JP4613633B2 - Epoxy compound and epoxy resin cured product - Google Patents

Description

  The present invention relates to an epoxy compound and a cured epoxy resin.

  An epoxy resin cured product obtained by curing an epoxy compound derived from 4,4'-dihydroxybiphenyl is known (for example, see Patent Document 1). Such a cured epoxy resin has characteristics such as excellent heat resistance, but the epoxy compound as a raw material has a problem that it has a high melting point and is difficult to use (for example, see Patent Document 1).

Japanese Patent No. 2551475

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ同一または相異なって、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、シアノ基またはニトロ基を表わし、Ｒ^９およびＲ^１０はそれぞれ同一または相異なって、水素原子または炭素数１〜１０のアルキル基を表わす。Ｘ^１およびＸ^２はそれぞれ同一または相異なって、下記（Ｘ−１）〜（Ｘ−３）で示されるいずれかの基を表わす。

ここで、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０はそれぞれ同一または相異なって、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、シアノ基またはニトロ基を表わす。ｍは１〜１０の整数を表わす。）
で示されるエポキシ化合物が新規であって、融点が低く、また、硬化剤により硬化せしめることによりエポキシ樹脂硬化物を製造できることを見出し、本発明に至った。 Under such circumstances, the present inventors have intensively studied to develop a novel epoxy compound that has a low melting point and can be used as a raw material for the cured epoxy resin.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, Represents an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group, and R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ¹ and X ² are Each of these groups is the same or different and represents any of the following groups (X-1) to (X-3).

Here, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and each represents a hydrogen atom, a halogen atom, 8 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. m represents an integer of 1 to 10. )
The inventors have found that an epoxy compound represented by the formula (1) is novel, has a low melting point, and can be cured with a curing agent to produce a cured epoxy resin, resulting in the present invention.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ同一または相異なって、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、シアノ基またはニトロ基を表わし、Ｒ^９およびＲ^１０はそれぞれ同一または相異なって、水素原子または炭素数１〜１０のアルキル基を表わす。Ｘ^１およびＸ^２はそれぞれ同一または相異なって、下記（Ｘ−１）〜（Ｘ−３）で示されるいずれかの基を表わす。

ここで、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０はそれぞれ同一または相異なって、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、シアノ基またはニトロ基を表わす。ｍは１〜１０の整数を表わす。）
で示されるエポキシ化合物、該エポキシ化合物と硬化剤とを含んでなるエポキシ組成物、該エポキシ組成物を硬化せしめてなるエポキシ樹脂硬化物等を提供するものである。 That is, the present invention provides the formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, Represents an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group, and R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ¹ and X ² are Each of these groups is the same or different and represents any of the following groups (X-1) to (X-3).

Here, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and each represents a hydrogen atom, a halogen atom, 8 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. m represents an integer of 1 to 10. )
Are provided, an epoxy composition comprising the epoxy compound and a curing agent, a cured epoxy resin obtained by curing the epoxy composition, and the like.

  Since the novel epoxy compound of the present invention has a low melting point, it can be melt-mixed with a curing agent at a temperature lower than the curing temperature, and an epoxy resin cured product can be easily obtained. Moreover, the cured epoxy resin of the present invention exhibits a relatively good thermal conductivity, and is useful as an insulating material that requires high heat dissipation such as a printed wiring board.

で示されるエポキシ化合物（以下、エポキシ化合物（１）と略記する。）について説明する。
エポキシ化合物（１）の式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ同一または相異なって、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、シアノ基またはニトロ基を表わす。ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。炭素数１〜８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、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、１，１，３，３−テトラメチルブチル基等の直鎖状もしくは分枝鎖状の炭素数１〜８のアルキル基が挙げられる。炭素数１〜８のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−オクチルオキシ基、１，１，３，３−テトラメチルブトキシ基等の直鎖状もしくは分枝鎖状の炭素数１〜８のアルコキシ基が挙げられる。 First, the following new formula (1) of the present invention

Will be described below (hereinafter abbreviated as epoxy compound (1)).
In the formula of the epoxy compound (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and are each a hydrogen atom, a halogen atom, 8 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -A linear or branched alkyl group having 1 to 8 carbon atoms such as a hexyl group, an n-octyl group, and a 1,1,3,3-tetramethylbutyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group. , N-hexyloxy group, n-octyloxy group, 1,1,3,3-tetramethylbutoxy group and the like linear or branched alkoxy groups having 1 to 8 carbon atoms.

