JP2011246689A - Diepoxy compound, method for manufacturing the same, composition containing the compound, and cured material obtained by curing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new cured material, and to provide a diepoxy compound which provides the cured material.SOLUTION: The diepoxy compound is represented by formula (1), wherein Rto Reach independently represent hydrogen atom or 1-3C alkyl group, and Rto Reach independently represent hydrogen atom or methyl group. A composition contains the diepoxy compound represented by the formula (1), a curing agent, and alumina. The cured material is obtained by curing the composition.

Description

  The present invention relates to a diepoxy compound, a method for producing the compound, a composition containing the compound, a cured product obtained by curing the composition, and the like.

で表わされるジエポキシ化合物及び該化合物を硬化して得られる硬化物が記載されている。 A cured product obtained by curing a diepoxy compound is widely used industrially because it exhibits excellent mechanical and electrical properties in addition to good heat resistance and moisture resistance. For example, the formula (A)

And a cured product obtained by curing the compound.

Macromol. Chem. Phys. 1998, 199, 853.

  Under such circumstances, a novel cured product and a diepoxy compound capable of giving the cured product have been demanded.

（式中、Ｒ^１〜Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜３のアルキル基を表わし、Ｒ^５〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表わされるジエポキシ化合物。
＜２＞ 式（１）で表わされる化合物が、式（１’）

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされる立体異性体であることを特徴とする＜１＞記載のジエポキシ化合物。 In order to solve this problem, the present inventors have intensively studied, and as a result, have reached the following present invention.
<1> Formula (1)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A diepoxy compound represented by:
<2> The compound represented by the formula (1) is represented by the formula (1 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The diepoxy compound according to <1>, which is a stereoisomer represented by the formula:

（式中、Ｒ^１〜Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜３のアルキル基を表わし、Ｒ^５〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表わされるジアリル化合物をエポキシ化させる工程を有することを特徴とする式（１）

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされるジエポキシ化合物の製造方法。 <3> Formula (2) in the presence of an oxidizing agent

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
Having the step of epoxidizing the diallyl compound represented by formula (1)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The manufacturing method of the diepoxy compound represented by these.

（式中、Ｒ^１〜Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜３のアルキル基を表わし、Ｒ^５〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表わされるジアリル化合物。
＜５＞ 式（２）で表される化合物が、式（２’）

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされる立体異性体であることを特徴とする＜４＞記載のジアリル化合物。 <4> Formula (2)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A diallyl compound represented by:
<5> The compound represented by the formula (2) is represented by the formula (2 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
<4> The diallyl compound according to <4>, which is a stereoisomer represented by the formula:

（式中、Ｒ^１〜Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜３のアルキル基を表わし、Ｒ^５〜Ｒ^７はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表される芳香族カルボン酸クロリドと式（４）

（式中、Ｒ^８〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表されるアルコール化合物とを、
エステル化反応させる工程を有することを特徴とする式（２）

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表されるジアリル化合物の製造方法。 <6> In the presence of a base, the formula (3)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ⁷ each independently represents a hydrogen atom or a methyl group.)
Aromatic carboxylic acid chloride represented by the formula (4)

(Wherein R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
An alcohol compound represented by
Formula (2) characterized by having the process of esterifying

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The manufacturing method of the diallyl compound represented by these.

（式中、Ｒ^８〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表されるアルコール化合物。 <7> Formula (4)

(Wherein R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
An alcohol compound represented by

（式中、Ｒ^１〜Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜３のアルキル基を表わし、Ｒ^５〜Ｒ^１０はそれぞれ独立して、水素原子またはメチル基を表わす。）
で表わされるジエポキシ化合物、硬化剤及びアルミナを含有することを特徴とする組成物。
＜９＞ 硬化剤が、アミン硬化剤、フェノール硬化剤及び酸無水物硬化剤からなる群より選ばれる少なくとも１種の硬化剤であることを特徴とする＜８＞記載の組成物。
＜１０＞ 硬化剤が、アミン硬化剤であることを特徴とする＜８＞又は＜９＞記載の組成物。
＜１１＞ アミン硬化剤が、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエタン、１，５−ジアミノナフタレン及びｐ−フェニレンジアミンからなる群より選ばれる少なくとも１種のアミン硬化剤であることを特徴とする＜１０＞記載の組成物。
＜１２＞ 前記式（１）で表されるジエポキシ化合物と硬化剤とアルミナとの合計１００重量部に対して、アルミナを７５重量部〜９５重量部含むことを特徴とする＜８＞〜＜１１＞のいずれか記載の組成物。
＜１３＞ アルミナが、２μｍ以上１００μｍ以下のＤ５０（累積体積５０％の粒子径）を有するアルミナＡと、１μｍ以上１０μｍ以下のＤ５０を有するアルミナＢと、０．０１μｍ以上５μｍ以下のＤ５０を有するアルミナＣとの混合物であり、かつ、アルミナＡとアルミナＢとアルミナＣとの合計１００体積％に占める各アルミナの割合が、アルミナＡが５０〜９０体積％、アルミナＢが５〜４０体積％、アルミナＣが１〜３０体積％であることを特徴とする＜８＞〜＜１２＞のいずれか記載の組成物。 <8> Formula (1)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A composition comprising a diepoxy compound represented by the formula: a curing agent and alumina.
<9> The composition according to <8>, wherein the curing agent is at least one curing agent selected from the group consisting of an amine curing agent, a phenol curing agent, and an acid anhydride curing agent.
<10> The composition according to <8> or <9>, wherein the curing agent is an amine curing agent.
<11> The amine curing agent is at least one amine curing agent selected from the group consisting of 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene and p-phenylenediamine. <10> The composition according to <10>.
<12><8> to <11, wherein 75 parts by weight to 95 parts by weight of alumina are included with respect to a total of 100 parts by weight of the diepoxy compound represented by the formula (1), the curing agent, and alumina. > The composition in any one of>.
<13> Alumina having an A50 having a D50 (particle diameter of 50% cumulative volume) of 2 μm to 100 μm, an alumina B having a D50 of 1 μm to 10 μm, and an alumina having a D50 of 0.01 μm to 5 μm The ratio of each alumina in the mixture of C and 100% by volume of alumina A, alumina B and alumina C is 50 to 90% by volume for alumina A, 5 to 40% by volume for alumina B, alumina C is 1-30 volume%, The composition in any one of <8>-<12> characterized by the above-mentioned.

