogen groups such as fluorine, chlorine and bromine.

  Among them, the non-mesogenic divalent aromatic group has a structure with little steric hindrance and excellent symmetry from the viewpoint of high heat resistance, high thermal conductivity, low thermal expansion, and low hygroscopicity. In particular, 2,6-naphthylene group, 1,5-naphthylene group, 4,4′-diphenylmethane group, 4,4′-diphenyl ether group and 1,4-phenylene group are suitably selected.

  In the general formula (1), l is a number of 3 to 30, but 3 to 12 is preferable from the viewpoint of low viscosity and high heat resistance, and 12 to 12 from the viewpoint of low hygroscopicity and flexibility. 30 is preferred. From the viewpoint of heat resistance and high thermal conductivity, it is 4 to 16, and even numbers are particularly preferable. When it is larger than 30, the heat resistance is lowered, the solvent solubility is deteriorated, and the practicality is inferior. On the other hand, if it is smaller than 3, the moisture resistance is inferior and the effect of improving the thermal conductivity is small. It should be noted that l different units may be included.

  In the general formula (1), m represents a number from 0.1 to 15, and this number is an average value (number average). m is a number from 0.1 to 15, preferably 0.1 to 10, more preferably 0.2 to 5, and still more preferably 0.3 to 2. From another viewpoint, the epoxy resin of the present invention is preferably an epoxy resin in which m is an integer of 1 to 15 in the general formula (1). In this case, m is preferably an integer of 1. The epoxy resin (A) in which m is a number from 0.1 to 15 is a concept including the epoxy resin (B) in which m is an integer from 1 to 15. However, when the two are distinguished, Is called an epoxy resin (A), and the latter is called an epoxy resin (B). The epoxy resin (B) is a single compound (with respect to m) of the epoxy resin represented by the general formula (1) in which m is an integer of 1 to 15, and the epoxy resin (A) has an m of 0 to It can be said that it is a mixture (with respect to m) of the epoxy resin represented by the general formula (1) which is an integer of 15.

  Usually used as a mixture with other multimers containing m = 0. And the preferable value of m differs according to the application to apply. For example, for a semiconductor encapsulant that requires a high filling rate of the filler, a material having a low viscosity is desirable, and in the case of a mixture, the number average value of m is 0.1 to 5, preferably 0. .2-2. More preferably, m is 1 and 30 wt% or more is included.

  n represents a number from 0 to 15, and a preferable value of n varies depending on the application to be applied. This number is an average value (number average). For example, for the use of a semiconductor encapsulant that requires a high filling rate of the filler, a material having a low viscosity is desirable, and the value of n is 0 to 5, preferably 0 to 2, and more preferably n. 0 is contained at 30 wt% or more. When the epoxy resin of this invention is a mixture from which the value of m differs, it is 0.1-5 as a number average value of n, Preferably it is 0.2-2. More preferably, those having n of 0 are contained at 30 wt% or more.

  The epoxy resin of the present invention is produced, for example, by reacting the phenolic resin represented by the general formula (2) with epichlorohydrin. In the general formula (2), A, l and m have the same meaning as described in the general formula (1). The epoxy resin produced by reacting the phenolic resin represented by the general formula (2) and epichlorohydrin contains the epoxy resin represented by the general formula (1) as a main component. The phenolic resin represented by the general formula (2) may be a mixture of isomers. When the epoxy resin (B) is intended, the phenolic resin represented by the general formula (2) is a single compound (with respect to m) in which m is an integer of 1 to 15.

  In the case of producing the epoxy resin of the present invention by reacting the phenolic resin represented by the general formula (2) with epichlorohydrin, or in the method for producing the epoxy resin of the present invention, it is represented by the general formula (2). A phenolic resin and epichlorohydrin are reacted. For the reaction between the phenolic resin and epichlorohydrin, 0.80 to 1.20 times equivalent, preferably 0.85 to 1.05 times equivalent of sodium hydroxide, potassium hydroxide, etc. with respect to the hydroxyl group in the phenolic resin. Alkali metal hydroxides are used. If it is less than this, the amount of residual hydrolyzable chlorine increases, which is not preferable. The metal hydroxide is used in an aqueous solution or solid state.

  In the reaction, an excessive amount of epichlorohydrin is used with respect to the bisphenol compound. Usually, 1.5 to 15 times mole of epichlorohydrin is used with respect to 1 mole of hydroxyl group in the bisphenol compound, but preferably in the range of 2 to 8 times mole. If it is more than this, the production efficiency will be reduced, and if it is less than this, the amount of epoxy resin high molecular weight will be increased and the viscosity will be high.

