WO2005058791A1

WO2005058791A1 - Carboxylic acid compound, epoxy compound obtained from the carboxylic acid compound, and cured epoxy resin

Info

Publication number: WO2005058791A1
Application number: PCT/JP2004/016740
Authority: WO
Inventors: Shinya Tanaka; Yoshitaka Takezawa; Hiroyuki Takahashi
Original assignee: Sumitomo Chemical Company, Limited; Hitachi, Ltd.
Priority date: 2003-11-12
Filing date: 2004-11-11
Publication date: 2005-06-30
Also published as: TW200526570A

Abstract

A carboxylic acid compound represented by the formula (1); [Chemical formula 1] and an epoxy compound having a structural unit derived from the carboxylic acid compound and an epoxy group.

Description

Specification

Carboxylic acid compound, epoxy compound and epoxy resin cured product obtained by carboxylic acid bonding

Technical field

The present invention relates to a novel carboxylic acid compound, an epoxy compound obtained from the carboxylic acid compound, and a cured epoxy resin.

Background art

[0002] It is known that a cured epoxy resin obtained by curing an epoxy compound having a mesogen group using a curing agent such as a diamine conjugate shows liquid crystallinity (see, for example, JP-A-9-111873). JP reference.) ₀ However, the force Cal epoxy compound has a high melting temperature, for example Jiaminojifue using a curing agent such as a two Rumetan, it has been difficult to be cured by melt mixing the following curing temperatures.

Patent Document 1: JP-A-9-118673

Disclosure of the invention

Problems to be solved by the invention

[0003] A main object of the present invention is to provide an epoxy compound having a mesogen group which has a low melting temperature and can give a cured epoxy resin exhibiting liquid crystallinity by being cured with a curing agent. It is.

Means for solving the problem

[0004] The present invention relates to the formula (1)

[Chemical 1]

(Wherein, RRRRR ⁵ , R ⁶ , RRR ⁹ and R ^1Q are the same or different and each represents a hydrogen atom or an alkyl group having 118 carbon atoms. Z is a group having 2-18 carbon atoms. Force representing an alkylene group, or

[Formula 2]

R ^u , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^2Q are the same or different and each represents hydrogen Atom, C11-C18 alkyl group, amino group substituted by one or two C1-C18 alkyl groups, or

[Formula 3]

(CH ₂ ) _n

N represents a cyclic amino group represented by N, and m represents an integer of 4-12. Here, one methylene group or two or more non-adjacent methylene groups constituting the alkylene group having 218 carbon atoms is represented by O—, NH—, —S—, Si (R ²¹ ) (R ²² ) — or a C 5-12 cycloalkylene group, and the alkylene group may contain a double bond.

R ²¹ and R ²² are the same or different and each represents a lower alkyl group or a phenyl group. In addition, one methylene group or two or more non-adjacent methylene groups constituting the above-mentioned alkyl group having 118 carbon atoms and the above-mentioned cyclic amino group are substituted with O—, —S or NH—! Well! / ,.

Y represents a single bond, O—, one S or Si (R ²³ ) (R ²⁴ ),

R ²³ and R ²⁴ are the same or different and are each a lower alkyl group or a phenyl group; Represents )

And a carboxylic acid conjugate having a structural unit derived from the carboxylic acid compound and an epoxy group, and a cured epoxy resin.

The invention's effect

[0005] The cured epoxy resin of the present invention exhibits liquid crystallinity, has high thermal conductivity, and is useful as an electronic material or the like that requires thermal conductivity.

BEST MODE FOR CARRYING OUT THE INVENTION

[0006] First, the following equation (1)

[Formula 4]

The carboxylic acid conjugate (hereinafter abbreviated as the carboxylic acid conjugate (1)) represented by the formula (1) will be described.

In the formula of the carboxylic acid compound (1),

R ⁹ and R ^1Q are the same or different and each represents a hydrogen atom or an alkyl group having 118 carbon atoms. Examples of the alkyl group having 118 carbon atoms include methyl, ethyl, n-propyl, isopropyl, _n -butyl, isobutyl, _sec -butyl, tert-butyl, n-pentyl, n-pentyl —A straight-chain or branched-chain alkyl having 118 carbon atoms, such as hexyl, 4-methylpentyl, n-octyl, 1,1,3,3-tetramethylbutyl and n-decyl. Groups. Among them, R ¹ R ² ,

Preferred are carboxylic acid conjugates wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^1Q are hydrogen atoms.

In the formula of the carboxylic acids (1), Z represents a force representing an alkylene group having 2 to 18 carbon atoms or

R, R, R, R, R, R, R, R, R and R ^2Q are the same or different and are each a hydrogen atom, an alkyl having 11-18 carbon atoms. Group, an amino group substituted by one or two alkyl groups having 1 to 18 carbon atoms, or the following

[Formula 6]

And m represents an integer of 4-12. Among them, carboxylic acids in which R ^u , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ^19, and R ² ° are hydrogen atoms, because of their ease of production.匕匕匕 (1) is preferred! / ,.

Examples of the alkylene group having 2 to 18 carbon atoms include linear or branched alkylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, an otatamethylene group, and a 2-methyl-1,4-butanediyl group. One methylene group or two or more non-adjacent methylene groups constituting a powerful alkylene group is O NH — S —Si (R ²¹ ) (R ²² ) or a cycloalkylene group having 5 to 12 carbon atoms. And the alkylene group may contain a double bond. Here, R ²¹ and R ²² are the same or different and each represents a lower alkyl group or a phenyl group. Examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include a linear or branched alkyl group having 16 carbon atoms, such as an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

The group represented by -Si (R ²¹ ) (R ²² ) — is, for example, a dimethylsilylene group, And a methylphenylsilylene group, a diphenylsilylene group and the like. Examples of the cycloalkylene group having 5 to 12 carbon atoms include a cyclopentylene group, a cyclohexylene group, and a cyclootathylene group. One methylene group or two or more non-adjacent methylene groups constituting the above alkylene group O NH — S —Si (R ²¹ ) (R ²² ) or substituted with a C 5-12 cycloalkylene group Examples of the substituted alkylene group and the alkylene group containing a double bond include, for example, a group represented by CH CH —O—CH CH, CH CH

2 2 2 2 2

-O-CH CH -O-CH CH One of the groups represented by (CH CH O) CH CH

2 2 2 2 2 2 k 2 2 groups (k represents an integer of 1 to 6), for example, a 2 pentylene group, for example,

[Formula 7]

And the like.

[0009] Examples of the above-mentioned alkyl group having 118 carbon atoms are the same as those described above. Examples of the amino group substituted with one or two alkyl groups having 11 to 18 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group, a (1,1,3, And monoalkylamino groups such as (3-tetramethylbutyl) amino group, for example, dialkylamino groups such as dimethylamino group, getylamino group, di-propylamino group, diisopropylamino group, and di-n-butylamino group. One methylene group or two or more non-adjacent methylene groups constituting such an alkyl group having 118 carbon atoms may be substituted with O—, —S— or NH—, for example, a methoxy group, an ethoxy group or the like. And xyl groups and the like.