<14> A cured product obtained by curing the composition according to any one of <8> to <13>.
<15> The cured product according to <14>, wherein the content of alumina in the cured product is 50 to 80% by volume with respect to 100% by volume of the cured product.
<16> A prepreg obtained by applying or impregnating a base material with the composition according to any one of <8> to <13> and then semi-curing it.

  ADVANTAGE OF THE INVENTION According to this invention, the diepoxy compound which can give a novel hardened | cured material and this hardened | cured material can be provided.

Hereinafter, the present invention will be described in detail.
The present invention is a diepoxy compound represented by the formula (1) (hereinafter sometimes referred to as diepoxy compound (1)).
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Preferred R ^{1 to} R ⁴ are a hydrogen atom or a methyl group, and preferably a hydrogen atom.

As the diepoxy compound (1), for example,
4- [2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2,3-dimethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2,5-dimethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2,6-dimethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3,5-dimethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2,3,5,6-tetramethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,

2-ethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-ethyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2-propyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-propyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2- [Isopropyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-isopropyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
4- (2-methyl-2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2-methyl-2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,

2-methyl-4- (2-methyl-2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2-methyl-2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2-methyl-2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2-methyl-2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
4- [2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
4- (3-methyl-2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (3-methyl-2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (3-methyl-2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (3-methyl-2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (3-methyl-2,3-epoxybutan-1-yloxy) benzoic acid 4- [4- (3-methyl-2,3-epoxybutan-1-yloxy) cyclohexyl] cyclohexyl,
Etc.

Preferably, for example,
4- [2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
4- (2-methyl-2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2-methyl-2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
Etc.

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされる立体異性体（トランス、トランス体）を挙げることができる。 As the diepoxy compound (1), for example, the formula (1 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
And stereoisomers represented by the formula (trans, trans isomer).

Specifically, for example,
4- (2,3-epoxypropan-1-yloxy) benzoic acid trans-4- [trans-4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid trans-4- [trans-4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2,3-epoxypropan-1-yloxy) benzoic acid trans-4- [trans-4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
4- (2-methyl-2,3-epoxypropan-1-yloxy) benzoic acid trans-4- [trans-4- (2-methyl-2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl,
Etc.

  The diepoxy compound (1) of the present invention has a melting point of about 60 to 150 ° C., which is lower than the melting point (183 ° C.) of the compound represented by the formula (A) described in Patent Document 1, and the composition of the present invention. When manufacturing a product, the diepoxy compound (1) and the curing agent can be melt-mixed at a lower temperature and cured, and processing at a lower temperature is also possible.

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされるジアリル化合物（以下、ジアリル化合物（２）と記すことがある）を、エポキシ化させる工程（以下、エポキシ化工程と記すことがある）を含む方法等を挙げることができる。 As a manufacturing method of diepoxy compound (1), for example, in the presence of an oxidizing agent, formula (2)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The method etc. which include the process (henceforth an epoxidation process) etc. which epoxidize the diallyl compound (henceforth a diallyl compound (2)) represented by these can be mentioned.

As the diallyl compound (2), for example,
4- [2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2,3-dimethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2,5-dimethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2,6-dimethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3,5-dimethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2,3,5,6-tetramethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,

2-ethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-ethyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2-propyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-propyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2-isopropyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-isopropyl-4- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
4- [2-methyl-2-propen-1-yloxy) benzoic acid 4- [4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexyl,

2-methyl-4- (2-methyl-2-propen-1-yloxy) benzoic acid 4- [4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2-methyl-2-propen-1-yloxy) benzoic acid 4- [4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexyl,
4- [2-buten-1-yloxy) benzoic acid 4- [4- (2-buten-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2-buten-1-yloxy) benzoic acid 4- [4- (2-buten-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2-buten-1-yloxy) benzoic acid 4- [4- (2-buten-1-yloxy) cyclohexyl] cyclohexyl,
4- [3-methyl-2-buten-1-yloxy) benzoic acid 4- [4- (3-methyl-2-buten-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (3-methyl-2-buten-1-yloxy) benzoic acid 4- [4- (3-methyl-2-buten-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (3-methyl-2-buten-1-yloxy) benzoic acid 4- [4- (3-methyl-2-buten-1-yloxy) cyclohexyl] cyclohexyl,
Etc.

（式中、Ｒ^１〜Ｒ^１０は前記と同じ意味を表わす。）
で表わされる立体異性体（トランス、トランス体）等を挙げることができる。 Preferred diallyl compound (2) is, for example, formula (2 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
And stereoisomers represented by the formula (trans, trans isomer) and the like.

Specifically, for example,
4- (2-propen-1-yloxy) benzoic acid trans-4- [trans-4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
2-methyl-4- (2-propen-1-yloxy) benzoic acid trans-4- [trans-4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
3-methyl-4- (2-propen-1-yloxy) benzoic acid trans-4- [trans-4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl,
4- (2-methyl-2-propen-1-yloxy) benzoic acid trans-4- [trans-4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexyl,
Etc.

Examples of the oxidant in the epoxidation step include organic peracids such as peracetic acid, performic acid, trifluoroperacetic acid, perbenzoic acid, and m-chloroperbenzoic acid, such as tert-butyl hydroperoxide and cumene hydroperoxide. Organic peroxides such as dioxirane compounds such as dimethyldioxirane, methylethyldioxirane, methylisobutyldioxirane, such as ammonium peroxide, alkali metal peroxide, ammonium persulfate, alkali metal persulfate, perborate Inorganic oxides such as ammonium, alkali metal perborate, ammonium percarbonate, alkali metal percarbonate, alkaline earth metal peroxide, zinc peroxide, such as persulfuric acid, percarbonate, permonophosphoric acid, etc. Inorganic peracids such as hydrogen peroxide can be mentioned, and preferred examples include peracetic acid, peroxygen, and the like. Ikikosan, peroxy compound such as m- chloroperbenzoic acid and the like, and more preferably include m- chloroperbenzoic acid.
These oxidizing agents may be used alone, or two or more arbitrary oxidizing agents may be mixed and used.