  The reaction is usually performed at a temperature of 120 ° C. or lower. If the temperature is high during the reaction, the amount of so-called hardly hydrolyzable chlorine increases and it becomes difficult to achieve high purity. Preferably it is 100 degrees C or less, More preferably, it is the temperature of 85 degrees C or less.

  In the reaction, a quaternary ammonium salt or a polar solvent such as dimethyl sulfoxide or diglyme may be used. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the addition amount is preferably in the range of 0.1 to 2.0 wt% with respect to the bisphenol compound. . If the amount is less than this, the effect of adding a quaternary ammonium salt is small. If the amount is more than this, the amount of hardly hydrolyzable chlorine produced increases, and high purity becomes difficult. Further, the addition amount of the polar solvent is preferably in the range of 10 to 200 wt% with respect to the bisphenol compound. If the amount is less than this, the effect of addition is small.

  After completion of the reaction, excess epichlorohydrin and solvent are distilled off, the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts and residual solvent, and then the solvent is distilled off. It can be set as an epoxy resin.

  Advantageously, the obtained epoxy resin is further added with 1 to 30 times the amount of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide with respect to the remaining hydrolyzable chlorine, and a re-ring closure reaction is carried out. Is called. The reaction temperature at this time is usually 100 ° C. or lower, preferably 90 ° C. or lower.

  The phenolic resin represented by the general formula (2) can be obtained by a known method. Advantageously, there is a method of reacting the bisphenol compound represented by the general formula (3) with the condensing agent represented by the general formula (4). Here, A and l have the same meaning as in the general formula (2). X represents a group (atom) that undergoes a condensation reaction with OH, and is preferably a halogen. If 2 moles of the bisphenol compound are used with respect to the condensing agent, a phenolic resin mainly comprising a phenolic resin in which m is 1 or more in the general formula (2) can be obtained. If the bisphenol compound is used in an amount exceeding 2 moles, a phenolic resin containing an unreacted bisphenol compound in which m is 0 can be obtained. In order to ensure that both ends are phenolic groups, the bisphenol compound should be used in an amount of more than 2 times mol, preferably 3 to 10 times mol.

  The epoxy resin composition of the present invention is an epoxy resin produced by reacting an epoxy resin represented by the above general formula (1) or a phenolic resin represented by the general formula (2) with epichlorohydrin (hereinafter, referred to as “epoxy resin”). These are collectively referred to as the epoxy resin of the present invention) and a curing agent as essential components. As a hardening | curing agent mix | blended with the epoxy resin composition of this invention, what is generally known as a hardening | curing agent of an epoxy resin can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines.

  Specifically, as polyhydric phenols, for example, bisphenol A, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy Diphenylsulfone, fluorene bisphenol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, hydroquinone, resorcin, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7 -Divalent phenols such as naphthalenediol, or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol Novolac, a trihydric or higher phenols typified by polyvinyl phenol. Furthermore, monohydric phenols such as phenols and naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4, 4'-biphenol, 2, 2'-biphenol, hydroquinone, resorcin, naphthalenediol, etc. And polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, and the like. Moreover, you may use the phenolic resin represented by the said General formula (2) as a part or all of a hardening | curing agent.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, and trimellitic anhydride.

  Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. There are aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  Among the curing agents, it is preferable to use a phenolic curing agent from the viewpoints of electrical insulation, low moisture absorption, high thermal conductivity, low thermal expansion, and the like. In particular, from the viewpoint of high thermal conductivity based on the liquid crystallinity or crystallinity of the cured product, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxybiphenyl, hydroquinone, 1 , 5-naphthalenediol, 2,6-naphthalenediol, and a reaction product of these bifunctional phenols with epichlorohydrin, a reaction product of these bifunctional phenols with a bifunctional epoxy compound, or the above general formula (2) Is preferably used. From the viewpoint of heat resistance, it is preferable to use an aromatic diamine curing agent.

  In the resin composition of the present invention, one or more of the above curing agents can be mixed and used.

  Moreover, you may mix | blend another kind of epoxy resin other than the epoxy resin of this invention as an epoxy resin component in the epoxy resin composition of this invention. As the epoxy resin in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include bisphenol A, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenylsulfone, fluorene bisphenol, 4,4′-. Dihydric phenols such as dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, hydroquinone, resorcin, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, Alternatively, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydride) Xylphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2, 3, 4-trihydroxybenzophenone, phenol aralkyl resins, dicyclopentadiene resins and other trivalent or higher phenols, or glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A . These epoxy resins can be used alone or in combination of two or more. And in the case of the composition which uses the epoxy resin of this invention as an essential component, the compounding quantity of the epoxy resin of this invention is 30-100 wt% in the whole epoxy resin, Preferably it is good to be the range of 60-100 wt%. If the amount is less than this, the crystallinity of the cured product is poor and the effect of improving the thermal conductivity is small.

