JP2006274124A - Epoxy compound and epoxy resin cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new epoxy compound that has a low melting point and can be a raw material of an epoxy resin cured product. <P>SOLUTION: The epoxy compound is represented by formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are the same or different and are each a hydrogen atom, a halogen atom, a 1-8C alkyl group, a 1-8C alkoxy group, a cyano group or a nitro group; X<SP>1</SP>and X<SP>2</SP>are the same or different and are each a branched chain 2-18C alkylene group, provided that one methylene group or two or more methylene groups not neighboring to each other constituting the alkylene group may be replaced by an oxygen atom; and m is an integer of 1-10). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  As an epoxy resin obtained by curing an epoxy compound having a biphenyl skeleton in the molecule, 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およびＲ^４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、Ｘ^１およびＸ^２はそれぞれ同一または相異なって、分枝鎖状の炭素数２〜１８のアルキレン基を表わす。ここで、該アルキレン基を構成する一つもしくは隣接しない二つ以上のメチレン基が酸素原子に置換していてもよい。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な化合物であって、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 inventor has intensively studied to develop a novel epoxy compound that has a low melting point and can be a raw material for the cured epoxy resin.

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or Represents a nitro group, and X ¹ and X ² are the same or different and each represents a branched alkylene group having 2 to 18 carbon atoms, wherein one or two non-adjacent ones constituting the alkylene group (The above methylene group may be substituted with an oxygen atom. M represents an integer of 1 to 10.)
It was found that the epoxy compound represented by the formula (1) is a novel compound, has a low melting point, and can be cured by curing with a curing agent to produce a cured epoxy resin.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４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、Ｘ^１およびＸ^２はそれぞれ同一または相異なって、分枝鎖状の炭素数２〜１８のアルキレン基を表わす。ここで、該アルキレン基を構成する一つもしくは隣接しない二つ以上のメチレン基が酸素原子に置換していてもよい。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)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or Represents a nitro group, and X ¹ and X ² are the same or different and each represents a branched alkylene group having 2 to 18 carbon atoms, wherein one or two non-adjacent ones constituting the alkylene group (The above methylene group may be substituted with an oxygen atom. 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 produced. Further, since the cured epoxy resin of the present invention exhibits liquid crystallinity, it can also be used as a cured epoxy resin.

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。 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), m represents an integer of 1 to 10, and R ¹ , R ² , R ^3, and R ⁴ are the same or different and each has a hydrogen atom, a halogen atom, or a carbon number of 1 to 8 An alkyl group, an alkoxy group having 1 to 8 carbon atoms, a cyano group or a nitro group is represented. 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.

In the above formula (1), X ¹ and X ² are the same or different and each represents a branched chain alkylene group having 2 to 18 carbon atoms. Two or more methylene groups may be substituted with oxygen atoms. Examples of the alkylene group include ethane-1,1-diyl group, propane-1,2-diyl group, 1-oxapropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and pentane. -1,4-diyl group, 4-methylheptane-1,7-diyl group, 2-oxapentane-1,4-diyl group, 2,5-dioxaoctane-1,7-diyl group, 2-oxa Examples include a -3-methylbutane-1,4-diyl group and a 2,5-dioxa-3-methyloctane-1,7-diyl group.

