TW201800468A - Epoxy resin molding material, molded product, cured molded product and method of producing molded product - Google Patents

Abstract

An epoxy resin molding material includes: an epoxy resin A having a mesogenic structure and having a phase transition temperature of 140 DEG C or lower; a curing agent; and an inorganic filler.

Description

Epoxy resin molding material, molded article, molded hardened article, and manufacturing method of molded article

The present invention relates to an epoxy resin molding material, a molded product, a molded hardened product, and a method for manufacturing a molded product.

Insulating materials used in industrial and automotive motors, inverters, and other devices are widely used from the viewpoints of high insulation performance, ease of molding, and heat resistance. In recent years, the high output and miniaturization of these devices have been rapidly performed, and the level of characteristics required of insulating materials has been considerably improved. In particular, there is a tendency that the amount of heat generated from a conductor that is accompanied by the miniaturization of the device and the increase in density tends to increase, so how to dissipate the heat becomes an important issue. Therefore, various strategies have been tried to improve the thermal conductivity of the thermosetting resin after molding.

As the thermosetting resin having high thermal conductivity, a cured product of a resin composition has been proposed, and the resin composition includes an epoxy resin having a liquid crystal-based skeleton (for example, refer to Patent Document 1). The epoxy resin having a liquid crystal-based skeleton is, for example, those described in Patent Documents 2 to 4. As a thermosetting resin having high thermal conductivity and low softening point (melting point), an epoxy resin having a specific structure as described in Patent Document 5 has been proposed.

In addition, as a method for improving the thermal conductivity of the thermosetting resin after molding, a method of a composite material is obtained by mixing a thermosetting resin with a highly thermally conductive inorganic filler (for example, (See Patent Document 6). [Prior Art Literature] (Patent Literature)

Patent Literature 1: Japanese Patent No. 4118691 Patent Literature 2: Japanese Patent No. 4619770 Patent Literature 3: Japanese Patent Laid-Open No. 2010-241797 Patent Literature 4: Japanese Patent No. 5471975 Patent Literature 5: Japanese Patent No. 5127164 Patent Literature 6: Japanese Patent Laid-Open No. 2008-13759

[Problems to be Solved by the Invention] When an inorganic filler is mixed with a thermosetting resin, as the amount of the inorganic filler increases, the viscosity of the resin composition will increase, and workability will deteriorate, or the inorganic filler will deteriorate. Dispersibility tends to decrease. Furthermore, there are many cases where the affinity between the organic substance, that is, the thermosetting resin and the inorganic filler, causes pores at the interface between the thermosetting resin and the inorganic filler. Therefore, a decrease in thermal conductivity as a composite material and a deterioration in long-term reliability may occur.

In addition, an epoxy resin having a liquid crystal-based skeleton tends to have a high melting point due to the characteristics of the skeleton, and there is a problem that the fluidity of the resin composition is reduced and it becomes difficult to mold. As a countermeasure against this problem, it is generally considered that a method of improving the fluidity of the resin composition by adding a dispersant can be used. However, such a method may not exhibit high thermal conductivity after hardening.

The problem to be solved by the present invention is to provide an epoxy resin molding material that exhibits high thermal conductivity after curing, a molded article and a molded hardened product using the epoxy resin molding material, and a method for manufacturing the molded article. [Technical means to solve the problem]

The specific means for solving the aforementioned problems are as follows.

<1> An epoxy resin molding material comprising: epoxy resin A, which has a liquid crystal-based skeleton and whose phase transition temperature from a crystalline phase phase to a liquid crystal phase is 140 ° C or lower; a hardener; and, an inorganic filler.

<2> The epoxy resin molding material according to <1>, wherein the epoxy resin A includes a reactant, and the reactant is a dihydric phenol compound having two hydroxyl groups on one benzene ring and epoxy resin. Resin B. The epoxy resin B has a liquid crystal-based skeleton and has a property that a crystal phase can be changed into a liquid crystal phase.

<3> The epoxy resin molding material according to <2>, wherein the phase transition temperature of the epoxy resin B is 140 ° C or higher.

<4> The epoxy resin molding material according to <2> or <3>, wherein the epoxy resin A includes a reactant, and the reactant is an equivalent number of a phenolic hydroxyl group of the dihydric phenol compound and The ratio of the equivalent number of epoxy groups of the epoxy resin B, that is, the equivalent number of epoxy groups / the equivalent number of phenolic hydroxyl groups is set to 100/10 to 100/20.

<5> The epoxy resin molding material according to any one of <2> to <4>, wherein the epoxy resin B includes a compound represented by the following general formula (I).

In the general formula (I), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

<6> The epoxy resin molding material according to any one of <2> to <5>, wherein the dihydric phenol compound includes hydroquinone.

<7> The epoxy resin molding material according to any one of <1> to <6>, wherein the hardener includes a phenol-based hardener.

<8> The epoxy resin molding material according to <7>, wherein the phenol-based hardener contains a compound having a compound selected from the following general formula (II-1) and the following general formula (II- 2) At least one structural unit represented by the general formula in the group.

In the general formula (II-1) and the general formula (II-2), R ¹ each independently represents an alkyl group, an aryl group, or an aralkyl group, and the alkyl group, the aryl group, and the aralkyl group may have a substituent, R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and the alkyl group, aryl group, and aralkyl group may have a substituent, m each independently represents an integer of 0 to 2, and n Each independently represents an integer of 1 to 7.

<9> The epoxy resin molding material according to <7> or <8>, wherein the phenol-based hardened material contains a compound having a compound selected from the following formula (III-1) to the following general formula: A structural unit represented by at least one general formula in the group consisting of formula (III-4).

In the general formulae (III-1) to (III-4), m and n each independently represent a positive integer, and Ar each independently represents the following general formula (III-a) or the following general formula (III-b).

In the general formulae (III-a) and (III-b), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbon number of 1 to 8 alkyl.

<10> The epoxy resin molding material according to any one of <1> to <9>, further comprising a silane coupling agent.

<11> The epoxy resin molding material according to <10>, wherein the silane coupling agent includes a silane coupling agent having a phenyl group.

<12> The epoxy resin molding material according to <11>, wherein the silane coupling agent having a phenyl group has a structure in which a phenyl group is directly bonded to a silicon atom.

<13> The epoxy resin molding material according to any one of <10> to <12>, wherein an amount of silicon atoms derived from the silane coupling agent per unit specific surface area of the inorganic filler is attached. It is 5.0 × 10 ^-6 mol / m ² to 10.0 × 10 ^-6 mol / m ² .

<14> The epoxy resin molding material according to any one of <1> to <13>, wherein the inorganic filler includes at least one selected from the group consisting of magnesium oxide and aluminum oxide.

<15> The epoxy resin molding material according to any one of <1> to <14>, wherein the content of the inorganic filler is 60% to 90% by volume in the solid content.

<16> The epoxy resin molding material according to any one of <1> to <15>, wherein the epoxy resin molding material is in an A-stage state.

<17> The epoxy resin molding material according to <16>, wherein the mass reduction rate after heating at 180 ° C for 1 hour is 0.1% by mass or less.

<18> A molded article obtained by molding the epoxy resin molding material according to any one of <1> to <17>.

<19> The shaped article according to <18>, wherein the shaped article has a diffraction angle 2θ of 3.0 ° to 3.5 in an X-ray diffraction spectrum obtained by an X-ray diffraction method using CuKα rays. There is a diffraction peak in the range of °.

<20> A molded hardened product obtained by hardening the molded product according to <18> or <19>.

<21> The molded hardened product according to <20>, wherein the molded hardened product is obtained by hardening the molded product by heating.

<22> The shaped hardened product according to <20> or <21>, wherein the shaped hardened product is at a diffraction angle in an X-ray diffraction spectrum obtained by an X-ray diffraction method using CuKα rays. There is a diffraction peak in a range of 2θ from 3.0 ° to 3.5 °.

<23> A method for producing a molded article, which comprises an epoxy resin-containing resin according to any one of <1> to <17> within a temperature range of the phase transition temperature of the epoxy resin A and 150 ° C or lower. The epoxy resin molding material of A is molded. [Effect of the invention]

According to the present invention, it is possible to provide an epoxy resin molding material that exhibits high thermal conductivity after curing, a molded article and a molded cured product using the epoxy resin molding material, and a method for manufacturing the molded article.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps, etc.) are not necessary except for the case where they are specifically stated. The numerical values and their ranges are also not intended to limit the present invention.

In this specification, the use of a numerical range indicated by "~" means that the numerical values described before and after "~" are included as the minimum and maximum values, respectively. In the numerical ranges described in this specification in stages, the upper limit or lower limit of the numerical ranges described in one stage may be replaced by the upper or lower limits of the numerical ranges described in other stages. . In addition, in the numerical range described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the embodiment. Further, in this specification, each component may include a plurality of substances corresponding to the component. When a plurality of substances corresponding to each component are present in the composition, the content rate or content of each component means the total amount of the plurality of substances present in the composition unless otherwise specified. In the present specification, the particles corresponding to each component may include a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value of a mixture of the plurality of particles in the composition unless otherwise specified. In addition, in this specification, the term "step" is not only a step that is independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the desired purpose of the step can be achieved, it is also included in the step.