  In the epoxy resin composition of the present invention, an appropriate amount of an inorganic filler can be blended in order to improve the thermal conductivity of the cured epoxy resin. Examples of the inorganic filler include metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon materials. As the metal, silver, copper, gold, platinum, zircon, etc., as the metal oxide, silica, alumina, magnesium oxide, titanium oxide, tungsten trioxide, etc., as the metal nitride, boron nitride, aluminum nitride, silicon nitride, etc. Metal carbide as silicon carbide, metal hydroxide as aluminum hydroxide, magnesium hydroxide, etc., carbon material as carbon fiber, graphitized carbon fiber, natural graphite, artificial graphite, spherical graphite particles, mesocarbon microbeads, Examples include whisker-like carbon, microcoil-like carbon, nanocoil-like carbon, carbon nanotube, and carbon nanohorn. As the shape of the inorganic filler, a crushed shape, a spherical shape, a whisker shape, and a fibrous shape can be applied, but a spherical shape is preferable in order to increase the filling rate. In order to ensure insulation and high thermal conductivity of the cured epoxy resin, a metal oxide is preferable as the inorganic filler, and spherical alumina is particularly preferable. These inorganic fillers may be blended singly or in combination of two or more. Ordinary coupling agent treatment may be applied to the inorganic filler for the purpose of improving the wettability between the inorganic filler and the epoxy resin, reinforcing the interface of the inorganic filler, and improving the dispersibility.

  The blending amount of the inorganic filler is preferably 50 wt% or more, more preferably 70 wt% or more. If it is less than this, the effect of improving thermal conductivity is small. The amount of the inorganic filler used is usually 75 wt% or more from the viewpoint of low hygroscopicity and high solder heat resistance, and particularly preferably 80 wt% or more. The preferable thermal conductivity of the cured product obtained by combining with the inorganic filler is 3 W / m · K or more, particularly preferably 6 W / m · K or more.

  A conventionally well-known hardening accelerator can be used for the epoxy resin composition of this invention. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate Tetra-substituted phosphonium / tetra-substituted borate such as tetrabutyl phosphonium / tetrabutyl borate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl borate, etc. . As addition amount, it is the range of 0.2-10 weight part normally with respect to 100 weight part of epoxy resins.

  Furthermore, in the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, phenoxy resin may be appropriately blended, You may mix | blend additives, such as a pigment, a refractory agent, a thixotropic agent, a coupling agent, and a fluidity improver. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite. Further, if necessary, the resin composition of the present invention includes halogen-based flame retardants such as brominated epoxies, phosphorus-based flame retardants such as red phosphorus, phosphate esters, and phosphorus atom-containing epoxy resins, and antimony trioxide. Flame retardant aids, mold release agents such as carnauba wax and ester wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, low stress agents such as silicone oil, calcium stearate And other additives such as epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane, organic titanate, aluminum alcoholate and the like.

  The epoxy resin composition of the present invention is generally kneaded with a mixing roll, an extruder, etc., after thoroughly mixing the above-mentioned epoxy resin, curing agent component and other compounding components at a predetermined compounding amount with a mixer or the like, It can be obtained by cooling and grinding.

  Alternatively, the above blended components may be aromatic solvents such as benzene, toluene, xylene, chlorobenzene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon solvents such as hexane, heptane, methylcyclohexane, ethanol, Alcohol solvents such as isopropanol, butanol, ethylene glycol, ether solvents such as diethyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, polarities such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone It can be dissolved in a solvent to obtain a varnish-like epoxy resin composition. The varnish-like epoxy resin composition can be made into a prepreg-like epoxy composition by impregnating a fibrous filler such as glass fiber, carbon fiber, or aramid fiber and then removing the organic solvent by drying.

  In order to obtain a cured product using the epoxy resin composition of the present invention, for example, methods such as transfer molding, press molding, cast molding, injection molding, and extrusion molding are applied. Moreover, methods, such as a vacuum press, are taken as a method for hardening the prepreg-like epoxy resin composition. The temperature at this time is usually in the range of 120 to 220 ° C.

