JP2011246440A - Diepoxy compound, method for preparing the same, and cured product obtained by curing the compound - Google Patents

Abstract

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされるジエポキシ化合物、
前記式（１）で表わされるジエポキシ化合物及び硬化剤を含むことを特徴とする組成物、並びに、前記組成物を硬化して得られる硬化物。
【選択図】なしThere is a need for a novel cured product and a diepoxy compound capable of giving the cured product.
SOLUTION: Formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A diepoxy compound represented by:
A composition comprising a diepoxy compound represented by the formula (1) and a curing agent, and a cured product obtained by curing the composition.
[Selection figure] None

Description

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

で表わされるジエポキシ化合物（融点２４０℃）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。
また、非特許文献２には、式（Ｂ）

で表わされるジエポキシ化合物（融点１８７℃）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。 It is known that a cured product obtained by curing a diepoxy compound exhibits good heat resistance and mechanical properties.
For example, Non-Patent Document 1 includes a formula (A)

And a cured product obtained by curing the compound is described.
Further, Non-Patent Document 2 includes a formula (B).

And a cured product obtained by curing the compound is described.

Macromol. Chem. Phys. 1994, 195, 2307. J. et al. Polym. Sci. PartA. Polym. Chem. 1999, 37, 419.

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

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
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^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６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 , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A diepoxy compound represented by:
<2> The compound represented by the formula (1) is represented by the formula (1 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have 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^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされるジヒドロキシ化合物と式（３）

（式中、Ｘ^１はハロゲン原子を表わす。）
で表わされるエピハロヒドリンとを反応させる工程を含むことを特徴とする式（１）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６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。
＜４＞ 前記工程が、無機塩基及び４級アンモニウム塩の存在下、前記式（２）で表わされるジヒドロキシ化合物と前記式（３）で表わされるエピハロヒドリンとを反応させる工程であることを特徴とする＜３＞記載の製造方法。
＜５＞ 前記工程が、下記工程Ａ及び工程Ｂを含むことを特徴とする＜４＞記載のジエポキシ化合物の製造方法。
工程Ａ：前記式（２）で表わされるジヒドロキシ化合物、前記式（３）で表わされるエピハロヒドリン、及び４級アンモニウム塩を混合する工程。
工程Ｂ：工程Ａで得られた混合物に無機塩基を混合する工程。
＜６＞ 前記無機塩基が、アルカリ金属水酸化物であることを特徴とする＜３＞〜＜５＞のいずれか記載のジエポキシ化合物の製造方法。 <3> In the presence of an inorganic base, the formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
And a dihydroxy compound represented by the formula (3)

(In the formula, X ¹ represents a halogen atom.)
Comprising the step of reacting with an epihalohydrin represented by the formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above.)
The manufacturing method of the diepoxy compound represented by these.
<4> The step is a step of reacting the dihydroxy compound represented by the formula (2) and the epihalohydrin represented by the formula (3) in the presence of an inorganic base and a quaternary ammonium salt. <3> The production method according to the above.
<5> The method for producing a diepoxy compound according to <4>, wherein the step includes the following step A and step B.
Step A: A step of mixing the dihydroxy compound represented by the formula (2), the epihalohydrin represented by the formula (3), and a quaternary ammonium salt.
Step B: A step of mixing an inorganic base with the mixture obtained in Step A.
<6> The method for producing a diepoxy compound according to any one of <3> to <5>, wherein the inorganic base is an alkali metal hydroxide.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされるジヒドロキシ化合物。
＜８＞ 式（２）で表わされる化合物が式（２’）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされる立体異性体であることを特徴とする＜７＞記載のジヒドロキシ化合物。
＜９＞ 酸の存在下、式（６）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされるヒドロキシナフトエ酸と、式（７）

で表わされる４−ヒドロキシ−１−（４−ヒドロキシフェニル）シクロヘキサンとを反応させる工程を含むことを特徴とするジヒドロキシ化合物の製造方法。 <7> Formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The dihydroxy compound represented by these.
<8> The compound represented by formula (2) is represented by formula (2 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
<7> The dihydroxy compound according to <7>, which is a stereoisomer represented by the formula:
<9> Formula (6) in the presence of an acid.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A hydroxynaphthoic acid represented by formula (7)

The manufacturing method of the dihydroxy compound characterized by including the process with which 4-hydroxy-1- (4-hydroxyphenyl) cyclohexane represented by these is made to react.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされるジエポキシ化合物及び硬化剤を含むことを特徴とする組成物。
＜１１＞ 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＜１０＞記載の組成物。
＜１２＞ 硬化剤が、アミン硬化剤であることを特徴とする＜１０＞又は＜１１＞記載の組成物。
＜１３＞ 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＜１２＞記載の組成物。 <10> Formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The composition characterized by including the diepoxy compound represented by these, and a hardening | curing agent.
<11> The composition according to <10>, 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.
<12> The composition according to <10> or <11>, wherein the curing agent is an amine curing agent.
<13> 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. <12> The composition according to <12>.

<14> The composition according to any one of <10> to <13>, further comprising alumina.
<15> The composition according to <14>, 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. object.
<16> Alumina having an alumina A having a D50 (particle diameter of 50% cumulative volume) of 2 μm or more and 100 μm or less, an alumina B having a D50 of 1 μm or more and 10 μm or less, and an alumina having a D50 of 0.01 μm or more and 5 μm or less 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 <14> or <15>, wherein C is 1 to 30% by volume.

<17> A cured product obtained by curing the composition according to any one of <10> to <16>.
<18> A prepreg obtained by applying or impregnating a base material with the composition according to any one of <10> to <16> and then semi-curing it.
<19> A cured product obtained by curing the composition according to any one of <14> to <16>, wherein the content ratio of alumina contained in the cured product is 100% by volume of the cured product. Hardened | cured material characterized by being 50-80 volume%.