<Epoxy resin molding material> 的 The epoxy resin molding material of this embodiment contains: epoxy resin A, which has a liquid crystal-based skeleton, and whose phase transition temperature from a crystalline phase phase to a liquid crystal phase is 140 ° C. or less; and a hardener; and , Inorganic filler. The epoxy resin molding material of this embodiment may further contain other components as needed.

According to the epoxy resin molding material of this embodiment, high thermal conductivity can be exhibited after hardening. Although the reason is not clear, it can be considered that if the phase transition temperature of the epoxy resin is 140 ° C or lower, the epoxy resin will be easily melted when the epoxy resin molding material is produced. Therefore, It becomes easy to homogenize the epoxy resin molding material by kneading, and as a result, it is possible to suppress variations related to the generation of the liquid crystal phase. Hereinafter, each component contained in the epoxy resin molding material of this embodiment will be described in detail.

<Epoxy resin> The epoxy resin molding material contains epoxy resin A, which has a liquid crystal-based skeleton and has a phase transition temperature from a crystalline phase to a liquid crystal phase of 140 ° C. or lower. An epoxy resin having a liquid crystal-based skeleton has a tendency to easily form a high-order structure when cured, and to achieve a higher thermal conductivity when made into a cured product of an epoxy resin molding material.

In the present specification, the "liquid crystal-based skeleton" means a molecular structure having a possibility of expressing liquid crystallinity. Specific examples include a biphenyl skeleton, a phenyl benzoate skeleton, an azobenzene skeleton, a stilbene skeleton, and derivatives thereof. An epoxy resin having a liquid crystal-based skeleton has a tendency to easily form a high-order structure when hardened, and to achieve a higher thermal conductivity when made into a hardened material.

Here, the term "high-order structure" means a state in which its constituent elements are arranged minutely, and corresponds to, for example, a crystalline phase and a liquid crystal phase. Whether such a high-order structure exists can be easily determined by observing with a polarizing microscope. That is, when the interference fringes due to depolarization can be seen in the observation of the crossed-nicol state, it can be determined that a higher-order structure exists. Higher-order structures usually exist as islands in the resin and form a domain structure. Each of the islands forming a regional structure is called a high-order structure. In general, the structural units constituting a higher-order structure are bonded by covalent bonds.

The phase transition temperature of the epoxy resin A is 140 ° C or lower, and preferably 135 ° C or lower.

The phase transition temperature can be measured using a differential scanning calorimetry (DSC) measurement device (for example, Pyris 1 manufactured by PerkinElmer). Specifically, under the conditions of a nitrogen atmosphere with a temperature rising temperature of 20 ° C / min, a measurement temperature range of 25 ° C to 350 ° C, and a flow rate of 20 ± 5mL / min, 3 mg to 5 mg of a sealed aluminum pan was implemented The differential scanning calorimetry of the sample, and the energy change (endothermic reaction) accompanying the phase change can be measured as the temperature at which the phase change occurs. An example of the graph obtained by this measurement is shown in FIG. The temperature of the endothermic reaction peak appearing in Fig. 1 was taken as the phase transition temperature.

The epoxy resin A is not particularly limited as long as it has a liquid crystal-based skeleton and the phase transition temperature from a crystalline phase phase to a liquid crystal phase is 140 ° C or lower. For example, the epoxy resin A may be an epoxy compound or an oligomer of the epoxy compound. The oligomer may be a reactant of epoxy compounds, or may be in a state of a prepolymer obtained by partially reacting a part of the epoxy compound with a hardener or the like. The curing agent used for prepolymerization may be the same as or different from the curing agent contained in the epoxy resin composition. Partial polymerization of an epoxy compound having a liquid crystal-based skeleton may improve moldability in some cases. The epoxy compound used for the pre-polymerization is preferably epoxy resin B, which has a liquid crystal-based skeleton and has a property of changing from a crystalline phase phase to a liquid crystal phase. The phase transition temperature of the epoxy resin B may be 140 ° C or lower, or may exceed 140 ° C.

In particular, when the phase transition temperature of the epoxy resin B exceeds 140 ° C., the epoxy resin B is preferably used as a reactant in which the epoxy resin B has 2 on one benzene ring. A dihydric phenol compound having a hydroxyl group as a substituent is reacted and prepolymerized. The use of such a dihydric phenol compound is preferable from the viewpoint of controlling the molecular weight, thermal conductivity, and glass transition temperature (Tg) of the epoxy resin. In addition, if the epoxy resin B and the dihydric phenol compound are partially reacted to perform prepolymerization, the phase transition temperature can be reduced. Therefore, even if the phase transition temperature of the epoxy resin B exceeds 140 ° C, it can be easily used. In general, because the phase transition temperature of an epoxy resin having a liquid crystal-based skeleton is high, it is beneficial to a method for prepolymerization.

When the phenol compound used for prepolymerization is a monovalent phenol compound having one hydroxyl group in one molecule, the thermal conductivity may be lowered due to a decrease in the crosslinking density after curing. On the other hand, when the phenol compound used for the prepolymerization has three or more hydroxyl groups in one molecule, it is difficult to control the reaction during the prepolymerization, and there is a case of gelation. In addition, when a dihydric phenol compound having two or more benzene rings is used, the structure of the epoxy resin becomes hard, and although it has a favorable effect on the high thermal conductivity, the softening point becomes high and there is The handleability tends to decrease (for example, refer to Japanese Patent No. 5019272).

The compound that reacts with the epoxy resin B may be an amine compound in addition to the specific dihydric phenol compound. However, when an amine compound is used, secondary or tertiary amines are generated in the epoxy resin obtained by prepolymerization, so the storage stability of the epoxy resin itself and the epoxy resin may be deteriorated in some cases. The storage stability of the epoxy resin molding material after blending with the hardener may decrease.

The epoxy resin B may be used individually by 1 type, and may use 2 or more types together. Specific examples of the epoxy resin B are described in, for example, Japanese Patent No. 4118691. Specific examples of the epoxy resin B are shown below, but the present invention is not limited to these examples.

Examples of the epoxy resin B include 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1- Cyclohexene, 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -benzene, 4- (2, 3-epoxypropoxy) benzoic acid = 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl and the like. Among these epoxy resins, it is preferable to use a material selected from the group consisting of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4 -Oxiranylmethoxyphenyl) -benzene and 4- (2,3-epoxypropoxy) benzoic acid = 4- {4- (2,3-epoxypropoxy) benzene At least one of the group consisting of cyclohexyl ester.

Further, from the viewpoint of improving the fluidity of the molding material, when the epoxy resin B is changed from a crystalline phase to a liquid crystal phase, although a nematic liquid crystal structure with low order can be formed by a single type, The polymerization is preferably an epoxy resin capable of forming a more ordered smectic liquid crystal structure. Examples of such a resin include compounds represented by the following general formula (I).

Among the compounds represented by the general formula (I), compounds represented by the following general formula (I-1) are preferred.

In the general formula (I) and the general formula (I-1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Examples of the dihydric phenol compound having two hydroxyl groups on one benzene ring include catechol, resorcinol, hydroquinone, and derivatives of these dihydric phenol compounds. Examples of the derivative include compounds in which a benzene ring is substituted with an alkyl group having 1 to 8 carbon atoms. Among these dihydric phenol compounds, hydroquinone is preferably used from the viewpoint of improving thermal conductivity. Hydroquinone has a structure in which two hydroxyl groups are substituted in a para positional relationship, so a prepolymerized epoxy resin obtained by reacting with an epoxy resin has a linear structure. Therefore, it is considered that the stackability of the molecules is high and a high-order structure is easily formed. Dihydric phenol compounds can be used alone or in combination of two or more

When the epoxy resin A is a reactant of the epoxy resin B and the dihydric phenol compound, the epoxy resin A can be synthesized, for example, by dissolving the epoxy resin B, the dihydric phenol compound, and the reaction catalyst. In a synthetic solvent, stirring was performed while applying heat. Although the epoxy resin A can be synthesized by melting and reacting the epoxy resin B and the dihydric phenol compound without using a synthetic solvent, it is necessary to raise the temperature to a temperature at which the epoxy resin melts. Therefore, from the viewpoint of safety, a synthetic method using a synthetic solvent is preferred.

When synthesizing the reaction product of epoxy resin B and a dihydric phenol compound, the ratio of the number of phenolic hydroxyl equivalents of the dihydric phenol compound to the number of epoxy equivalents of epoxy resin B, that is, the equivalent of epoxy groups The number / equivalent number of phenolic hydroxyl group is preferably 100/10 to 100/30, more preferably 100/10 to 100/20, and still more preferably 100/10 to 100/15.

The synthesis solvent is not particularly limited as long as it is a solvent that can be heated to a temperature necessary for the reaction between the epoxy resin B and the dihydric phenol compound. Specific examples include cyclohexanone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether, and N-methylpyrrolidone.

The amount of the synthesis solvent is preferably an amount capable of dissolving all of the epoxy resin B, the dihydric phenol compound, and the curing catalyst at the reaction temperature. Although solubility varies depending on the kind of raw materials, the kind of solvent, and the like before the reaction, it is preferable to set the concentration of the synthetic solid content to 20 to 60% by mass. When the amount of such a synthetic solvent is set, the viscosity of the resin solution after synthesis tends to be in a preferable range.

