JP2011046623A - New epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new epoxy compound that has a low melting point, exhibits excellent solvent solubility and is easily handleable and highly heat-resistant. <P>SOLUTION: The epoxy compound is represented by general formula (1) (wherein R<SB>1</SB>'s and R<SB>2</SB>'s are each independently a 1-8C alkyl group, a 1-8C alkoxy group, a phenyl group or a halogen atom; a and b are each independently 0 or an integer of 1-4; R<SB>1</SB>'s, R<SB>2</SB>'s, a's and b's are each the same or different; A is a 1-20C alkylene group; and R<SB>3</SB>'s are the same or different and are each a hydrogen atom or a 1-4C alkyl group). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel epoxy compound, and more particularly to a diglycidyl ether compound of bis (hydroxyphenylcyclohexenyl) alkane.

  Conventionally, as an epoxy compound having a central skeleton such as a rigid p-polyphenyl group, for example, a p-terphenyl group or a p-quaterphenyl group, for example, 1- ( Dimethylidyl ether compound of 3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene (Patent Document 1), unsubstituted 4,4 ′ ″-diglycidyloxy-p-quarter Phenyl (Non-patent Document 1), 2,2-bis (4- (4-hydroxyphenyl) phenyl) propane diglycidyl ether compound (Patent Document 2) having a structure containing an alkylene group in the central skeleton Compounds are known. Such a compound is useful as a resin raw material in the field of electronic materials because of its excellent heat resistance, low water absorption and flame retardancy. However, these epoxy compounds having a p-polyphenyl group are difficult to handle because of their high melting point and low solvent solubility, and their improvement is desired.

JP 2005-206814 A International Publication No. 2004/037879 Pamphlet

Proceedings of the 4th International Conference on Calorimetry in High Energy Physics, 1994

  Accordingly, the present invention is an improvement of a high heat-resistant epoxy compound having a p-polyphenyl group in the central skeleton, and particularly has excellent heat resistance and low water absorption when used as a cured resin. The object is to provide a highly heat-resistant epoxy compound that is low in solvent solubility and easy to handle.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a structure including four ring structures in which an alkylene group is bonded to the central skeleton and cyclohexenylphenyl groups are bonded to both ends thereof. The present inventors have found that the diglycidyl compound of hydroxyphenyl) cyclohexenyl] alkanes is an epoxy compound having excellent heat resistance, a low melting point, and excellent solvent solubility.

（式中、Ｒ_１、Ｒ_２は各々独立して、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、フェニル基又はハロゲン原子を表し、ａ、ｂは各々独立して０又は１〜４の整数を表し、Ｒ_１、Ｒ_２、ａ及びｂはそれぞれ同一でも異なっていても良く、Ａは炭素原子数１〜２０のアルキレン基を表し、Ｒ_３は水素原子又は炭素原子数１〜４のアルキル基を表し、それぞれ同一でも異なっていても良い。）
で表されるエポキシ化合物が提供される。 That is, according to the present invention, the general formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, A represents an alkylene group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
The epoxy compound represented by these is provided.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ａ、ｂは一般式（１）のそれと同じであり、Ｒ_４、Ｒ_５は各々独立して、水素原子、又は炭素原子数１〜８のアルキル基を表し、Ｒ_４、Ｒ_５は互いに結合して環を形成してもよい。）
で示されるエポキシ化合物は本発明の好ましい態様である。
また、前記一般式（１）又は一般式（２）において、Ｒ_３がすべて水素原子であるエポキシ化合物は本発明のより好ましい態様である。 In addition, the general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , a and b are the same as those in the general formula (1), and R ₄ and R ₅ are each independently a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. Represents an alkyl group, and R ₄ and R ₅ may combine with each other to form a ring.)
The epoxy compound represented by is a preferred embodiment of the present invention.
In the general formula (1) or general formula (2), an epoxy compound in which all R ₃ are hydrogen atoms is a more preferred embodiment of the present invention.

The epoxy compound of the present invention has a structure having four ring structures in which rigid (4-oxyphenyl) cyclohexenyl skeletons are bonded to both ends via an alkylene group in the central skeleton, and is excellent in heat resistance. Further, 4,4 ′ ″-diglycidyloxy-p-quaterphenyl having a structure having the same four ring structures, 2,2-bis (4- (4-diglycidyloxyphenyl) phenyl) propane, and the like Compared with the low melting point, the solvent solubility is high, and the curing temperature when used as a resin raw material can be lowered. Therefore, handling is easy.
Further, the resin obtained from the epoxy compound of the present invention can be expected to be excellent in heat resistance, low water absorption, flexibility and / or toughness, and therefore useful as various resin raw materials such as epoxy resins in the field of electronic materials. It is.