  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.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または炭素数１〜３のアルキル基を表わす。）
で表わされる化合物（以下、ジエポキシ化合物（１）と記すことがある）である。
炭素数１〜３のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基等を挙げることができ、メチル基が好ましい。
好ましいＲ^１〜Ｒ^６としては、それぞれ独立して、水素原子及びメチル基が挙げられ、より好ましくは、Ｒ^１〜Ｒ^６のいずれも水素原子である。 Hereinafter, the present invention will be described in detail.
The present invention relates to formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
(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, and a methyl group is preferable.
Preferable R ^{1 to} R ⁶ each independently include a hydrogen atom and a methyl group, and more preferably any of R ^{1 to} R ⁶ is a hydrogen atom.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は前記と同じ意味を表わす。）
で表わされる立体異性体（トランス体）を挙げることができる。 Preferred diepoxy compounds (1) include, for example, formula (1 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above.)
And stereoisomers (trans isomers) represented by

  Examples of the diepoxy compound (1) include 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl-6- (2,3-epoxypropoxy) -2-naphthoate, preferably trans- 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl-6- (2,3-epoxypropoxy) -2-naphthoate and the like can be mentioned.

  The diepoxy compound (1) of the present invention has a melting point lower than that of the diepoxy compound represented by the formula (A) or formula (B), and the diepoxy compound (1) and the curing agent are melt-mixed at a lower temperature. And can be cured, and processing at a low temperature is also possible.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、前記と同じ意味を表わす。）
で表わされるジヒドロキシ化合物（以下、ジヒドロキシ化合物（２）と記すことがある）と式（３）

（式中、Ｘ^１はハロゲン原子を表わす。）
で表わされるエピハロヒドリン（以下、エピハロヒドリン（３）と記すことがある）とを反応させる工程を含む方法（以下、グリシジルエーテル化工程と記すことがある）； As a manufacturing method of diepoxy compound (1), for example, in the presence of an inorganic base, formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above.)
A dihydroxy compound represented by the formula (hereinafter sometimes referred to as dihydroxy compound (2)) and formula (3)

(In the formula, X ¹ represents a halogen atom.)
A method comprising the step of reacting with an epihalohydrin represented by the following (hereinafter sometimes referred to as epihalohydrin (3)) (hereinafter sometimes referred to as glycidyl etherification step);

（式中、Ｘ^２はＸ^１と同じ意味を表わす。）
で表わされる化合物（以下、化合物（４）と記すことがある。）とを反応させて、式（５）

で表わされるジアリル化物（以下、ジアリル化物（５）と記すことがある。）を得、次いで、該アリル化物（５）を酸化剤で酸化する工程（以下、アリ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。 For example, in the presence of a base, the dihydroxy compound (2) and the formula (4)

(Wherein X ² represents the same meaning as X ¹ )
Is reacted with a compound represented by formula (hereinafter sometimes referred to as compound (4)) to give a compound of formula (5)

And then a step of oxidizing the allylated product (5) with an oxidizing agent (hereinafter sometimes referred to as an allylation step). And the like.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は前記と同じ意味を表わす。）
で表わされる立体異性体（トランス体）を挙げることができる。 R ^{1 to} R ⁶ in the dihydroxy compound (2) used in both the glycidyl etherification step and the allylation step have the same meaning as R ^{1 to} R ⁶ in the diepoxy compound (1). Preferred dihydroxy compounds (2) are those of formula (2 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above.)
And stereoisomers (trans isomers) represented by

  Examples of the dihydroxy compound (2) include 4- (4-hydroxyphenyl) cyclohexyl-6-hydroxy-2-naphthoate, and preferably trans-4- (4-hydroxyphenyl) cyclohexyl-6-hydroxy. -2-Nafto art can be mentioned.

First, the glycidyl etherification step will be described.
X ¹ in the epihalohydrin (3) represents a halogen atom such as a chlorine atom or a bromine atom, preferably a chlorine atom. Examples of the epihalohydrin (3) include epichlorohydrin and epibromohydrin. In the glycidyl etherification step, plural kinds of epihalohydrins (3) may be used in combination. Preferable epihalohydrin (3) includes, for example, epichlorohydrin.
The usage-amount of epihalohydrin (3) is 2-200 mol etc. with respect to 1 mol of dihydroxy compounds (2), for example, Preferably, the range of 5-150 mol is mentioned, for example.

Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate, such as sodium hydride and potassium hydride. Alkali metal hydride can be used. A plurality of inorganic bases may be used in combination as the inorganic base.
Preferable inorganic bases include, for example, alkali metal hydroxides, alkali metal carbonates, and more preferably, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
The amount of the inorganic base used may be, for example, in the range of 0.1 to 20 mol, preferably in the range of 0.5 to 10 mol, with respect to 1 mol of the dihydroxy compound (2). Can be mentioned.
Examples of the inorganic base include a solid form such as a granular form. When the inorganic base uses an inorganic base that is stable to water such as an alkali metal hydroxide or alkali metal carbonate, for example, the shape of an aqueous solution prepared to a concentration of about 1 to 60% by weight can be mentioned. .

The glycidyl etherification step is preferably performed in the presence of a quaternary ammonium salt (hereinafter sometimes simply referred to as an ammonium salt) in addition to the inorganic base. The quaternary ammonium salt is a salt containing a cation in which four hydrocarbon groups are bonded to a nitrogen atom in the molecule. Examples of the anion contained in the quaternary ammonium salt include chloride ion, bromide ion, and iodide. Examples thereof include halide ions such as ions. Preferred ammonium salts include, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide Benzyltrimethylammonium bromide, benzyltriethylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, benzyltributylammonium iodide, etc., preferably quaternary ammonium bromide, More preferably, the Tetrabutylammonium bromide, and the like benzyltrimethylammonium bromide.
A plurality of ammonium salts may be used in combination as the ammonium salt.
The amount of the ammonium salt used is, for example, in the range of 0.0001 to 1 mol, preferably in the range of 0.001 to 0.5 mol, etc. with respect to 1 mol of the dihydroxy compound (2). Can be mentioned.
When the glycidyl etherification step is performed in the presence of an ammonium salt, the inorganic base is preferably an alkali metal hydroxide or an alkali metal carbonate.