Examples of the cyclic amino group include a cyclic amino group having a nitrogen atom as a ring-constituting atom, such as a pyrrolidine-1-yl group and a piperidine-1-yl group. One methylene group or two or more non-adjacent methylene groups constituting a powerful cyclic amino group may be substituted with O—S— or NH—, and the cyclic group in which the powerful methylene group is substituted. Examples of the amino group include a morpholine yl group.

[0010] below

[Formula 8]

The divalent group selected is, for example, a pyridine 2,4 diyl group, a pyridine 2,5 diyl group, a pyridine 3,5 diyl group, a pyridine-2,3-diyl group, a pyridine 2,6-diyl group , 4 methylpyridine 2,6-diyl group, 2-methylpyridine 4,6 diyl group, pyridazine 3,6-diyl group, pyridazine 4,5-diyl group, 4-methylpyridazine 3,6-diyl group, pyrimidine 2 , 4 diyl group, pyrimidine 4,6-diyl group, 4-methylpyrimidine 2,6-diyl group, 5-methylpyrimidine-2,6-diyl group, 5-methylpyrimidine-2,4-diyl group, 6-methyl Pyrimidine 2,4 diyl group, pyrazine 2,3-diyl group, pyrazine 2,6-diyl group, triazine-2,6-diyl group, 4- (1 morpholine 1-yl) triazine 2,6-diyl group, 4 {(1 , 1,3,3-tetrabutyl) amino} triazine 2,6 di And a 1,3-phenylene group.

Among the groups represented by Z, the alkylene group having 2 to 18 carbon atoms and one methylene group constituting the alkylene group are preferable in that the production of the carboxylic acid conjugate (1) is relatively easy. Or a non-adjacent group in which two or more methylene groups are substituted with O—, preferably a group represented by (CH 2 O) CH CH 1 (k represents an integer of 16) Is particularly good

2 2 k 2 2

Good.

In the formula of the above carboxylic acid conjugate (1), Y represents a single bond, OS or Si (R ²³ ) (R ²⁴ ) —, and R ²³ and R ²⁴ are the same or different and each represents a lower alkyl group. Represents a group or a phenyl group. Examples of the lower alkyl group include the same as those described above. Examples of the group represented by Si (R ²³ ) (R ²⁴ ) — include a dimethylsilylene group, a getylsilylene group, a methylphenylsilylene group, and a diphenyl- group. And a lusilylene group. Above all, a carboxylic acid conjugate in which Y is -O- is preferable in that the raw material is easily available and can be produced relatively easily. Among the powerful carboxylic acids (1), the formula (2)

[Formula 9]

(In the formula, Z represents the same meaning as described above.)

Particularly preferred is a carboxylic acid compound represented by the formula: Z force (CH CH O) CH CH-

A carboxylic acid conjugate which is a group represented by 22 k 22 (where k represents an integer of 16) is preferable because its production is easy.

Examples of the strong carboxylic acid compound (1) include 1,4-bis (6 carboxynaphthalene-2-yloxy) butane, 1,8 bis (6 carboxynaphthalene-2-yloxy) otatan, and bis {(6 carboxynaphthalene 2 1,2-bis {2- (6-carboxynaphthalene-2-yloxy) ethoxy} ethane, 2,4-bis (6-carboxynaphthalene-2-yloxy) pyridine, 2,5-bis (6-carboxynaphthalene 2-) Roxy) pyridine, 3,5-bis (6 carboxynaphthalene-2-yloxy) pyridine, 2,3 bis (6 carboxynaphthalene-2-yloxy) pyridine, 2,6-bis (6 carboxysinaphthalene-2-yloxy) pyridine, 4-methyl-2 2,6-bis (6-carboxynaphthalene-2-yloxy) pyridine, 2-methyl-4,6-bis (6 Xinaphthalene-2-yloxy) pyridine, 3,6-bis (6-carboxynaphthalene-2-yloxy) pyridazine, 4,5-bis (6-carboxynaphthalene-2-yloxy) pyridazine, 4-methyl-3,6-bis (6-carboxynaphthalene-2-yloxy) ) Pyridazine, 2,4 bis (6 carboxynaphthalene 2-yloxy) pyrimidine, 4,6 bis (6 carboxynaphthalene 2-yloxy) pyrimidine, 4-methyl-2,6-bis (6 carboxynaphthalene 2-yloxy) pyrimidine, 5 —Methyl-2,6-bis (6-carboxynaphthalene-2-yloxy) pyrimidine, 5-methyl-2,4-bis (6-carboxynaphthalene-2-yloxy) pyrimidine, 6-methyl-2,4-bis (6-carboxynaphthalene-2-yloxy) pyrimidine, 2,3 bis (6 carboxy naphthalene 2 yl Carboxymethyl) pyrazine, 2, 6-bis (6 carboxynaphthalene 2 I Ruokishi) pyrazine, 2, 6-bis (6 carboxynaphthalene 2 Iruokishi) triazine, 4- (1 morpholino) -2,6 bis (6 carboxynaphthalene-2-yloxy) triazine, 4 {(1,1,3,3-tetramethylbutyl) amino} — 2,6 bis (6 carboxynaphthalene 2-yloxy) Triazine, 1,3-bis (6-carboxynaphthalene-2-yloxy) benzene, 1,4-bis (6-methoxycarbolnaphthalene-2-yloxy) butane, 1,8-bis (6-methoxycarbol-naphthalene-2-yloxy) Octane, bis {(6-methoxycarbolnaphthalene-2-yloxy) ethyl} ether, 1,2 bis {2- (6-methoxycarbolnaphthalene-2-yloxy) ethoxy} ethane, 2,4bis (6-methoxycarbo) -Le naphthalene-2-yloxy) pyridine, 2,5 bis (6-methoxycarbol-naphthalene-2-yloxy) pyridine, 3,5 bis (6-methoxycarbol-lunaf) Talene 2- (yloxy) pyridine, 2,3-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyridine, 2,6-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyridine, 4-methyl-2,6-bis ( 6-Methoxycarb-l-naphthalene-2-yloxy) pyridine, 2-methyl-4,6-bis (6-methoxycarb-l-naphthalene-2-yloxy) pyridine, 3,6-bis (6-methoxycarb-l-naphthalene-2-yloxy) Pyridazine, 4,5-bis (6-methoxycarbolnaphthalene-2-yloxy) pyridazine, 4-methyl-3,6-bis (6-methoxycarbolnaphthalene-2-yloxy) pyridazine, 2,4bis (6-methoxycarbol) Naphthalene 2- (yloxy) pyrimidine, 4,6-bis (6-methoxycarbonaphthalene 2-yloxy) pyrimidine, 4-me Leu 2,6-bis (6-methoxycarbornaphthalene 2-yloxy) pyrimidine, 5-methyl-2,6-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyrimidine, 5-methyl-2,4-bis ( 6-methoxycarbo-lunanaphthalene 2-yloxy) pyrimidine, 6-methyl-2,4bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyrimidine, 2,3-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyrazine , 2,6-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) pyrazine, 2,6-bis (6-methoxycarbo-lunanaphthalene-2-yloxy) triazine, 4- (1 morpholino) -2,6bis (6- Methoxycarbolnaphthalene 2- (yloxy) triazine, 4- {(1,1,3,3-tetramethylbutyl) amino} 2,6 bis (6-methoxycarbolnaphtha) Down 2 Iruokishi) bets triazine, 1, 3- bis (6-methoxycarbonyl - Le naphthalene 2 Iruokishi) benzene. Next, the method for producing the carboxylic acid conjugate (1) will be described with reference to the carboxylic acid conjugate (1) in the case where Y is an oxygen atom.