  As usage-amount of an oxidizing agent, the range of 2-20 mol etc. is mentioned with respect to 1 mol of diallyl compounds (2), Preferably, the range of 2-10 mol etc. are mentioned, for example, More preferably, it is. In the range of 2.2 to 5 mol.

The epoxidation step is preferably performed in the presence of a solvent. Examples of the solvent include halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2, -tetrachloroethane, and 1-chlorobutane, such as pentane, hexane, cyclohexane, and methylcyclohexane. Aliphatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene and other aromatic hydrocarbon solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like Amide solvents such as nitrile solvents such as acetonitrile and benzonitrile, organic acid solvents such as formic acid, acetic acid and propionic acid, and nitro compound solvents such as nitromethane and nitrobenzene, such as carbon disulfide .
Alternatively, a mixture of these solvents can be used.
Preferably, a halogenated hydrocarbon solvent etc. are mentioned, for example, More preferably, a dichloromethane, chloroform etc. are mentioned, for example.
As the usage-amount of these solvents, the range of 0.1-200 ml per 1g of diallyl compounds (2) etc. can be mentioned, for example.

The epoxidation step may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
As reaction temperature of an epoxidation process, the inside of the range of -20 degreeC-120 degreeC etc. can be mentioned, for example, Preferably, the range of -10 degreeC-100 degreeC etc. are mentioned, More preferably, it is 0 It is in the range of from 60 ° C to 60 ° C.
The reaction time of the epoxidation step can be followed by measurement such as liquid chromatography, and it is preferable to carry out the reaction until no increase in diepoxy compound (1) is observed. Specifically, for example, the range can be 0.5 to 500 hours, and preferably 0.5 to 100 hours, for example.

After the epoxidation step, if necessary, for example, a step of decomposing the remaining oxidant with sodium thiosulfate or the like and concentrating it to obtain a diepoxy compound (1) may be further performed.
Moreover, the obtained diepoxy compound (1) can be further purified by subjecting it to ordinary purification means such as recrystallization, if necessary.

（式中、Ｒ^１〜Ｒ^７は前記と同じ意味を表わす。）
で表される芳香族カルボン酸クロリド（以下、芳香族カルボン酸クロリド（３）と記すことがある）と式（４）

（式中、Ｒ^８〜Ｒ^１０は前記と同じ意味を表わす。）
で表されるアルコール化合物（以下、アルコール化合物（４）と記すことがある）とを、塩基存在下、エステル化反応させる工程（以下、エステル化工程と記すことがある）を含む方法等を挙げることができる。 As a manufacturing method of diallyl compound (2), for example, formula (3)

(In the formula, R ^{1 to} R ⁷ represent the same meaning as described above.)
Aromatic carboxylic acid chloride represented by the formula (hereinafter sometimes referred to as aromatic carboxylic acid chloride (3)) and formula (4)

(Wherein R ^{8 to} R ¹⁰ represent the same meaning as described above.)
And a method including an esterification reaction with an alcohol compound represented by the formula (hereinafter sometimes referred to as an alcohol compound (4)) in the presence of a base (hereinafter referred to as an esterification step). be able to.

Here, R ^{1 to} R ¹⁰ in the aromatic carboxylic acid chloride (3) and the alcohol compound (4) represent the same meaning as R ^{1 to} R ¹⁰ in the diallyl compound (2).
As the aromatic carboxylic acid chloride (3), for example,
4- (2-propen-1-yloxy) benzoic acid chloride,
2-methyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3-methyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2,3-dimethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2,5-dimethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2,6-dimethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3,5-dimethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2,3,5,6-tetramethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2-ethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3-ethyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2-propyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3-propyl-4- (2-propen-1-yloxy) benzoic acid chloride,
2-isopropyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3-isopropyl-4- (2-propen-1-yloxy) benzoic acid chloride,
4- (2-methyl-2-propen-1-yloxy) benzoic acid chloride,
2-methyl-4- (2-methyl-2-propen-1-yloxy) benzoic acid chloride,
3-methyl-4- (2-methyl-2-propen-1-yloxy) benzoic acid chloride,
4- (2-buten-1-yloxy) benzoic acid chloride,
2-methyl-4- (2-buten-1-yloxy) benzoic acid chloride,
3-methyl-4- (2-buten-1-yloxy) benzoic acid chloride,
4- (3-methyl-2-buten-1-yloxy) benzoic acid chloride,
2-methyl-4- (3-methyl-2-buten-1-yloxy) benzoic acid chloride,
Etc.

Preferably, for example,
4- (2-propen-1-yloxy) benzoic acid chloride,
2-methyl-4- (2-propen-1-yloxy) benzoic acid chloride,
3-methyl-4- (2-propen-1-yloxy) benzoic acid chloride,
4- (2-methyl-2-propen-1-yloxy) benzoic acid chloride,
Etc.

As the alcohol compound (4),
4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexanol,
4- [4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexanol,
4- [4- (2-buten-1-yloxy) cyclohexyl] cyclohexanol,
4- [4- (3-methyl-2-buten-1-yloxy) cyclohexyl] cyclohexanol,
Etc.
Preferably, for example,
Trans-4- [trans-4- (2-propen-1-yloxy) cyclohexyl] cyclohexanol,
Trans-4- [trans-4- (2-methyl-2-propen-1-yloxy) cyclohexyl] cyclohexanol,
Etc.

（式中、Ｒ^１〜Ｒ^７は前記と同じ意味を表わす。）
で表される芳香族カルボン酸（以下、芳香族カルボン酸（３’）と記すことがある）を、塩化チオニル、塩化オキサリル、オキシ塩化リン、塩化スルフリル、塩化ｐ−トルエンスルホニル等のクロロ化剤と反応させる工程を行うことで合成することができ、芳香族カルボン酸（３’）は例えばＢｉｏｏｒｇ．Ｍｅｄ．Ｃｈｅｍ．Ｌｅｔｔ．，１７，９６４（２００７）等に記載の公知の方法に準じて製造することができる。
アルコール化合物（４）は、例えばＪ．Ｏｒｇ．Ｃｈｅｍ．，７３，６８７３（２００８）等に記載の公知の方法に準じて製造することができる。 The aromatic carboxylic acid chloride (3) is, for example, the formula (3 ′)

(In the formula, R ^{1 to} R ⁷ represent the same meaning as described above.)
A chlorinating agent such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, sulfuryl chloride, p-toluenesulfonyl chloride, etc. The aromatic carboxylic acid (3 ′) can be synthesized by, for example, Bioorg. Med. Chem. Lett. , 17 , 964 (2007) and the like.
The alcohol compound (4) is, for example, J.A. Org. Chem. , 73 , 6873 (2008) and the like.