The glycidyl etherification step may be performed without a solvent or in the presence of a solvent.
Examples of the solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 2-octanol, 4-decanol, 2-dodecanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 3-methyl-2-pentanol, 5-methyl-2-hexanol, 4-methyl -3-heptanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3 -Ethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 3-ethyl- , 2-dimethyl-3-pentanol, 2-methyl-2-hexanol, alcohol solvents such as 3,7-dimethyl-3-octanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile, dimethylsulfoxide and other aprotic polar solvents, diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, Examples include ether solvents such as anisole.

As the solvent, a plurality of different solvents may be used in combination.
As the usage-amount in the case of using a solvent, the range of 0.01-100 weight part etc. can be mentioned with respect to 1 weight part of dihydroxy compound (2), Preferably, for example, it is 0.1-50. For example, the range of parts by weight.

The glycidyl etherification 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.
In the glycidyl etherification step, the dihydroxy compound (2), epihalohydrin (3), ammonium salt and inorganic base, and a solvent may be mixed in any order as necessary.
As reaction temperature of a glycidyl etherification process, the range of -20 degreeC-150 degreeC can be mentioned, for example, Preferably the range of -10 degreeC-120 degreeC is mentioned.
The progress of the reaction in the glycidyl etherification step can be confirmed by the amount of dihydroxy compound (2) decreased or the amount of diepoxy compound (1) produced by an analytical means such as liquid chromatography. The diepoxy compound (1) It is preferable to carry out the reaction until no increase in the amount is observed. Specific examples of the reaction time include a range of 1 to 150 hours.

As the glycidyl etherification step, a method including the following step A and step B is preferable.
Process A: The process of mixing a dihydroxy compound (2), an epihalohydrin (3), and an ammonium salt, and a solvent as needed.
Step B: A step of further mixing an inorganic base with the mixture obtained in Step A.
Step A 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.

Examples of the mixing temperature in Step A include a range of −10 ° C. to 150 ° C., and preferably include a range of 0 ° C. to 120 ° C., for example.
The mixing time in step A varies depending on the mixing temperature and the like, and examples thereof include a range of 0.5 to 72 hours.
The mixture obtained in step A may contain a diepoxy compound (1) obtained by reacting the dihydroxy compound (2) and the epihalohydrin (3).

Step B may be performed under normal pressure conditions, may be performed under pressurized 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.
Examples of the mixing temperature in Step B include a range of −20 ° C. to 120 ° C., and preferably include a range of −10 ° C. to 80 ° C., for example.
It is preferable to carry out the reaction until the degree of progress of the reaction in Step B can be adjusted by following the measurement such as liquid chromatography and no increase in diepoxy compound (1) is observed. Specific reaction time varies depending on the mixing temperature and the like, and examples thereof include a range of 0.5 to 72 hours.

After completion of Step B, for example, after adding water to the reaction solution, a layer containing the diepoxy compound (1) is obtained by adding a solvent insoluble in water as necessary, washed with water, and then insoluble as necessary. Is removed by filtration, and excess epihalohydrin and the solvent are distilled off from the layer to obtain a diepoxy compound (1).

Here, the water-insoluble solvent is a solvent that can be separated from water and can dissolve the diepoxy compound (1). For example, halogenated compounds such as methylene chloride, chloroform, chlorobenzene, and dichlorobenzene. Examples of hydrocarbon solvents include ester solvents such as ethyl acetate and butyl acetate, aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, and mesitylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. .
As usage-amount of the solvent insoluble in water, the range of 1-300 weight part etc. is mentioned with respect to 1 weight part of diepoxy compounds (1), for example, Preferably, it is 10-200 weight part, for example. The range etc. are mentioned.

Next, the allylation process will be described.
Examples of the compound (4) used in the allylation step include allyl chloride and allyl bromide.
As usage-amount of a compound (4), the range of 2-200 mol etc. can be mentioned with respect to 1 mol of dihydroxy compounds (2), Preferably the range of 2-100 mol is mentioned. In addition, you may use together 2 or more types of compounds (4) as needed.

Examples of the base used in the allylation step include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, for example, inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, for example And organic bases such as pyridine. A plurality of types of bases may be used in combination as the base.
Preferable bases include inorganic bases such as alkali metal carbonates, and more preferably sodium carbonate and potassium carbonate.
As the usage-amount of a base, in the case of an inorganic base, the range etc. of 2-10 mol etc. can be mentioned with respect to 1 mol of dihydroxy compounds (2). In the case of an organic base, it may be 2 mol or more, and when an organic base is used as a solvent, the organic base may be used in a large excess.

  The reaction between the dihydroxy compound (2) and the compound (4) is preferably performed in a solvent. Examples of the solvent include the same solvents as those used in the reaction between the dihydroxy compound (2) and the epihalohydrin (3). As described above, when an organic base is used, such a base may be used as a solvent.

The dihydroxy compound (2), the compound (4) and the base, and if necessary, the solvent is mixed in an arbitrary order, and the dihydroxy compound (2) and the compound (4) are reacted to give the dihydroxy compound (2 ) Diallylated product (5).
This reaction 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 this reaction, the range of -20 degreeC-120 degreeC etc. can be mentioned, for example, Preferably, the range of -10 degreeC-100 degreeC etc. are mentioned, for example.
The progress of the reaction for obtaining the diallylated product (5) can be adjusted by following the measurement by liquid chromatography or the like, and it is preferable to carry out the reaction until no increase in the diallylated product (5) is observed.