R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group And a linear or branched alkyl group having 1 to 10 carbon atoms such as an n-decyl group.

X ¹ and X ² are the same or different and each represents one of the groups represented by the following (X-1) to (X-3).

Here, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and each represents a hydrogen atom, a halogen atom, 8 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. m represents an integer of 1 to 10. Examples of the halogen atom, the alkyl group having 1 to 8 carbon atoms, and the alkoxy group having 1 to 8 carbon atoms are the same as those described above. Examples of the group represented by (X-1) include a 1,4-phenylene group and a 1,3-phenylene group. Examples of the group represented by (X-2) include naphthalene-2,6- Examples thereof include a diyl group and a naphthalene-3,6-diyl group. Examples of the group represented by (X-3) include a 4,4′-biphenylene group.

  Examples of the epoxy compound (1) include 2,2′-bis {4 (4-oxiranylmethoxybenzoyloxy) phenyl} propane, 2,2′-bis [4- {4- (2-oxiranyl). Ethoxy) benzoyloxy} phenyl] propane, 2,2′-bis [4- {4- (3-oxiranylpropoxy) benzoyloxy} phenyl] propane, 2,2′-bis {4- (4-oxira) Nylmethoxybenzoyloxy) phenyl} butane, 2,2′-bis [4- {4- (2-oxiranylethoxy) benzoyloxy} phenyl] butane, 2,2′-bis [4- {4- (3 -Oxiranylpropoxy) benzoyloxy} phenyl] butane, 3,3′-bis {4- (4-oxiranylmethoxybenzoyloxy) phenyl} pentane, 3,3 ′ Bis [4- {4- (2-oxiranylethoxy) benzoyloxy} phenyl] pentane, 3,3′-bis [4- {4- (3-oxiranylpropoxy) benzoyloxy} phenyl] pentane, 2 , 2′-bis {4- (2-oxiranylmethoxy-6-naphthoyloxy) phenyl} propane, 2,2′-bis [4- {2- (2-oxiranylethoxy) -6-naphtho Yloxy} phenyl] propane, 2,2′-bis [4- {2- (3-oxiranylpropoxy) -6-naphthoyloxy} phenyl] propane, 2,2′-bis {4- (2- Oxiranylmethoxy-6-naphthoyloxy) phenyl} butane, 2,2′-bis [4- {2- (2-oxiranylethoxy) -6-naphthoyloxy} phenyl] butane, 2,2 ′ -Screw [ - {2- (3-oxiranylmethoxy propoxy) -6-naphthoyloxy} phenyl] butane,

3,3′-bis {4- (2-oxiranylmethoxy-6-naphthoyloxy) phenyl} pentane, 3,3′-bis [4- {2- (2-oxiranylethoxy) -6 Naphthoyloxy} phenyl] pentane, 3,3′-bis [4- {2- (3-oxiranylpropoxy) -6-naphthoyloxy} phenyl] pentane, 2,2′-bis [4- {4 -(4-oxiranylmethoxyphenyl) benzoyloxy} phenyl] propane, 2,2′-bis [4- [4- {4- (2-oxiranylethoxy) phenyl} benzoyloxy] phenyl] propane, 2 , 2′-bis [4- [4- {4- (3-oxiranylpropoxy) phenyl} benzoyloxy] phenyl] propane, 2,2′-bis [4- {4- (4-oxiranylmethoxy) Phenyl Benzoyloxy} phenyl] butane, 2,2′-bis [4- [4- {4- (2-oxiranylethoxy) phenyl} benzoyloxy] phenyl] butane, 2,2′-bis [4- [4 -{4- (3-oxiranylpropoxy) phenyl} benzoyloxy] phenyl] butane, 3,3′-bis [4- {4- (4-oxiranylmethoxyphenyl) benzoyloxy} phenyl] pentane, 3 , 3′-bis [4- [4- {4- (2-oxiranylethoxy) phenyl} benzoyloxy] phenyl] pentane, 3,3′-bis [4- [4- {4- (3-oxy Ranylpropoxy) phenyl} benzoyloxy] phenyl] pentane and the like.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｘ^１、Ｘ^２およびｍは上記と同一の意味を表わす。）
で示される化合物（以下、化合物（２）と略記する。）と酸化剤とを反応させることにより製造することができる。 The epoxy compound (1) has the formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ , X ² and m represent the same meaning as described above. )
It can manufacture by making the compound (henceforth abbreviated as a compound (2)) shown by these, and an oxidizing agent react.