Then, the process (esterification process) which carries out esterification reaction of aromatic carboxylic acid chloride (3) and alcohol compound (4) in the presence of a base is demonstrated.
Examples of the base include tertiary amine compounds such as trimethylamine, triethylamine, tri-n-butylamine, N, N-diisopropylethylamine, N-methylmorpholine,
For example, pyridine compounds such as pyridine, picoline, lutidine, collidine, N, N-dimethylaminopyridine, 5-ethyl-2-methylpyridine,
For example, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkaline earth metal bicarbonate, alkali metal phosphate, alkaline earth Metal phosphates, alkali metal hydrides, alkaline earth metal hydrides, alkyllithium compounds, alkylmagnesium compounds,
Preferred are tertiary amine compounds or pyridine compounds, and more preferred are triethylamine, tri-n-butylamine, pyridine, N, N-dimethylaminopyridine and the like.
These bases may be used alone, or two or more arbitrary bases may be mixed and used.
The usage-amount of these bases can mention the range of 1-100 mol etc. with respect to 1 mol of aromatic carboxylic acid chloride (3). In addition, when the base is liquid under the reaction conditions, the base may be used as a solvent.

In the esterification step, an epoxidation reaction is carried out by mixing the aromatic carboxylic acid chloride (3) and the alcohol compound (4) in the presence of a base and optionally in the presence of a solvent.
Examples of the solvent for the esterification step include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and cumene. Ether solvents such as diethyl ether, methyl-tert-butyl ether, di-n-butyl ether, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, diglyme, anisole, such as N, N-dimethylformamide, N, N- Aprotic polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, nitrobenzene, such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2, -tetrachloroethane, 1 Halogenated hydrocarbon solvents such as chlorobutane,
Or a mixture of these can be used.
Among these, aromatic hydrocarbon solvents, ether solvents, and halogenated hydrocarbon solvents are preferable, and toluene, tetrahydrofuran, N, N-dimethylformamide, and chloroform are more preferable.

The esterification step may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
As reaction temperature of an esterification process, the inside of the range of -20 degreeC-120 degreeC etc. can be mentioned, for example, Preferably, the inside of the range of -10 degreeC-100 degreeC etc. is mentioned, for example.
The reaction time of the esterification step can be followed by measurement such as liquid chromatography, and it is preferable to carry out the reaction until no increase in diallyl compound (2) is observed.

Then, the composition (henceforth this composition) containing diepoxy compound (1) and a hardening | curing agent is demonstrated.
This composition contains at least one diepoxy compound (1) and a curing agent, and may contain two or more different curing agents different from two or more different diepoxy compounds (1). .
Examples of the method for producing the present composition include a method of mixing the diepoxy compound (1) and the curing agent in a solvent. Examples of the solvent used in the production method include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, such as butyl acetate. Examples include ester solvents such as glycol solvents such as propylene glycol monomethyl ether, and preferable examples include methyl isobutyl ketone and N, N-dimethylformamide.
Even if the solvent is removed from the present composition by dissolving the diepoxy compound (1) and the curing agent in the solvent, there is a tendency that a uniform mixture is obtained. Moreover, even if it removes the said solvent from this composition obtained by mixing diepoxy compound (1), a hardening | curing agent, the alumina mentioned later, and a solvent, there exists a tendency for a uniform mixture to be obtained.

  The curing agent is one having at least one functional group capable of undergoing a curing reaction with the epoxy group in the diepoxy compound (1), or a curing catalyst exhibiting a catalytic action in the curing reaction of the diepoxy compound (1). Specifically, an amine curing agent in which the functional group is an amino group, a phenol curing agent in which the functional group is a hydroxyl group, an acid anhydride curing agent and a curing catalyst in which the functional group is an acid anhydride group, Amine curing agents, phenol curing agents and curing catalysts are preferred.

  Examples of the amine curing agent include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine (that is, fatty acids having 2 to 20 carbon atoms). Compounds in which a plurality of hydrogen atoms contained in the group hydrocarbon are substituted with amino groups), for example, p-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'- Diaminodiphenylsulfone, bis (4 Aromatic polyamines such as aminophenyl) phenylmethane (that is, a plurality of hydrogen atoms contained in the aromatic hydrocarbon group in the hydrocarbon having 6 to 20 carbon atoms having an aromatic hydrocarbon group are substituted with amino groups) Compound), for example, alicyclic polyvalent amine such as 4,4′-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane (that is, hydrocarbon having 5 to 20 carbon atoms having an alicyclic hydrocarbon group) In which a plurality of hydrogen atoms contained in the alicyclic hydrocarbon group are substituted with amino groups), for example, dicyandiamide and the like, preferably, for example, aromatic polyvalent amine and dicyandiamide are more preferable. Is, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p Phenylenediamine, dicyandiamide, and the like.

  Examples of the phenol curing agent include a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), a naphthol aralkyl resin, and a polyoxystyrene resin. Examples of the phenol resin include resol type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin, phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, novolac type phenol resin such as nonylphenol novolac resin, and dicyclopentadiene modified. Special phenol resins such as phenol resin, terpene-modified phenol resin, and triphenolmethane type resin can be mentioned. Examples of the polyoxystyrene resin include poly (p-oxystyrene).

  Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dicarboxylic acid anhydride). Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and the like.

  Examples of the curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and benzyldimethylamine.

  What is necessary is just to select suitably content of the hardening | curing agent in this composition according to the kind of hardening | curing agent to be used, and if it is an amine hardening | curing agent or a phenol hardening | curing agent, for example, it is a function which can carry out hardening reaction with the epoxy group in this hardening | curing agent. The total mole number of groups is 0.5 to 1.5 moles, preferably 0.9 to 1.1 moles per mole of epoxy groups in the diepoxy compound (1).