The carboxylic acid conjugate (1) wherein Y is an oxygen atom can be prepared, for example, by reacting the compound of the formula (5) in an organic solvent in the presence of a base.

[Formula 10]

(Where

R ⁴ and R ⁵ have the same meaning as described above. )

(Hereinafter abbreviated as compound (5)) and a compound of formula (6)

[Formula 11]

(Where

R ⁹ and R ^1q have the same meaning as described above. )

(Hereinafter abbreviated as compound (6)) and a compound represented by the formula (7)

[Formula 12]

X ¹ —— Z ^ X ² )

(In the formula, Z represents the same meaning as described above, and X ¹ and X ² each represent the same or different and represent a halogen atom.)

(Hereinafter abbreviated as dihalogeno compound (7)).

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

The compound (5) and the compound (6) may be the same or different, for example, 6-hydroxy-1 naphthoic acid, 6-hydroxy-2 naphthoic acid, 7-hydroxy-1-naphthoic acid, 7 —Hydroxy-2 naphthoic acid and the like. When compound (5) and compound (6) are the same Is usually used in a molar amount of 11 to 2.4 times, preferably 1.6 to 2.2 times the molar amount of the dinoperogeno compound (7). When the compound (5) is different from the compound (6), the amount of the compound (5) to be used is generally 0.5 to 1.2 mol times, preferably 0.8 to 1 times, relative to the dihalogeno compound (7). The amount of the compound (6) to be used is generally 0.5 to 1.2 mol times, preferably 0.8 to 1.1 mol times, relative to the dihalogeno compound (7).

Examples of the dihalogeno compound (7) include 2,3-dichloropyridine, 2,4-dichloropyridin, 2,5-dichloropyridine, 2,6-dichloropyridine, 3,5-dichloropyridine, 2,6 —Dibromopyridine, 2,6-dichloro-4-methylpyridine, 2-methyl-4,6-dichloropyridine, 2,4-dichloropyrimidine, 4,6-dichloropyrimidine, 2,4-dichloro-5-methylpyrimidine, 2 , 4-Dichloro-6-methylpyrimidine, 2,6-dichloro-4-methylpyrimidine, 2,6-dichloro-5-methylpyrimidine, 3,6-dichloropyridazine, 4,5-dichloropyridazine, 2,6-dichloropyrazine 1,2-dichloropyrazine, 1,3-dichlorobenzene, 1,3-dibromobenzene, 1,2-dibromoethane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,5-dichloropentane , 1, 8-dichloro-octane, bis (2-Kuroroechiru) ether, 1, 2-bi scan (2-black port ethoxy) Etan like.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, for example, sodium carbonate. And alkali metal carbonates such as potassium carbonate, for example, alkali metal bicarbonates such as sodium bicarbonate, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide and potassium tert-butoxide Among them, alkali metal hydroxides and alkali metal carbonates are preferred, and alkali metal hydroxides are particularly preferred. The amount of the powerful base to be used is generally 2 to 10 mol times, preferably 2 to 4 mol times, relative to the dihalogeno compound (7).

The reaction temperature is usually about 30-150 ° C, preferably about 50-120 ° C.

The organic solvent may be any solvent that is inert to the reaction, for example, alcoholic solvents such as methanol, ethanol, propyl alcohol, butanol, ethylene glycol, propylene glycol, etc., for example, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents such as N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolide Aprotic polar solvents such as butane, etc., and singly or mixed solvents such as ether solvents such as tetrahydrofuran, dioxane, methoxymethyl ether and dietoxetane.

Among them, aprotic polar solvents are preferred. The amount of the strong organic solvent to be used is generally 0.5 to 50 times by weight, preferably 2 to 10 times by weight, relative to compound (5) or compound (6). The reaction is usually carried out by mixing compound (5), compound (6), dihalogeno compound (7) and a base in a solvent. When the compound (5) and the compound (6) are the same, the mixing order is not particularly limited! However, when the compound (5) and the compound (6) are different, the desired carboxylic acid (1 For example, the compound (5) and the dihalogeno compound (7) are reacted in the presence of a base, and then the compound (6) is reacted, or the compound (6) and the dihalogeno compound (7) are reacted with a base. It is preferable to react the compound (5) after the reaction in the presence of After completion of the reaction, if there is any insoluble matter in the reaction solution as it is or after the insoluble matter is filtered off, the carboxylic acid conjugate (1) in which Y is an oxygen atom is obtained by cooling. Can be taken out. The removed carboxylic acid conjugate (1) may be washed with a water-soluble organic solvent, water or a mixed solvent of the organic solvent and water, if necessary, for example, by recrystallization. And the like.

The compound (5) and in place of the compound (6), Y gar ^{S-, -Si (R 23) (} R 24) By using the hydroxy group of the compound such as thiol groups, hydrin Roshiriru group - like (1) can be produced.

The carboxylic acid conjugate (1) of the present invention may be used as it is as a monomer of polyester or polyamide exhibiting liquid crystallinity, and after being converted into an epoxy compound as described later, is reacted with a curing agent. Liquid crystalline epoxy resin may be used.

Next, an epoxy conjugate having a structural unit derived from the carboxylic acid conjugate (1) and an epoxy group in the molecule will be described.

The epoxidized conjugate of the present invention comprises a structural unit derived from the carboxylic acid conjugate (1) and an epoxy group in the molecule. The structural units derived from

The powerful epoxyy conjugate is exemplified by the following formula (3):

(3)

(Where R ² ,

R ⁹ , Z and Y have the same meanings as described above, and R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³ ° are the same or different and are each a hydrogen atom or a carbon atom. Represents one to eighteen alkyl groups. Q ¹ and Q ² are the same or different and each represent a linear alkylene group having 119 carbon atoms, and the methylene group constituting the linear alkylene group is an alkyl group having 118 carbon atoms. It may be substituted, or O or N (R ³¹ ) — may be inserted between the methylene groups. Here, R ³¹ represents a hydrogen atom or an alkyl group having 118 carbon atoms. )

Epoxy conjugates represented by the following formula (4)

[Formula 15]

(Four)

(Where R ² ,

R ⁹ , Z and Y have the same meanings as described above, and n represents an integer of 19. )

Among the preferred epoxy conjugates, the epoxy conjugate material with n being 1 is easily available and easy to produce!