For example, the diepoxy compound (1) may be produced by subjecting the reaction solution containing the diallylated product (5) to an oxidation reaction with an oxidizing agent as it is, and the reaction solution containing the diallylized product (5) may be washed with water, for example. Thus, the diepoxy compound (1) may be produced by removing the generated salt and then performing an oxidation reaction with an oxidizing agent.
The oxidizing agent may be any oxidizing agent that can oxidize a carbon-carbon double bond to an epoxy group, and examples thereof include peracids such as m-chloroperbenzoic acid. The usage-amount of an oxidizing agent can mention the range of 2-20 mol etc. with respect to 1 mol of diallyl compounds (5), for example.

The oxidation reaction may be performed under normal pressure conditions, may be performed under pressurized 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 a reaction temperature of an oxidation reaction, the range of -20 degreeC-120 degreeC etc. can be mentioned, for example, Preferably, the range of -10 degreeC-100 degreeC etc. are mentioned, for example.
In the oxidation reaction, the progress of the reaction can be measured by liquid chromatography or the like, and it is preferable to carry out the reaction until no increase in diepoxy compound (1) is observed. Although specific reaction time changes also with reaction temperature etc., the range etc. of 0.5 to 72 hours etc. can be mentioned, for example.

  After the oxidation reaction is completed, for example, the remaining oxidant is decomposed as necessary, and then concentrated, whereby the diepoxy compound (1) can be obtained.

  The diepoxy compound (1) obtained in the glycidyl etherification step or the allylation step can be further purified by applying purification means such as recrystallization as necessary.

  Here, the manufacturing method of the dihydroxy compound (2) used in a glycidyl etherification process or an allylation process is demonstrated.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は前記と同じ意味を表わす。）
で表わされるヒドロキシナフトエ酸（以下、ヒドロキシナフトエ酸（６）と記すことがある）と式（７）

で表わされる４−（４−ヒドロキシシクロヘキシル）フェノール（以下、フェノール（７）と記すことがある）とを反応させる工程（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 method for producing the dihydroxy compound (2), for example, in the presence of an acid, the formula (6)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above.)
Hydroxynaphthoic acid represented by the formula (hereinafter sometimes referred to as hydroxynaphthoic acid (6)) and formula (7)

And a method including a step of reacting 4- (4-hydroxycyclohexyl) phenol represented by the following (hereinafter sometimes referred to as phenol (7)) (hereinafter also referred to as esterification step). it can.

で表わされるトランス体（トランス−４−ヒドロキシ−１−（４−ヒドロキシフェニル）シクロヘキサン）が好ましい
フェノール（７）の使用量は、ヒドロキシナフトエ酸（６）１モルに対して、例えば、１〜３０モルの範囲等が挙げられ、好ましくは、１〜１５モルの範囲等が挙げられる。 As the phenol (7), the formula (7 ′)

The trans isomer represented by the formula (trans-4-hydroxy-1- (4-hydroxyphenyl) cyclohexane) is preferred. The amount of phenol (7) used is, for example, 1 to 30 with respect to 1 mol of hydroxynaphthoic acid (6). The range of a mole etc. are mentioned, Preferably the range of 1-15 mol etc. are mentioned.

  Examples of the acid used in the esterification step include sulfuric acid and p-toluenesulfonic acid. As for the usage-amount, the range etc. of 0.001-0.3 mol are mentioned with respect to 1 mol of hydroxy naphthoic acids (6). If necessary, two or more acids may be used in combination.

  The esterification step is preferably performed in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, and octane, and aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. The amount used is, for example, in the range of 1 to 200 parts by weight, preferably in the range of 5 to 100 parts by weight, with respect to 1 part by weight of hydroxynaphthoic acid (6).

The esterification step is performed by mixing hydroxynaphthoic acid (6), phenol (7), an acid and, if necessary, a solvent in any order. 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 range of 50-250 degreeC etc. can be mentioned, for example, Preferably, the range of 60-200 degreeC etc. are mentioned, for example.
Although reaction time changes also with reaction temperature etc., the range etc. of 0.5 to 72 hours etc. can be mentioned, for example.
It is preferable to remove the water produced by the esterification step out of the reaction system.

Then, the composition (henceforth this composition) containing diepoxy compound (1) and a hardening | curing agent is demonstrated.
The present composition contains at least one diepoxy compound (1) and at least one curing agent. In addition to the diepoxy compound (1) and the curing agent, the present composition can contain a solvent. In terms of easy preparation, the present composition preferably contains a solvent.
Examples of the solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and ester solvents such as butyl acetate, such as propylene glycol. Examples include glycol solvents such as monomethyl ether, preferably ketone solvents and aprotic polar solvents such as methyl isobutyl ketone and N, N-dimethylformamide.
As a manufacturing method of this composition, the method etc. which mix a diepoxy compound (1) and a hardening | curing agent in a solvent can be mentioned, for example.
Even if the solvent is removed from the solution obtained by dissolving the diepoxy compound (1) and the curing agent of the present invention in a solvent, a uniform mixture tends to be obtained. Moreover, even if it removes the said solvent from the mixture 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 some of the 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, for example, alicyclic polyamines such as 4,4′-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane, such as dicyandiamide, and the like are preferable. Examples thereof include aromatic polyvalent amines and dicyandiamide, and more preferably, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p-phenylenediamine. And dicyandiamide.

  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.

  The amount of the curing agent used may be appropriately selected according to the type of the curing agent to be used. If it is an amine curing agent or a phenol curing agent, for example, the total of functional groups capable of undergoing a curing reaction with the epoxy group in the curing agent. The number of moles used is 0.5 to 1.5 moles, preferably 0.9 to 1.1 moles, per mole of epoxy groups in the diepoxy compound (1).

In this composition, in addition to the diepoxy compound (1), the curing agent and the solvent, the cured product obtained by curing the composition causes a decrease in desired performance such as solubility, heat resistance and thermal conductivity. As long as it is not, it may contain other epoxy compounds.
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.