（式中、Ｒ_１、Ｒ_２は各々独立して、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、フェニル基又はハロゲン原子を表し、ａ、ｂは各々独立して０又は１〜４の整数を表し、Ｒ_１、Ｒ_２、ａ及びｂはそれぞれ同一でも異なっていても良く、Ａは炭素原子数１〜２０のアルキレン基を表し、Ｒ_３は水素原子又は炭素原子数１〜４のアルキル基を表し、それぞれ同一でも異なっていても良い。）
で表される。 The novel epoxy compound of the present invention has the following general formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, A represents an alkylene group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
It is represented by

In the formula, each of R ₁ and R ₂ independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, or a halogen atom. An alkyl group is preferred. Specifically, as the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, and an alkyl group having 3 or more carbon atoms may be linear, branched, or cyclic. Examples include n-propyl group, isopropyl group, butyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like. Preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 5 to 8 carbon atoms. These alkyl groups may be substituted with an aromatic hydrocarbon group, and examples thereof include a benzyl group, a phenethyl group, and an α-methylbenzyl group.

Specific examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, and an alkoxy group having 3 or more carbon atoms may be linear, branched, or cyclic. -Propoxy group, isopropoxy group, butoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group and the like. Preferably, it is a linear or branched alkoxy group having 1 to 4 carbon atoms. The alkoxy group may be substituted with an aromatic hydrocarbon group.
Examples of the phenyl group include a phenyl group, an alkyl group such as a 4-methylphenyl group, a dimethylphenyl group, and a methoxyphenyl group, or an alkoxyl-substituted phenyl group. Examples of the halogen atom include a chlorine atom and a bromine atom.

Further, a, b each independently represents a 0 or an integer of 1 to 4, if R ₁ has two or more on the same or different phenylene groups, or different and each R ₁ is the same, R ₂ Are two or more on the same or different cyclohexene groups, R ₂ may be the same or different, and each is preferably substituted with a different carbon atom on the cyclohexene ring.
Moreover, it is preferable that b of different cyclohexene groups is the same, More preferably, both are 0 or 1. If b are both 1, it is preferable substitution position of R ₂ is 3-position with respect to the binding position of A group. When b is 1 or 2, the substitution position of R ₂ is preferably the 3-position and / or 5-position with respect to the bonding position with the A group.
R ₂ is preferably an alkyl group, and a methyl group is particularly preferable.

Moreover, it is preferable that a of different phenylene groups is the same, More preferably, both are 0, 1 or 2. When a is 1 or 2, the substitution position of R ₁ is preferably ortho to the glycidyl ether group.
R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and carbon. The alkyl group having 3 or more atoms may be linear or branched, and examples thereof include an n-propyl group, an isopropyl group, a butyl group, and a t-butyl group. A hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

  In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and examples of the alkylene group having 1 to 20 carbon atoms include linear, branched, or cyclic alkylene groups. The number of carbon atoms is preferably 1 to 8, and more preferably 1 to 4 carbon atoms.

（式中、Ｒ_４、Ｒ_５は一般式（２）のそれと同じである。） Further, the alkylene group having a preferred structure is specifically represented by the following general formula (3).

(In the formula, R ₄ and R ₅ are the same as those in the general formula (2).)

In the alkylene group represented by the general formula (3), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₄ and R ₅ are bonded to each other to form a ring. However, when no ring is formed, it is preferable that at least one or both of R ₄ and R ₅ are a hydrogen atom, a primary alkyl group, or a secondary alkyl group. The alkyl group having 1 to 8 carbon atoms is preferably linear or branched, and is preferably a primary alkyl group or a secondary alkyl group. More preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a primary alkyl group or a secondary alkyl group such as a methyl group, an ethyl group, an isopropyl group or an isobutyl group. Therefore, specific examples of the alkylene group represented by the general formula (3) include a methylene group, a 1-methylmethylidene group, a 1-ethylmethylidene group, a 1-isopropylmethylidene group, and a 2,2-propylidene group. Can do. When R ₄ and R ₅ are bonded to each other to form a ring, the total number of carbon atoms of R ₄ + R ₅ is 16 or less, and 4 to 10 is preferable. Accordingly, specific examples of the alkylene group represented by the general formula (3) when R ₄ and R ₅ are bonded to each other to form a ring include a 1,1-cyclopentylidene group, a 1,1-cyclohexene group. Examples include a silidene group, a 4-methyl-1,1-cyclohexylidene group, and a 3,3,5-trimethyl-1,1-cyclohexylidene group. Preferably, it is a 1,1-cyclohexylidene group.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ａ、ｂは一般式（１）のそれと同じであり、Ｒ_４、Ｒ_５は各々独立して、水素原子、又は炭素原子数１〜８のアルキル基を表し、Ｒ_４、Ｒ_５は互いに結合して環を形成してもよい。） Accordingly, in the general formula (1), when A is an alkylene group represented by the general formula (3), the general formula (1) is represented by the general formula (2).