Examples of the alkyl group having 11 to 18 carbon atoms include the same as those described above. Examples of the straight-chain alkylene group of the formula 19 include a group in which 119 methylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and a nonamethylene group are linearly bonded. Is mentioned. The methylene group that constitutes the straight-chain alkylene group having 11 to 19 carbon atoms may be substituted with an alkyl group having 11 to 18 carbon atoms, and O or N (R ³¹ ) — may be inserted, and a carbon atom substituted with such an alkyl group having 11 to 18 carbon atoms, or O or N (R ³¹ ) — may be inserted between the methylene groups. Examples of the alkylene group include a 2-methyltrimethylene group, a 1,2-dimethylethylene group, a 3-oxatetramethylene group, and a 3-oxapentamethylene group. Examples of powerful epoxy conjugates include 1,4 bis {6 (oxylanylmethoxy) carbolnaphthalene 2-yloxy} butane and 1,8-bis {6 (oxyl-lmethoxy) carbole Naphthalene 2-yloxy} octane, bis [2- {6- (oxyl-methoxy) carbolnaphthalene 2-yloxy} ethyl] ether, 1,2 bis [2- {6 (oxyl-lmethoxy) carbol-naphthalene — 2-yloxy} ethoxy] ethane, 2,4-bis {6- (oxyl-methoxy) carbo-lnaphthalene 2-yloxy} pyridine, 2,5-bis {6- (oxyl-lmethoxy) carbo-l-naphthalene 2-yloxy } Pyridine, 3,5 bis {6 — (oxyla-methoxy) carbol-naphthalene 2-yloxy} pyridine, 2,3 bis {6— (oxyla-methoxy) carbo-lunanaphthalene 2-yl Xy} pyridine, 2,6-bis {6- (oxyl-lmethoxy) carbo-l-naphthalene 2-yloxy} pyridine, 4-methyl-2,6-bis {6- (oxyl-l-methoxy) carbo-l-naphthalene 2-yloxy } Pyridin, 2-methyl-4,6-bis {6- (oxyl-methoxy) carbol-naphthalene 2-yloxy} pyridine, 3,6-bis {6- (oxo-yl-methoxy) carbol-naphthalene 2- 2,4-bis (6-methoxy) carbo-lnaphthalene 2-pyrazine, 4-methyl-3,6-bis {6 -— (oxy-l-methoxy) carbo-lunaphthalene 2-yloxy} pyridazine 2,4-bis {6- (oxyl-l-methoxy) carbolnaphthalene 2-yloxy} pyrimidine, 4,6-bis {6- (oxyl-l-methoxy) power reportol-naphthalene 2 —Yloxy} pyrimidine, 4-methyl-2,6-bis {6 -— (oxyl-methoxy) carbol-naphthalene 2-yloxypyrimidine, 5-methyl-2,6-bis {6- (oxyl-methoxy) carbol-naphthalene 2 —Yloxy} pyrimidine, 5-meth Lou 2,4-bis {6- (oxyl-lmethoxy) carbo-l-naphthalene 2-yloxy} pyrimidine, 6-methyl-2,4-bis {6- (oxyl-l-methoxy) carbo-l-naphthalene-2-yloxy} Pyrimidine, 2,3 bis {6- (oxyl-lmethoxy) carbo-l-naphthalene 2-yloxy} pyrazine, 2,6 bis {6- (oxyl-l-methoxy) carbo-lnaphthalene 2-yloxy} pyrazine, 2,6 bis { 6— (Oxyla-methoxy) carbo-lnaphthalene —2-yloxy} triazine, 4— (1-morpholino) —2,6 bis {6— (Oxyla-methoxy) carbo-lunanaphthalene 2-yloxy} triazine, 4 { (1,1,3,3-tetramethylbutyl)}-2,6-bis {6- (oxyl-methoxy) carbo-l-naphthalene 2-yloxy} triazine, 1,3-bis {6- (oxyl-methoxy) ) Carbon-lnaphthalene 2-yloxy} benzene, 1,4-bis [6- {2- (oxyl-l-methoxy) ethoxy} carbo-l-naphtalene-2-yloxy] butane, 1,8-bis [6-—2- (2- (oxyl- Rumethoxy) ethoxy} power rupo-lunanaphthalene 2-yloxy] octane, bis [2- [6- {2- (oxyla-methoxy) ethoxy] carbo-lunanaphthalene 2-yloxy] ethyl] ether, 1,2-bis [ 2 — [6-— {2- (Oxyla-methoxy) ethoxy) carbo-lnaphthalene 2-yloxy] ethoxy] ethane, 2,4 bis [6-—2-Oxyla-methoxy) ethoxy} carbo-naphthalene-2 Yloxy] pyridine, 1,4-bis [6 — {(2-methyl-2,3 epoxypropoxy) carbol} naphthalene 2 yloxy] butane, 1,8 bis [6 — {(2-methyl-2,3— Epoxypropoxy) carbo- } Naphthalene-2-yloxy] octane, bis [2-[{6- (2-methyl-2,3 epoxypropoxy) carbol] naphthalene-2-yloxy] ethyl] ether, 1,2 bis [2 — [{6— (2 —Methyl-2,3-epoxypropoxy) canolepo-norre} naphthalene 2-yloxy] ethoxy] ethane, 2,4-bis [{6- (2-methyl-2,3-epoxypropoxy) carbol} naphthalene-2-yloxy] pyridine , 1,4-bis [{6- (5-methyl-3-oxa-5,6-epoxyhexyloxy) carbonyl] naphthalene 2-yloxy] butane, 1,8-bis [{6- (5-methyl-3-oxa —5, 6 epoxyhexyloxy) carbol} naphthalene 2-yloxy] octane, bis [2-({6- (5-methyl-3-oxa 5,6 epoxyhexyloxy) carbol} naphthalene-2-yloxy] e Chill] ether, 1, 2— The [2- [{6- carbonitrile (5-methyl-3 Okisa -5, carboxymethyl Ruokishi to 6 epoxy) - Le} naphthalene 2 Iruokishi] ethoxy] Etan, 2, 4-bis [{6- ( 5-methyl-3-oxa-5,6-epoxyhexyloxy) carbonyl} naphthalene 2-yloxy] pyridine.

The method for producing a powerful epoxy conjugate will be described with reference to the epoxy conjugate represented by the above formula (3) as an example. Epoxy conjugates represented by the formula (3) include, for example, carboxylic acid conjugates (1) and (8)

[Formula 16]

(In the formula, R ²⁵ , R ²⁶ , R ²⁷ and Q ¹ represent the same meaning as described above, and X ³ represents a halogen atom.)

(Hereinafter abbreviated as compound (8)) and a compound represented by the formula (9)

[Formula 17]

(In the formula, R ²⁸ , R ²⁹ , R ³ ° and Q ² represent the same meaning as described above, and X ⁴ represents a halogen atom.)

(Hereinafter abbreviated as compound (9)) in the presence of a base, a method comprising reacting a carboxylic acid compound (1) with a compound represented by the formula (10)

[Formula 18]

(In the formula, R ²⁵ , R ²⁶ , R ²⁷ , Q ¹ and X ³ represent the same meaning as described above.)

(Hereinafter abbreviated as compound (11)) and a compound represented by the formula (11)

[Formula 19]

(In the formula, R ²⁸ , R ²⁹ , R ³ °, Q ² and X ⁴ represent the same meaning as described above.) (Hereinafter abbreviated as compound (11)) in the presence of a base, and then reacting with an oxidizing agent such as m-chloroperbenzoic acid. The former method of reacting the carboxylic acid conjugate (1), the compound (8) and the compound (9) in the presence of a base is preferred.