  Examples of the compound (2) include 2,2′-bis {4- (4-allyloxybenzoyloxy) phenyl} propane, 2,2′-bis [4- {4- (3-butenyloxy) benzoyloxy}. Phenyl] propane, 2,2′-bis [4- {4- (4-pentenyloxy) benzoyloxy} phenyl] propane, 2,2′-bis {4- (4-allyloxybenzoyloxy) phenyl} butane, 2,2′-bis [4- {4- (3-butenyloxy) benzoyloxy} phenyl] butane, 2,2′-bis [4- {4- (4-pentenyloxy) benzoyloxy} phenyl] butane, 3 , 3′-bis {4- (4-allyloxybenzoyloxy) phenyl} pentane, 3,3′-bis [4- {4- (3-butenyloxy) benzoyloxy } Phenyl] pentane, 3,3′-bis [4- {4- (4-pentenyloxy) benzoyloxy} phenyl] pentane, 2,2′-bis {4- (2-allyloxy-6-naphthoyloxy) Phenyl} propane, 2,2′-bis [4- {2- (3-butenyloxy) -6-naphthoyloxy} phenyl] propane, 2,2′-bis [4- {2- (4-pentenyloxy) -6-naphthoyloxy} phenyl] propane, 2,2'-bis {4- (2-allyloxy-6-naphthoyloxy) phenyl} butane, 2,2'-bis [4- {2- (3- Butenyloxy) -6-naphthoyloxy} phenyl] butane, 2,2′-bis [4- {2- (4-pentenyloxy) -6-naphthoyloxy} phenyl] butane,

3,3′-bis {4- (2-allyloxy-6-naphthoyloxy) phenyl} pentane, 3,3′-bis [4- {2- (3-butenyloxy) -6-naphthoyloxy} phenyl] Pentane, 3,3′-bis [4- {2- (4-pentenyloxy) -6-naphthoyloxy} phenyl] pentane, 2,2′-bis [4- {4- (4-allyloxyphenyl) Benzoyloxy} phenyl] propane, 2,2′-bis [4- [4- {4- (3-butenyloxy) phenyl} benzoyloxy] phenyl] propane, 2,2′-bis [4- [4- {4 -(4-pentenyloxy) phenyl} benzoyloxy] phenyl] propane, 2,2'-bis [4- {4- (4-allyloxyphenyl) benzoyloxy} phenyl] butane, 2,2'- [4- [4- {4- (3-Butenyloxy) phenyl} benzoyloxy] phenyl] butane, 2,2′-bis [4- [4- {4- (4-pentenyloxy) phenyl} benzoyloxy] Phenyl] butane, 3,3′-bis [4- {4- (4-allyloxyphenyl) benzoyloxy} phenyl] pentane, 3,3′-bis [4- [4- {4- (3-butenyloxy)] Phenyl} benzoyloxy] phenyl] pentane, 3,3′-bis [4- [4- {4- (4-pentenyloxy) phenyl} benzoyloxy] phenyl] pentane, and the like.

  The oxidizing agent may be any oxidizing agent that can epoxidize a carbon-carbon double bond, and examples thereof include m-chloroperbenzoic acid. The usage-amount of this oxidizing agent is 0.5-10 mol times normally with respect to a compound (2).

  The reaction between the compound (2) and the oxidizing agent is usually carried out in a solvent, and the solvent is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbon solvents such as dichloromethane and chloroform, A single or mixed solvent such as water can be used. The amount of such solvent used is not particularly limited.

  The reaction temperature is usually 0-50 ° C.