  The composition further comprises various additives such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, and accelerators such as 2-phenylimidazole such as γ-glycidoxy. Coupling agents such as propyltrimethoxysilane, colorants such as carbon black, low-stress components such as silicone oil and silicone rubber, mold release agents such as natural wax, synthetic wax, higher fatty acids or metal salts thereof, and paraffin , Antioxidants and the like, for example, fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder and the like, or powders thereof such as α-alumina or transition alumina (γ-alumina, θ-alumina) , Δ-alumina) and the like or powder thereof, such as titanium white, aluminum hydroxide, and tar Clay, clay, mica, glass fiber and the like may be contained. The content of various additives in the composition is such that a desired performance such as a melting point is not lowered.

When the present composition contains alumina, it is preferable because the resulting cured product tends to have excellent thermal conductivity. That is, as the present composition, a composition containing alumina in addition to the diepoxy compound (1) and the curing agent (hereinafter sometimes referred to as an alumina-containing composition) is preferable. Moreover, when an alumina containing composition contains the said organic solvent, since there exists a tendency for mixing of an alumina containing composition to become easy, it is preferable.
As content of the alumina in an alumina containing composition, the range of 75 weight part-95 weight part can be mentioned, for example with respect to a total of 100 weight part of diepoxy compound (1), a hardening | curing agent, and an alumina, Preferably Is 83 to 90 parts by weight. When the alumina is 75 parts by weight or more, the thermal conductivity of the resulting cured product tends to be improved, and when it is 95 parts by weight or less, the alumina-containing composition tends to be easily molded.

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.
Moreover, it is preferable that the content rate of the alumina contained in the hardened | cured material mentioned later is 50-80 volume% with respect to 100 volume% of hardened | cured materials, Preferably it is 60-74 volume%.

The cured product of the present invention is obtained by curing the present composition (hereinafter sometimes referred to as the present cured product).
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: Melting the composition, pouring the resulting melt into a preheated mold and curing; Partially curing the composition, pulverizing the partially cured product, and obtaining the obtained powder into gold A method of filling a mold and melt-molding the filled powder; the composition is dissolved in a solvent as necessary, partially cured with stirring, the obtained solution is cast, and then the solvent is dried by air drying or the like The method of removing for a predetermined time, applying pressure with a press etc. as needed is mentioned. The cured product tends to be excellent in thermal conductivity.

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.

  Further, among the cured products, those obtained by curing the alumina-containing composition (hereinafter sometimes referred to as alumina-containing cured products) are further excellent in thermal conductivity. As a method for producing an alumina-containing cured product, for example, a method in which an alumina-containing composition is directly heated to a predetermined temperature and cured; a part of the alumina-containing composition (for example, a diepoxy compound and a curing agent) is heated and melted to obtain gold. A method of pouring the mold into a mold and further heating and molding; partially curing the alumina-containing composition, filling the mold with powder obtained by pulverizing the partially cured product, and melt-molding the filled powder And the like.

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

ディーンスターク装置を取り付けた反応容器内にて、６−ヒドロキシ−２−ナフトエ酸７．０ｇ（３７．２ｍｍｏｌ）、トランス−４−ヒドロキシ−１−（４−ヒドロキシフェニル）シクロヘキサン１０．０ｇ（５２．１ｍｍｏｌ）、ｐ−トルエンスルホン酸０．７１ｇ（３．７２ｍｍｏｌ）及びキシレン８０ｇを室温（約２５℃）で混合した。得られた混合物を還流下で７時間３０分攪拌した後、室温まで冷却した。尚、反応の進行に伴って生成した水はディーンスターク装置によって反応容器から除去された。その後、析出した固体を濾過し、該固体をメタノール２００ｍＬで洗浄した後、５０℃で４時間減圧乾燥させて、白色結晶２．７９ｇを得た。
該結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラフの面積百分率を算出したところ、９６．９％であり、該結晶中の上記式（２−１）で表わされるジヒドロキシ化合物（以下、ジヒドロキシ化合物（２−１）と記すことがある）の含有量を９６．９重量％とすると、６−ヒドロキシ−２−ナフトエ酸を基準とするジヒドロキシ化合物（２−１）の収率は、２０％であった。 [Production Example 1 of dihydroxy compound (2)]

In a reaction vessel equipped with a Dean-Stark apparatus, 7.0 g (37.2 mmol) of 6-hydroxy-2-naphthoic acid and 10.0 g of trans-4-hydroxy-1- (4-hydroxyphenyl) cyclohexane (52. 1 mmol), 0.71 g (3.72 mmol) of p-toluenesulfonic acid and 80 g of xylene were mixed at room temperature (about 25 ° C.). The resulting mixture was stirred for 7 hours 30 minutes under reflux and then cooled to room temperature. In addition, the water produced | generated with progress of reaction was removed from the reaction container with the Dean-Stark apparatus. Thereafter, the precipitated solid was filtered, and the solid was washed with 200 mL of methanol, and then dried under reduced pressure at 50 ° C. for 4 hours to obtain 2.79 g of white crystals.
The crystal was analyzed by liquid chromatography, and the area percentage of the obtained chromatograph was calculated to be 96.9%. The dihydroxy compound represented by the above formula (2-1) in the crystal (hereinafter, dihydroxy compound). When the content of the compound (2-1) may be 96.9% by weight, the yield of the dihydroxy compound (2-1) based on 6-hydroxy-2-naphthoic acid is 20%. Met.