First, the former method of reacting the carboxylic acid conjugate (1), the compound (8), and the compound (9) in the presence of a base will be described. In the compound (8), X ³ and X ⁴ each independently represent a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom. The powerful compound (8) and the compound (9) may be the same or different, for example, epichlorohydrin, epibu mouth mohydrin, 2- (chloroethyl) oxylan, 2- (promoethyl) ) Oxysilane and the like.

When the compound (8) and the compound (9) are the same, the amount of the compound to be used is generally 2 to 100 mol times, preferably 2 to 50 mol times, relative to the carboxylic acid conjugate (1). When the compound (8) and the compound (9) are different, the amount of the compound (8) and the compound (9) to be used is each 1 to 50 mol times, preferably 1 to 50 times the carboxylic acid conjugate (1). It is 25 mole times.

Examples of the base include inorganic bases such as sodium hydroxide and potassium hydroxide. The amount of the base is usually 1.8-2.2 with respect to the carboxylic acid conjugate (1). It is molar times. The reaction between the carboxylic acid conjugate (1), the compound (8) and the compound (9) is usually carried out in a solvent using a carboxylic acid conjugate (1), a compound (8), and a compound (9). And the base is mixed, and the mixing order is not particularly limited. However, when the compound (8) and the compound (9) are different, the carboxylic acid conjugate (1) and the compound (8) are mixed. After the reaction, the compound (9) is preferably reacted, or the carboxylic acid conjugate (1) is reacted with the compound (9), and then the compound (8) is preferably reacted. The solvent is not particularly limited as long as it is a solvent inert to the reaction, but a hydrophilic solvent is preferable in that the generation of by-products is easily suppressed. Examples of the hydrophilic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol; ketone solvents such as methylethyl ketone and methyl isobutyl ketone; N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide and N-methylpyrrolidone; ether-based solvents such as tetrahydrofuran, dioxane, methoxymethyl ether and dietoxetane; Dimethyl sulfoxide is particularly preferred, among which ether solvents, aprotic polar solvents, and aprotic polar solvents preferred by mixed solvents thereof are more preferred. . The amount of the solvent to be used is generally 0.01 to 50 parts by weight, preferably 0.1 to 5 parts by weight, based on the carboxylic acid conjugate (1).

The reaction may be performed under normal pressure conditions or may be performed under reduced pressure conditions. The reaction temperature is usually 10-150 ° C. In this reaction, water is by-produced as the reaction proceeds, but it is preferable to carry out the reaction while removing the by-produced water out of the reaction system. It is preferred to carry out the reaction at a reaction pressure.

After completion of the reaction, for example, the remaining compound (8) and the conjugated product (9) are removed, a hydrophilic solvent is added if necessary, the insoluble matter is filtered off, and the mixture is cooled to give an epoxy compound. The material can be taken out as a crystal. The removed epoxy compound may be further purified by a usual purification means such as recrystallization.

Subsequently, the latter carboxylic acid conjugate (1), compound (10) and compound (11) are reacted in the presence of a base, and then reacted with an oxidizing agent such as m-chloroperbenzoic acid. A method for producing an epoxy compound will now be described.

The compound (10) and the compound (11) may be the same or different, and examples thereof include aryl chloride and aryl bromide.

When the compound (10) and the compound (11) are the same, the amount to be used is usually 2 to 100 times, preferably 2 to 50 times the mole of the carboxylic acid conjugate (1). When the compound (10) and the compound (11) are different, the amount of the compound (10) and the compound (11) to be used is each 1 to 50 times by mole, preferably 1 to 50 times the carboxylic acid conjugate (1). It is 25 times by mole.

Examples of the base include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as pyridine. The amount of the base is usually the same as that of the carboxylic acid conjugate (1). 2-5 mole times. When an organic base that is liquid under the reaction conditions is used, such an organic base may be used in an excess amount also as a reaction solvent.

The reaction of the carboxylic acid conjugate (1), the compound (10) and the compound (11) is usually carried out in a solvent using the carboxylic acid conjugate (1), the compound (10) and the compound (11). This is carried out by mixing with a base, and the mixing order is not particularly limited, but the compound (10) is different from the compound (11). In this case, after reacting the carboxylic acid conjugate (1) with the compound (10), the compound (11) is reacted, or the carboxylic acid conjugate (1) and the compound (11) are reacted. ), And then the compound (10) is preferably reacted. Examples of the solvent include the same solvents as those used in the reaction between the carboxylic acid conjugate (1), the compound (8), and the compound (9). Further, as described above, when an organic base which is liquid under the reaction conditions is used as the base, the organic base may be used as a reaction solvent.

After the reaction is completed, the oxidizing agent may be allowed to act as it is, or, for example, a reaction solution and water are mixed, and the reaction product of the carboxylic acid compound (1), the compound (10), and the compound (11) is taken out. After that, an oxidizing agent may be allowed to act. The oxidizing agent may be any oxidizing agent capable of oxidizing a carbon-carbon double bond into an epoxy group, and examples thereof include m-chloroperbenzoic acid. The amount of the oxidizing agent to be used is usually 2 to 10 times the molar amount of the reaction product of the carboxylic acid compound (1), the compound (10) and the compound (11).

After the oxidizing agent is acted on, for example, the remaining oxidizing agent is decomposed, if necessary, and then concentrated, whereby the epoxylated product can be taken out.

Further, among the epoxy conjugates represented by the above formula (3), Q ¹ and Q ² are the same or different linear alkylene groups having 119 carbon atoms, and Epoxy conjugates in which O or N (R ³¹ ) — is inserted between methylene groups constituting the group can also be produced by the following method.

Q ¹ and Q ² are the same or different linear alkylene groups having 1 to 9 carbon atoms, and O or N (R ³¹ ) is inserted between methylene groups constituting the linear alkylene group The following formula (12)

[Formula 20]

(Wherein, Y and Z represent the same meaning as described above, and Q ³ represents

CH) — O— (CH)

2 p 2 q

Wherein p and q each represent an integer of 118, and the sum thereof is 9 or less. ) The production method will be described with reference to the epoxy resin conjugate represented by the following formula. For example, the epoxy resin conjugate represented by the formula (12) is represented by the formula (13)

[Formula 21]

( 13)

(In the formula, Υ and Ζ have the same meaning as described above.)

And a compound represented by the formula (14)

[Formula 22]

ΗΟ—— (CH ₂ ) _P ^ X ⁵ (14)

(In the formula, X ⁵ represents a halogen atom, and p represents the same meaning as described above.)

Is reacted with a compound represented by the formula (15)

[Formula 23]

(15)

(Where Y, Ζ, and ρ have the same meaning as described above.)

And a compound represented by the formula (15) and a compound represented by the formula (16) are obtained.

[Formula 24]

ο

(16)

-(CH ₂ ) _q — X '

(In the formula, X ⁶ represents a halogen atom, and q represents the same meaning as described above.)