(In the formula, R ₁ , R ₂ , R ₃ , a and b are the same as those in the general formula (1), and R ₄ and R ₅ are each independently a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. Represents an alkyl group, and R ₄ and R ₅ may combine with each other to form a ring.)

In the epoxy compound represented by the general formula (2), among them, R ₁ and R ₂ are linear or branched alkyl groups having 1 to 4 carbon atoms or cyclic alkyl having 5 to 8 carbon atoms. A, b are both 0 or 1, R ₃ is a hydrogen atom, R ₄ and R ₅ are a hydrogen atom, a linear or branched primary having 1 to 4 carbon atoms. Epoxy compounds that are alkyl groups or secondary alkyl groups are particularly preferred.

２，２−ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−グリシジルオキシ−３−フェニルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−グリシジルオキシ−２−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−エチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−イソプロピルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−ｔ−ブチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−シクロヘキシルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−メトキシフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３−クロロフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−３，５−ジメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシ−２，３，５−トリメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−グリシジルオキシフェニル）−３−メチル−３−シクロヘキセン−１−イル］プロパン、
ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］メタン、
１，２−ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］エタン、
３−メチル−２，２−ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］ペンタン、
１，１−ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］シクロヘキサン、
２−［４−（４−グリシジルオキシフェニル）−３−シクロヘキセン−１−イル］−２−［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
などが挙げられる。 As an epoxy compound represented by such general formula (1) or general formula (2), specifically, for example,
2,2-bis [4- (4-glycidyloxyphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-glycidyloxy-3-phenylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-glycidyloxy-2-methylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-ethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-isopropylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-tert-butylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-cyclohexylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-methoxyphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3-chlorophenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-3,5-dimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxy-2,3,5-trimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-glycidyloxyphenyl) -3-methyl-3-cyclohexen-1-yl] propane,
Bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] methane,
1,2-bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] ethane,
3-methyl-2,2-bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] pentane,
1,1-bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] cyclohexane,
2- [4- (4-glycidyloxyphenyl) -3-cyclohexen-1-yl] -2- [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,
Etc.

（式中、Ｒ_１、Ｒ_２、ａ、ｂ、およびＡは一般式（１）のそれと同じである。）
を直接原料とし、これを溶媒中、一般式（５）

（式中、Ｒ_３は一般式（１）のそれと同じであり、Ｘはハロゲン原子を表す。）
で示されるハロヒドリン化合物とを塩基触媒の存在下に反応させることにより得ることができる。 There is no restriction | limiting in particular about the manufacturing method of such an epoxy compound represented by General formula (1) of this invention, It can manufacture using a well-known method. Specifically, for example, a bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane (hereinafter also referred to as a diol compound) represented by the general formula (4) corresponding to the epoxy compound of the general formula (1) of the present invention. Call it.)

(In the formula, R ₁ , R ₂ , a, b, and A are the same as those in the general formula (1).)
Is directly used as a raw material in a solvent in the general formula (5)

(In the formula, R ₃ is the same as that in the general formula (1), and X represents a halogen atom.)
It can obtain by making it react with the halohydrin compound shown by presence of a base catalyst.

  Alternatively, the diol compound represented by the general formula (4) is reacted with a vinyl halide compound such as allyl chloride and allyl bromide in a solvent in the presence of a base, and then after completion of the reaction, the m- An oxidant capable of oxidizing a carbon-carbon double bond such as chloroperbenzoic acid to an epoxy group is allowed to act, or, for example, a reaction solution and water are mixed, and the reaction product is taken out. After the oxidant is allowed to act, for example, the epoxy compound can be obtained by decomposing the remaining oxidant as necessary, followed by concentration treatment.