The spectrum data of the obtained dihydroxy compound (2-1) were as follows.
¹ H-NMR (δ: ppm, DMSO-d ₆ ) 10.18 (s, 1H), 9.14 (s, 1H), 8.47 (s, 1H), 7.98 (d, 1H), 7.86 (d, 1H), 7.76 (d, 1H), 7.16 (m, 2H), 7.03 (d, 2H), 6.67 (d, 2H), 4.95 (m , 1H), 1.23-2.55 (c, 9H)

冷却装置を取り付けた反応容器内にて、［ジヒドロキシ化合物（２）の製造例１］で得られたジヒドロキシ化合物（２−１）１．５０ｇ（４．０ｍｍｏｌ）、テトラブチルアンモニウムブロミド０．０６８ｇ（０．２１ｍｍｏｌ）、エピクロロヒドリン１６ｇ（１７３ｍｍｏｌ）、及び２−メチル−２−プロパノール１０．４ｇ（１４０ｍｍｏｌ）を室温で混合し、さらに、７０℃で６時間攪拌した後、さらにテトラブチルアンモニウムブロミド０．３４ｇ（１．１ｍｍｏｌ）を添加し、さらに８時間攪拌した。その後、１３℃まで冷却した。次に、１５重量％の水酸化ナトリウム水溶液３．４０ｇ（１３ｍｍｏｌ）を徐々に加えて、１３℃で２時間攪拌した後、０℃まで冷却した。
次に、イオン交換水を２５ｍＬ加え、室温で、クロロホルム７５ｍＬを加えた後混合し、有機層と水層とを得た。有機層は、さらにイオン交換水で３回洗浄した後、水洗された有機層に含まれる不溶分を濾過して除去し、得られた濾液を濃縮して粗生成物を得た。
粗生成物にトルエン及び２−プロパノールを加えて７０℃まで昇温して同温度で１時間攪拌した後、得られた混合物を室温まで冷却し、終夜静置した。その後、析出した固体を濾過し、２−プロパノールで洗浄した後、乾燥させて、白色結晶２．２１ｇを得た。得られた結晶に、トルエン及び２−プロパノールを加えて７０℃まで昇温して同温度で１時間攪拌した後、得られた混合物を室温まで冷却し、終夜静置した。その後、析出した固体を濾過し、２−プロパノールで洗浄した後、乾燥させて、上記式（１−１）で表わされるジエポキシ化合物（以下、ジエポキシ化合物（１−１）と記すことがある）を含む白色結晶１．１６ｇを得た。
該結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラフの面積百分率を算出したところ、９１．８％であり、該結晶中のジエポキシ化合物（１−１）の含有量を９１．８重量％とすると、ジヒドロキシ化合物（２−１）を基準とするジエポキシ化合物（１−１）の収率は、５５％であった。融点１６２℃。 [Example 1]

In a reaction vessel equipped with a cooling device, 1.50 g (4.0 mmol) of the dihydroxy compound (2-1) obtained in [Production Example 1 of dihydroxy compound (2)], 0.068 g of tetrabutylammonium bromide ( 0.21 mmol), epichlorohydrin 16 g (173 mmol), and 2-methyl-2-propanol 10.4 g (140 mmol) were mixed at room temperature, and further stirred at 70 ° C. for 6 hours, and further tetrabutylammonium bromide. 0.34 g (1.1 mmol) was added, and the mixture was further stirred for 8 hours. Then, it cooled to 13 degreeC. Next, 3.40 g (13 mmol) of a 15 wt% aqueous sodium hydroxide solution was gradually added and stirred at 13 ° C. for 2 hours, and then cooled to 0 ° C.
Next, 25 mL of ion-exchanged water was added, and 75 mL of chloroform was added at room temperature, followed by mixing to obtain an organic layer and an aqueous layer. The organic layer was further washed three times with ion-exchanged water, and then insoluble components contained in the washed organic layer were removed by filtration. The obtained filtrate was concentrated to obtain a crude product.
Toluene and 2-propanol were added to the crude product, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 1 hour. The resulting mixture was cooled to room temperature and allowed to stand overnight. Thereafter, the precipitated solid was filtered, washed with 2-propanol, and then dried to obtain 2.21 g of white crystals. Toluene and 2-propanol were added to the obtained crystals, the temperature was raised to 70 ° C. and the mixture was stirred at the same temperature for 1 hour, and then the obtained mixture was cooled to room temperature and allowed to stand overnight. Thereafter, the precipitated solid is filtered, washed with 2-propanol, dried, and the diepoxy compound represented by the above formula (1-1) (hereinafter sometimes referred to as diepoxy compound (1-1)). 1.16 g of white crystals were obtained.
The crystal was analyzed by liquid chromatography, and the area percentage of the obtained chromatograph was calculated to be 91.8%, and the content of diepoxy compound (1-1) in the crystal was 91.8% by weight. Then, the yield of the diepoxy compound (1-1) based on the dihydroxy compound (2-1) was 55%. Melting point 162 ° C.

The spectrum data of the diepoxy compound (1-1) obtained in Example 1 were as follows.
¹ H-NMR (δ: ppm, CDCl ₃ ) 8.53 (s, 1H), 8.05 (dd, 1H), 7.87 (d, 1H), 7.75 (d, 1H), 7. 07-7.35 (c, 4H), 6.88 (d, 2H), 5.09 (m, 1H), 4.39 (dd, 1H), 4.20 (dd, 1H), 4.08 (M, 1H), 3.96 (m, 1H), 3.44 (m, 1H),
3.35 (m, 1H), 2.89-3.01 (c, 2H), 2.70-2.88 (c, 2H), 2.55 (m, 1H), 2.18-2. 38 (c, 2H), 1.89-2.12 (c, 2H), 1.50-1.82 (c, 4H)