  After completion of the reaction, for example, sodium thiosulfate or the like is added to the reaction solution, the oxidizing agent remaining in the reaction solution is decomposed, and then water and an organic solvent insoluble in water are added as necessary, followed by liquid separation treatment. By doing, the organic layer containing an epoxy compound (1) can be obtained. By concentrating the obtained organic layer, the epoxy compound (1) can be taken out. The taken out epoxy compound (1) may be further purified by ordinary purification means such as silica gel column chromatography.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は上記と同一の意味を表わす。）
で示される化合物（以下、化合物（３）と略記する。）と式（４）

（式中、Ｘ^１およびｍは上記と同一の意味を表わし、Ｘ^３はハロゲン原子を表わす。）
で示される化合物（以下、化合物（４）と略記する。）と式（５）

（式中、Ｘ^２およびｍは上記と同一の意味を表わし、Ｘ^４はハロゲン原子を表わす。）
で示される化合物（以下、化合物（５）と略記する。）とを、塩基の存在下に反応させることにより製造することができる。 Compound (2) has the formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above.)
(Hereinafter abbreviated as compound (3)) and formula (4)

(Wherein X ¹ and m represent the same meaning as described above, and X ³ represents a halogen atom.)
(Hereinafter abbreviated as compound (4)) and formula (5)

(Wherein X ² and m represent the same meaning as described above, and X ⁴ represents a halogen atom.)
In the presence of a base (hereinafter abbreviated as compound (5)).

  Examples of the compound (3) include 2,2′-bis (4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxyphenyl) butane, 3,3′-bis (4-hydroxyphenyl) pentane, and the like. Is mentioned.

In the formulas of the compound (4) and the compound (5), X ³ and X ⁴ represent a halogen atom, and examples of the halogen atom include those described above.

  The compound (4) and the compound (5) may be the same or different. For example, 4-allyloxybenzoic acid chloride, 4-allyloxybenzoic acid bromide, 4- (3-butenyloxy) benzoic acid chloride 4- (3-butenyloxy) benzoic acid bromide, 4- (4-pentenyloxy) benzoic acid chloride, 4- (4-pentenyloxy) benzoic acid bromide, 2-allyloxy-6-naphthoic acid chloride, 2-allyloxy- 6-naphthoic acid bromide, 2- (3-butenyloxy) -6-naphthoic acid chloride, 2- (3-butenyloxy) -6-naphthoic acid bromide, 2- (4-pentenyloxy) -6-naphthoic acid chloride, 2 -(4-Pentenyloxy) -6-naphthoic acid bromide, 4- (4-allyloxyphenyl) benzoate Acid chloride, 4- (4-allyloxyphenyl) benzoic acid bromide, 4- {4- (3-butenyloxy) phenyl} benzoic acid chloride, 4- {4- (3-butenyloxy) phenyl} benzoic acid bromide, 4- Examples include {4- (4-pentenyloxy) phenyl} benzoic acid chloride, 4- {4- (4-pentenyloxy) phenyl} benzoic acid bromide, and the like.

  When the compound (4) and the compound (5) are different from each other, the amount used is usually 0.5 to 50 mol times based on the compound (3). When the compound (4) and the compound (5) are the same, the amount used thereof is usually 1 to 100 times the compound (3).

  Examples of the base include organic bases such as triethylamine, pyridine, dimethylaniline, and tetramethylurea, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. With respect to 3), it is usually 2 mol times or more, and there is no particular upper limit. For example, when a base that is liquid under reaction conditions is used, a large excess amount may be used also as a reaction solvent.

  The reaction is usually carried out in a solvent, and examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, and single or mixed solvents such as ether solvents such as diethyl ether and tetrahydrofuran. Further, as described above, a base that is liquid under reaction conditions may be used as a solvent. The amount of such solvent used is not particularly limited.

  The reaction temperature is usually 0-50 ° C.

  After completion of the reaction, an organic layer containing the compound (2) is obtained by adding water and, if necessary, an organic solvent insoluble in water to the reaction solution and performing a liquid separation treatment, and the organic layer is concentrated. Thus, the compound (2) can be taken out. The extracted compound (2) may be further purified by ordinary purification means such as silica gel column chromatography.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物と式（７）

（式中、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は上記と同一の意味を表わす。）
で示される化合物と式（８）

（式中、Ｒ^９およびＲ^１０は上記と同一の意味を表わす。）
で示されるケトン化合物とを、酸触媒の存在下に縮合反応せしめることにより製造したものを用いてもよい。 In addition, what is marketed may be used for a compound (3), for example, according to the manufacturing method of bisphenol A (2,2'-bis (4-hydroxyphenyl) propane), Formula (6)

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above.)
And a compound of formula (7)

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above.)
And a compound of formula (8)

(Wherein R ⁹ and R ¹⁰ represent the same meaning as described above.)
A product produced by subjecting a ketone compound represented by the above to a condensation reaction in the presence of an acid catalyst may be used.