で示される。 In the manufacturing method of the epoxy compound of this invention, the manufacturing method with which the diol compound represented by General formula (4) and the halohydrin compound represented by General formula (5) are made to react in the presence of a base is preferable. Here, when the production method of reacting the diol compound represented by the general formula (4) and the halohydrin compound represented by the general formula (5) in the presence of a base is represented by the reaction formula, for example, the reaction formula (1)

Indicated by

２，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−ヒドロキシ−３−フェニルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−ヒドロキシ−２−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−エチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−イソプロピルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−ｔ−ブチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−シクロヘキシルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−メトキシフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−クロロフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３，５−ジメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−２，３，５−トリメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシフェニル）−３−メチル−３−シクロヘキセン−１−イル］プロパン、
ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］メタン、
１，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］エタン、
３−メチル−２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］ペンタン、
１，１−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］シクロヘキサン、
２−［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］−２−［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
等を挙げることができる。 Here, specifically as a diol compound represented by General formula (4), for example,
2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-3-phenylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-2-methylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-ethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-isopropylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-tert-butylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-cyclohexylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-methoxyphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-chlorophenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3,5-dimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-2,3,5-trimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxyphenyl) -3-methyl-3-cyclohexen-1-yl] propane,
Bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] methane,
1,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] ethane,
3-methyl-2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] pentane,
1,1-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] cyclohexane,
2- [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] -2- [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,
Etc.

In the halohydrin compound represented by the general formula (5), examples of the halogen atom include a chlorine atom and a bromine atom. Therefore, specific examples of the halohydrin compound represented by the general formula (5) include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepichlorohydrin, 2- Examples thereof include chloromethyl-3-methyloxirane and 2-chloromethyl-2-methyl-3-methyloxirane.
In the reaction of the diol compound represented by the general formula (4) and the halohydrin compound represented by the general formula (5), the amount of the halohydrin compound used is 1 mol of the diol compound represented by the general formula (4). When the halohydrin compound is used as a reaction solvent, it is used more frequently. Therefore, it is usually in the range of 2 to 100 mol times, preferably in the range of 2 to 50 mol times.

Specific examples of the base catalyst used in the reaction include inorganic substances such as hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, and sodium carbonate. Examples include bases, organic bases such as pyridine and triethylamine, and ammonium salts such as tetrabutylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, and benzyltrimethylammonium chloride. Tetrabutylammonium bromide is preferred.
The base catalyst may be additionally added during the reaction. In particular, when the raw material diol compound disappears, an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate is preferable. The amount of base used is usually in the range of 2 to 5 moles per mole of the diol compound represented by the general formula (4) in the case of an inorganic base, and is usually 0 in the case of an organic base or an ammonium salt. The range is 0.01 to 10 mole times, preferably 0.05 to 1 mole times.

  The solvent used is not particularly limited as long as it is an inert solvent for the reaction. Moreover, you may use simultaneously the halohydrin represented by General formula (5) which is a reaction raw material as a reaction solvent. Specific examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, 3, 3, 5 -Ketones such as trimethylcyclohexanone, methylpentyl ketone, 2-octanone, 2-tridecanone, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, cycloheptane, benzene, Aromatic hydrocarbons such as toluene, xylene, mesitylene, pseudocumene, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. It is below. Such a solvent may be used alone or in combination of two or more. Further, the amount of the solvent is not particularly limited, but is usually 0.1 to 50 parts by weight with respect to 1 part by weight of the diol compound represented by the general formula (4) of the raw material due to volume efficiency and the like. The range is preferably 1 to 20 parts by weight.

The reaction may be performed under normal pressure conditions or under reduced pressure conditions. The reaction temperature is usually in the range of 20 to 100 ° C, preferably in the range of 30 to 70 ° C. Under such reaction conditions, the reaction is usually completed in 5 to 30 hours. In order to make these reaction products of epoxidation reaction into epoxy compounds with less hydrolyzable halogen, add alkali metal hydroxide as needed after dissolving in toluene, methyl isobutyl ketone, etc. according to conventional methods. In addition, further reactions can be performed to ensure ring closure.
After completion of the reaction, a method for purifying the target product from the obtained reaction-terminated mixture can be performed using a known method. For example, after adding distilled water and the above-mentioned solvent as necessary to the reaction mixture, and stirring, if necessary, neutralize and / or wash the oil layer with water, and crystallize the target product from the obtained oil layer. Thus, the precipitated crystals can be obtained by filtration. Such crystallization or precipitation may be performed once to several times if necessary, for example, if the purity of the crystal is low.
Moreover, the diol compound represented by General formula (4) which is a raw material can be manufactured according to the well-known method of Unexamined-Japanese-Patent No. 2005-247809 etc., for example.