The type of the reaction catalyst is not particularly limited, and a suitable reaction catalyst can be selected from the viewpoints of reaction rate, reaction temperature, storage stability, and the like. Specific examples of the reaction catalyst include imidazole-based compounds, organic phosphorus-based compounds, tertiary amines, and quaternary ammonium salts. These reaction catalysts may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of heat resistance, at least one selected from the group consisting of: an organic phosphine compound; a compound having an intramolecular polarization is preferred, which is to have a π bond Compound added to an organic phosphine compound, the compound having a π bond is maleic anhydride, a quinone compound (1,4-benzoquinone, 2,5-methylquinone, 1,4-naphthoquinone, 2,3 -Dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4 -Benzoquinone, phenyl-1,4-benzoquinone, etc.), diazotoluene, phenol resin, etc .; and organic phosphine compounds and organic boron compounds (tetraphenyl borate, tetra-p-tolyl borate, tetra-n-borate) Butyl ester, etc.).

Examples of the organic phosphine compound include triphenylphosphine, diphenyl (p-toluene) phosphine, tri (alkylbenzene) phosphine, tri (alkoxybenzene) phosphine, tri (alkylalkoxybenzene) phosphine, and tri ( Dialkylbenzene) phosphine, tris (trialkylbenzene) phosphine, tris (tetraalkylbenzene) phosphine, tris (dialkoxybenzene) phosphine, tris (trialkoxybenzene) phosphine, tris (tetraalkoxy) Phenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and the like.

The amount of the reaction catalyst is not particularly limited. From the viewpoint of reaction rate and storage stability, it is preferably 0.1% by mass to 1.5% by mass, and more preferably 0.2% by mass to 1% by mass based on the total mass of the epoxy resin B and the dihydric phenol compound.

The reaction product of the epoxy resin B and the dihydric phenol compound can be synthesized using a glass flask if it is a small scale, and a stainless steel reactor can be used if it is a large scale. Specific synthesis methods are described below, for example. First, the epoxy resin B is put into a flask or a reactor, and then a synthetic solvent is poured, and the epoxy resin B is dissolved by heating to a reaction temperature by an oil bath or a heating medium. Then, the dihydric phenol compound was charged into the flask or reactor, and after confirming that the dihydric phenol compound was sufficiently dissolved in the synthetic solvent, the reaction catalyst was charged and the reaction was started. As long as the reaction solution is taken out after a certain time, a reactant solution of the epoxy resin B and the dihydric phenol compound can be obtained. In addition, in a flask or a reactor, as long as the synthesis solvent is distilled off under reduced heating conditions, the reactant of the epoxy resin B and the dihydric phenol compound can be used at room temperature (for example, 25 ° C). Obtained as a solid.

The reaction temperature is not limited as long as it is a temperature at which an epoxy group and a phenolic hydroxyl group can react in the presence of a reaction catalyst. For example, the reaction temperature is preferably in the range of 100 ° C to 180 ° C, and more preferably 120 ° C to 170. ℃ range. By setting the reaction temperature to 100 ° C or higher, there is a tendency that the time until the reaction is completed can be further shortened. On the other hand, by setting the reaction temperature to 180 ° C. or lower, gelation tends to be suppressed.

The epoxy group equivalent of the epoxy resin A is preferably 130 g / eq to 500 g / eq, more preferably 135 g / eq to 400 g / eq, and still more preferably 140 g / eq to 300 g / eq. The epoxy group equivalent can be measured by a perchloric acid titration method in accordance with Japanese Industrial Standard JIS K7236: 2009.

<Hardener> An epoxy resin molding material contains a hardener. As the hardener, a hardener generally used in the technical field can be used without particular limitation. Examples of the curing agent include polyaddition-type curing agents such as acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, and thiol-based curing agents; and other latent curing agents such as imidazole. From the viewpoints of heat resistance and adhesiveness, an amine-based hardener or a phenol-based hardener is preferred. Furthermore, from the viewpoint of storage stability, a phenol-based hardener is more preferable.

As a phenolic hardening | curing agent, the phenolic hardening | curing agent used normally can be used, It does not specifically limit. For example, a phenol compound and a phenol resin obtained by novolacizing a phenol compound can be used.

Examples of the phenol compound include monofunctional phenol compounds such as phenol, o-cresol, m-cresol, and p-cresol; bifunctional phenol compounds such as catechol, resorcin, and hydroquinone; 1, Trifunctional phenol compounds such as 2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene. Examples of the phenol resin include a phenol novolak resin, which is obtained by bonding these phenol compounds with a methylene chain or the like to form a novolac.

As the phenol-based hardener, from the viewpoint of thermal conductivity, bifunctional phenol compounds such as catechol, resorcinol, and hydroquinone, or bifunctional phenol compounds are preferably carried out in a methylene chain. From the viewpoint of heat resistance, a phenol novolak resin obtained by bonding is more preferably a phenol novolak resin obtained by bonding a bifunctional phenol compound with a methylene chain.

Examples of the phenol novolak resin include novolacization of one of the phenol compounds, such as cresol novolac resin, catechol novolac resin, resorcinol novolac resin, and hydroquinone novolac resin. Resin produced; catechol resorcinol novolac resin, resorcinol hydroquinone novolac resin, and the like obtained by novolacizing two or more phenol compounds.

When a phenol novolak resin is used as the phenol-based hardener, it is preferable to include a compound having a group selected from the group consisting of the following general formula (II-1) and the following general formula (II-2) A structural unit represented by at least one of the general formulae.

In the general formula (II-1) and the general formula (II-2), R ¹ each independently represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, and aralkyl group represented by R ¹ may further have a substituent. Examples of the substituent include an alkyl group (except when R ¹ is an alkyl group), an aryl group, a halogen atom, a hydroxyl group, and the like. m each independently represents an integer of 0 to 2. When m is 2, the two R ¹ may be the same or different. m is preferably each independently 0 or 1, and more preferably 0. In addition, n each independently represents an integer of 1 to 7.

In the general formula (II-1) and the general formula (II-2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, and aralkyl group represented by R ² and R ³ may further have a substituent. Examples of the substituent include an alkyl group (except when R ² and R ³ are alkyl groups), an aryl group, a halogen atom, a hydroxyl group, and the like.

As R ² and R ³ in the general formulae (II-1) and (II-2), from the viewpoint of storage stability and thermal conductivity, a hydrogen atom, an alkyl group or an aryl group is preferred, and hydrogen is more preferred. An atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms is more preferably a hydrogen atom.

Among compounds having a structural unit represented by the general formula (II-1), as a partial structure derived from a phenol compound other than resorcinol, it is preferably derived from the viewpoint of thermal conductivity and adhesiveness. Free phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene The partial structure of at least one of the groups is more preferably a partial structure derived from at least one selected from the group consisting of catechol and hydroquinone.

Among the compounds having a structural unit represented by the general formula (II-2), as a partial structure derived from a phenol compound other than catechol, it is preferably derived from the viewpoint of thermal conductivity and adhesiveness. Free phenol, cresol, resorcinol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene The partial structure of at least one of these is more preferably a partial structure derived from at least one selected from the group consisting of resorcinol and hydroquinone.

Here, the partial structure derived from a phenol compound means a mono- or di-valent group formed by removing one or two hydrogen atoms from a benzene ring portion of the phenol compound. The position at which the hydrogen atom is removed is not particularly limited.

Moreover, in the compound which has a structural unit represented by General formula (II-1), the content rate of the partial structure derived from resorcinol is not specifically limited. From the viewpoint of the elastic modulus, the content ratio of the partial structure derived from resorcinol to the total mass of the compound having a structural unit represented by the general formula (II-1) is preferably 55% by mass or more. From the viewpoint of the glass transition temperature (Tg) and linear expansion coefficient of the hardened material, it is more preferably 60% by mass or more, and still more preferably 80% by mass or more. From the viewpoint of thermal conductivity, it is particularly preferably 90% by mass. the above.

Moreover, in the compound which has a structural unit represented by General formula (II-2), the content rate of the partial structure derived from a catechol is not specifically limited. From the viewpoint of the elastic modulus, the content ratio of the partial structure derived from catechol to the total mass of the compound having a structural unit represented by the general formula (II-2) is preferably 55% by mass or more. From the viewpoint of the glass transition temperature (Tg) and linear expansion coefficient of the hardened material, it is more preferably 60% by mass or more, and still more preferably 80% by mass or more. From the viewpoint of thermal conductivity, it is particularly preferably 90% by mass. the above.

The molecular weight of the compound having a structural unit represented by at least one general formula selected from the group consisting of general formula (II-1) and general formula (II-2) is not particularly limited. From the viewpoint of fluidity, the number average molecular weight (Mn) is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 350 to 1500. The weight average molecular weight (Mw) is preferably 2,000 or less, more preferably 1500 or less, and still more preferably 400 to 1500. These Mn and Mw can be measured by a general method using gel permeation chromatography (GPC).