冷却装置を取り付けた反応容器内にて、ジヒドロキシ化合物（２−１）１５．０ｇ（液体クロマトグラフィーによって分析し、得られたクロマトグラフの面積百分率を含有量（重量％）とすると９６．８重量％、４０．１ｍｍｏｌ）、テトラブチルアンモニウムブロミド４．０ｇ（１２．４ｍｍｏｌ）、及びエピクロロヒドリン１５３ｇ（１６５４ｍｍｏｌ）を室温で混合し、さらに、７０℃で７時間攪拌した。その後、１８℃まで冷却した。次に、１５重量％の水酸化ナトリウム水溶液３３．１ｇ（１２４ｍｍｏｌ）を徐々に加えて、１８℃で４時間攪拌した後、０℃まで冷却した。
次に、イオン交換水を２５０ｍＬ加え、室温で、クロロホルム７５０ｍＬを加えた後混合し、有機層と水層とを得た。有機層は、さらにイオン交換水で３回洗浄した後、水洗された有機層に含まれる不溶分を濾過して除去し、得られた濾液を濃縮して粗生成物［１］２３．４ｇを得た。
続いて、冷却装置を取り付けた反応容器内にて、粗生成物［１］の一部２２．３ｇ、テトラブチルアンモニウムブロミド４．０ｇ（１２．４ｍｍｏｌ）、クロロホルム６４４ｇ（５３９５ｍｍｏｌ）、及び２−メチル−２−プロパノール１７５ｇ（２３６１ｍｍｏｌ）を室温で混合し、１８℃まで冷却した。次に、１５重量％の水酸化ナトリウム水溶液３０．９ｇ（１１６ｍｍｏｌ）を徐々に加えて、１８℃で２時間攪拌した後、０℃まで冷却した。
次に、イオン交換水を８００ｍＬ加えた後混合し、有機層と水層とを得た。有機層は、さらにイオン交換水で３回洗浄した後、水洗された有機層に含まれる不溶分を濾過して除去し、得られた濾液を濃縮して粗生成物［２］を得た。得られた粗生成物［２］にトルエン及び２−プロパノールを加えて７０℃まで昇温して同温度で１時間攪拌した後、得られた混合物を室温まで冷却し、終夜静置した。その後、析出した固体を濾過し、２−プロパノールで洗浄した後、乾燥させて、ジエポキシ化合物（１−１）を含む白色結晶１５．１ｇを得た。
該結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラフの面積百分率を算出したところ、９５．２％であった。 [Example 2]

In a reaction vessel equipped with a cooling device, 15.0 g of dihydroxy compound (2-1) (analyzed by liquid chromatography, and the area percentage of the obtained chromatograph is 96.8 wt.%) %, 40.1 mmol), 4.0 g (12.4 mmol) of tetrabutylammonium bromide, and 153 g (1654 mmol) of epichlorohydrin were mixed at room temperature, and further stirred at 70 ° C. for 7 hours. Then, it cooled to 18 degreeC. Next, 33.1 g (124 mmol) of a 15 wt% aqueous sodium hydroxide solution was gradually added, and the mixture was stirred at 18 ° C for 4 hours, and then cooled to 0 ° C.
Next, 250 mL of ion-exchanged water was added, and 750 mL of chloroform was added at room temperature, followed by mixing to obtain an organic layer and an aqueous layer. The organic layer is further washed three times with ion-exchanged water, and then insoluble matters contained in the washed organic layer are removed by filtration. The obtained filtrate is concentrated to obtain 23.4 g of a crude product [1]. Obtained.
Subsequently, in a reaction vessel equipped with a cooling device, 22.3 g of the crude product [1], 4.0 g (12.4 mmol) of tetrabutylammonium bromide, 644 g (5395 mmol) of chloroform, and 2-methyl 175 g (2361 mmol) of 2-propanol was mixed at room temperature and cooled to 18 ° C. Next, 30.9 g (116 mmol) of a 15 wt% aqueous sodium hydroxide solution was gradually added, and the mixture was stirred at 18 ° C. for 2 hours, and then cooled to 0 ° C.
Next, 800 mL of ion exchange water was added and mixed to obtain an organic layer and an aqueous layer. The organic layer was further washed three times with ion-exchanged water, and then insoluble components contained in the washed organic layer were removed by filtration. The obtained filtrate was concentrated to obtain a crude product [2]. Toluene and 2-propanol were added to the obtained crude product [2], and the mixture was heated to 70 ° C. and stirred at the same temperature for 1 hour, and then the resulting mixture was cooled to room temperature and allowed to stand overnight. Thereafter, the precipitated solid was filtered, washed with 2-propanol, and then dried to obtain 15.1 g of white crystals containing a diepoxy compound (1-1).
The crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatograph was calculated to be 95.2%.

[Example 3: Production Example 1 of the present composition and its cured product]
100 parts by weight of the diepoxy compound (1-1), 21 parts by weight of 4,4′-diaminodiphenylmethane (manufactured by Wako Pure Chemical Industries) as a curing agent, and N, N-dimethylformamide as a solvent are mixed, A composition was obtained.
The obtained composition was concentrated with a centrifugal concentrator and the solvent was distilled off to obtain a uniform powdery present composition. The obtained powdery composition was filled in an alumina pan. The alumina pan filled with this composition was left in the furnace of a differential scanning calorimeter (DSC Q2000 manufactured by TA Instruments). After putting the inside of the furnace in a nitrogen atmosphere, the alumina pan was heated at 140 ° C. for 20 minutes, then heated to 140 ° C. to 180 ° C. at a temperature rising rate of 1 ° C./min, and further at 200 ° C. for 30 minutes. It heated and cooled to 20 degreeC and the hardened | cured material was obtained in the alumina pan. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed.
The produced cured product was again heated from room temperature to 200 ° C. with a differential scanning calorimeter at a rate of temperature increase of 20 ° C./min. As a result, 166 ° C. was measured as the glass transition point of the cured product.

[Example 4: Production Example 2 of the present composition and its cured product]
This solution was prepared in the same manner as in Example 3 except that 17 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 21 parts by weight of 4,4′-diaminodiphenylmethane. I got a thing. The obtained solution-like present composition was concentrated with a centrifugal concentrator to obtain a uniform powder-like present composition. The obtained powdery composition was heated in the same manner as in Example 3 to obtain a cured product. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed. The glass transition point of the cured product was 139 ° C. as a result of measurement in the same manner as in Example 3.

[Example 5: Production Example 3 of the present composition and its cured product]
Instead of 21 parts by weight of 4,4′-diaminodiphenylmethane, 32 parts by weight of cis-4-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and 2-phenylimidazole was used as a curing accelerator. Except having further added 2.8 weight part, it carried out similarly to Example 3 and obtained this solution-form composition. The obtained solution-like present composition was concentrated with a centrifugal concentrator to obtain a uniform powder-like present composition. The obtained powdery composition was heated in the same manner as in Example 3 to obtain a cured product. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed. The glass transition point of the cured product was 106 ° C.