Specifically, for example, as shown in reaction formula (2), bis {4,4-di (hydroxyphenyl) cyclohexyl represented by the following general formula (6) corresponding to the diol compound of general formula (4) } It can be obtained by directly using alkane as a raw material and thermally decomposing it in a solvent, preferably in the presence of an alkali.
Reaction formula (2)

In the general formula (6), in the formula, R ₁ , R ₂ , a, b and A are the same as those in the general formula (4).
As such bis (4,4-dihydroxyphenylcyclohexyl) alkane represented by the general formula (6), specifically, for example,
2,2-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-phenylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3,5-dimethylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) -3-methylcyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] methane,
1,1-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] cyclohexane,
2- [4,4-di (4-hydroxyphenyl) cyclohexyl] -2- [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
Etc.

  The thermal decomposition of the raw material bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane represented by the general formula (6) is preferably performed in the presence of an alkali catalyst. Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Examples thereof include alkali metal phenoxides such as hydrogen salt, sodium phenoxide and potassium phenoxide, and alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide. Among these, sodium hydroxide or potassium hydroxide is particularly preferably used.

An alkali catalyst is normally used in 0.01-30 weight part with respect to 100 weight part of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane. The thermal decomposition of the above bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane is carried out during the reaction by using bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane as a starting material and the target product, biscyclohexane. Since the melting point of hexenyl alkanes is high, a solvent is usually used.
Examples of such a solvent include polyethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol, and polyhydric alcohols such as tripropylene glycol, tetrapropylene glycol, and glycerin.
In addition, “Therm S” (manufactured by Nippon Steel Chemical Co., Ltd.) or “SK-OIL” (manufactured by Soken Chemical Co., Ltd.) which is a commercially available organic heat medium can be used.

Such a solvent is normally used in the range of 20 to 2000 parts by weight with respect to 100 parts by weight of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes.
The thermal decomposition of bis (4,4-dihydroxyphenylcyclohexyl) alkanes generally has a reaction rate of slow when the thermal decomposition temperature is too low, and many undesirable side reactions occur when the thermal decomposition temperature is too high. Performed at a temperature in the range of ~ 300 ° C.
In addition, the reaction pressure for the pyrolysis is not particularly limited, but is preferably a pressure at which the generated phenols can be distilled while performing the pyrolysis reaction, and is usually in the range of normal pressure to reduced pressure. Yes, for example, in the range of 1 to 101 kPa (gauge pressure).
Under such reaction conditions, the thermal decomposition of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes is usually completed in about 1 to 6 hours. The end point of the thermal decomposition reaction can be, for example, a point in time when phenol produced by the decomposition reaction is no longer distilled.

According to a preferred embodiment, for example, a reaction vessel is charged with a solvent such as bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes, tetraethylene glycol and sodium hydroxide, at a temperature of 190 to 220 ° C., and a pressure of 10 to 40 kPa. It is carried out by stirring while distilling off the phenols produced by the decomposition reaction at (gauge pressure) for about 3 to 6 hours. After completion of the reaction, a method for taking out the target product from the obtained reaction completion liquid can be performed by a known method. For example, neutralize the reaction completion liquid as necessary, add distilled water and a solvent as necessary, wash with water, concentrate if necessary, and collect the precipitated crystalline or amorphous solid by filtration. To do. When the purity of the obtained crystals and solids is low, such crystallization or precipitation filtration may be further performed once to plural times as necessary.
Thus, by thermally decomposing bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes represented by the general formula (6) of the corresponding structure, the book represented by the general formula (4) The diol compound which is a direct raw material of the epoxy compound of the invention can be obtained with high yield and high purity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

温度計、撹拌器、蒸留装置を備えた２００ｍＬ容量の四つ口フラスコに、２，２−ビス［４，４−ジ（４−ヒドロキシ−３−メチルフェニル）シクロヘキシル］プロパン２０ｇとテトラエチレングリコール３５ｇと水酸化ナトリウム０．６ｇを仕込み、系内を窒素ガス置換した後、撹拌下に、内温２００℃、１０ｋＰａでｏ−クレゾールを留出させながら４時間反応を行った。反応終了後、得られた反応液を４５℃まで冷却した後、酢酸０．９ｇを加えて中和し、メチルイソブチルケトン８０ｇ、蒸留水４０ｇを順に加えて撹拌した後、静置して水層を分離、除去した。得られた油層に水を加えて撹拌した後、静置して水層を除去した。
さらに、同様の操作を２回行い、油層を水洗した。得られた油層を減圧下に濃縮し、残った液にトルエン４０ｇを加え、晶析を行った。析出した結晶をろ別して回収し、得られた結晶を減圧下、１５０℃で乾燥させ、目的物の２，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン７．４ｇを純度９８％（高速液体クロマトグラフィー分析による）の薄茶色結晶として得た。
原料の２，２−ビス［４，４−ジ（４−ヒドロキシ−３−メチルフェニル）シクロヘキシル］プロパンに対する収率は５６モル％であった。
融点；１８５．９℃（示差走査熱量測定（ＤＳＣ））
分子量；４１５（Ｍ−Ｈ）^−
１Ｈ−ＮＭＲ（４００ＭＨｚ、溶媒:ＤＭＳＯ−ｄ６）測定