  Examples of the epoxy compound (1) include 4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl, 4,4′-bis {4- (oxiranylmethoxy) -3-methylbutoxy}. Biphenyl, 4,4′-bis {3- (oxiranylmethoxy) -2-oxabutoxy} biphenyl, 4,4′-bis {3- (oxiranylmethoxy) butoxy} biphenyl, 4,4′-bis {5- (oxiranylmethoxy) hexyloxy} biphenyl, 4,4′-bis {8- (oxiranylmethoxy) -5-methyloctyloxy} biphenyl, 4,4′-bis {5- (oxira Nylmethoxy) -3-oxahexyloxy} biphenyl, 4,4′-bis {8- (oxiranylmethoxy) -3,6-dioxanonyloxy} biphenyl, 4,4 -Bis {8- (oxiranylmethoxy) -3,6-dioxa-4-methylnonyloxy} biphenyl, 4,4'-bis {5- (oxiranylmethoxy) -3-oxa-4-methylpentyl Oxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4 , 4′-bis {4- (oxiranylmethoxy) -3-methylbutoxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {3- (oxiranylmethoxy) -2-oxabutoxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {3- (oxiranylmethoxy) butoxy} biphenyl, 3,3 ′, 5,5′- Tetramethyl-4,4′-bis { -(Oxiranylmethoxy) hexyloxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {8- (oxiranylmethoxy) -5-methyloctyloxy} biphenyl, 3 , 3 ′, 5,5′-tetramethyl-4,4′-bis {5- (oxiranylmethoxy) -3-oxahexyloxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4 , 4′-bis {8- (oxiranylmethoxy) -3,6-dioxanonyloxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {8- (oxy Ranylmethoxy) -3,6-dioxa-4-methylnonyloxy} biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis {5- (oxiranylmethoxy) -3- Oxa-4-methylpentyloxy} bi Phenyl,

3-fluoro-4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl, 3-fluoro-4,4′-bis {4- (oxiranylmethoxy) -3-methylbutoxy} biphenyl, 3-fluoro-4,4′-bis {3- (oxiranylmethoxy) -2-oxabutoxy} biphenyl, 3-fluoro-4,4′-bis {3- (oxiranylmethoxy) butoxy} biphenyl, 3-fluoro-4,4′-bis {5- (oxiranylmethoxy) hexyloxy} biphenyl, 3-fluoro-4,4′-bis {8- (oxiranylmethoxy) -5-methyloctyloxy} Biphenyl, 3-fluoro-4,4′-bis {5- (oxiranylmethoxy) -3-oxahexyloxy} biphenyl, 3-fluoro-4,4′-bis {8- (o Silanylmethoxy) -3,6-dioxanonyloxy} biphenyl, 3-fluoro-4,4′-bis {8- (oxiranylmethoxy) -3,6-dioxa-4-methylnonyloxy} biphenyl, 3-Fluoro-4,4′-bis {5- (oxiranylmethoxy) -3-oxa-4-methylpentyloxy} biphenyl, 3-methoxy-4,4′-bis {2- (oxiranylmethoxy) ) Propoxy} biphenyl, 3-methoxy-4,4′-bis {4- (oxiranylmethoxy) -3-methylbutoxy} biphenyl, 3-methoxy-4,4′-bis {3- (oxiranylmethoxy) ) -2-oxabutoxy} biphenyl, 3-methoxy-4,4′-bis {3- (oxiranylmethoxy) butoxy} biphenyl, 3-methoxy-4,4′-bis {5 (Oxiranylmethoxy) hexyloxy} biphenyl, 3-methoxy-4,4′-bis {8- (oxiranylmethoxy) -5-methyloctyloxy} biphenyl, 3-methoxy-4,4′-bis { 5- (oxiranylmethoxy) -3-oxahexyloxy} biphenyl, 3-methoxy-4,4′-bis {8- (oxiranylmethoxy) -3,6-dioxanonyloxy} biphenyl, 3- Methoxy-4,4′-bis {8- (oxiranylmethoxy) -3,6-dioxa-4-methylnonyloxy} biphenyl, 3-methoxy-4,4′-bis {5- (oxiranylmethoxy) ) -3-oxa-4-methylpentyloxy} biphenyl and the like.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ^１およびＸ^２は上記と同一の意味を表わす。）
で示されるアルコール化合物（以下、アルコール化合物（２）と略記する。）と式（３）

（式中、ｍは上記と同一の意味を表わし、Ｘ^３はハロゲン原子、アルキルスルホニルオキシ基またはアリールスルホニルオキシ基を表わす。）
で示される化合物（以下、化合物（３）と略記する。）とを、塩基の存在下に反応させる方法により製造することができる。 Such an epoxy compound (1) has, for example, the formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² represent the same meaning as described above.)
(Hereinafter abbreviated as alcohol compound (2)) and formula (3)

(Wherein m represents the same meaning as described above, and X ³ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group.)
(Hereinafter abbreviated as compound (3)) can be produced by a method of reacting in the presence of a base.