The hydroxyl equivalent of the compound having a structural unit represented by at least one general formula selected from the group consisting of general formula (II-1) and general formula (II-2) is not particularly limited. From the viewpoint of the crosslinking density contributing to heat resistance, the hydroxyl equivalent is an average value, preferably 50 g / eq to 150 g / eq, more preferably 50 g / eq to 120 g / eq, and still more preferably 55 g / eq ～ 120g / eq. The hydroxy equivalent means a value measured in accordance with Japanese Industrial Standard JIS K0070: 1992.

When a compound having a structural unit represented by at least one general formula selected from the group consisting of the general formula (II-1) and the general formula (II-2) is used as the phenol-based hardener, the compound is hardened in the phenol-based system. The proportion of the compound having a structural unit represented by at least one general formula selected from the group consisting of general formula (II-1) and general formula (II-2) in the agent is preferably 50% by mass The above is more preferably 80% by mass or more, and still more preferably 90% by mass or more.

When a phenol novolak resin is used as the phenol-based hardener, the phenol novolak resin preferably contains a compound having a compound selected from the following formula (III-1) to the following formula (III-4) At least one structural unit represented by the general formula in the group consisting of).

In the general formulae (III-1) to (III-4), m and n each independently represent a positive integer, and m or n represents the number of respective structural units to which they are attached. In addition, Ar each independently represents a group represented by the following general formula (III-a) or the following general formula (III-b).

In the general formula (III-a) and the general formula (III-b), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

A compound having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) is capable of being novolacized by dihydric phenol compounds. A compound produced by a manufacturing method.

A structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) can be included as a main chain skeleton of a phenol novolac resin, or as a phenol novolac Part of the side chain of the varnish resin is contained. Further, each of the structural units constituting a partial structure represented by any one of the general formulae (III-1) to (III-4) may be included randomly or may be included regularly, It may be contained in blocks. In addition, in the general formulae (III-1) to (III-4), the substitution position of the hydroxyl group is not particularly limited as long as it is on the aromatic ring.

Regarding the respective general formulae (III-1) to (III-4), the plurality of Ars present may be all the same atomic groups, or may include two or more kinds of atomic groups. In addition, Ar each independently represents a group represented by the general formula (III-a) or the general formula (III-b).

R ¹¹ and R ¹⁴ in the general formula (III-a) and the general formula (III-b) each independently represent a hydrogen atom or a hydroxyl group, and from the viewpoint of thermal conductivity, a hydroxyl group is preferred. The substitution positions of R ¹¹ and R ¹⁴ are not particularly limited.

In addition, R ¹² and R ¹³ in the general formula (III-a) each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms in R ¹² and R ¹³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and pentyl. , Hexyl, heptyl, and octyl. The substitution positions of R ¹² and R ¹³ in the general formula (III-a) are not particularly limited.

From the viewpoint of achieving more excellent thermal conductivity, Ar in the general formulae (III-1) to (III-4) is preferably selected from the group consisting of a dihydroxybenzene-derived group (in the general formula (III) In -a), R ¹¹ is a hydroxyl group and R ¹² and R ¹³ are a hydrogen atom group) and a dihydroxynaphthalene-derived group (in the general formula (III-b), R ¹⁴ is a hydroxyl group ) At least one of the groups.

Here, the "dihydroxybenzene-derived group" means a binary group formed by removing two hydrogen atoms from the aromatic ring portion of the dihydroxybenzene, and the position where the hydrogen atom is removed is not particularly limited. . In addition, the meaning of "group derived from dihydroxynaphthalene" has the same meaning.

From the viewpoint of productivity and fluidity of the epoxy resin molding material, Ar is more preferably a group derived from dihydroxybenzene, and more preferably selected from the group consisting of 1,2-dihydroxybenzene (o-benzene). At least one of the group consisting of a diphenol) group and a group derived from 1,3-dihydroxybenzene (resorcinol). In particular, from the viewpoint of particularly improving thermal conductivity, it is preferable that Ar includes at least a resorcinol-derived group. From the viewpoint of particularly improving thermal conductivity, the structural unit represented by the structural unit n preferably contains a resorcinol-derived group.

When a compound having a structure represented by at least one selected from the group consisting of general formulae (III-1) to (III-4) contains a resorcinol-derived structural unit, resorcinol-derived The content rate of the structural unit of phenol is a compound having a structure represented by at least one selected from the group consisting of general formulae (III-1) to (III-4) from the viewpoint of the elastic modulus. Of the total weight, 55% by mass or more is preferred. From the viewpoint of the Tg and linear expansion coefficient of the cured product, it is more preferably 60% by mass or more, and even more preferably 80% by mass or more. From the viewpoint of thermal conductivity Look, especially good is 90% by mass or more.

Regarding m and n in the general formulae (III-1) to (III-4), from the viewpoint of fluidity, m / n = 20/1 to 1/5, and more preferably 20 / 1 to 5/1, and more preferably 20/1 to 10/1. From the viewpoint of fluidity, (m + n) is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The lower limit of (m + n) is not particularly limited.

Compound having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4), especially when Ar is a substituted or unsubstituted dihydroxybenzene In the case of at least one of a group derived from a substituted or unsubstituted dihydroxynaphthalene, the comparison of such a compound with a phenol resin obtained only by novolacization, etc., is easy to synthesize, and A tendency to obtain a hardener having a low softening point. Therefore, by including such a phenol resin as a hardener, there are advantages such that manufacturing and handling of an epoxy resin molding material become easy.

Further, whether or not the phenol novolac resin has a partial structure represented by any one of the general formulae (III-1) to (III-4) is determined by a field desorption mass spectrometer (FD-MS) by It can be judged whether the fragment component contains the component corresponding to the partial structure represented by any one of said general formula (III-1)-said general formula (III-4).

The molecular weight of the compound having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) is not particularly limited. From the viewpoint of fluidity, the number average molecular weight (Mn) is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 350 to 1500. The weight average molecular weight (Mw) is preferably 2,000 or less, more preferably 1500 or less, and still more preferably 400 to 1500. These Mn and Mw can be measured by a general method using GPC (gel permeation chromatography).

The hydroxyl equivalent of the compound having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) is not particularly limited. From the viewpoint of the crosslinking density contributing to heat resistance, the hydroxyl equivalent is an average value, preferably 50 g / eq to 150 g / eq, more preferably 50 g / eq to 120 g / eq, and still more preferably 55 g / Eq ～ 120g / eq.

When a compound having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) is used as the phenolic hardener, the phenolic hardener Among them, the proportion of compounds having a structure represented by at least one general formula selected from the group consisting of general formulae (III-1) to (III-4) is preferably 50% by mass or more, It is more preferably 80% by mass or more, and still more preferably 90% by mass or more.

As the phenolic hardener, a compound having a structural unit represented by at least one general formula selected from the group consisting of general formula (II-1) and general formula (II-2) is used, or a compound having a In the case of a compound having a structure represented by at least one general formula in the group consisting of general formula (III-1) to general formula (III-4), the phenol-based hardener may include a phenol compound, that is, a monomer. The compound constitutes a compound having a structural unit represented by at least one general formula selected from the group consisting of general formula (II-1) and general formula (II-2), or a compound having a structural unit selected from general formula (III-1) ) To a compound having a structure represented by at least one general formula in the group consisting of general formula (III-4). The content ratio of the phenol compound, that is, the monomer (hereinafter, also referred to as "monomer content") is not particularly limited. From the viewpoint of thermal conductivity and moldability, the phenol-based hardener is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass. %.

By using the monomer content ratio of 80% by mass or less, monomer components that do not contribute to cross-linking during the hardening reaction will be reduced, and high-molecular-weight molecules that undergo cross-linking will increase, so a higher-density high-order structure can be formed. And there is a tendency to improve thermal conductivity. Moreover, since the monomer content ratio is 5 mass% or more, since it is easy to flow during molding, adhesion to the inorganic filler can be further improved, and more excellent thermal conductivity and heat resistance tend to be achieved.

The content of the hardener is not particularly limited. For example, when a phenolic hardener is used as the hardener, the number of equivalents of active hydrogen of the phenolic hydroxyl group (equivalent number of phenolic hydroxyl group) contained in the phenolic hardener and the epoxy group contained in the epoxy resin The ratio of the number of equivalents, that is, the number of equivalents of the phenolic hydroxyl group / the number of equivalents of the epoxy group, is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2.

<Inorganic Filler> An epoxy resin molding material contains at least one inorganic filler. By including an inorganic filler and a cured product of an epoxy resin molding material, thermal conductivity can be improved. The inorganic filler is preferably insulating. In this specification, the "insulation property" of an inorganic filler refers to a property that an inorganic filler itself does not flow a current even when a voltage of about several hundred to several thousand volts is applied, and this property is due to its own price The electron energy band (valence band) is caused by a large energy gap to the next band (conduction band) above it. The valence electron energy band is the highest energy level occupied by the electron.

Specific examples of the inorganic filler include boron nitride, aluminum oxide, silicon dioxide, aluminum nitride, magnesium oxide, silicon oxide, aluminum hydroxide, and barium sulfate. Among them, at least one selected from the group consisting of magnesium oxide and aluminum oxide is preferable from the viewpoints of fluidity, thermal conductivity, and electric insulation. Further, as long as the fluidity is not impaired, boron nitride, silicon dioxide, aluminum nitride, and the like may be further contained.