（式中、ｍは上記と同一の意味を表わし、Ｘ^５はハロゲン原子を表わす。）
で示される化合物（以下、化合物（９）と略記する。）と式（１０）

（式中、Ｘ^１は上記と同一の意味を表わす。）
で示される化合物（以下、化合物（１０）と略記する。）とを塩基の存在下に反応させた後、例えば塩化チオニル等のハロゲン化剤を作用させる方法により製造することができ、化合物（５）も化合物（４）と同様にして製造することができる。 In addition, the compound (4) is, for example, the formula (9)

(Wherein m represents the same meaning as described above, and X ⁵ represents a halogen atom.)
(Hereinafter abbreviated as compound (9)) and formula (10)

(Wherein X ¹ represents the same meaning as described above.)
Can be produced by reacting a compound represented by formula (hereinafter abbreviated as compound (10)) in the presence of a base and then reacting with a halogenating agent such as thionyl chloride. ) Can also be produced in the same manner as compound (4).

  Examples of the compound (9) include allyl chloride, allyl bromide, 3-butenyl chloride, 3-butenyl bromide, 4-pentenyl chloride, 4-pentenyl bromide and the like. Examples of the compound (10) include 4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4- (4-hydroxyphenyl) benzoic acid and the like.

  The amount of compound (9) to be used is generally 1 to 5 mol times based on compound (10).

  As a base, inorganic bases, such as sodium hydroxide and potassium hydroxide, are mentioned, for example, The usage-amount is 1-10 mole times normally with respect to a compound (10). Such a base may be used as it is, or an aqueous solution may be used.

  The reaction of the compound (9) and the compound (10) is usually carried out in a solvent, and examples of the solvent include alcohol solvents such as methanol and ethanol, single or mixed solvents such as water, and the amount used is There is no particular limitation.

  After completion of the reaction, if necessary, an organic solvent insoluble in water is added to the reaction solution for washing treatment, and then the reaction product can be taken out as crystals, for example, by adding an acid to the reaction solution for neutralization treatment. .

  Examples of the method of allowing the halogenating agent to act on the extracted reaction product include a method of producing a carboxylic acid halide from a known carboxylic acid.

  Then, the epoxy composition of this invention is demonstrated. The epoxy composition of the present invention is an epoxy composition comprising an epoxy compound (1) and a curing agent. Such an epoxy composition can be obtained by mixing the epoxy compound (1) and a curing agent as they are or in a solvent. The epoxy composition may contain a kind of epoxy compound (1) and a curing agent, or may contain two or more different epoxy compounds (1) and a curing agent. Examples of the solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as dimethyl sulfoxide and N-methylpyrrolidone, ester solvents such as butyl acetate, and glycols such as propylene glycol monomethyl ether. System solvents and the like.

  Any curing agent may be used as long as it cures the epoxy compound (1). Examples thereof include amine curing agents, phenol curing agents, acid anhydride curing agents, and catalyst curing agents, and amine curing agents. A phenol-based curing agent or a catalyst-based curing agent is preferable.

  Examples of amine curing agents include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine, such as p-xylenediamine and m-xylene. Diamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'- Aromatic polyamines such as diaminodiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylmethane, 4,4′-diaminodicyclohexane 1,3 Examples include alicyclic polyamines such as bisaminomethylcyclohexane, such as dicyandiamide, and aromatic polyamines and dicyandiamide are preferred. 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5 -Diaminonaphthalene, p-phenylenediamine, and dicyandiamide are more preferable.

  Examples of the phenolic curing agent include phenol resin, phenol aralkyl resin (having a phenylene skeleton, diphenylene skeleton, etc.), naphthol aralkyl resin, polyoxystyrene resin, and the like. Examples of the phenol resin include resol-type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin, for example, novolac-type phenol resins such as phenol novolak resin, cresol novolac resin, tert-butylphenol novolak resin, and nonylphenol novolak resin, such as dicyclopentadiene. Special phenol resins such as a modified phenol resin, a terpene modified phenol resin, and a triphenol methane type resin can be used. 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, and the like.