Can be produced by reacting a compound represented by the formula with a base.

Examples of the no and logen atoms include a chlorine atom, a bromine atom and an iodine atom. Examples of the compound represented by the formula (14) include 2-chloroethanol, 2-bromoethanol, 3-chlorobutanol, 4-chlorobutanol, 5-chloropentanole, and 6-chlorohexanol. , 7-chloroheptanol, 8-chlorooctanol and the like. The amount of the compound represented by the formula (14) is usually 2 to 100 times, preferably 2 to 10 times the molar amount of the compound represented by the formula (13).

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples thereof include inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, and the amount of the base is usually 2 to 5 moles compared to the compound represented by the formula (13). Such a base may be used as it is or as an aqueous solution.

In the reaction between the compound represented by the formula (13) and the compound represented by the formula (14), the compound represented by the formula (13), the compound represented by the formula (14) and a base are usually contacted and mixed in a solvent. This is carried out, and the mixing order is not particularly limited. The solvent is not particularly limited as long as it is a solvent inert to the reaction. However, considering the solubility of the compound represented by the formula (13), for example, tonolenene, xylene, ethylbenzene, cyclobenzene, dichlorobenzene, etc. Aromatic hydrocarbon solvents, the above-mentioned hydrophilic solvents and mixed solvents thereof are preferred, and among them, ether solvents, aprotic polar solvents and mixed solvents thereof are preferred, and aprotic polar solvents are particularly preferred. The amount of the solvent to be used is usually 0.1 to 50 times, preferably 0.5 to 5 times the weight of the compound represented by the formula (13). The reaction temperature of the reaction between the compound represented by the formula (13) and the compound represented by the formula (14) is usually 10 to 100 ° C, preferably 30 to 50 ° C. The reaction may be carried out under normal pressure conditions or under reduced pressure conditions.

After completion of the reaction, for example, water and an organic solvent insoluble in water are added to the reaction solution, if necessary, followed by extraction, and the resulting organic layer is concentrated to give the compound represented by the formula (15). Can be taken out.

The amount of the compound represented by the formula (16) in the reaction between the compound represented by the formula (15) and the compound represented by the formula (16) is usually 2 to 100 relative to the compound represented by the formula (15). The molar amount is preferably 2 to 50 times.

As the base, those similar to the above-mentioned bases can be mentioned, and the amount of the base is usually 2 to 5 moles compared to the compound represented by the formula (15).

In the reaction between the compound represented by the formula (15) and the compound represented by the formula (16), the compound represented by the formula (15), the compound represented by the formula (16) and a base are usually contacted and mixed in a solvent. The mixing order is not particularly limited. The solvent is not particularly limited as long as it is a solvent inert to the reaction, but ether solvents and aprotic polar solvents are preferred among the above hydrophilic solvents in that the generation of by-products is easily suppressed. And In particular, aprotic polar solvents are preferred, and mixed solvents thereof are preferred. The amount of the solvent to be used is generally 0.1 to 50 times by weight, preferably 0.5 to 5 times by weight, relative to the compound represented by the formula (15).

The reaction temperature of the reaction between the compound represented by the formula (15) and the compound represented by the formula (16) is usually 10 to 150 ° C, preferably 30 to 70 ° C. In this reaction, water may be by-produced as the reaction proceeds. In this case, it is preferable to carry out the reaction while removing the by-produced water out of the reaction system.

After the completion of the reaction, for example, a hydrophilic solvent is added to the reaction solution, if necessary, and the insoluble matter is filtered off, followed by cooling to obtain the epoxylated compound represented by the formula (12). . The extracted epoxy compound represented by the formula (12) may be further purified by a usual purification means such as recrystallization.

Next, an epoxy composition comprising the epoxy conjugate and the curing agent of the present invention will be described. The epoxy composition of the present invention can be obtained by mixing the epoxy conjugate and the curing agent as they are or in a solvent. The epoxy composition of the present invention may contain one type of epoxy compound and a curing agent, or may contain two or more different types of epoxy conjugates and a stiffening 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 propylene darigol monomethyl ether and the like. Glycol-based solvents.

Any curing agent may be used as long as it has at least two functional groups capable of undergoing a curing reaction with an epoxy group in its molecule.For example, an amine-based curing agent in which the functional group is an amino group and a hydroxyl group in the functional group And an acid-based curing agent whose functional group is a carboxyl group, and an amine-based curing agent or a phenol-based curing agent is preferred.

Examples of the amine-based curing agent include aliphatic polyvalent amines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine. For example, p-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4, diaminodiphenyl Tan, 4,4, diaminodiphenyl Aromatic polyvalent amines such as propane, 4,4, diaminodiphenyl ether, 1,1 bis (4-aminodiphenyl) cyclohexane, 4,4'-diaminodiphenylsulfone, bis (4-aminodiphenyl) phenylmethane For example, alicyclic polyamines such as 4,4, diaminodicyclohexane and 1,3 bis (aminomethyl) cyclohexane, for example, dicyandiamide, and aromatic polyamines are preferred. 4,4, Diaminodiphenylmethane, 4,4, diaminodiphenylethane, 1,5-diaminonaphthalene and p-phenylenediamine are more preferred.

Examples of the phenolic hardener include phenol resin, phenol aralkyl resin (having a phenol-skeleton, diphenyl-skeleton, etc.), naphthol aralkyl resin, and polyoxystyrene resin. . Examples of the phenol resin include resole-type phenol resins such as phosphorus-modified resin resin and dimethyl ether resole resin, such as phenol novolak resin, cresol novolac resin, tert-butylphenol novolak resin, and nonylphenol. Novolak type phenolic resins such as novolak resin, for example, special phenolic resins such as dicyclopentagen-modified phenolic resin, terpene-modified phenolic resin, and triphenol methane-type resin, and the like. An example is poly (P-oxystyrene).

Examples of the acid anhydride-based curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride and the like.

The powerful curing agent is usually 0.5 to 1.5 mole times, preferably 0 to 1.5 times the total amount of epoxy groups in the epoxy compound in the total amount of functional groups capable of curing reaction with the epoxy groups in the curing agent. . 9- 1. The amount used is 1 mole times.

The epoxy composition of the present invention may contain, as described above, the above-mentioned solvent in addition to the epoxy conjugate and the curing agent, and a desired epoxy resin cured product obtained by curing the epoxy composition. As long as it does not hinder the performance of the present invention, it may contain an epoxy conjugate other than the epoxide conjugate of the present invention, and may also contain various additives. Epoxy conjugates other than the epoxy conjugate of the present invention include, for example, bisphenol A-type epoxy conjugates, orthocresol-type epoxy compounds such as biphenol diglycidyl ether, 4,4'bis (3,4 Epoxybutene 1 yloxy) phenol zoate, naphthalene diglycidyl ether, α-methylstilbene 4,4, diglycidyl ether, etc. Commercially available epoxy compounds may be mentioned. Examples of the additive include silica powder such as fused silica powder, fused spherical silica powder, crystalline silica powder, and secondary aggregated silica powder, for example, alumina, titanium white, aluminum hydroxide, talc, clay, myriki, and glass. Fillers such as fibers, for example, curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-indene, 2-methylimidazole, for example, γ-glycidoxypropyltrimethoxysilane Coupling agents such as carbon black, etc .; low-stress components such as silicone oil and silicone rubber; natural wax, synthetic wax, higher fatty acids or metal salts thereof, release agents such as paraffin, acid And the like. The content of the epoxy compound and additives other than the epoxy compound of the present invention is not particularly limited as long as the desired performance of the cured epoxy resin obtained by curing the epoxy composition of the present invention is not impaired.