In the inorganic filler, the total proportion of at least one inorganic filler selected from the group consisting of magnesium oxide and aluminum oxide is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably It is 90% by mass or more.

The inorganic filler may have a single peak or a plurality of peaks when the particle size distribution curve is plotted with the horizontal axis as the particle diameter and the vertical axis as the frequency. By using an inorganic filler having a plurality of wave peaks in a particle size distribution curve, there is a tendency that the filling property of the inorganic filler can be improved and the thermal conductivity of the epoxy resin molding material as a molding hardened material can be improved.

When the particle size distribution curve is drawn, when the inorganic filler has a single peak, it corresponds to a cumulative average particle diameter (D50) of 50%. From the viewpoint of thermal conductivity, it is preferably 0.1 μm to 100 μm, and more preferably 0.1 μm to 70 μm, and this cumulative 50% is obtained by accumulating the small particle diameter side of the weight cumulative particle size distribution of the inorganic filler. The average particle diameter of the inorganic filler can be measured using a particle size distribution obtained by a laser diffraction method, and can be implemented using a laser diffraction scattering particle size distribution device (for example, Beckman Coulter, LS230).

The inorganic filler having a particle size distribution curve having a plurality of peaks can be configured by, for example, combining two or more inorganic fillers having different average particle diameters.

The content of the inorganic filler in the epoxy resin molding material is not particularly limited. From the viewpoint of thermal conductivity and moldability, when the total volume of the solid content of the epoxy resin molding material is 100% by volume, the content of the inorganic filler is preferably 60% to 90% by volume, and more preferably It is 70% to 85% by volume. By using the content of the inorganic filler at 60% by volume or more, higher thermal conductivity can be achieved. On the other hand, an epoxy resin molding material having excellent moldability can be obtained by using a content of the inorganic filler of 90% by volume or less.

In addition, the solid content of the epoxy resin molding material in the present invention means a component remaining after the volatile component is removed from the epoxy resin molding material.

The content (vol%) of the inorganic filler in the epoxy resin molding material is a value obtained by the following formula. Content of inorganic filler (volume%) = {(Cw / Cd) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd) + (Ew / Ed) + (Fw ／ Fd))} × 100

Here, each variable is as follows. Aw: mass composition ratio (mass%) of epoxy resin A Bw: mass composition ratio (mass%) of hardener Cw: mass composition ratio (mass%) of inorganic filler Dw: hardening accelerator used as required Mass composition ratio (mass%) Ew: Mass composition ratio (mass%) of the silane coupling agent used as required Fw: Mass composition ratio (mass%) of other components used as needed Ad: Specific gravity of epoxy resin A Bd: Specific gravity of the hardener Cd: Specific gravity of the inorganic filler Dd: Specific gravity of the hardening accelerator used as required Ed: Specific gravity of the silane coupling agent used as required Fd: Specific gravity of other components used as required

<Hardening Accelerator> An epoxy resin molding material may contain a hardening accelerator as needed. (2) By using a hardening accelerator together with a hardener, the epoxy resin molding material can be further hardened sufficiently. The type and compounding amount of the hardening accelerator are not particularly limited, and an appropriate hardening accelerator can be selected from the viewpoints of reaction rate, reaction temperature, and storage properties.

Specific examples of the hardening accelerator include imidazole-based compounds, organic phosphorus-based compounds, tertiary amines, and quaternary ammonium salts. These hardening accelerators may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of heat resistance, at least one selected from the group consisting of: an organic phosphine compound; a compound having an intramolecular polarization is preferred, which is to have a π bond Compound added to an organic phosphine compound, the compound having a π bond is maleic anhydride, a quinone compound (1,4-benzoquinone, 2,5-methylquinone, 1,4-naphthoquinone, 2,3 -Dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4 -Benzoquinone, phenyl-1,4-benzoquinone, etc.), diazotoluene, phenol resin, etc .; and organic phosphine compounds and organic boron compounds (tetraphenyl borate, tetra-p-tolyl borate, tetra-n-borate) Butyl ester, etc.).

Specific examples of the organic phosphine compound include triphenylphosphine, diphenyl (p-toluene) phosphine, tri (alkylbenzene) phosphine, tri (alkoxybenzene) phosphine, and tri (alkylalkoxybenzene). Phosphine, tris (dialkylbenzene) phosphine, tris (trialkylbenzene) phosphine, tris (tetraalkylbenzene) phosphine, tris (dialkoxybenzene) phosphine, tris (trialkoxybenzene) phosphine, tris (Tetraalkoxybenzene) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and the like.

When the epoxy resin molding material contains a hardening accelerator, the content of the hardening accelerator in the epoxy resin molding material is not particularly limited. From the viewpoint of fluidity and moldability, the content of the hardening accelerator is preferably 0.1% to 1.5% by mass, and more preferably 0.2% to 1% by mass relative to the total mass of the epoxy resin and the curing agent. %.

<Silane coupling agent> The epoxy resin molding material may contain a silane coupling agent as required. By using a silane coupling agent, the surface of the inorganic filler material can interact with the epoxy resin surrounding it to improve fluidity and achieve high thermal conductivity. It can also prevent moisture from penetrating. The tendency to improve insulation reliability.

The type of the silane coupling agent is not particularly limited, and one type may be used alone, or two or more types may be used in combination. Among these, a silane coupling agent having a phenyl group is preferred. Silane coupling agents with phenyl groups easily interact with epoxy resins with a liquid crystal-based skeleton. Therefore, when an epoxy resin molding material is made into a hardened | cured material by containing the silane coupling agent containing a phenyl group, there exists a tendency for the more excellent thermal conductivity.

The type of the silane coupling agent having a phenyl group is not particularly limited. Specific examples of the silane coupling agent having a phenyl group include 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, and N-methylanilinepropyl Trimethoxysilane, N-methylanilinopropyltriethoxysilane, 3-phenyliminopropyltrimethoxysilane, 3-phenyliminopropyltriethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and the like. Silane coupling agents having a phenyl group may be used singly or in combination of two or more kinds. Commercially available silane coupling agents having a phenyl group can also be used.

The proportion of the silane coupling agent having a phenyl group in the entire silane coupling agent is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

A silane coupling agent containing a phenyl group directly bonded to a silicon (Si) atom is more preferable from the viewpoint that the surface of the inorganic filler is brought close to the epoxy resin surrounding the inorganic filler to achieve excellent thermal conductivity.

In the silane coupling agent having a phenyl group, the proportion of the silane coupling agent in which a phenyl group is directly bonded to a silicon (Si) atom is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably It is 80% by mass or more.

When the epoxy resin molding material contains a silane coupling agent, the silane coupling agent may exist in a state of being attached to the surface of the inorganic filler, or may exist in a state of not being attached to the surface of the inorganic filler. These states are mixed.

When the adhesion amount of Silane coupling agent attached to at least a portion of the surface of the inorganic filler, the inorganic filler per unit derived from a silane-coupling agent in the specific surface area of silicon atoms, is preferably 5.0 × 10 ^{- 6} mole / m ² ~ 10.0 × 10 ^{- 6} mole / m ^2, more preferably is 5.5 × 10 ^{- 6} mole ^{/ m 2 ~ 9.5 × 10 -} 6 mole / m ^2, further preferably is 6.0 × 10 ^{- 6} mole / m ² ~ 9.0 × 10 ^{- 6} mole / m ^2.

The measuring method of the adhesion amount of the silicon atom derived from the silane coupling agent per unit specific surface area of an inorganic filler is as follows. First, as a method for measuring the specific surface area of the inorganic filler, a BET method can be mainly used. The so-called BET method is a gas adsorption method in which inert gas molecules such as nitrogen (N ₂ ), argon (Ar), and krypton (Kr) are adsorbed on solid particles, and then the amount of the adsorbed gas molecules To determine the specific surface area of the solid particles. The specific surface area can be measured using a specific surface area pore distribution measurement device (for example, Beckman Coulter, SA3100).

Furthermore, the silicon atom derived from the silane coupling agent existing on the surface of the inorganic filler was quantified. Examples of the quantitative method include ²⁹ Si CP / MAS (Cross polarization / magic angle spinning) solid state NMR (nuclear magnetic resonance). A nuclear magnetic resonance device (for example, JNM-ECA700 manufactured by Japan Electronics Co., Ltd.) has high decomposition ability, so even when the epoxy resin molding material contains silicon dioxide as an inorganic filler, it can be derived from The silicon atom of silicon dioxide is distinguished from the silicon atom derived from a silane coupling agent. When the epoxy resin molding material does not contain a silicon atom other than the silicon atom derived from the silane coupling agent, the silane coupling agent can also be subjected to an X-ray fluorescence analysis device (for example, manufactured by Science Division, Supermini200). Quantification of silicon atoms.

Based on the specific surface area of the inorganic filler obtained as described above, and the amount of silicon atoms derived from the silane coupling agent present on the surface of the inorganic filler, the silane couple origin per unit specific surface area of the inorganic filler can be calculated The amount of silicon atoms attached to the mixture.

By performing the above measurement, the inorganic filler contained in the epoxy resin molding material can be taken out from the epoxy resin molding material by, for example, the methods listed below. (1) An epoxy resin molding material is placed in a ceramic crucible, and the resin component is burned by heating (for example, 600 ° C.) using a muffle furnace or the like. (2) The resin component of the epoxy resin molding material is dissolved in an appropriate solvent, the inorganic filler is recovered by filtration, and then dried.