The content of alumina in the present composition is preferably 75 parts by weight to 95 parts by weight, more preferably 83 parts by weight with respect to 100 parts by weight as a total of the diepoxy compound (1), the curing agent, and alumina. ~ 90 parts by weight. If the alumina is 75 parts by weight or more, the thermal conductivity of the resulting cured product tends to be improved, and if it is 95 parts by weight or less, the composition tends to be easily molded.
By adjusting the alumina content in the present composition within the above range, the alumina content in the cured product obtained by curing the present composition described later is 50-80% by volume with respect to 100% by volume of the cured product. Adjustable to range.

The alumina is preferably in the form of particles. As the particulate alumina, for example, alumina A having a D50 of 2 μm or more and 100 μm or less when the particle diameter of 50% of the cumulative volume from the fine particle side of the weight cumulative particle size distribution is D50 (average particle diameter by laser diffraction method). It is preferably a mixture of alumina B having a D50 of 1 μm or more and 10 μm or less and alumina C having a D50 of 0.01 μm or more and 5 μm or less. In particular, the proportion of each alumina in the total 100 volume% of alumina A, alumina B and alumina C is 50 to 90 volume% for alumina A, 5 to 40 volume% for alumina B, and 1 to 30 volume% for alumina C. Preferably there is.
Such alumina can be prepared, for example, by appropriately mixing commercially available alumina having various average particle sizes.

In addition to the diepoxy compound (1), the curing agent and the solvent, the present composition may contain other epoxy compounds as long as the cured product obtained by curing the composition does not interfere with the desired performance. Or various additives may be included.
Examples of other epoxy compounds include bisphenol A type epoxy compounds, orthocresol type epoxy compounds, biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenyl benzoate, and naphthalene diglycidyl ether. , Α-methylstilbene-4,4′-diglycidyl ether and the like.

  Examples of various additives include curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-phenylimidazole, and the like, such as γ-glycidoxypropyltrimethoxysilane. Coupling agents such as carbon black and the like, low stress components such as silicone oil and silicone rubber, such as natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, mold release agents such as paraffin, antioxidants, etc. For example, silica such as fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder or powder thereof, such as titanium white, aluminum hydroxide, talc, clay, mica, glass fiber, etc. It may be. The content of various additives in the composition is such that the desired performance such as thermal conductivity is not lowered.

  This composition can be used as, for example, a cured product and a thermosetting adhesive described later.

The cured product of the present invention (hereinafter sometimes referred to as the present cured product) is obtained by curing the present composition.
As a method for producing the cured product, for example, a method of heating the composition as it is to a predetermined temperature and curing; the composition is heated and melted and poured into a mold or the like, and the mold is further heated and molded. Method: A method of melting the present composition and injecting the resulting melt into a preheated mold and curing; A powder obtained by partially curing the present composition and pulverizing the obtained partially cured product into the mold A method of filling and melt-molding the filled powder; the composition is dissolved in a solvent as necessary, partially cured with stirring, the resulting solution is cast, and then the solvent is dried by air drying or the like. A method of heating for a predetermined time while applying pressure with a press machine or the like, if necessary, may be mentioned. The diepoxy compound (1) of the present invention has a low melting point and is excellent in workability during production of the cured product.

  It is preferable that the content rate of the alumina contained in this hardened | cured material is 50-80 volume% with respect to 100 volume% of this hardened | cured material, and it is more preferable that it is 60-74 volume%.

Next, the manufacturing method of the prepreg using this composition is demonstrated. First, the present composition containing an organic solvent is directly diluted as necessary with an organic solvent, applied to or impregnated on a base material, and then the obtained base material is heated to obtain a diepoxy in the base material. A prepreg is obtained by semi-curing the compound (1). The organic solvent used at this time is an organic solvent used in the method for producing the composition, such as methyl isobutyl ketone. A laminate can be prepared by laminating a plurality of the prepregs thus obtained and pressing and heating them with a press or the like.
Examples of the substrate used for the prepreg include woven or nonwoven fabrics of inorganic fibers such as glass fibers and carbon fibers, and woven or nonwoven fabrics of organic fibers such as polyester.

The cured product of the present invention tends to be excellent in thermal conductivity.
The cured product obtained by curing the cured product of the present invention as it is or by curing the prepreg can be used for, for example, an insulating material, a heat sink and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

で表わされるトランス−４−［トランス−４−（２−プロペン−１−イルオキシ）シクロヘキシル］シクロヘキサノール（以下、化合物（４−１）と記すことがある）の製造例。

温度計、冷却管及び攪拌装置を備えた四つ口フラスコに、水素化ナトリウム（含量：６０重量％）２．０２ｇ、トランス，トランス−１，１’−ビシクロヘキサン−４，４’−ジオール １０．０ｇ及びテトラヒドロフラン１００ｍＬを仕込み、内温６０℃で反応させた。発泡が収まったことを確認後、２５℃まで冷却し、アリルブロミド７．３２ｇを仕込み、６０℃に加熱して４時間反応させた。反応終了後、反応液中の不溶分を濾別した後、不溶分を酢酸エチルで洗浄した。濾液と洗浄液を合一し、水で３回洗浄した後、減圧条件下で濃縮処理した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、化合物（４）３．３８ｇを白色固体として得た。純度：９４．３％（ＧＣ面積百分率値）。見かけ収率：２８．２％。 [Production Example of Alcohol Compound (4)]
Formula (4-1)

Production example of trans-4- [trans-4- (2-propen-1-yloxy) cyclohexyl] cyclohexanol represented by the formula (hereinafter sometimes referred to as compound (4-1)).

In a four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 2.02 g of sodium hydride (content: 60% by weight), trans, trans-1,1′-bicyclohexane-4,4′-diol 10 0.0 g and 100 mL of tetrahydrofuran were charged and reacted at an internal temperature of 60 ° C. After confirming that foaming had subsided, the mixture was cooled to 25 ° C., charged with 7.32 g of allyl bromide, heated to 60 ° C., and reacted for 4 hours. After completion of the reaction, the insoluble matter in the reaction solution was filtered off, and the insoluble matter was washed with ethyl acetate. The filtrate and the washing solution were combined, washed with water three times, and then concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography to obtain 3.38 g of compound (4) as a white solid. Purity: 94.3% (GC area percentage value). Apparent yield: 28.2%.