  Examples of the catalyst curing agent 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, and if it is an amine curing agent or a phenol curing agent, for example, a functional group capable of undergoing a curing reaction with an epoxy group in the curing agent. The total amount of is usually 0.5 to 1.5 times, preferably 0.9 to 1.1 times the total amount of epoxy groups in the epoxy compound (1).

  In addition to the epoxy compound (1) and the curing agent, the epoxy composition of the present invention may contain the solvent as described above, or a desired epoxy resin cured product obtained by curing the epoxy composition. As long as performance is not hindered, other epoxy compounds may be included, and various additives may be included. Examples of other epoxy compounds include bisphenol A type epoxy compounds, orthocresol type epoxy compounds such as biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenyl benzoate, and naphthalene diglycidyl. And epoxy compounds such as ether and α-methylstilbene-4,4′-diglycidyl ether. Examples of additives include silica powder such as fused crushed silica powder, fused spherical silica powder, crystalline silica powder, and secondary agglomerated silica powder, such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, and glass fiber. Fillers, for example, curing accelerators such as triphenylphosphine and 1,8-azabicyclo [5.4.0] -7-undecene, coupling agents such as γ-glycidoxypropyltrimethoxysilane, such as carbon black And low-stress components such as silicone oil and silicone rubber, for example, natural wax, synthetic wax, higher fatty acids or metal salts thereof, mold release agents such as paraffin, and antioxidants. The content of such other epoxy compounds and additives is not particularly limited as long as it is an amount that does not impair the desired performance of the cured epoxy resin obtained by curing the epoxy composition of the present invention.

  Then, the epoxy resin hardened | cured material of this invention is demonstrated. The cured epoxy resin of the present invention can be produced by curing an epoxy composition comprising the epoxy compound (1) and a curing agent.

  The epoxy resin cured product of the present invention may be an epoxy resin cured product obtained by curing one kind of epoxy compound and a curing agent, or an epoxy resin cured product obtained by curing two or more different epoxy compounds and a curing agent. It may be a thing.

  Examples of the method for curing the epoxy composition include a method in which the epoxy composition is heated and cured as it is, a method in which the epoxy composition is heated and melted and poured into a mold or the like, and the mold is further heated to be molded. A method of melting the composition, injecting the resulting melt into a preheated mold with a transfer molding machine and curing, partially curing the epoxy composition called B-stage, and crushing the resulting partially cured product A method of filling the resulting powder into a mold, melt-molding the filler, dissolving the epoxy composition in a solvent as necessary, converting to B-stage while stirring, casting the resulting solution, For example, a method of drying and removing by ventilation drying or the like, and heating for a predetermined time while applying pressure with a press machine or the like as necessary may be mentioned.

  Finally, a prepreg obtained by impregnating or coating the base material with the epoxy composition of the present invention and semi-curing it will be described. By diluting the epoxy composition of the present invention with a solvent as necessary, and then impregnating or coating the substrate, heating the impregnated or coated substrate, and semi-curing the epoxy compound in the substrate. A prepreg can be produced. Examples of the substrate include woven or nonwoven fabrics of inorganic fibers such as glass fiber woven fabrics, and woven or nonwoven fabrics of organic fibers such as polyester. By using such a prepreg, a laminate or the like can be easily produced by a usual method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the high performance liquid chromatography (LC) method was used for the analysis.

Example 1 <Production Example of Epoxy Compound>
In a 1 L four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 90 g of 4-hydroxybenzoic acid, 400 mL of methanol, 105 g of potassium hydroxide and 125 mL of water were charged, and the temperature was raised to the reflux temperature. To this, 90 g of allyl bromide was added dropwise over 2 hours, and then reacted under reflux conditions for 13 hours. After completion of the reaction, 250 mL of methanol was distilled off with an evaporator. To the concentrated residue, 2.5 L of water and 250 mL of hexane were added, stirred and allowed to stand, and then the hexane layer was separated and removed. To the aqueous layer, 300 mL of 20 wt% hydrochloric acid was added, and the precipitated crystals were collected by filtration. The crystals collected by filtration were washed with water and dried. Then, it was recrystallized from ethanol to obtain 80.2 g of 4-allyloxybenzoic acid in the form of white powder. Purity: 99% (LC area percentage value).