When an epoxy resin molding material contains a silane coupling agent, the method of adding a silane coupling agent to an epoxy resin molding material is not specifically limited. Specifically, the following methods can be enumerated: an integral method in which a silane coupling agent is added when mixing other materials such as an epoxy resin and an inorganic filler; and a masterbatch method in which a specific amount is added After mixing the silane coupling agent in a small amount of resin, the mixture is mixed with other materials such as inorganic fillers; the pre-treatment method is to mix the inorganic filler with the silane coupling agent before mixing with other materials such as epoxy resin. They are mixed and treated with a silane coupling agent on the surface of the inorganic filler in advance. Examples of the pretreatment method include: a dry method in which a stock solution or solution of a silane coupling agent is dispersed by high-speed stirring together with an inorganic filler, and a wet method uses a dilute solution of a silane coupling agent. The inorganic filler is slurried, or the silane coupling agent is immersed in the inorganic filler, and the surface of the inorganic filler is treated with a silane coupling agent.

<Other components> In addition to the above-mentioned components, the epoxy resin molding material may contain other components. Examples of other components include: release agents such as oxidized or non-oxidized polyolefins, carnauba wax, octadecanoate, octadecanoic acid, and stearic acid; silicone oil, silicone rubber powder, etc. Stress relaxant; glass fiber and other reinforcing materials. Other components may be used individually by 1 type, and may use 2 or more types together.

<The preparation method of an epoxy resin molding material> The preparation method of an epoxy resin molding material is not specifically limited. As a general method, the following method can be mentioned: after fully mixing the component of a specific compounding quantity with a mixer, melt-kneading the mixture, cooling, and pulverizing. Melt kneading can be performed, for example, using a kneader, a mixing roll, an extruder, or the like that is heated to 70 ° C to 140 ° C in advance. An epoxy resin molding material is easy to use if it is formed into a tablet in a size and quality that match the molding conditions.

<State of the epoxy resin molding material> The epoxy resin molding material is preferably in an A-stage state. If the epoxy resin molding material is in the A-stage state, when the epoxy resin molding material is heat-treated for hardening, compared with the epoxy resin molding material in the B-stage state, a hardening reaction occurs between the epoxy resin and the hardener. The amount of reaction heat generated at this time increases, and the hardening reaction becomes easy to proceed. In this specification, the definitions of the terms used in A-stage and B-stage are based on Japanese Industrial Standard JIS K 6800: 1985.

Whether the epoxy molding material is in the A-stage state can be judged by the following criteria. Put a certain amount of epoxy resin molding material into an organic solvent (tetrahydrofuran, acetone, etc.) that can dissolve the epoxy resin contained in the epoxy resin molding material, and filter the residual inorganic filler material after a certain period of time. Filter out. If the difference between the dried mass obtained by filtration and the mass of the ash after high temperature treatment is within 0.5% by mass, it can be judged that the epoxy resin molding material is in the A-stage state. The ash mass is calculated by measuring in accordance with the Japanese Industrial Standard JIS K 7250-1: 2006. Alternatively, a differential scanning calorimetry device (DSC) (for example, Pyris1, manufactured by PerkinElmer, Inc.) is used to measure the heat of reaction per unit specific mass of the epoxy resin molding material in the A-stage state, Then set the reference value. As long as the difference between the measured value of the reaction heat per unit specific mass prepared by the epoxy resin molding material and the aforementioned reference value is within ± 5%, it can be judged that it is in the A-stage state.

When the epoxy resin molding material is in the A-stage state, the mass reduction rate after heating the epoxy resin material in the A-stage state at 180 ° C. for 1 hour is preferably 0.1% by mass or less. The so-called mass reduction rate of the epoxy resin material in the A-stage state at 180 ° C for 1 hour is 0.1% by mass or less, which means that the epoxy resin molding material in the A-stage state is a so-called "solvent-free" Type "epoxy molding material. If the epoxy resin molding material is a solvent-free type, a molded product of the epoxy resin molding material can be obtained without a drying step, and the steps for obtaining a molded product or a molded hardened product can be simplified.

<Molded Article and Molded Hardened Article> The molded article of this embodiment can be produced by molding the epoxy resin molding material of this embodiment. The molded and cured product of this embodiment can be produced by subjecting the molded product of this embodiment to heat treatment (post-curing).

The method for molding the epoxy resin molding material is not particularly limited, and can be selected by a known method such as a press molding method depending on the application. The most common method is transfer molding, and compression molding may also be used. The temperature of the mold at the time of the press molding is preferably at least the phase transition temperature of the epoxy resin A and at most 150 ° C, more preferably at most 140 ° C. If it is the phase transition temperature of the epoxy resin A or more, the epoxy resin A will be sufficiently melted during molding, and it is easy to be molded. If it is 150 ° C or lower, the thermal conductivity of the molded product tends to be excellent.

The mold temperature during pressure molding is generally 150 ° C to 180 ° C from the viewpoint of fluidity. Since a general epoxy resin is not easily melted at a temperature of 150 ° C or lower, it tends to be difficult to form. However, the epoxy resin molding material of this embodiment can be molded even at 150 ° C.

In the X-ray diffraction spectrum obtained by the X-ray diffraction method using CuKα rays, the formed product preferably has a diffraction peak within a range of a diffraction angle 2θ of 3.0 ° to 3.5 °. A molded article having such a diffraction peak can form a highly ordered smectic liquid crystal structure among high-order structures, and has excellent thermal conductivity.

The details of the X-ray diffraction measurement using CuKα rays in the present invention are as follows. [Measurement conditions] Apparatus: X-ray diffraction device ATX-G (manufactured by Science Division) for evaluation of film structure X-ray type: CuKα-ray scanning mode: 2θ / ω Output: 50kV, 300mA S1 slit: 0.2mm width S10 slit with height 10mm: 0.2mm width, 10mm height RS slit: 0.2mm width, 10mm height Measurement range: 2θ = 2.0 ° ～ 4.5 ° Sampling width: 0.01 °

After molding, the epoxy resin molding material may be directly used in a state of being released from a mold, or may be used after post-curing by heating with an oven or the like, if necessary.

The molded hardened product is obtained by heating and hardening the molded product. The heating conditions of the molded article can be appropriately selected according to the type and amount of the epoxy resin A, the hardener, and the like contained in the epoxy resin molding material. For example, the heating temperature of the molded product is preferably 130 ° C to 200 ° C, and more preferably 150 ° C to 180 ° C. The heating time of the molded product is preferably 1 hour to 10 hours, and more preferably 2 hours to 6 hours.

In the X-ray diffraction spectrum obtained by applying CuKα rays and using the X-ray diffraction method, the cured product of the molded product has a diffraction angle 2θ of 3.0 ° to 3.5 ° in the same manner as the molded product before post-curing There are diffraction peaks in the range. This indicates that a highly ordered smectic liquid crystal structure formed in a molded article can be maintained after post-curing by heating, and a molded cured article having excellent thermal conductivity can be obtained.

The molded product and molded cured product of the epoxy resin molding material of this embodiment can be used not only in industrial and automotive motors and inverters, but also in technical fields such as printed wiring boards and sealing materials for semiconductor devices. . [Example]

Next, the present invention will be described by examples, but the scope of the present invention is not limited to these examples.

<Preparation of epoxy resin molding material> Each of the following components was prepared by using the mass parts shown in Tables 3 and 6 below, and roller kneading was performed under the conditions of a kneading temperature of 80 ° C and a kneading time of 10 minutes. The epoxy resin molding materials of Examples 1 to 10 and Comparative Examples 1 to 10 were prepared. Spaces in the table indicate "Unprovisioned".

The epoxy resin molding materials of Examples 1 to 10 and Comparative Examples 1 to 10 are all in the A-stage state. In addition, when the epoxy resin molding materials of Examples 1 to 10 and Comparative Examples 1 to 10 were heated at 180 ° C. for 1 hour, the mass reduction rates were all 0.1% by mass or less.

The raw materials used and their abbreviations are shown below. [Epoxy resin] ‧Epoxy resin 1 trans-4- (2,3-epoxypropoxy) benzoic acid = 4- {4- (2,3-epoxypropoxy) phenyl} Cyclohexyl ester (epoxy resin represented by the following structural formula, refer to Japanese Patent No. 5471975; epoxy equivalent: 212 g / eq).

在表中，Ep是環氧樹脂1的環氧基的當量數，Ph是對苯二酚的酚性羥基的當量數。有關環氧樹脂2～6的合成方法將於後述。‧Epoxy resins 2 to 6 A compound obtained by reacting an epoxy resin 1 represented by the above-mentioned structure with an amount of hydroquinone shown below to prepolymerize a part thereof. [Table 1]

In the table, Ep is the equivalent number of epoxy groups of epoxy resin 1, and Ph is the equivalent number of phenolic hydroxyl groups of hydroquinone. The synthetic methods of the epoxy resins 2 to 6 will be described later.

‧Epoxy resin 7 YYSLV-80XY (bisphenol F-type epoxy resin without liquid crystal-based skeleton; manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; epoxy equivalent: 195g / eq; To harden).