  The epoxy resin cured product of the present invention preferably has crystallinity from the viewpoint of high thermal conductivity. The degree of crystallinity can be evaluated from the endothermic amount associated with melting in differential scanning calorimetry. The endothermic peak in the differential scanning calorimetry is usually observed in the range of 100 ° C. to 300 ° C., but the preferred endothermic amount is 5 J / g or more per unit weight of the resin component excluding the filler. More preferably, it is 10 J / g or more, and particularly preferably 30 J / g or more. If it is smaller than this, the effect of improving the thermal conductivity as a cured epoxy resin is small. Here, the endothermic amount herein refers to an endothermic amount obtained by differential scanning calorimetry and measured under a nitrogen stream under a temperature rising rate of 10 ° C./min.

  The cured epoxy resin of the present invention can be obtained by heating and curing with the above molding method. Usually, the molding temperature is 80 ° C. to 250 ° C., and the molding time is 1 minute to 20 hours. In order to increase the crystallinity of the cured epoxy resin, it is desirable to cure at a low temperature for a long time. The preferred curing temperature is in the range of 100 ° C to 180 ° C, more preferably 120 ° C to 160 ° C. The preferable curing time is 10 minutes to 6 hours, more preferably 30 minutes to 3 hours. Further, the crystallinity can be further increased by post-cure after molding. Usually, the post-cure temperature is 130 ° C. to 250 ° C., and the time is in the range of 1 hour to 20 hours, but preferably 1 hour at a temperature 5 ° C. to 40 ° C. lower than the endothermic peak temperature in differential thermal analysis. It is desirable to perform post-cure over 24 hours from the beginning.

  The cured epoxy resin of the present invention can be laminated with another type of substrate. As the base material to be laminated, it is in the form of a sheet, a film, a metal base material such as copper foil, aluminum foil, stainless steel foil, polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate, Examples of the polymer base material include polyethylene naphthalate, liquid crystal polymer, polyamide, polyimide, and Teflon (registered trademark).

FIG. 1 shows a GPC chart of the epoxy resin of Example 1. FIG. 2 shows an infrared absorption spectrum of the epoxy resin of Example 1. FIG. 3 shows the H ¹ -NMR spectrum of the epoxy resin of Example 1. FIG. 4 shows a GPC chart of the epoxy resin of Example 2. FIG. 5 shows a GPC chart of the phenol resin of Reference Example 1. FIG. 6 shows an infrared absorption spectrum of the phenol resin of Reference Example 1. FIG. 7 shows a GPC chart of the phenol resin of Reference Example 2. FIG. 8 shows a GPC chart of the phenol resin of Reference Example 3. FIG. 9 shows a GPC chart of the phenol resin of Reference Example 4. FIG. 10 shows a GPC chart of the phenol compound crystal of Reference Example 5.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, the molecular weight, physical properties, and the like were measured by sample preparation and measurement according to the following methods.

1) Molecular weight distribution of phenolic resin and epoxy resin Using a GPC measuring device (manufactured by Nippon Waters, 515A type GPC), three TSKgel G2000HXL (manufactured by Tosoh) and one TSKgel G4000HXL (manufactured by Tosoh) are used for detection. The measurement was carried out with RI as the solvent, tetrahydrofuran as the solvent, a flow rate of 1.0 ml / min, and a column temperature of 38 ° C.

2) Measurement of melting point (capillary method)
Using a melting point measuring device (BUCHI B-535 type), a sample in powder form was packed in a capillary tube (inner diameter: 1 mm) with one end sealed, and measured with a melting point measuring device at a heating rate of 3 ° C./min.
3) Measurement of melting point and heat of fusion (DSC method)
Using a differential scanning calorimeter (Seiko Instruments DSC6200 type), the temperature was increased at a rate of 10 ° C / min.

4) Infrared absorption spectrum It measured by the KBr tablet method with the JEOL make and JIR-100 type | mold measuring apparatus.

5) H ¹ -NMR spectrum Using a JNM-LA400 type nuclear magnetic resonance spectrometer manufactured by JEOL, chloroform-d ₁ was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard.

6) Melt viscosity It measured at 150 degreeC using the CAP2000H type | mold rotational viscometer made from BROOKFIELD.

7) Measurement of hydroxyl group equivalent Using a potentiometric titrator, 1,4-dioxane is used as a solvent, acetylation is performed with 1.5 mol / L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol / L. -Titration using potassium hydroxide.

8) Measurement of epoxy equivalent Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and the potential was measured using a 0.1 mol / L perchloric acid-acetic acid solution.