  Examples of the alcohol compound (2) include 4,4′-bis (2-hydroxypropoxy) biphenyl, 4,4′-bis (4-hydroxy-3-methylbutoxy) biphenyl, 4,4′-bis (3- Hydroxy-2-oxabutoxy) biphenyl, 4,4′-bis (3-hydroxybutoxy) biphenyl, 4,4′-bis (5-hydroxyhexyloxy) biphenyl, 4,4′-bis (8-hydroxy-5) -Methyloctyloxy) biphenyl, 4,4'-bis (5-hydroxy-3-oxahexyloxy) biphenyl, 4,4'-bis (8-hydroxy-3,6-dioxanonyloxy) biphenyl, 4, 4′-bis (8-hydroxy-3,6-dioxa-4-methylnonyloxy) biphenyl, 4,4′-bis (5-hydroxy-3- Xa-4-methylpentyloxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-hydroxypropoxy) biphenyl, 3,3 ′, 5,5′-tetramethyl- 4,4′-bis (4-hydroxy-3-methylbutoxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (3-hydroxy-2-oxabutoxy) biphenyl, 3, , 3 ′, 5,5′-tetramethyl-4,4′-bis (3-hydroxybutoxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (5-hydroxyhexyl) Oxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (8-hydroxy-5-methyloctyloxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4 , 4′-bis (5- Droxy-3-oxahexyloxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (8-hydroxy-3,6-dioxanonyloxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis (8-hydroxy-3,6-dioxa-4-methylnonyloxy) biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′ -Bis (5-hydroxy-3-oxa-4-methylpentyloxy) biphenyl,

3-fluoro-4,4′-bis (2-hydroxypropoxy) biphenyl, 3-fluoro-4,4′-bis (4-hydroxy-3-methylbutoxy) biphenyl, 3-fluoro-4,4′-bis (3-hydroxy-2-oxabutoxy) biphenyl, 3-fluoro-4,4′-bis (3-hydroxybutoxy) biphenyl, 3-fluoro-4,4′-bis (5-hydroxyhexyloxy) biphenyl, 3 -Fluoro-4,4'-bis (8-hydroxy-5-methyloctyloxy) biphenyl, 3-fluoro-4,4'-bis (5-hydroxy-3-oxahexyloxy) biphenyl, 3-fluoro-4 , 4′-bis (8-hydroxy-3,6-dioxanonyloxy) biphenyl, 3-fluoro-4,4′-bis (8-hydroxy-3) 6-dioxa-4-methylnonyloxy) biphenyl, 3-fluoro-4,4′-bis (5-hydroxy-3-oxa-4-methylpentyloxy) biphenyl, 3-methoxy-4,4′-bis ( 2-hydroxypropoxy) biphenyl, 3-methoxy-4,4′-bis (4-hydroxy-3-methylbutoxy) biphenyl, 3-methoxy-4,4′-bis (3-hydroxy-2-oxabutoxy) biphenyl 3-methoxy-4,4′-bis (3-hydroxybutoxy) biphenyl, 3-methoxy-4,4′-bis (5-hydroxyhexyloxy) biphenyl, 3-methoxy-4,4′-bis (8 -Hydroxy-5-methyloctyloxy) biphenyl, 3-methoxy-4,4'-bis (5-hydroxy-3-oxahexyloxy) Phenyl, 3-methoxy-4,4′-bis (8-hydroxy-3,6-dioxanonyloxy) biphenyl, 3-methoxy-4,4′-bis (8-hydroxy-3,6-dioxa-4) -Methylnonyloxy) biphenyl, 3-methoxy-4,4'-bis (5-hydroxy-3-oxa-4-methylpentyloxy) biphenyl, and the like.

In the formula of compound (3), X ³ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom, For example, a methylsulfonyloxy group, an ethylsulfonyloxy group, and the like, and examples of the arylsulfonyloxy group include a phenylsulfonyloxy group, a 4-methylphenylsulfonyloxy group, and the like.

  Examples of the compound (3) include epichlorohydrin, epibromohydrin, glycidyl methanesulfonate, glycidyl benzenesulfonate, and glycidyl p-toluenesulfonate.