  30 g of 4-allyloxybenzoic acid obtained above, 365 g of thionyl chloride and 1 mL of pyridine were charged into a 1 L four-necked flask equipped with a thermometer, a condenser and a stirrer, and reacted at reflux temperature for 8 hours. After completion of the reaction, the reaction solution was concentrated to obtain 39 g of oily crude 4-allyloxybenzoic acid chloride.

  Into a 1 L four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 20 g of the crude 4-allyloxybenzoic acid chloride obtained above was charged, and 2,2′-bis (4-hydroxyphenyl) was cooled with ice. A solution prepared by dissolving 11.6 g of propane in 139 g of pyridine was added dropwise over 1 hour. Thereafter, the mixture was stirred and reacted at room temperature for 8 hours. After completion of the reaction, the reaction solution was poured into 1 L of water. Chloroform was added thereto, and 300 g of 1N hydrochloric acid was further added thereto, followed by liquid separation treatment to obtain a chloroform layer. The resulting chloroform layer was concentrated to obtain 26 g of oily crude 2,2'-bis {4- (4-allyloxybenzoyloxy) phenyl} propane. Purity: 60% (LC area percentage value).

  The crude 2,2′-bis {4- (4-allyloxybenzoyloxy) phenyl} propane obtained above was purified with a silica gel column (chloroform / methanol = 100/1), and purified 2,2′-bis { 4- (4-Allyloxybenzoyloxy) phenyl} propane was obtained. In a 300 mL four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 5 g of 2,2′-bis {4- (4-allyloxybenzoyloxy) phenyl} propane, 100 g of chloroform and 5% by weight sodium hydrogen carbonate 18g was charged. At room temperature, 13.5 g of m-chloroperbenzoic acid was added thereto and stirred and reacted for 10 days. After completion of the reaction, the reaction solution was washed with a saturated aqueous sodium thiosulfate solution, a saturated aqueous sodium bicarbonate solution, and then saturated brine. After drying over anhydrous magnesium sulfate, concentration treatment was performed to obtain 6 g of crude 2,2′-bis {4- (4-oxiranylmethoxybenzoyloxy) phenyl} propane. This was purified by a silica gel column (chloroform / ethyl acetate = 10/1) to obtain 1 g of 2,2′-bis {4- (4-oxiranylmethoxybenzoyloxy) phenyl} propane white crystals. Purity: 93% (LC area percentage value). Melting point: 138 ° C.

Example 2 <Example of production of epoxy composition and cured epoxy resin>
20 parts by weight of 2,2′-bis {4- (4-oxiranylmethoxybenzoyloxy) phenyl} propane obtained in Example 1 and 3.4 parts by weight of 4,4′-diaminodiphenylmethane as a curing agent Were mixed to obtain an epoxy composition. The molten epoxy composition was poured into a plate-shaped hollow portion of a mold heated to about 140 ° C., and further heated at about 160 to 180 ° C. for about 5 hours to obtain a plate-shaped epoxy resin cured product. . A thin plate sample of 5 mm × 10 mm was cut out from this cured epoxy resin, and the thermal conductivity was measured (measurement conditions were performed at room temperature in accordance with the optical alternating current method), and it was 0.25 W / m · K. It was.

Example 3 <Preparation example of prepreg>
2,2′-bis {4- (4-oxiranylmethoxybenzoyloxy) phenyl} propane obtained in Example 1 is mixed with 1,5-diaminonaphthalene as a curing agent and methyl ethyl ketone as a solvent. As a result, an epoxy composition is obtained. A glass fiber woven fabric is impregnated with the epoxy composition, heated and semi-cured to obtain a prepreg.

Claims (4)

Formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, Represents an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group, and R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ¹ and X ² are Each of these groups is the same or different and represents any of the following groups (X-1) to (X-3).

Here, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and each represents a hydrogen atom, a halogen atom, 8 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. m represents an integer of 1 to 10. )
An epoxy compound represented by An epoxy composition comprising the epoxy compound according to claim 1 and a curing agent. A cured epoxy resin obtained by curing the epoxy composition according to claim 2. A prepreg obtained by impregnating or coating a base material with the epoxy composition according to claim 2 and semi-curing the base material.