¹ H-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ 0.89 to 1.29 (m, 10H), 1.70 to 1.81 (m, 4H), 1.94 to 2.12 (m, 4H), 3.19 (tt, J = 10.8 Hz) , 4.2 Hz, 1H), 3.45 to 3.58 (m, 1H), 4.01 (d, J = 5.6 Hz, 2H), 5.14 (d, J = 10.3 Hz, 1H) , 5.26 (d, J = 17.2 Hz, 1H), 5.92 (ddt, J = 17.2 Hz, 10.3 Hz, 5.6 Hz, 1H)
¹³ C-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ 28.2, 28.3, 32.4, 35.8, 41.7, 41.9, 68.9, 71.0, 77.8, 116.4, 135.6

で表わされる４−（２−プロペン−１−イルオキシ）安息香酸（以下、芳香族カルボン酸（３−２）と記すことがある）の製造例。

温度計、冷却管及び撹拌装置を備えた四つ口フラスコに、４−ヒドロキシ安息香酸メチル１００．１ｇ、炭酸カリウム６８．６ｇ、アリルブロミド９８．０ｇ及びエタノール１６３．６ｇを仕込み、５０℃で３時間、続いて還流条件下で５時間反応させた。反応後、５０℃に冷却し、３４％水酸化ナトリウム水溶液１５２．６ｇを仕込み、同温度にて１．５時間反応させた。反応終了後、反応液を塩酸で中和し、析出した固体を酢酸エチルで抽出した。抽出液を水で２回洗浄した後、減圧条件下で濃縮処理した。濃縮残渣をエタノールに懸濁させ、還流条件下で２時間撹拌した。懸濁液を室温（約２５℃）まで冷却して固体を濾別し、濾別した固体をエタノールで２回洗浄した。得られた固体を真空乾燥して化合物（３−２）の白色結晶１００．７ｇを得た。純度：９９．５％（ＬＣ面積百分率値）。見かけ収率：８５．９％。
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ基準，単位：ｐｐｍ）
δ４．６３（ｄ，Ｊ＝５．３Ｈｚ，２Ｈ），５．２６（ｄ，Ｊ＝１０．５Ｈｚ，１Ｈ），５．３９（ｄ，Ｊ＝１７．３Ｈｚ，１Ｈ），６．０３（ｄｄｔ，Ｊ＝１７．３Ｈｚ，１０．５Ｈｚ，５．３Ｈｚ，１Ｈ），７．０１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．８７（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ基準，単位：ｐｐｍ）
δ６８．４，１１４．４，１１７．８，１２３．１，１３１．３，１３３．２，１６１．８，１６７．０ [Production example of aromatic carboxylic acid]
Formula (3-2)

Production example of 4- (2-propen-1-yloxy) benzoic acid represented by the formula (hereinafter sometimes referred to as aromatic carboxylic acid (3-2)).

A four-necked flask equipped with a thermometer, a condenser tube and a stirrer was charged with 100.1 g of methyl 4-hydroxybenzoate, 68.6 g of potassium carbonate, 98.0 g of allyl bromide and 163.6 g of ethanol, and 3 at 50 ° C. The reaction was continued for 5 hours under reflux conditions. After the reaction, the mixture was cooled to 50 ° C., charged with 152.6 g of a 34% sodium hydroxide aqueous solution, and reacted at the same temperature for 1.5 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the precipitated solid was extracted with ethyl acetate. The extract was washed twice with water and then concentrated under reduced pressure. The concentrated residue was suspended in ethanol and stirred for 2 hours under reflux conditions. The suspension was cooled to room temperature (about 25 ° C.), the solid was filtered off, and the filtered solid was washed twice with ethanol. The obtained solid was vacuum-dried to obtain 100.7 g of white crystals of compound (3-2). Purity: 99.5% (LC area percentage value). Apparent yield: 85.9%.
¹ H-NMR (DMSO-d ₆ , TMS standard, unit: ppm)
δ 4.63 (d, J = 5.3 Hz, 2H), 5.26 (d, J = 10.5 Hz, 1H), 5.39 (d, J = 17.3 Hz, 1H), 6.03 (ddt , J = 17.3 Hz, 10.5 Hz, 5.3 Hz, 1H), 7.01 (d, J = 8.5 Hz, 2H), 7.87 (d, J = 8.5 Hz, 2H)
¹³ C-NMR (DMSO-d ₆ , TMS standard, unit: ppm)
δ 68.4, 114.4, 117.8, 123.1, 131.3, 133.2, 161.8, 167.0

で表わされる４−（２−プロペン−１−イルオキシ）安息香酸クロリド（以下、芳香族カルボン酸クロリド（３−１）と記すことがある）の製造例。

温度計、冷却管及び撹拌装置を備えた四つ口フラスコに、化合物（３−２）２．７８ｇ、塩化チオニル２．８５ｇ、Ｎ，Ｎ−ジメチルホルムアミド２３ｍｇ及びトルエン１１．１ｍＬを仕込み、５０℃で２時間反応させた。反応後、４０度に冷却し、減圧条件下で濃縮処理した。濃縮残渣にテトラヒドロフラン１６．９ｍＬを仕込み、化合物（３−１）のテトラヒドロフラン溶液を得た。 [Production Example of Aromatic Carboxylic Acid Chloride]
Formula (3-1)

Production example of 4- (2-propen-1-yloxy) benzoic acid chloride represented by the formula (hereinafter sometimes referred to as aromatic carboxylic acid chloride (3-1)).

A four-necked flask equipped with a thermometer, a condenser and a stirrer was charged with 2.78 g of compound (3-2), 2.85 g of thionyl chloride, 23 mg of N, N-dimethylformamide and 11.1 mL of toluene, and 50 ° C. For 2 hours. After the reaction, it was cooled to 40 degrees and concentrated under reduced pressure. Tetrahydrofuran (16.9 mL) was charged into the concentrated residue to obtain a tetrahydrofuran solution of the compound (3-1).