  The usage-amount of a compound (3) is 2-100 mol times normally with respect to an alcohol compound (2). When compound (3) is a liquid under the reaction conditions, a large excess amount may be used also as a reaction solvent.

  As a base, inorganic bases, such as sodium hydroxide and potassium hydroxide, are mentioned, for example, The usage-amount is 2-20 mol times normally with respect to alcohol compound (2).

  The reaction between the alcohol compound (2) and the compound (3) may be performed without a solvent or in a solvent. Examples of the solvent include hydrophilic alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol, and aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. Examples thereof include a single or mixed solvent such as a hydrophilic ether solvent such as tetrahydrofuran, dioxane, methoxymethyl ether, and diethoxyethane. The amount of the solvent used is usually 1 to 50 parts by weight with respect to the alcohol compound (2). . Further, as described above, when the compound (3) is a liquid under the reaction conditions, the compound (3) may be used as a reaction solvent.

  The reaction between the alcohol compound (2) and the compound (3) may be performed in the presence of a tertiary amine or a phase transfer catalyst. As the tertiary amine, for example, triethylamine and the like can be mentioned, and the amount used is usually 0.01 to 1 mol times based on the alcohol compound (2). Examples of the phase transfer catalyst include quaternary ammonium salts such as tetraethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, benzyltriethylammonium chloride, and the like. Is usually 0.005 to 0.5 mol times with respect to the alcohol compound (2).

  The reaction between the alcohol compound (2) and the compound (3) may be carried out under normal pressure conditions or under reduced pressure conditions. The reaction temperature is usually 10 to 150 ° C. In this reaction, depending on the type of base used, water is by-produced as the reaction proceeds. In this case, the reaction may be carried out while removing the by-produced water from the reaction system. .

  After completion of the reaction, for example, the reaction solution and water are mixed, and the epoxy compound (1) can be taken out as it is or by adding an organic solvent insoluble in water and performing a liquid separation treatment. The taken out epoxy compound (1) may be further purified by ordinary purification means such as recrystallization and column chromatography. Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene.

（式中、ｍおよびＸ^３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（４）と略記する。）とを、塩基の存在下に反応させた後、酸化せしめることによっても製造することができる。 Further, the epoxy compound (1) comprises the alcohol compound (2) and the formula (4).

(In the formula, m and X ³ represent the same meaning as described above.)
Can be produced by reacting in the presence of a base and then oxidizing the compound (hereinafter abbreviated as compound (4)).

  Examples of the compound (4) include allyl chloride, allyl bromide, allyl methanesulfonate, allyl benzenesulfonate, and allyl p-toluenesulfonate.

  The usage-amount of a compound (4) is 2-100 mol times normally with respect to an alcohol compound (2).

  As a base, inorganic bases, such as sodium hydroxide and potassium hydroxide, are mentioned, for example, The usage-amount is 2-20 mol times normally with respect to alcohol compound (2).

  The reaction between the alcohol compound (2) and the compound (4) may be performed without a solvent or in a solvent. Examples of the solvent include hydrophilic alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol, and aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. Examples thereof include a single or mixed solvent such as a hydrophilic ether solvent such as tetrahydrofuran, dioxane, methoxymethyl ether, and diethoxyethane. The amount of the solvent used is usually 1 to 50 parts by weight with respect to the alcohol compound (2). .

  The reaction temperature is usually 10 to 150 ° C.

  After completion of the reaction, for example, an oxidizing agent may be allowed to act on the reaction solution as it is. For example, the reaction solution and water are mixed, and the reaction product of the alcohol compound (2) and the compound (4) is taken out and then oxidized An agent may be allowed to act. The oxidizing agent may be any oxidizing agent that can oxidize a carbon-carbon double bond to an epoxy group, and examples thereof include m-chloroperbenzoic acid. The usage-amount of an oxidizing agent is 2-10 mol times normally with respect to the reaction product of an alcohol compound (2) and a compound (4).