[Hardener] ‧CRN (Cresol resorcinol novolac resin, synthetic mass ratio (C / R) of catechol (C) and resorcinol (R): 5/95). The synthesis method of CRN will be described later.

[Inorganic Filler] ‧ Pyrokisuma 3350 (magnesium oxide, manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter 50 μm, specific surface area 0.1 m ² / g). ‧Pyrokisuma 3320 (magnesium oxide, manufactured by Kyowa Chemical Industry Co., Ltd., with an average particle diameter of 20 μm and a specific surface area of 0.2 m ² / g). ‧STARMAG SL (magnesium oxide, manufactured by Kojima Chemical Industry Co., Ltd., with an average particle size of 8 μm and a specific surface area of 1 m ² / g). ‧AL35-63 (Alumina, manufactured by Nippon Steel & Sumikin Material Co., Ltd., with an average particle size of 50 μm and a specific surface area of 0.1 m ² / g). ‧AL35-45 (alumina, manufactured by Nippon Steel & Sumikin Material Co., Ltd., with an average particle diameter of 20 μm and a specific surface area of 0.2 m ² / g). ‧AX3-32 (alumina, manufactured by Nippon Steel & Sumikin Material Co., Ltd., with an average particle size of 4 μm and a specific surface area of 1 m ² / g).

[Silane coupling agent] ‧KBM-202SS (diphenyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 244). ‧KBM-573 (3-phenylaminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 255).

[Hardening accelerator] ‧TPP (triphenylphosphine, manufactured by Beixing Chemical Co., Ltd.).

[Releasing Agent] ‧ Octacosate (Licowax E, manufactured by Clariant Japan).

(Synthesis (prepolymerization) of epoxy resins 2 to 6) Measure 50 g (0.118 mol) of epoxy resin 1 into a 500 mL three-necked flask, and add 80 g of propylene glycol monomethyl ether to the flask. Comes as a solvent. A cooling tube and a nitrogen introduction tube were provided in the three-necked flask, and a stirring blade was provided so as to be able to be immersed in a solvent. The three-necked flask was immersed in an oil bath at 120 ° C, and stirring was started. After a few minutes, after confirming that the epoxy resin 1 had dissolved and became a transparent solution, hydroquinone was added so that Ep / Ph became the above value, and 0.5 g of triphenylphosphine was further added, and then the oil bath was 120 ° C. The temperature continued to heat. After heating for 5 hours, the propylene glycol monomethyl ether was distilled off from the reaction solution under reduced pressure, and the residue was cooled to room temperature (25 ° C.) to obtain an epoxy resin obtained by prepolymerizing a part of the epoxy resin 1. Resin 2 to 6.

The solid content of the epoxy resins 1 to 6 was measured by a heating reduction method. In addition, the amount of solid content is a sample of 1.0 to 1.1 g in an aluminum cup, and then based on the measured amount after 30 minutes in a dryer set at 180 ° C and the measured amount before heating The amount is calculated by the following formula.

Amount of solid content (%) = (Measured amount (g) after standing for 30 minutes / Measured amount (g) before heating) × 100.

The number average molecular weight of epoxy resins 1 to 6 was determined by gel permeation chromatography (GPC). This measurement was performed using a high-speed liquid chromatograph manufactured by Hitachi, Ltd. under the trade name L6000, and a data analysis device manufactured by Shimadzu Corporation, under the trade name C-R4A. GPC columns for analysis were made by TOSOH Co., Ltd., and their trade names were G2000HXL and 3000HXL. The sample concentration was set to 0.2% by mass, and the moving phase was measured using tetrahydrofuran at a flow rate of 1.0 mL / minute. A polystyrene standard sample was used to prepare a calibration curve, and then this calibration curve was used to calculate polystyrene-equivalent values to calculate the number average molecular weight.

The epoxy group equivalents of epoxy resins 1 to 6 were measured by a perchloric acid titration method.

The phase transition temperature of the epoxy resins 1 to 6 was measured using a differential scanning calorimetry (DSC) measurement device (PerkinElmer, Pyris 1). Differential scanning of a 3 mg to 5 mg sample sealed in an aluminum sample pan under conditions of a nitrogen atmosphere with a heating temperature of 20 ° C./minute, a measurement temperature range of 25 ° C. to 350 ° C., and a flow rate of 20 ± 5 mL / minute The temperature is measured, and the temperature (temperature of the endothermic reaction peak) generated by the energy change accompanying the phase change is taken as the phase change temperature. FIG. 1 shows a graph obtained by DSC measurement of epoxy resins 1 and 3.

These measurement results are summarized in Table 2 below. [Table 2]

(Synthesis of CRN) 627In a 3 L separable flask equipped with a stirrer, cooler and thermometer, add 627 g of resorcinol, 33 g of catechol, 316.2 g of 37% by mass formaldehyde, 15 g of oxalic acid, and 300 g of Water was heated to 100 ° C. while heating in an oil bath. The reflux was performed at about 104 ° C, and the reaction was continued at the reflux temperature for 4 hours. Thereafter, the temperature in the flask was raised to 170 ° C while distilling off water, and the reaction was continued for 8 hours while maintaining the temperature at 170 ° C. After the reaction, concentration was performed under reduced pressure for 20 minutes, and water and the like in the system were removed to obtain a phenol resin (CRN).

Regarding the obtained CRN, when the structure was confirmed by FD-MS (field desorption mass spectrometer), it was confirmed that all the partial structures represented by the general formulae (III-1) to (III-4) existed. .

Furthermore, it is considered that, under the above reaction conditions, a compound having a partial structure represented by the general formula (III-1) will be produced first, and further dehydration reaction by the compound will produce a compound having the general structure (III- 2) A compound having a partial structure represented by at least one general formula (III-4).

About the obtained CRN, the number average molecular weight and weight average molecular weight were measured by GPC (gel permeation chromatography). This measurement was performed using a high-speed liquid chromatograph manufactured by Hitachi, Ltd. under the trade name L6000, and a data analysis device manufactured by Shimadzu Corporation, under the trade name C-R4A. GPC columns for analysis were made by TOSOH Co., Ltd., and their trade names were G2000HXL and 3000HXL. The sample concentration was 0.2% by mass, and tetrahydrofuran was used as a mobile phase. The measurement was performed at a flow rate of 1.0 mL / minute. A polystyrene standard sample was used to prepare a calibration curve, and then this calibration curve was used to calculate polystyrene conversion values to calculate the number average molecular weight and weight average molecular weight.

Regarding the obtained CRN, the measurement of the hydroxyl equivalent was performed in the following manner. The hydroxyl equivalent was measured by acetamidine chloride-potassium hydroxide titration. Furthermore, because the color of the solution is dark, the determination of the titration end point is not performed by the colorimetric method of the indicator, but by the potentiometric method. Specifically, it is a method in which a hydroxyl group of a measurement resin is acetylated with chloroacetic acid in a pyridine solution, and an excess reagent is decomposed with water, and then the generated acetic acid is titrated with a potassium hydroxide / methanol solution.

The obtained CRN is a mixture containing a compound having a partial structure represented by at least one of the general formulae (III-1) to (III-4), and the CRN is a phenol resin (hydroxyl Equivalent weight: 65 g / eq; number average molecular weight: 422; weight average molecular weight: 564), which contains 35% by mass of a monomer component (resorcinol) as a low-molecular diluent, wherein Ar is the following group: R ¹¹ in formula (III-a) is a hydroxyl group and R ¹² and R ¹³ are each a hydrogen atom, that is, a group derived from 1,2-dihydroxybenzene (catechol) and derived from 1,3- Dihydroxybenzene (resorcinol) group.

(Measurement of Silicon Atom Adhesion Amount Derived from Silane Coupling Agent) The epoxy resin molding materials of Examples 1 to 10 and Comparative Examples 1 to 10 used the following method to measure the medium source per unit specific surface area of the inorganic filler. The amount of silicon atoms attached from the silane coupling agent. First, the specific surface area of the inorganic filler is measured by a BET method using a specific surface area pore distribution measuring device (for example, Beckman Coulter, SA3100). Next, using a nuclear magnetic resonance apparatus (manufactured by Japan Electronics Co., Ltd., JNM-ECA700), 29Si CP / MAS solid state NMR was performed to quantify the silicon atoms derived from the silane coupling agent existing on the surface of the inorganic filler. From the obtained values, the adhesion amount of silicon atoms derived from the silane coupling agent per unit specific surface area of the inorganic filler was calculated. The inorganic filler is taken out by placing an epoxy resin molding material into a ceramic crucible, and then heating the resin composition at 600 ° C. in a flameproof furnace to burn the resin component.

(Production of molded articles and molded hardened articles) The epoxy resin molding materials of Examples 1 to 10 and Comparative Examples 1 to 10 were subjected to a transfer molding machine under conditions of a molding pressure of 20 MPa and a molding temperature of 140 ° C to 180 ° C. Forming to obtain a molded article. When it is intended to post-cured the molded product to obtain a molded cured product, the curing conditions are set to 180 ° C. for 5 hours. Each of the following indications indicates the following: In the "presence or absence of post-hardening" field, the sample with "yes" is evaluated for forming hardened products, and the sample with "no" is evaluated for shaped products (after not implemented) (Hardened), and the samples marked with "-" are not in the "No" state, so subsequent evaluations were not performed.