9) Hydrolyzable chlorine 0.5 g of sample was dissolved in 30 ml of dioxane, 10 ml of 1N KOH was added and the mixture was boiled and refluxed for 30 minutes, cooled to room temperature, and further 100 ml of 80% acetone water was added. Measurement was performed by potentiometric titration with 002N-AgNO ₃ aqueous solution.

10) Thermal conductivity The thermal conductivity was measured by the unsteady hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH. The results are shown in Table 1.

11) Linear expansion coefficient, glass transition point (Tg)
Using a TMA120C thermomechanical measuring device manufactured by Seiko Instruments Inc., the temperature was increased at a rate of 10 ° C./min.

12) Water absorption rate A disk with a diameter of 50 mm and a thickness of 3 mm was formed, and after post-curing, the weight change rate after absorbing for 100 hours under the conditions of 85 ° C. and relative humidity of 85% was used.

13) Adhesive strength A molded product of 25 mm x 12.5 mm x 0.5 mm was molded between two 42 alloy plates at 150 ° C with a compression molding machine, post-cured at 175 ° C for 6 hours, and then tensile shear strength Was evaluated.

Reference example 1
A 1 L separable flask equipped with a stirrer was charged with 200 ml of 99% ethanol, degassed by flowing nitrogen, and the inside of the system was kept under a nitrogen atmosphere. This 4,4 '- dihydroxydiphenyl ether (DHPE) 202 g (1 mole), 1,3 - after dissolved by adding dibromopropane 50 g (0.25 mol), 86% potassium hydroxide 49g of (0.75 mol) 250 ml of dissolved 99% ethanol solution was added over 30 minutes. The mixture was further refluxed for 4 hours with stirring. Then, it cooled to room temperature, neutralized the reaction liquid using 30 weight% sulfuric acid, and also filtered, washed with water, and dried, and 208 g of milky white crystalline resin was obtained. A GPC chart is shown in FIG. Each peak corresponds to m = 0, m = 1, m = 2, m = 3, and m = 4 in the general formula (2) from the right, and the peak areas are 43.3% and 33.33, respectively. They were 0%, 13.1%, 4.6%, and 1.4%. An infrared absorption spectrum is shown in FIG. The melting point based on the capillary method was 142.7 ° C. to 151.4 ° C. The melting point peaks based on the DSC method were observed at 99.6 ° C. and 157.0 ° C., and the heats of fusion were 23.3 J / g and 65.1 J / g, respectively. The melt viscosity at 170 ° C. was 7.5 mPa · s.

Reference example 2
Reference Example 1 except that 300 ml of 99% ethanol, 100 g (0.50 mol) of 1,3 -dibromopropane, and 500 ml of 99% ethanol solution in which 98 g (1.51 mol) of 86% potassium hydroxide were dissolved were used. Reaction was similarly performed to obtain 201 g of milky white crystalline resin. A GPC chart is shown in FIG. Each peak corresponds to m = 0, m = 1, m = 2, m = 3, m = 4, m = 5, m = 6 in the general formula (2) from the right, and the peak areas are respectively 24.1%, 28.6%, 20.3%, 13.3%, 6.7%, 2.6%, and 1.0%. The hydroxyl group equivalent calculated from the area ratio of each peak in the GPC chart was 203.6. The melting point based on the capillary method was 94.7 ° C. to 104.0 ° C. The melting point peaks based on the DSC method were 90.6 ° C. and 101.4 ° C., and the heat of fusion was 87 J / g in total. The melt viscosity at 150 ° C. was 37.2 mPa · s.

Reference example 3
99% ethanol 250 ml, 4, 4 '- dihydroxydiphenyl ether (DHPE) 166 g (0.82 mol), 1,6 - dibromohexane 50 g (0.25 mol), dissolved potassium hydroxide 107 g (1.64 mol) The reaction was conducted in the same manner as in Reference Example 1 except that 546 ml of 99% ethanol solution was used, and 140.5 g of a light pinkish white crystalline resin was obtained. A GPC chart is shown in FIG. Each peak corresponds to m = 0, m = 1, m = 2, and m = 3 in the general formula (2) from the right, and the peak areas are 35.9%, 45.4%, and 14 respectively. 0.9% and 1.3%. The hydroxyl group equivalent calculated from the area ratio of each peak in the GPC chart was 181.4. The melting point based on the capillary method was 137.6 ° C. to 141.0 ° C. The melting point peaks based on the DSC method were 131.6 ° C. and 136.2 ° C., and the total heat of fusion was 137 J / g. The melt viscosity at 150 ° C. was 19.8 mPa · s.