  After allowing the oxidizing agent to act, for example, the epoxy compound (1) can be taken out by subjecting the remaining oxidizing agent to decomposition treatment as necessary and then concentration treatment.

（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。）
で示されるビフェノール化合物（以下、ビフェノール化合物（５）と略記する。）と式（６）

（式中、Ｘ^１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（６）と略記する。）と式（７）

（式中、Ｘ^２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（７）と略記する。）とを、塩基の存在下に反応させる方法により製造することができる。 The alcohol compound (2) is, for example, the formula (5)

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above.)
(Hereinafter abbreviated as biphenol compound (5)) and formula (6)

(Wherein, X ¹ represents the same meaning as described above, and X ⁴ represents a halogen atom.)
(Hereinafter abbreviated as compound (6)) and formula (7)

(In the formula, X ² represents the same meaning as described above, and X ⁵ represents a halogen atom.)
(Hereinafter abbreviated as compound (7)) can be produced by a method of reacting in the presence of a base.

  Examples of the biphenol compound (5) include 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 3-fluoro-4,4′-biphenol, 3- And methoxy-4,4′-biphenol.

  Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

  Compound (6) and compound (7) may be the same or different. For example, 2-hydroxypropyl chloride, 2-hydroxypropyl bromide, 4-hydroxy-3-methylbutyl chloride, 4-hydroxy -3-methylbutyl bromide, 3-hydroxy-2-oxabutyl chloride, 3-hydroxy-2-oxabutyl bromide, 3-hydroxybutyl chloride, 3-hydroxybutyl bromide, 5-hydroxyhexyl chloride, 5-hydroxyhexyl bromide 8-hydroxy-5-methyloctyl chloride, 8-hydroxy-5-methyloctyl bromide, 5-hydroxy-3-oxahexyl chloride, 5-hydroxy-3-oxahexyl bromide, 8-hydroxy-3,6-di Oxanonyl chloride, 8-H Roxy-3,6-dioxanonyl bromide, 8-hydroxy-3,6-dioxa-4-methylnonyl chloride, 8-hydroxy-3,6-dioxa-4-methylnonyl bromide, 5-hydroxy-3-oxa Examples include -4-methylpentyl chloride and 5-hydroxy-3-oxa-4-methylpentyl bromide.

  Such compound (6) and compound (7) may be used as they are, or may be used after protecting the hydroxyl group with a usual hydroxyl-protecting group such as benzyl group or tetrahydropyranyl group. A method for protecting the hydroxyl group of the compound (6) and the compound (7) may be carried out in accordance with a known hydroxyl group protecting method.

  Each usage-amount in case a compound (6) and a compound (7) differ is 0.5-10 mol times normally with respect to a biphenol compound (5). When the compound (6) and the compound (7) are the same, the amount of use is usually 1 to 20 moles relative to the biphenol compound (5).

  Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the amount used is usually 2 to 10 moles relative to the biphenol compound (5).

  The reaction may be performed without a solvent or in a solvent. Examples of the solvent include hydrophilic alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and propylene glycol, and aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, such as tetrahydrofuran. , Single or mixed solvents such as hydrophilic ether solvents such as dioxane and methoxymethyl ether. The usage-amount of this solvent is 1-50 weight times normally with respect to a biphenol compound (5).

  The reaction may be carried out under normal pressure conditions or under reduced pressure conditions. The reaction temperature is usually 10 to 150 ° C. In this reaction, depending on the type of base used, water is by-produced as the reaction proceeds. In this case, the reaction may be carried out while removing the by-produced water from the reaction system. .

  After completion of the reaction, for example, after mixing the reaction solution and water, the alcohol compound (2) can be taken out by filtration. The taken out alcohol compound (2) may be further purified by ordinary purification means such as silica gel column chromatography.