[Example 6: Production Example 4 of the present composition and its cured product]
Instead of 21 parts by weight of 4,4′-diaminodiphenylmethane, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) ) A solution in the form of a solution was obtained in the same manner as in Example 3 except that 28 parts by weight was used and 2.6 parts by weight of 2-phenylimidazole was further added as a curing accelerator. The obtained solution-like present composition was concentrated with a centrifugal concentrator to obtain a uniform powder-like present composition. The obtained powdery composition was heated in the same manner as in Example 3 to obtain a cured product. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed. The glass transition point of the cured product was 128 ° C.

[Example 7: Production Example 5 of the present composition and its cured product]
Instead of 21 parts by weight of 4,4′-diaminodiphenylmethane, 87 parts by weight of a phenol novolak curing agent “MEH-7851H” (manufactured by Meiwa Kasei Co., Ltd.) is used, and 4.1 parts by weight of triphenylphosphine is further added as a curing accelerator. A solution-like composition was obtained in the same manner as Example 3 except for the addition. The obtained solution-like present composition was concentrated with a centrifugal concentrator to obtain a uniform powder-like present composition. The obtained powdery composition was heated in the same manner as in Example 3 to obtain a cured product. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed. The glass transition point of the cured product was 112 ° C.

[Example 8: Production Example 6 of the present composition and its cured product]
Implemented except that 10 parts by weight of dicyandiamide (Wako Pure Chemical Industries, Ltd.) was used instead of 21 parts by weight of 4,4′-diaminodiphenylmethane, and 2.2 parts by weight of 2-phenylimidazole was further added as a curing accelerator. In the same manner as in Example 3, a solution-like composition was obtained. The obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery present composition. The obtained powdery composition was heated in the same manner as in Example 3 to obtain a cured product. When the temperature was raised to 140 ° C., an exotherm indicating that the diepoxy compound (1-1) and the curing agent had undergone a curing reaction was observed. The glass transition point of the cured product was 168 ° C.

[Example 9: Production example 1 of alumina-containing composition and cured product thereof]
100 parts by weight of diepoxy compound (1-1), 17 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and 1076 parts by weight of alumina (manufactured by Sumitomo Chemical Co., Ltd .; 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) = 796/151/129, volume ratio (alumina A1 / alumina B1 / alumina C1) = 74/14/12) and methyl as solvent 430 parts by weight of isobutyl ketone and 12 parts by weight of N, N-dimethylformamide are mixed to prepare a solution-like alumina-containing composition. It was.
The prepared alumina-containing composition was applied onto a polyethylene terephthalate (PET) film with an applicator so as to have a thickness of 400 μm. The PET film coated with the alumina-containing composition was dried at room temperature for 1 hour, further dried at 150 ° 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 molding (press temperature: 150 ° C., vacuum degree: 1 kPa, press pressure: 6 MPa, treatment time: 20 minutes) was performed. Thereafter, the press temperature was raised to 180 ° C. over 40 minutes. The aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 351 μm. When the thermal conductivity of the cured product was measured with a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 10.7 W / (m · K).
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 obtained cured product was calculated as / cm ³ , the content ratio of alumina in the cured product was 74% by volume.

[Example 10: Production example of the present composition and its prepreg]
100 parts by weight of diepoxy compound (1-1), 17 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, 430 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 (19)

Formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A diepoxy compound represented by: The compound represented by the formula (1) is represented by the formula (1 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have 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 inorganic base, formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
And a dihydroxy compound represented by the formula (3)

(In the formula, X ¹ represents a halogen atom.)
Comprising the step of reacting with an epihalohydrin represented by the formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above.)
The manufacturing method of the diepoxy compound represented by these.   The step is a step of reacting the dihydroxy compound represented by the formula (2) and the epihalohydrin represented by the formula (3) in the presence of an inorganic base and a quaternary ammonium salt. The manufacturing method as described. The said process includes the following process A and process B, The manufacturing method of the diepoxy compound of Claim 4 characterized by the above-mentioned.
Step A: A step of mixing the dihydroxy compound represented by the formula (2), the epihalohydrin represented by the formula (3), and a quaternary ammonium salt.
Step B: A step of mixing an inorganic base with the mixture obtained in Step A.   The method for producing a diepoxy compound according to any one of claims 3 to 5, wherein the inorganic base is an alkali metal hydroxide. Formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The dihydroxy compound represented by these. The compound represented by the formula (2) is represented by the formula (2 ′)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The dihydroxy compound according to claim 7, which is a stereoisomer represented by the formula: In the presence of an acid, the formula (6)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A hydroxynaphthoic acid represented by formula (7)

The manufacturing method of the dihydroxy compound characterized by including the process with which 4-hydroxy-1- (4-hydroxyphenyl) cyclohexane represented by these is made to react. Formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The composition characterized by including the diepoxy compound represented by these, and a hardening | curing agent.   The composition according to claim 10, 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 10 or 11, 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. 13. A composition according to claim 12 characterized in that   Furthermore, an alumina is contained, The composition in any one of Claims 10-13 characterized by the above-mentioned.   The composition according to claim 14, comprising 75 parts by weight to 95 parts by weight of alumina with respect to 100 parts by weight of the total of the diepoxy compound represented by the formula (1), the curing agent, and alumina.   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. The composition according to claim 14 or 15, which is -30% by volume.   Hardened | cured material obtained by hardening | curing the composition in any one of Claims 10-16.   A prepreg obtained by applying or impregnating a composition according to any one of claims 10 to 16 to a substrate, followed by semi-curing.   A cured product obtained by curing the composition according to any one of claims 14 to 16, wherein the content of alumina contained in the cured product is 50 to 80% by volume with respect to 100% by volume of the cured product. A cured product characterized in that