Reference example 4
In a 2 L separable flask equipped with a stirrer, 800 ml of 99% ethanol was added, deaerated by flowing nitrogen, and the inside of the system was kept under a nitrogen atmosphere. To this, 0.5 g of hydrosulfite sodium, 220 g of hydroquinone (2.0 mol), 122 g of 1,6 -dibromohexane (0.50 mol) were added and dissolved, and 98 g of 86% aqueous potassium hydroxide (1.5 mol) was added. A 99% ethanol solution in which 500 ml was dissolved was added over 30 minutes. The mixture was further refluxed for 8 hours with stirring. Then, it cooled to room temperature, neutralized the reaction liquid using 30 weight% sulfuric acid, and also filtered, washed with water, and dried, and 123 g of milky white crystalline resin was obtained. A GPC chart is shown in FIG. Each peak corresponds to m = 1, m = 2, m = 3, and m = 4 in the general formula (2) from the right, and the peak areas are 53.9%, 31.8%, and 9 respectively. .3% and 1.1%. The hydroxyl group equivalent calculated from the area ratio of each peak in the GPC chart was 202.2. The melting point based on the capillary method was 147.2 ° C. to 168.2 ° C. The melting point peaks based on the DSC method were 144.0 ° C. and 158.6 ° C., and the heat of fusion was 165 J / g in total. The melt viscosity at 170 ° C. was 9.8 mPa · s.

Reference Example 5
In a 2 L separable flask equipped with a stirrer, 200 ml of 99% ethanol was introduced, and deaerated by flowing nitrogen, and the system was kept under a nitrogen atmosphere. To this, 0.2 g of hydrosulfite sodium, 101 g of hydroquinone (0.9 mol) and 25 g (0.09 mol) of 1,8 -dibromooctane were added and dissolved, and then 18 g of 86% potassium hydroxide (0.3 mol) was added. 200 ml of dissolved 99% ethanol solution was added over 30 minutes. Furthermore, it heated and refluxed for 8 hours, stirring. Then, it cooled to room temperature, neutralized the reaction liquid using 30 weight% sulfuric acid, and also filtered, and collect | recovered the filtrate. The residue was further washed with hot ethanol and added to the filtrate. The filtrate was evaporated and the resulting solid residue was washed with 4 L of water, dried, further washed with petroleum ether, and recrystallized from a 75% aqueous ethanol solution to obtain 5.7 g of milky white crystals. . The melting point peak was 150.6 ° C. to 152.8 ° C. The melting point peak based on the DSC method was 152.8 ° C., and the heat of fusion was 188 J / g. The melt viscosity at 170 ° C. was 5.9 mPa · s. A GPC chart is shown in FIG. A peak corresponding to m = 1 in the general formula (2) as the main component was observed, and the peak area was 95.1%.

Reference Example 6
A 500 mL separable flask equipped with a stirrer was charged with 200 ml of 99% ethanol, deaerated by flowing nitrogen, and the inside of the system was kept under a nitrogen atmosphere. To this, 0.2 g of hydrosulfite sodium, 110 g of hydroquinone (1.0 mol) and 22 g of 1,4 -dibromobutane (0.10 mol) were added and dissolved, and then 20 g of potassium hydroxide (0.3 mol) was dissolved. 100 ml of a 99% ethanol solution was added over 30 minutes. Furthermore, it heated and refluxed for 4 hours, stirring. Then, it cooled to room temperature, neutralized the reaction liquid using 30 weight% sulfuric acid, and also filtered, and collect | recovered the filtrate. The residue was further washed with hot ethanol and added to the filtrate. The filtrate was evaporated, and the resulting solid residue was washed with 2 L of water, dried, further washed with petroleum ether, and recrystallized from a 75% aqueous ethanol solution to obtain 2.4 g of milky white crystals. . As a result of GPC measurement, it was confirmed that the compound was almost a single compound having no molecular weight distribution. The melting point peak based on the capillary method was 197.1 ° C. to 200.0 ° C. The melting point peak based on the DSC method was 196.3 ° C., and the heat of fusion was 180 J / g.