[Reference Example 1]
Synthesis of 2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane

In a 200 mL four-necked flask equipped with a thermometer, stirrer and distillation apparatus, 20 g of 2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane and 35 g of tetraethylene glycol were added. And 0.6 g of sodium hydroxide were charged, and the system was purged with nitrogen gas. Then, the reaction was carried out for 4 hours while stirring and distilling o-cresol at an internal temperature of 200 ° C. and 10 kPa. After completion of the reaction, the resulting reaction liquid was cooled to 45 ° C., neutralized by adding 0.9 g of acetic acid, added with 80 g of methyl isobutyl ketone and 40 g of distilled water in this order and stirred, and then left to stand to form an aqueous layer. Was separated and removed. Water was added to the obtained oil layer and stirred, and then allowed to stand to remove the water layer.
Furthermore, the same operation was performed twice and the oil layer was washed with water. The obtained oil layer was concentrated under reduced pressure, and 40 g of toluene was added to the remaining liquid for crystallization. The precipitated crystals were collected by filtration, and the obtained crystals were dried at 150 ° C. under reduced pressure to obtain the desired 2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexene-1 7.4 g of yl] propane were obtained as pale brown crystals with a purity of 98% (according to high performance liquid chromatography analysis).
The yield based on the raw material 2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane was 56 mol%.
Melting point: 185.9 ° C. (differential scanning calorimetry (DSC))
Molecular weight: 415 (M−H) ^−
1 H-NMR (400 MHz, solvent: DMSO-d6) measurement

撹拌装置を備えた１００ｍLの四つ口フラスコに参考例１で得られた２，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン（以下４Ｈ−ＯＣＢＰＡと称呼する。）４．２ｇとテトラブチルアンモニウムブロミド０．６ｇ、エピクロロヒドリン２８．０ｇを仕込み、系内を窒素ガスで置換した後、５０℃で１２時間撹拌した。その反応液に水酸化ナトリウム１．２ｇを加えた後、５０℃に保持したまま更に３時間撹拌した。その後、過剰量存在するエピクロロヒドリンを減圧濃縮で回収し、そこにメチルイソブチルケトン２０gと蒸留水２０ｇを加えて撹拌した後、水層を除去した。水層のｐＨが７付近になるまで水洗を繰り返して行い、得られた油層を蒸留により濃縮した後、残液にメタノール５．０ｇを加えて晶析を行い、析出した結晶をろ別した。得られた結晶を５０℃で減圧乾燥して、純度９６％（高速液体クロマトグラフィー分析による）の白色粉末状の２，２−ビス［４−（４−グリシジルオキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン４．４ｇを得た。原料の４Ｈ−ＯＣＢＰＡに対する収率は８２．４モル％であった。
融点：１０３℃（示差走査熱量測定法による）
プロトンＮＭＲ測定結果（４００ＭＨｚ、ＣＤＣｌ_３）：
０．８４（ｔ，６Ｈ），１．２８−１．３９（ｍ，２Ｈ），１．６４−１．７３（ｍ，２Ｈ），１．９４−２．０４（ｍ，４Ｈ），２．１７−２．２４（ｍ，８Ｈ），２．３５−２．５１（ｍ，４Ｈ），２．７７（ｄｄ，２Ｈ），２．８９（ｔ，２Ｈ），３．３３−３．３７（ｍ，２Ｈ），３．９７（ｄｄ，２Ｈ），４．２０（ｄｄ，２Ｈ），６．０３（ｓ，２Ｈ），６．７４（ｄ，２Ｈ），７．１３−７．１９（ｍ，４Ｈ） [Example 1]
Synthesis of 2,2-bis [4- (4-glycidyloxy-3-methylphenyl) -3-cyclohexen-1-yl] propane