Next, the cured epoxy resin of the present invention will be described. The epoxy resin cured product of the present invention can be produced by curing an epoxy composition containing the epoxy conjugate and a curing agent. The resulting cured epoxy resin exhibits high thermal conductivity, not only exhibiting liquid crystal properties, and is therefore useful as an electronic material such as an insulating material that requires high heat dissipation such as a printed wiring board. .

The cured epoxy resin of the present invention may be a cured epoxy resin obtained by curing a kind of the epoxy resin conjugate of the present invention and a curing agent, or two or more different epoxy resins of the present invention. An epoxy resin cured product obtained by curing the epoxy conjugate and a curing agent may be used.

Examples of the method of curing the epoxy composition include a method of curing the epoxy composition as it is, a method of heating and melting the epoxy composition, pouring the epoxy composition into a mold or the like, and further heating the mold to mold. A method in which the epoxy composition is melted, the resulting melt is poured into a preheated mold and cured, and the epoxy composition is partially cured, and the obtained partially cured product is pulverized. A method in which the powder is filled in a mold, and the filled powder is melt-molded. The epoxy composition is dissolved in a solvent as necessary, and partially cured while stirring. 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. [0028] Lastly, a description will be given of a pre-preda prepared by impregnating or applying a base material with the epoxy composition of the present invention and then semi-cured. After diluting the epoxy composition of the present invention with a solvent, if necessary, for example, impregnating or coating the substrate, the obtained impregnated or coated substrate is heated, and the epoxy resin in the substrate is heated. By pre-curing the dagger, a pre-preda can be produced. Examples of the substrate include woven or nonwoven fabric of inorganic fibers such as glass fiber woven fabric, and woven or nonwoven fabric of organic fibers such as polyester. A laminated board or the like can be easily manufactured by a usual method using a powerful pre-preda.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

[0029] In a 1-L four-necked flask equipped with a thermometer, a condenser, and a stirrer, 126 parts by weight of 6-hydroxy-2 naphthoic acid, dimethyl sulfoxide, 115 parts by weight of a 48% by weight aqueous sodium hydroxide solution and water were added. Charged and dissolved at about 80 ° C. A dimethyl sulfoxide solution in which 60 parts by weight of 1,2 bis (2 chloroethoxy) ethane was added dropwise over 2 hours, the internal temperature was raised to 120 ° C, and the mixture was stirred and reacted at the same temperature for 10 hours. Was. After cooling to an internal temperature of about 100 ° C, insolubles were filtered off, water was added to the obtained filtrate, and the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals are collected by filtration, washed with water, and dried under reduced pressure at an internal temperature of 80 ° C. for 12 hours. 1,2 bis {2- (6 carboxynaphthalene-2-yloxy) ethoxy} ethane 92 parts by weight Was obtained (apparent yield: 59%).

Example 2

In a 1-L four-necked flask equipped with a thermometer, a condenser, and a stirrer, 40 parts by weight of 1,2 bis {2- (6 carboxynaphthalene-2-yloxy) ethoxy} ethane obtained in Example 1 above was added. , 160 parts by weight of epichlorohydrin, 8 parts by weight of sodium hydroxide, and dimethyl sulfoxide were charged, the pressure was reduced to about 6 kPa, and the mixture was reacted for 4 hours while refluxing at an internal temperature of about 50 ° C. The internal temperature was further raised to 70 ° C, and the reaction was carried out at the same temperature while refluxing for 1 hour. The water generated during the reflux is distilled out of the reaction system together with the solvent, the distillate is cooled outside the reaction system and subjected to liquid separation, water is removed, and only the solvent is placed in the four-necked flask. To return did. After the completion of the reaction, the pressure was returned to normal pressure, the insolubles were filtered off, and the obtained filtrate was heated again to an internal temperature of about 70 ° C under reduced pressure of about 6 kPa to distill off remaining epichlorohydrin. I left. Thereafter, water was added, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration. The obtained crystals are washed with 50% methanol water and dried under reduced pressure at an internal temperature of 80 ° C. for 12 hours to give 1,2-bis [2- {6- (oxyl-methoxy) carbol]. Naphthalene 2-yloxy} ethoxy] ethane (25 parts by weight) was obtained (apparent yield: 51%). Purity: 89%, melting temperature: 100-106 ° C

Example 3

[0031] 30 parts by weight of 1,2 bis [2- {6 (oxyl-methoxy) carbonylnaphthalene 2-yloxy} ethoxy] ethane obtained in Example 2 and 4,4, diaminodiphenylmethane 5 as a curing agent The parts by weight were mixed to obtain a composition. The composition was heated from room temperature to 180 ° C. using a hot stage (manufactured by Methrate Red; FP82HT and FP90) to obtain a cured epoxy resin. Observation with a polarizing optical microscope (Nikon; XTP-11) revealed a shading pattern at about 100 to 120 ° C., confirming that the cured product was a liquid crystalline epoxy resin.

Example 4

[0032] 50 parts by weight of 1,2 bis [2- {6 (oxyl-methoxy) carbol-naphtalene 2-yloxy} ethoxy] ethane obtained in Example 2 above, and 4,4, diaminodiphenylmethane as a curing agent And 8 parts by weight to obtain a composition. The composition is melted and charged in a plate-shaped hollow portion of a mold heated to about 120 ° C, and the mixture is allowed to stand at about 100 to 180 ° C for about 10 hours to obtain a plate-like cured epoxy resin. Obtained. The cured epoxy resin was cut into a disk having a diameter of lcm and a thickness of lcm, and the thermal conductivity in the thickness direction and the in-plane direction was measured at room temperature. The thermal conductivity was calculated from the product of the thermal diffusivity in the thickness direction and the in-plane direction determined by the laser flash method, the specific heat capacity, and the density of the sample. The thermal conductivity in the thickness direction was 0.52 W / m-K, and the thermal conductivity in the in-plane direction was 0.49 WZm'K.

Example 5

[0033] 50 parts by weight of 1,2 bis [2- {6 (oxyl-methoxy) carbol-naphtalene 2-yloxy} ethoxy] ethane obtained in Example 2 above and 4,4, diaminodiphenylmethane as a curing agent 9 parts by weight and 160 weight of alumina as filler (manufactured by Showa Denko; average particle size 2 m) The parts were mixed to obtain a composition. The composition is melted and charged in a plate-shaped hollow portion of a mold heated to about 120 ° C, and the mixture is allowed to stand at about 100 to 180 ° C for about 10 hours to obtain a cured plate-like epoxy resin. Got. The cured epoxy resin was cut into a disk having a diameter of lcm and a thickness of lcm, and the thermal conductivity in the thickness direction and the in-plane direction was measured at room temperature. For the thermal conductivity, the thermal diffusivity in the thickness direction and the in-plane direction obtained by the laser flash method, the specific heat capacity, and the product force of the sample density were also calculated. The thermal conductivity in the thickness direction was 1.9 W / mK, and the thermal conductivity in the in-plane direction was 1.7 WZm'K.