で表わされる４−（２−プロペン−１−イルオキシ）安息香酸４−［４−（２−プロペン−１−イルオキシ）シクロヘキシル］シクロヘキシル（以下、ジアリル化合物（２−１）と記すことがある）の製造例。

温度計、冷却管及び撹拌装置を備えた四つ口フラスコに、化合物（４−１）３．３８ｇ、ピリジン３．７０ｇ及びテトラヒドロフラン１６．９ｍＬを仕込み、０℃に冷却した。そこへ、［芳香族カルボン酸クロリドの製造例］記載の化合物（３−１）のテトラヒドロフラン溶液全量を、反応液の温度が１０℃を超えないような速度で滴下した。その後、室温で８時間反応させた。反応液に水３３．８ｍＬ及びメタノール６７．６ｍＬを加え、析出した固体を濾別し、さらにメタノールで洗浄した。得られた固体を真空乾燥してジアリル化合物（２−１）の白色結晶３．６２ｇを得た。純度９８．４％（ＬＣ面積百分率値）。見かけ収率：６４．１％。 [Example 1: Production example of diallyl compound (2)]
Formula (2-1)

4- [2- (2-propen-1-yloxy) benzoic acid 4- [4- (2-propen-1-yloxy) cyclohexyl] cyclohexyl (hereinafter may be referred to as diallyl compound (2-1)) Production example.

Into a four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 3.38 g of the compound (4-1), 3.70 g of pyridine and 16.9 mL of tetrahydrofuran were charged and cooled to 0 ° C. Thereto, the entire tetrahydrofuran solution of the compound (3-1) described in [Production Example of Aromatic Carboxylic Acid Chloride] was added dropwise at such a rate that the temperature of the reaction solution did not exceed 10 ° C. Then, it was made to react at room temperature for 8 hours. Water (33.8 mL) and methanol (67.6 mL) were added to the reaction solution, and the precipitated solid was separated by filtration and further washed with methanol. The obtained solid was vacuum-dried to obtain 3.62 g of white crystals of the diallyl compound (2-1). Purity 98.4% (LC area percentage value). Apparent yield: 64.1%.

¹ H-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ 0.91 to 1.30 (m, 8H), 1.34 to 1.52 (m, 2H), 1.72 to 1.86 (m, 4H), 2.02 to 2.15 (m, 4H) ), 3.20 (tt, J = 10.7 Hz, 4.2 Hz, 1H), 4.01 (d, J = 5.4 Hz, 2H), 4.58 (d, J = 5.1 Hz, 2H) , 4.84 (tt, J = 11.0 Hz, 4.4 Hz, 1 H), 5.15 (d, J = 10.3 Hz, 1 H), 5.27 (d, J = 17.1 Hz, 1 H), 5.30 (d, J = 10.4 Hz, 1H), 5.41 (d, J = 17.1 Hz, 1H), 5.85 to 6.11 (m, 2H), 6.91 (d, J = 8.5 Hz, 2H), 7.97 (d, J = 8.5 Hz, 2H)
¹³ C-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ 28.0, 28.2, 31.9, 32.4, 41.7, 41.8, 68.8, 68.9, 73.7, 77.8, 114.1, 116.3, 118. 0, 123.4, 131.4, 132.6, 135.6, 162.1, 165.8

で表わされる４−（２，３−エポキシプロパン−１−イルオキシ）安息香酸４−［４−（２，３−エポキシプロパン−１−イルオキシ）シクロヘキシル］シクロヘキシル（以下、ジエポキシ化合物（１−１）と記すことがある）の製造例。

温度計、冷却管及び撹拌装置を備えた四つ口フラスコに、ジアリル化合物（２−１）３．５６ｇ、ｍ−クロロ過安息香酸（含量：７０重量％）６．８３ｇ及びクロロホルム１８ｍＬを仕込み、室温にて３６時間反応させた。反応液にチオ硫酸ナトリウム水溶液を仕込み、未反応の過酸を分解した後に、炭酸水素ナトリウム水溶液で２回、続いて食塩水で１回洗浄した。洗浄後の有機層に硫酸マグネシウムを加えて水分を除去し、硫酸マグネシウムを濾別した。水分除去後の有機層を減圧条件下にて濃縮処理した。濃縮残渣をエタノールに懸濁させ、６０℃で２時間撹拌した。懸濁液を室温まで冷却して固体を濾別し、濾別した固体をエタノールで２回洗浄した。得られた固体を真空乾燥して化合物（１−１）の白色結晶３．１７ｇを得た。純度９３．３％（ＬＣ面積百分率値）、融点９１℃。見かけ収率：８２．６％。 [Example 2: Production example of diepoxy compound (1)]
Formula (1-1)

4- [2,3-epoxypropan-1-yloxy) benzoic acid 4- [4- (2,3-epoxypropan-1-yloxy) cyclohexyl] cyclohexyl (hereinafter referred to as diepoxy compound (1-1)) Manufacturing example).

A four-necked flask equipped with a thermometer, a condenser and a stirrer was charged with 3.56 g of diallyl compound (2-1), 6.83 g of m-chloroperbenzoic acid (content: 70% by weight) and 18 mL of chloroform, The reaction was allowed to proceed for 36 hours at room temperature. An aqueous sodium thiosulfate solution was charged into the reaction solution to decompose unreacted peracid, and then washed twice with an aqueous sodium hydrogen carbonate solution and then once with brine. Magnesium sulfate was added to the washed organic layer to remove water, and magnesium sulfate was filtered off. The organic layer after moisture removal was concentrated under reduced pressure. The concentrated residue was suspended in ethanol and stirred at 60 ° C. for 2 hours. The suspension was cooled to room temperature, the solid was filtered off, and the filtered solid was washed twice with ethanol. The obtained solid was vacuum-dried to obtain 3.17 g of a white crystal of compound (1-1). Purity 93.3% (LC area percentage value), melting point 91 ° C. Apparent yield: 82.6%.