2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane obtained in Reference Example 1 (hereinafter referred to as 4H) was added to a 100 mL four-necked flask equipped with a stirrer. -Called OCBPA.) 4.2 g, 0.6 g of tetrabutylammonium bromide, and 28.0 g of epichlorohydrin were charged, and the system was replaced with nitrogen gas, followed by stirring at 50 ° C. for 12 hours. After adding 1.2 g of sodium hydroxide to the reaction solution, the reaction solution was further stirred for 3 hours while maintaining at 50 ° C. Thereafter, excess epichlorohydrin was recovered by concentration under reduced pressure, 20 g of methyl isobutyl ketone and 20 g of distilled water were added thereto and stirred, and then the aqueous layer was removed. Washing with water was repeated until the pH of the aqueous layer was around 7, and the resulting oil layer was concentrated by distillation, and then 5.0 g of methanol was added to the remaining liquid for crystallization, and the precipitated crystals were filtered off. The obtained crystals were dried at 50 ° C. under reduced pressure, and 2,2-bis [4- (4-glycidyloxy-3-methylphenyl) -3 in the form of a white powder having a purity of 96% (according to high performance liquid chromatography analysis). -Cyclohexen-1-yl] propane 4.4g was obtained. The yield based on 4H-OCBPA as a raw material was 82.4 mol%.
Melting point: 103 ° C. (by differential scanning calorimetry)
Proton NMR measurement result (400 MHz, CDCl ₃ ):
0.84 (t, 6H), 1.28-1.39 (m, 2H), 1.64-1.73 (m, 2H), 1.94-2.04 (m, 4H), 2. 17-2.24 (m, 8H), 2.35-2.51 (m, 4H), 2.77 (dd, 2H), 2.89 (t, 2H), 3.33-3.37 ( m, 2H), 3.97 (dd, 2H), 4.20 (dd, 2H), 6.03 (s, 2H), 6.74 (d, 2H), 7.13-7.19 (m , 4H)

２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］プロパンの合成
温度計、撹拌器、蒸留装置を備えた２００ｍＬ容量の四つ口フラスコに、２，２−ビス［４，４−ジ（４−ヒドロキシフェニル）シクロヘキシル］プロパン２０ｇとエチレングリコール５０ｇと水酸化ナトリウム０．６ｇを仕込み、系内を窒素ガス置換した後、撹拌下に内温１８９℃、３０ｋＰａを保ち、フェノールを留出させながら５時間反応を行った。反応終了後、得られた反応液を９０℃まで冷却した後、酢酸０．９ｇを加えて中和し、メチルイソブチルケトン８０ｇ、蒸留水４０ｇを順に加えて撹拌した後、静置して水層を分離、除去した。得られた油層に水を加えて撹拌した後、静置して水層を除去した。
さらに、同様の操作を行い、油層を水洗した。得られた油層を減圧下に濃縮し、残った液にトルエン４０ｇを加え、晶析を行った。析出した結晶をろ別して回収し、得られた結晶を減圧下、１５０℃で乾燥させ、目的物の２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］プロパン８．６ｇを純度９７％（高速液体クロマトグラフィー分析による）の薄茶色結晶として得た。
原料の２，２−ビス［４，４−ジ（４−ヒドロキシフェニル）シクロヘキシル］プロパンに対する収率は６４モル％であった。
融点：２４３．５℃（示差走査熱量測定（ＤＳＣ））
分子量：３８７（Ｍ−Ｈ）^−
１Ｈ−ＮＭＲ（４００ＭＨｚ、溶媒：ＤＭＳＯ−ｄ６）測定

[Reference Example 2]

Synthesis of 2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane A 200 mL four-necked flask equipped with a thermometer, stirrer, and distillation apparatus was charged with 2,2- After charging 20 g of bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane, 50 g of ethylene glycol and 0.6 g of sodium hydroxide, the system was purged with nitrogen gas, and the internal temperature was 189 ° C. and 30 kPa with stirring. The reaction was carried out for 5 hours while distilling phenol. After completion of the reaction, the resulting reaction solution was cooled to 90 ° C., neutralized by adding 0.9 g of acetic acid, 80 g of methyl isobutyl ketone and 40 g of distilled water were sequentially added and stirred, and then left to stand to form an aqueous layer. Was separated and removed. Water was added to the obtained oil layer and stirred, and then allowed to stand to remove the water layer.
Furthermore, the same operation was performed and the oil layer was washed with water. The obtained oil layer was concentrated under reduced pressure, and 40 g of toluene was added to the remaining liquid for crystallization. The precipitated crystals were collected by filtration, and the obtained crystals were dried at 150 ° C. under reduced pressure to obtain the desired 2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane. 8.6 g was obtained as light brown crystals with a purity of 97% (according to high performance liquid chromatography analysis).
The yield based on 2,2-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane as a raw material was 64 mol%.
Melting point: 243.5 ° C. (differential scanning calorimetry (DSC))
Molecular weight: 387 (M−H) ^−
1 H-NMR (400 MHz, solvent: DMSO-d6) measurement