Example 6

[0034] 100 parts by weight of 1,2-bis [2- {6- (oxyl-methoxy) carbonylnaphthalene-2-yloxy} ethoxy] ethane obtained in Example 2 and 1,5-bis as a curing agent A composition was obtained by mixing 22 parts by weight of diamino naphthalene (manufactured by Wako Pure Chemical Industries) and 285 parts by weight of methyl isobutyl ketone as a solvent (solid content: 30% by weight). The composition was impregnated into a glass fiber woven fabric having a thickness of 0.2 mm, and dried by heating to obtain a prepreg. The four obtained pre-predaders were stacked, heated and pressed and integrated at a temperature of 125 ° C and a pressure of 4 MPa for 30 minutes, and then at a temperature of 175 ° C and a pressure of 4 MPa for 90 minutes. An 8 mm laminate was obtained. A plate sample of 60 mm × 120 mm was cut out from the laminated plate, and the thermal conductivity was measured (measurement conditions were based on a probe method and were performed at room temperature). The result was 0.83 WZm′K.

Comparative Example 1

[0035] 28 parts by weight of a bisphenol A-type epoxy compound (manufactured by Japan Epoxy Resin; EP-828) and 8 parts by weight of 4,4'-diaminodiphenylmethane as a curing agent were mixed to obtain a composition for comparison. The composition for comparison was heated from room temperature to 180 ° C. using a hot stage (manufactured by METTLER TOLEDO; FP82HT and FP90) to obtain a cured epoxy resin for comparison. Observation with a polarizing optical microscope (Nikon; XTP-11) showed that no depolarization was observed at temperatures from room temperature to 180 ° C, and that the epoxy resin was cured without liquid crystallinity. It could be confirmed.

Comparative Example 2

[0036] A comparative composition was obtained by mixing 50 parts by weight of the same bisphenol A-type epoxy compound as used in Comparative Example 1 and 15 parts by weight of 4,4'-diaminodiphenylmethane as a curing agent. It was. The composition is melted and charged in a plate-shaped hollow part of a mold heated to about 100 ° C, and the mixture is allowed to stand at about 100 to 180 ° C for about 10 hours. A cured product was obtained. The cured epoxy resin was cut into a disk having a diameter of lcm and a thickness of lcm, and the thermal conductivity in the thickness direction and the in-plane direction was measured at room temperature. For the thermal conductivity, the thermal diffusivity in the thickness direction and the in-plane direction obtained by the laser flash method, the specific heat capacity, and the product force of the sample density were also calculated. The thermal conductivity in the thickness direction was 0.21 W / mK, and the thermal conductivity in the in-plane direction was 0.18 W / m'K.

Comparative Example 3

[0037] The same bisphenol A-type epoxy compound as used in Comparative Example 1 was used in an amount of 100 parts by weight, 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries) was used in an amount of 40 parts by weight, and methylisobutylketone was used as a solvent. 327 parts by weight were mixed to obtain a composition for comparison (solid content: 30% by weight). The composition was impregnated into a 0.2 mm thick glass fiber woven fabric and dried by heating to obtain a prepreg. The four prepregs thus obtained were stacked, heated and pressed under a condition of a temperature of 175 ° C. and a pressure of 4 MPa for 90 minutes to be integrated, thereby obtaining a laminated plate having a thickness of 0.8 mm. A plate sample of 60 mm × 120 mm was cut out from this laminated plate, and its thermal conductivity was measured (measurement conditions were based on a probe method and were performed at room temperature). As a result, it was 0.45 WZm′K.

Industrial applicability

[0038] The epoxy resin conjugate produced from the novel carboxylic acid conjugate of the present invention can be cured with a curing agent having a low melting temperature to give a cured epoxy resin showing liquid crystallinity. Since the cured epoxy resin has high thermal conductivity, it is useful as an electronic material or the like that requires thermal conductivity.

Claims

Claims [1] Formula (1)

(1)

(Wherein R ⁹ and R ^1Q are the same or different and each represent a hydrogen atom or an alkyl group having 118 carbon atoms. Z is a force representing an alkylene group having 2 to 18 carbon atoms, or

[Formula 2]

[Formula 3]

And m represents an integer of 4-12. Here, one methylene group or two or more non-adjacent methylene groups constituting the alkylene group having 218 carbon atoms is represented by O NH — S Si (R ²¹ ) (R ²² ) — or 5-carbon atoms. 12 cycloal The alkylene group may contain a double bond.

twenty two

Is also good. R ²¹ and R are the same or different and each represents a lower alkyl group or

-Represents a phenyl group. Further, one methylene group or two or more non-adjacent methylene groups constituting the above-mentioned alkyl group having 118 carbon atoms and the above-mentioned cyclic amino group may be substituted with O—, —S— or NH—. . Y represents a single bond, O—, —S or —Si (R ²³ ) (R ²⁴ ), and R ²³ and R ²⁴ are the same or different and each represents a lower alkyl group or a phenyl group . )

A carboxylic acid compound represented by the formula:

[2] Carboxylic acid compound represented by the above formula (1) Formula (2)

[Formula 4]

(In the formula, Z represents the same meaning as described above.)

The carboxylic acid conjugate according to claim 1, which is a carboxylic acid conjugate represented by the formula:

[3] An epoxy conjugate having a structural unit derived from the carboxylic acid conjugate represented by the above formula (1) and an epoxy group in a molecule.

[4] An epoxy compound having a structural unit derived from the carboxylic acid conjugate represented by the above formula (1) and an epoxy group in the molecule is represented by the formula (3)

[Formula 5]

(3)

(Where R ² ,

Z and Y have the same meanings as described above, and R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³ ° are the same or different and are each a hydrogen atom or a carbon atom having 1-18 carbon atoms. Represents an alkyl group. Q ¹ and Q ² are the same or different and each represents a linear alkylene group having 11 to 19 carbon atoms; The formed methylene group may be substituted with an alkyl group having 11 to 18 carbon atoms, and O or N (R ³¹ ) — may be inserted between the methylene groups. Here, R ³¹ represents a hydrogen atom or an alkyl group having 118 carbon atoms. )

The epoxy conjugate according to claim 3, which is an epoxy conjugate represented by the formula:

Epoxy bond strength shown by formula (3) Formula (4)

[Formula 6]

(Where R ² ,

Z and Y have the same meaning as described above, and n represents an integer of 1 to 9. )

The epoxy conjugate according to claim 4, which is an epoxide conjugate represented by the formula:

[6] An epoxy composition comprising the epoxy compound according to claim 3, 4 or 5, and a curing agent.

[7] A cured epoxy resin obtained by curing the epoxy composition according to claim 6.

[8] A pre-predder obtained by impregnating or applying a substrate with the epoxy composition according to claim 6, and then semi-curing.