  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 the amine-based curing agent 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 novolak 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, magnesium oxide, zinc oxide, tin oxide, zircon, titanium white, and aluminum hydroxide. , Calcium carbonate, basic magnesium carbonate, barium sulfate, boron nitride, aluminum nitride, talc, clay, mica, zeolite, glass fiber and other fillers such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-Undecene and other curing accelerators, for example, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, low stress components such as silicone oil, silicone rubber, natural waxes, Synthetic wax, higher fatty acid or its metal salt Release agents such as paraffin, antioxidants, and the like. 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
A four-necked flask equipped with a thermometer, a condenser tube and a stirrer was charged with 20 parts by weight of 4,4′-biphenol, 21.3 parts by weight of potassium hydroxide, 42.5 parts by weight of water and 100 parts by weight of methanol. . To this, 30.5 parts by weight of 2-hydroxychloropropane was added dropwise over 1 hour at room temperature. Thereafter, the mixture was stirred and reacted at room temperature to 50 ° C. for 35 hours. After completion of the reaction, the reaction solution was poured into water, and the resulting crystals were collected by filtration and dried to obtain 29 parts by weight of crude 4,4′-bis (2-hydroxypropoxy) biphenyl. This was recrystallized from tetrahydrofuran to obtain purified 4,4′-bis (2-hydroxypropoxy) biphenyl. Purity: 99% (LC area percentage value). Mass spectrometric value (FD-MS): m / z = 302, melting point: 193.9 ° C.

  In a four-necked flask equipped with a thermometer, a condenser and a stirrer, 10 parts by weight of the purified 4,4′-bis (2-hydroxypropoxy) biphenyl obtained above, 61.2 parts by weight of epichlorohydrin, dimethyl 80 parts by weight of sulfoxide, 2 parts by weight of triethylamine and 15.9 parts by weight of sodium hydroxide were charged, and the mixture was stirred and reacted at an internal temperature of 50 ° C. for 11.5 hours. After completion of the reaction, the reaction solution was poured into water. After insoluble matter was filtered off, the obtained filtrate was subjected to liquid separation treatment to obtain crude 4,4'-bis {2- (oxiranylmethoxy) propoxy} biphenyl. This was purified by a silica gel column (hexane / ethyl acetate = 4/3) to obtain 5.8 parts by weight of 4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl. Purity: 99% (LC area percentage value). Melting point: 87.1 ° C.

¹ H-NMR (DMSO-d ₆ , TMS standard, unit: ppm)
δ 7.52 (4H, d), 7.02 (4H, d), 3.97 (4H, d), 3.96 to 3.98 (4H, m), 3.39 to 3.42 (2H, m), 2.71 to 2.74 (2H, m), 2.50 to 2.57 (4H, m), 1.22 (6H, d)

Example 2
20 parts by weight of 4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl obtained in Example 1 and 4.8 parts by weight of 4,4′-diaminodiphenylmethane were mixed as a curing agent. An epoxy composition was obtained. The epoxy composition was heated from room temperature to 120 ° C. using a hot stage (manufactured by METTLER TOLEDO; FP84HT and FP90) to obtain a cured epoxy resin. As a result of observation with a polarizing optical microscope (Nikon Corp .; E6TP-M61), a liquid crystal structure was observed, and it was found to be a cured epoxy resin having liquid crystallinity.

Example 3
20 parts by weight of 4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl obtained in Example 1 was mixed with 5.6 parts by weight of 4,4′-diaminodiphenylmethane as a curing agent. An epoxy composition was obtained. The molten epoxy composition was poured into a hollow part of a plate-shaped mold heated to about 120 ° C., and further heated at about 160 to 180 ° C. for about 5 hours to obtain a cured plate-shaped epoxy resin. . When a thin plate sample of 5 mm × 10 mm was cut out from this cured epoxy resin and the thermal conductivity was measured, it was 0.21 to 0.23 W / m · K (measurement conditions conform to the optical alternating current method, Performed at room temperature).

Example 4
By mixing 4,4′-bis {2- (oxiranylmethoxy) propoxy} biphenyl obtained in Example 1 above, 1,5-diaminonaphthalene as a curing agent, and methyl ethyl ketone as a solvent, an epoxy was obtained. A 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)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or Represents a nitro group, and X ¹ and X ² are the same or different and each represents a branched alkylene group having 2 to 18 carbon atoms, wherein one or two non-adjacent ones constituting the alkylene group (The above methylene group may be substituted with an oxygen atom. 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.