撹拌装置を備えた１００ｍＬの四つ口フラスコに参考例２で得られた２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］プロパン（以下４Ｈ−ＰＨＢＰＡと称呼する。）３．９ｇとテトラブチルアンモニウムブロミド０．６ｇ、エピクロロヒドリン２７．８ｇを仕込み、系内を窒素ガスで置換した後、５０℃で９時間撹拌した。その反応液に水酸化ナトリウム１．２ｇを加えた後、５０℃に保持したまま更に３時間撹拌した。
その後、過剰量存在するエピクロロヒドリンを減圧濃縮で回収し、そこにメチルイソブチルケトン７８．０ｇと蒸留水２．０ｇを加えて７０℃に昇温し、１時間撹拌して反応を完結させた。蒸留水を加えて水層のｐＨが７付近になるまで水洗を繰り返して行い、得られた油層を蒸留により濃縮した後、析出した結晶をろ別した。得られた結晶を５０℃で減圧乾燥して、純度９４．８％（高速液体クロマトグラフィー分析による）の白色粉末状の２，２−ビス［４−（４−グリシジルオキシフェニル）−３−シクロヘキセン−１−イル］プロパン３．５ｇを得た。原料の４Ｈ−ＰＨＢＰＡに対する収率は６９．９モル％であった。
融点：１７８℃（示差走査熱量測定法による）
^１Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ_３）測定
０．８５（ｔ，６Ｈ），１．３２−１．３７（ｍ，２Ｈ），１．６８−１．７１（ｍ，２Ｈ），１．９５−２．０５（ｍ，４Ｈ），２．１６−２．２４（ｍ，２Ｈ），２．４０−２．５２（ｍ，４Ｈ），２．７５（ｄｄ，２Ｈ），２．８９（ｔ，２Ｈ），３．３２−３．３６（ｍ，２Ｈ），３．９６（ｄｄ，２Ｈ），４．２０（ｄｄ，２Ｈ），６．０５（ｓ，２Ｈ），６．８６（ｄ，４Ｈ），７．３２（ｄ，４Ｈ） [Example 2]
Synthesis of 2,2-bis [4- (4-glycidyloxyphenyl) -3-cyclohexen-1-yl] propane

2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane (hereinafter referred to as 4H-PHBPA) obtained in Reference Example 2 in a 100 mL four-necked flask equipped with a stirrer. 3.9 g, tetrabutylammonium bromide 0.6 g, and epichlorohydrin 27.8 g were charged, and the system was replaced with nitrogen gas, followed by stirring at 50 ° C. for 9 hours. After adding 1.2 g of sodium hydroxide to the reaction solution, the reaction solution was further stirred for 3 hours while maintaining at 50 ° C.
Thereafter, excess epichlorohydrin is recovered by concentration under reduced pressure, 78.0 g of methyl isobutyl ketone and 2.0 g of distilled water are added thereto, the temperature is raised to 70 ° C., and the mixture is stirred for 1 hour to complete the reaction. It was. Distilled water was added and water washing was repeated until the pH of the aqueous layer became around 7. After concentrating the obtained oil layer by distillation, the precipitated crystals were separated by filtration. The obtained crystals were dried at 50 ° C. under reduced pressure to give 2,2-bis [4- (4-glycidyloxyphenyl) -3-cyclohexene as a white powder having a purity of 94.8% (according to high performance liquid chromatography analysis). 3.5 g of -1-yl] propane was obtained. The yield based on 4H-PHBPA of the raw material was 69.9 mol%.
Melting point: 178 ° C (by differential scanning calorimetry)
¹ H-NMR (400 MHz, CDCl ₃ ) measurement 0.85 (t, 6H), 1.32-1.37 (m, 2H), 1.68-1.71 (m, 2H), 1.95- 2.05 (m, 4H), 2.16-2.24 (m, 2H), 2.40-2.52 (m, 4H), 2.75 (dd, 2H), 2.89 (t, 2H), 3.32-3.36 (m, 2H), 3.96 (dd, 2H), 4.20 (dd, 2H), 6.05 (s, 2H), 6.86 (d, 4H) ), 7.32 (d, 4H)

Claims (3)

General formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, A represents an alkylene group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
An epoxy compound represented by The epoxy compound represented by the general formula (1) is represented by the general formula (2).

(In the formula, R ₁ , R ₂ , R ₃ , a and b are the same as those in the general formula (1), and R ₄ and R ₅ are each independently a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. Represents an alkyl group, and R ₄ and R ₅ may combine with each other to form a ring.)
The epoxy compound of Claim 1 shown by these. The epoxy compound according to claim 1 or 2, wherein in the general formula (1) or the general formula (2), all R ₃ are hydrogen atoms.