(Measurement of flow distance) The spiral flow was measured using the fluidity of the epoxy resin molding material at the time of molding as an indicator. The measurement method is to use a mold for swirl measurement according to EMMI-1-66, shape the epoxy resin molding material under the above conditions, and then obtain the flow distance (cm). The "whether molding" in Tables 3 to 6 refers to the case where the epoxy resin molding material can be flowed and filled into the mold as "yes", and the case where there is an unfilled portion is regarded as "no" .

(Measurement of glass transition temperature (Tg)) A molded article or a molded hardened article was cut into a rectangular parallelepiped of 5 mm × 50 mm × 3 mm, and a three-point bending was used in a dynamic viscoelasticity measuring device (using RSA-G2 manufactured by TA Instruments). The vibration test jig measures dynamic viscoelasticity in a temperature range of 40 to 300 ° C under the conditions of a frequency of 1 hertz (Hz) and a heating rate of 5 ° C / min. The glass transition temperature (Tg) is set as the temperature of the peak top portion of tan δ, which is obtained by the ratio of the storage elastic modulus and the loss elastic modulus obtained by the above method.

(Measurement of Density) A 10 mm square cube was produced by cutting a molded article or a molded hardened article, and then the density (g / cm ³ ) was measured by the Archimedes method.

(Measurement of Thermal Conductivity) A 10-mm-square cube was cut by cutting a molded article or a molded hardened article, and a blackening treatment was performed with a graphite spray. Thereafter, a xenon flash method (LFA447 nanoflash manufactured by NETZSCH) was used to evaluate the thermal diffusivity. The product of this value, the density measured by the Archimedes method, and the specific heat measured by DSC (using Pyris1 manufactured by PerkinElmer) are used to determine the molded product or molded hardened product. Thermal conductivity.

(Related X-ray Diffraction Method) 测定 The X-ray diffraction of a molded article or a molded hardened article is measured using an X-ray wide-angle diffraction device (manufactured by Science Scientific Corporation, ATX-G). CuKα rays were used as the X-ray source, and the output voltage was set to 50 kV, the output current was set to 300 mA, and the scanning speed was set to 1.0 ° / minute. FIG. 2 shows the X-ray diffraction spectra of the molded and cured products of Example 1 and Comparative Example 3. When there is a diffraction peak in the range of the diffraction angle 2θ of 3.0 ° to 3.5 °, it means that a smectic liquid crystal structure is formed in a molded article or a subsequent hardened article.

(Evaluation Results) 前述 The evaluation results described above are shown in Tables 3 to 6. In the table, regarding the samples that have been judged as "No" in "Whether it is formed", the aforementioned evaluation cannot be performed, so "-" is marked. The unit of the raw material is mass part.

[table 3]

[Table 4]

[table 5]

[TABLE 6]

Examples 1 to 5 and Comparative Examples 1 to 5 used magnesium oxide, and Examples 6 to 10 and Comparative Examples 6 to 10 used alumina.的 Comparative Examples 1, 2, 6, and 7 using an epoxy resin 1 or 2 having a phase transition temperature of 140 ° C or higher cannot be formed into a molded article. Next, comparison is made with other examples that can be formed and use the same inorganic filler. Examples 1 to 10 with a phase transition temperature of 140 ° C or lower are compared with the comparison using epoxy resin 7 without a liquid crystal-based skeleton. In Examples 3 to 5 and 8 to 10, the thermal conductivity increased by 2 W / (m‧k) to 3 W / (m‧k). Further, in Examples other than Examples 4 and 5 where the press forming temperature exceeds 150 ° C., in the X-ray diffraction spectrum obtained by the X-ray diffraction method using CuKα rays, the formed hardened product is The diffraction angle 2θ has a diffraction peak in a range of 3.0 ° to 3.5 °, and it was confirmed that a smectic liquid crystal structure was formed. In the comparative example, even if the press molding temperature was changed, a diffraction peak indicating that a smectic liquid crystal structure was formed was not confirmed.

The entire disclosures of Japanese Application No. 2015-034887 filed on February 25, 2016 and International Application PCT / JP2016 / 074878 filed on August 25, 2016 are incorporated herein by reference. . All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the extent that individual documents, patent applications, and technical specifications are incorporated, to the same extent as when they are specifically and individually described. Incorporated into this manual.

no

FIG. 1 is a diagram showing an example of a graph obtained by differential scanning calorimetry (DSC) measurement. (2) Fig. 2 is an X-ray diffraction spectrum of the hardened molded product of Example 1 and Comparative Example 3.

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Claims (23)

An epoxy resin molding material includes: epoxy resin A, which has a liquid crystal-based skeleton and a phase transition temperature from a crystalline phase to a liquid crystal phase is 140 ° C or lower; a hardener; and an inorganic filler. The epoxy resin molding material according to claim 1, wherein the epoxy resin A contains a reactant, which is a diphenol compound having two hydroxyl groups on one benzene ring and an epoxy resin B The reactant, the epoxy resin B has a liquid crystal-based skeleton and has a property that a crystalline phase phase can be changed into a liquid crystal phase. The epoxy resin molding material according to claim 2, wherein the phase transition temperature of the epoxy resin B is 140 ° C or higher. The epoxy resin molding material according to claim 2 or claim 3, wherein the epoxy resin A includes a reactant, and the reactant is an equivalent number of phenolic hydroxyl groups of the dihydric phenol compound and the epoxy resin. The ratio of the equivalent number of epoxy groups of the resin B, that is, the equivalent number of epoxy groups / the equivalent number of phenolic hydroxyl groups is set to 100/10 to 100/20. The epoxy resin molding material according to any one of claim 2 to claim 4, wherein the epoxy resin B contains a compound represented by the following general formula (I),

In the general formula (I), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The epoxy resin molding material according to any one of claim 2 to claim 5, wherein the dihydric phenol compound includes hydroquinone. The epoxy resin molding material according to any one of claim 1 to claim 6, wherein the hardener includes a phenol-based hardener. The epoxy resin molding material according to claim 7, wherein the phenol-based hardener contains a compound selected from the group consisting of the following general formula (II-1) and the following general formula (II-2) At least one structural unit represented by the general formula in the group,

In the general formula (II-1) and the general formula (II-2), R ¹ each independently represents an alkyl group, an aryl group, or an aralkyl group, and the alkyl group, the aryl group, and the aralkyl group may have a substituent, R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and the alkyl group, aryl group, and aralkyl group may have a substituent, m each independently represents an integer of 0 to 2, and n Each independently represents an integer of 1 to 7. The epoxy resin molding material according to claim 7, wherein the phenol-based cured product contains a compound selected from the group consisting of the following general formula (III-1) to the following general formula (III-4) At least one structural unit represented by the general formula in the group,

In the general formulae (III-1) to (III-4), m and n each independently represent a positive integer, and Ar each independently represents the following general formula (III-a) or the following general formula A group represented by (III-b),

In the general formulae (III-a) and (III-b), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbon number of 1 to 8 alkyl. The epoxy resin molding material according to any one of claim 1 to claim 9, further comprising a silane coupling agent. The epoxy resin molding material according to claim 10, wherein the silane coupling agent includes a silane coupling agent having a phenyl group. The epoxy resin molding material according to claim 11, wherein the silane coupling agent having a phenyl group has a structure in which a phenyl group is directly bonded to a silicon atom. The epoxy resin molding material according to any one of claim 10 to claim 12, wherein an adhesion amount of silicon atoms derived from the silane coupling agent per unit specific surface area of the inorganic filler is 5.0 × 10 ^-6 mol / m ² to 10.0 × 10 ^-6 mol / m ² . The epoxy resin molding material according to any one of claim 1 to claim 13, wherein the inorganic filler includes at least one selected from the group consisting of magnesium oxide and aluminum oxide. The epoxy resin molding material according to any one of claim 1 to claim 14, wherein the content of the inorganic filler is 60% to 90% by volume in the solid content. The epoxy resin molding material according to any one of claim 1 to claim 15, wherein the epoxy resin molding material is in an A-stage state. The epoxy resin molding material according to claim 16, wherein the mass reduction rate after heating at 180 ° C for 1 hour is 0.1% by mass or less. A molded article formed by molding the epoxy resin molding material according to any one of claims 1 to 17. The formed article according to claim 18, wherein in the X-ray diffraction spectrum obtained by the X-ray diffraction method using CuKα rays, the formed article has a diffraction angle 2θ in a range of 3.0 ° to 3.5 ° There are diffraction peaks inside. A molded hardened product obtained by hardening the molded product according to claim 18 or claim 19. The hardened article according to claim 20, wherein the hardened article is hardened by heating. The hardened article according to claim 20 or 21, wherein the hardened article has a diffraction angle 2θ of 3.0 in an X-ray diffraction spectrum obtained by an X-ray diffraction method using CuKα rays. There is a diffraction peak in the range of ° to 3.5 °. A method for manufacturing a molded article, which is a ring containing epoxy resin A according to any one of claims 1 to 17 within a temperature range of the phase transition temperature of the epoxy resin A and 150 ° C or lower. The oxyresin molding material is molded.