¹ H-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ 0.93 to 1.30 (m, 8H), 1.35 to 1.50 (m, 2H), 1.73 to 1.84 (m, 4H), 2.03 to 2.15 (m, 4H) ), 2.61 (dd, J = 5.1 Hz, 2.6 Hz, 1H), 2.77 (dd, J = 4.8 Hz, 2.5 Hz, 1H), 2.80 (dd, J = 4. 9 Hz, 4.1 Hz, 1 H), 2.92 (dd, J = 4.9 Hz, 4.2 Hz, 1 H), 3.11 to 3.16 (m, 1 H), 3.23 (tt, J = 10 .6 Hz, 4.2 Hz, 1 H), 3.34 to 3.40 (m, 1 H), 3.46 (dd, J = 11.4 Hz, 5.6 Hz, 1 H), 3.72 (dd, J = 11.5 Hz, 3.4 Hz, 1 H), 3.98 (dd, J = 11.1 Hz, 5.9 Hz, 1 H), 4.29 (dd, J = 11.0 Hz, 3.0 Hz, 1 ), 4.84 (tt, J = 11.0Hz, 4.4Hz, 1H), 6.92 (d, J = 8.9Hz, 2H), 7.98 (d, J = 8.9Hz, 2H)
¹³ C-NMR (CDCl ₃ , TMS standard, unit: ppm)
δ28.0, 28.1, 28.2, 31.9, 32.2, 32.4, 41.6, 41.8, 44.7, 49.8, 51.1, 68.7, 73. 7, 78.9, 114.0, 123.8, 131.5, 161.9, 165.7

[Example 3: Production example of the composition and the cured product]
100 parts by weight of diepoxy compound (1-1), 18 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, 1092 parts by weight of alumina (manufactured by Sumitomo Chemical Co., Ltd., α-alumina; laser) Alumina A1 having an average particle diameter (D50) of 18 μm measured by a diffraction method, alumina B1 having an average particle diameter (D50) of 3 μm, and alumina C1 having an average particle diameter (D50) of 0.4 μm , Weight ratio (alumina A1 / alumina B1 / alumina C1) = 808/153/131, volume ratio (alumina A1 / alumina B1 / alumina C1) = 74/14/12) and methyl as solvent 270 parts by weight of isobutyl ketone and 70 parts by weight of N, N-dimethylformamide were mixed to prepare a solution-like composition.
The composition was coated on a polyethylene terephthalate (PET) film with an applicator to a thickness of 350 μm. The PET film coated with the composition was dried for 1 hour at room temperature, further dried at 140 ° C. for 3 minutes, the solvent was distilled off, and the PET film was peeled off to obtain a sheet. The obtained sheet was sandwiched between aluminum foils having a thickness of 40 μm and vacuum press-molded (press temperature: 115 ° C. to 180 ° C., vacuum degree: 1 kPa, press pressure: 6 MPa, heating rate: 1.1 ° C./min, processing time. : 60 minutes). The aluminum foil was peeled off to obtain a sheet-like cured product (main cured product) having a thickness of 319 μm. It was 9.3 W / (m * K) when the heat conductivity of this hardened | cured material was measured by the xenon flash analyzer nanoflash LFA447 type made from NETZSCH.
The density of the cured product obtained by curing the composition containing the diepoxy compound (1-1) and 1,5-diaminonaphthalene and not containing alumina is 1.2 g / cm ³ , and the density of alumina is 3.97 g. When the content ratio of alumina in the cured product was calculated as / cm ³ , the content ratio of alumina in the cured product was 74% by volume.

[Example 4: Production example of the present composition and its prepreg]
100 parts by weight of diepoxy compound (1-1), 18 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, 270 parts by weight of methyl isobutyl ketone as a solvent, and N, N-dimethyl By mixing 70 parts by weight of formamide, the present composition in solution can be obtained. A prepreg can be obtained by impregnating the obtained composition into a glass fiber woven fabric having a thickness of 0.2 mm and then drying by heating. A laminate can be obtained by stacking four obtained prepregs and press-molding them for 90 minutes under conditions of a temperature of 175 ° C. and a pressure of 4 MPa.

  ADVANTAGE OF THE INVENTION According to this invention, the diepoxy compound which can give a novel hardened | cured material and this hardened | cured material can be provided.

Claims (16)

Formula (1)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A diepoxy compound represented by: The compound represented by the formula (1) is represented by the formula (1 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The diepoxy compound according to claim 1, which is a stereoisomer represented by the formula: In the presence of an oxidant, formula (2)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
Having the step of epoxidizing the diallyl compound represented by formula (1)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The manufacturing method of the diepoxy compound represented by these. Formula (2)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A diallyl compound represented by: The compound represented by the formula (2) is represented by the formula (2 ′)

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The diallyl compound according to claim 4, which is a stereoisomer represented by the formula: In the presence of a base, formula (3)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ⁷ each independently represents a hydrogen atom or a methyl group.)
Aromatic carboxylic acid chloride represented by the formula (4)

(Wherein R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
An alcohol compound represented by
Formula (2) characterized by having the process of esterifying

(In the formula, R ^{1 to} R ¹⁰ represent the same meaning as described above.)
The manufacturing method of the diallyl compound represented by these. Formula (4)

(Wherein R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
An alcohol compound represented by Formula (1)

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{5 to} R ¹⁰ each independently represents a hydrogen atom or a methyl group.)
A composition comprising a diepoxy compound represented by the formula: a curing agent and alumina.   The composition according to claim 8, wherein the curing agent is at least one curing agent selected from the group consisting of an amine curing agent, a phenol curing agent, and an acid anhydride curing agent.   The composition according to claim 8 or 9, wherein the curing agent is an amine curing agent.   The amine curing agent is at least one amine curing agent selected from the group consisting of 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene and p-phenylenediamine. A composition according to claim 10 characterized.   The alumina is contained in an amount of 75 to 95 parts by weight with respect to a total of 100 parts by weight of the diepoxy compound represented by the formula (1), the curing agent, and alumina. Composition.   Alumina having an A50 having a D50 of 2 μm or more and 100 μm or less (particle diameter of 50% cumulative volume), an alumina B having a D50 of 1 μm or more and 10 μm or less, and an alumina C having a D50 of 0.01 μm or more and 5 μm or less It is a mixture, and the ratio of each alumina to 100 volume% of the total of alumina A, alumina B, and alumina C is 50 to 90 volume% for alumina A, 5 to 40 volume% for alumina B, and 1 for alumina C. It is -30 volume%, The composition in any one of Claims 8-12 characterized by the above-mentioned.   Hardened | cured material obtained by hardening | curing the composition in any one of Claims 8-13.   The cured product according to claim 14, wherein the content of alumina in the cured product is 50 to 80% by volume with respect to 100% by volume of the cured product.   A prepreg obtained by applying or impregnating a composition according to any one of claims 8 to 13 to a substrate, followed by semi-curing.