Example 1
In a 1 L four-necked separable flask, 100 g of phenolic resin obtained in Reference Example 1, 400 g of epichlorohydrin and 80 g of diglyme were weighed and dissolved with stirring, and then 48% water at 60 ° C. under reduced pressure (about 120 mmHg). 50 g of an aqueous sodium oxide solution was added dropwise over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of dropping, the reaction was continued for another hour. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure, dissolved in 400 g of methyl isobutyl ketone, and then the salt produced by filtration was removed. Thereafter, 40 g of a 12% aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. After the reaction, filtration and washing with water, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 114 g of a light yellow crystalline epoxy resin (epoxy resin A). Epoxy equivalent is 216 eq / g, hydrolyzable chlorine is 440 ppm, melting point based on capillary method is 69 to 83 ° C., melting point peak based on DSC method is 66.0 ° C. and 81.0 ° C., heat of fusion Were 52.7 J / g and 6.80 J / g, respectively. The melt viscosity at 150 ° C. was 12.9 mPa · s. A GPC chart is shown in FIG. The infrared absorption spectrum is shown in FIG. 2, and the H ¹ -NMR spectrum is shown in FIG.

Example 2
100 g of the phenolic resin obtained in Reference Example 2 and 35 g of a 48% sodium hydroxide aqueous solution were used in the same manner as in Example 1 to obtain 112 g of epoxy resin (epoxy resin B). Epoxy equivalent is 287 g / eq, melting point based on capillary method is 96 to 99 ° C., melting point peak based on DSC method is 75.9 ° C. and 99.7 ° C., and heat of fusion is 35.7 J / g and 32 respectively. It was 5 J / g. The melt viscosity at 150 ° C. was 35.2 mPa · s. A GPC chart is shown in FIG.

Example 3
In a 1 L four-necked separable flask, 70 g of the phenolic resin obtained in Reference Example 3, 500 g of epichlorohydrin and 100 g of diglyme were weighed and dissolved with stirring, and then 48% water at 60 ° C. under reduced pressure (about 120 mmHg). Sodium oxide aqueous solution 32g was dripped over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of dropping, the reaction was continued for another hour. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure, dissolved in 1036 g of methyl isobutyl ketone, and then repeatedly washed with warm water several times to remove the generated salt. After the reaction, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 60 g of a milky white crystalline epoxy resin (epoxy resin C). The epoxy equivalent is 254 eq / g, the melting point based on the capillary method is 135 ° C. to 140 ° C., the melting point peaks based on the DSC method are 79.5 ° C. and 134.9 ° C., and the heat of fusion is 20.7 J / g, respectively. And 67.3 J / g. The melt viscosity at 150 ° C. was 17.1 mPa · s.

Example 4
The reaction was carried out in the same manner as in Example 1 using 100 g of the phenolic resin obtained in Reference Example 4, 600 g of epichlorohydrin, and 86 g of a 48% aqueous sodium hydroxide solution to obtain 124 g of an epoxy resin (epoxy resin D). The epoxy equivalent was 167 g / eq, the melting point based on the capillary method was 119.8 ° C. to 141.8 ° C., the melting point peaks based on the DSC method were 112.9 ° C. and 144.3 ° C., and the heat of fusion was 118 J / g. The melt viscosity at 150 ° C. was 54.2 mPa · s.

Example 5
The reaction was carried out in the same manner as in Example 1 using 10 g of the phenolic resin obtained in Reference Example 5, 100 g of epichlorohydrin, and 5.0 g of 48% aqueous sodium hydroxide to obtain 10.4 g of an epoxy resin. Epoxy equivalent was 239 g / eq, melting point peaks based on DSC method were 108.1 ° C. and 138.7 ° C., and heats of fusion were 81.9 J / g and 66.6 J / g, respectively. The melt viscosity at 150 ° C. was 35.3 mPa · s.

Examples 6-13 and Comparative Examples 1-3
As epoxy resin components, epoxy resins (epoxy resins A to D) synthesized in Examples 1 to 4, diphenyl ether type epoxy resin (epoxy resin E; manufactured by Tohto Kasei, YSLV-80DE, epoxy equivalent 163), biphenyl type epoxy resin ( Epoxy resin F; manufactured by Japan Epoxy Resin, YX-4000H, epoxy equivalent 195, melting point 105 ° C., o-cresol novolac type epoxy resin (epoxy resin G; manufactured by Nippon Kayaku Co., Ltd., EOCN-1020, epoxy equivalent 197, softening point 54) , Melt viscosity at 150 ° C. 90 mPa · s), as a curing agent, phenolic resins synthesized in Reference Examples 3 and 4 (curing agents A and B), 4,4′-dihydroxydiphenyl ether (curing agent C), phenol Novolac (curing agent D; OH equivalent 103, softening point 82 ° C.) 4,4′-di Minodiphenylmethane (curing agent E) is used, and spherical alumina (inorganic filler A: average particle size 12.2 μm), spherical fused silica (inorganic filler B: average particle size 14.8 μm) as filler, and curing accelerator Triphenylphosphine was kneaded with a heating roll in the formulation shown in Table 1 to obtain an epoxy resin composition. The epoxy resin composition was molded at 150 ° C., post-cured at 175 ° C. for 6 hours to obtain a cured product test piece, and then subjected to various physical property measurements. Table 1 shows the evaluation results. In addition, the compounding quantity shown in Table 1 is a weight part.

Comparative Example 4
A 1 L separable flask equipped with a stirrer was charged with 250 ml of methanol, deaerated by flowing nitrogen, and the system was kept under a nitrogen atmosphere. To this, 93 g (0.5 mol) of 4,4′- dihydroxybiphenyl and 146 g (1.1 mol) of 30% sodium hydroxide were added and dissolved, and then 41 g (0.17) of 1,6 -dibromohexane at 60 ° C. Mol) was added over 2 hours. Thereafter, the reaction was carried out for 4 hours with further stirring. The precipitated crystals were filtered, washed with water, suspended in 500 mL of water, neutralized with dilute hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain 41 g of white powdery crystals. The melting point based on the DSC method was 259.4 ° C. From the H ¹ -NMR measurement, it was confirmed that in the above general formula (2) , A was a 4,4′- biphenylene group, m was 1, and l was 6. Using this phenol compound, an epoxidation reaction was attempted in the same manner as in Example 1, but there was no solubility in epichlorohydrin and epoxidation could not be performed.

Industrial applicability

  The epoxy resin of the present invention is excellent in heat resistance, moisture resistance, low shrinkage and handling properties, and gives a cured product having a high degree of crystallinity. Therefore, the epoxy resin composition obtained by blending these has high thermal conductivity. When it is applied to sealing of semiconductor elements and printed wiring boards, it exhibits excellent high heat dissipation and dimensional stability.

Claims (9)

An epoxy resin composition comprising an epoxy resin and a curing agent, wherein an epoxy resin represented by the following general formula (1) is blended as an epoxy resin component , and 4,4′-dihydroxydiphenylmethane, 4,4 ′ as a curing agent -Dihydroxydiphenyl ether, 4,4'-dihydroxybiphenyl, hydroquinone, 1,5-naphthalenediol, 2,6-naphthalenediol, and reaction products of these bifunctional phenols with epichlorohydrin, these bifunctional phenols and bifunctional epoxy compounds In the differential scanning calorimetry characterized by blending at least one phenolic curing agent selected from the group consisting of the reaction product with the phenolic resin represented by the following general formula (2), from 100 ° C. It has an endothermic peak based on the melting point at 300 ° C. and converted to a resin component. The epoxy resin composition for heat to obtain a crystalline epoxy resin cured product is 5 J / g or more.

(In General Formula (1) and General Formula (2), A independently represents a non-mesogenic divalent aromatic group which may have a substituent, and l independently represents an integer of 3 to 30. M independently represents a number from 0.1 to 15, and n represents a number from 0 to 15. However, the non-mesogenic divalent aromatic group includes a phenylene group, a naphthylene group, an anthracene group, At least one selected from the group consisting of a diphenylmethane group, a 1,1-diphenylethane group, a 1,1,1-methyldiphenylethane group, a diphenyl ether group, a diphenyl sulfide group, a diphenyl sulfoxide group, a diphenyl sulfone group, and a diphenyl ketone group Species group.)   The epoxy resin composition according to claim 1, wherein in the general formula (1), m is an integer of 1 to 15. The epoxy resin composition according to claim 1 or 2 , wherein in the general formula (1), l is an integer of 6 to 8. The epoxy resin composition according to any one of claims 1 to 3, wherein the non-mesogenic divalent aromatic group is selected from a phenylene group, a naphthylene group, a diphenyl ether group, a diphenyl sulfide group, or a diphenylmethane group. The epoxy resin composition according to claim 1, wherein the non-mesogenic divalent aromatic group is a phenylene group or a diphenyl ether group . The epoxy resin composition according to any one of claims 1 to 5, wherein an inorganic filler is blended. The epoxy resin composition according to any one of claims 1 to 6, wherein the cured product obtained by curing the epoxy resin composition has an endothermic amount converted to a resin component of 10 J / g or more.   Hardened | cured material obtained by hardening the epoxy resin composition in any one of Claims 1-7.   9. The cured product according to claim 8, which has an endothermic peak based on a melting point from 100 ° C. to 300 ° C. in a differential scanning calorimetry, and an endothermic amount converted to a resin component is 5 J / g or more.

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