JPH06100631A - Trialkenyl ether and thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a trialkenyl ether useful as a starting material for a polyim ide having moldability and excellent in heat resistance and mechanical properties by using a specified ether compound having three alkenyl groups in the mole cule. CONSTITUTION:A trialkenyl ether of the formula (wherein R<1>, R<2> and R<3> are each H or methyl) is provided. A cured product of a resin composition comprising a trialkenyl ether of the formula and a polymaleimide compound is excellent in heat resistance and mechanical properties, and is useful as an electrical insulation material or a laminate-forming material. The compound of the formula can be easily produced, for example, from a trisphenol such as 1-[1,1-bis(4- hydroxyphenyl)ethyl]-4-[1-methyl-(4-hydroxyphenyl)ethyl]benzene and 3- halopropane and/or 3-halo-2-methylpropene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has three alkenyl groups in one molecule and is useful as a raw material for polymer synthesis in various industrial fields. Particularly, a cured resin product having excellent heat resistance. The present invention relates to a novel trialkenyl ether useful as a raw material for and a thermosetting resin composition containing the same. Since the thermosetting resin composition of the present invention can be made into a resin cured product having excellent heat resistance and mechanical properties by thermosetting, various properties such as electric insulating materials and substrate materials required to have these properties can be obtained. It is useful in the field.

[0002]

2. Description of the Related Art In recent years, the size and weight of electrical equipment have been further reduced, and the operating conditions have become more severe. Along with this, there is an increasing demand for heat resistance of cured resin products such as insulating materials and substrate materials used in electrical equipment.

Polyimide is a typical heat-resistant resin cured product. However, since polyimide is insoluble and infusible in various solvents, it is difficult to use it as a material for molding or film formation as it is. Generally, acid dianhydride and diamine are solution polymerized in a polar solvent to obtain a polyamic acid as a polyimide precursor, and then the polyamic acid solution is cast or impregnated into various fillers and fibers. Then, the solvent is removed, and the product is dehydrated and cyclized to prepare a molding material and a film. However, this manufacturing method has a problem that water is by-produced during molding.

Further, as an addition reaction type polyimide, for example, an adduct of bis (4-maleimidophenyl) methane and bis (4-aminophenyl) methane is a heat-resistant material which does not produce water as a by-product during the manufacturing process. Although it is known as a cured product of a heat-resistant resin, the obtained polyimide is a straight chain having no cross-linking point, and therefore has a relatively low glass transition point and cannot withstand the use conditions as a cured product of a high heat-resistant resin.

On the other hand, a polyimide obtained by a thermosetting reaction is known as a cured product of a high heat resistant resin, and as a typical example thereof, bis (4-maleimidophenyl) methane and 0.0'-diallylbisphenol A are used. There is a cured product. However, in this two-component thermosetting polyimide, mechanical properties such as tensile strength and Shore hardness have not reached the level required for practical materials.

As described above, a polymaleimide compound such as bismaleimide is used as one of the raw material compounds for obtaining a polyimide, which is a cured product of a high heat resistant resin, and various other raw material compounds to be reacted therewith are used as various raw material compounds. Polyamide compounds or bisalkenylphenol compounds are used. However, what has been known so far as a polyimide having molding processability is still insufficient in heat resistance and / or mechanical properties, and improvement of these properties is desired.

[0007]

In view of the current situation,
INDUSTRIAL APPLICABILITY The present invention is useful as a raw material for polymer synthesis in various industrial fields, and a novel compound particularly useful as a raw material compound for obtaining a polyimide having moldability and excellent heat resistance and mechanical properties. It is provided. Furthermore, the present invention provides a thermosetting resin composition that can easily obtain a resin cured product having excellent heat resistance and mechanical properties by utilizing the properties of the novel compound of the present invention.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems, and as a result, have shown that trialkyl having three alkenyl groups in one molecule represented by the following general formula (a). It was found that the alkenyl ether is an extremely excellent compound. It was also found that a cured product of a resin composition comprising a trialkenyl ether represented by the following general formula (a) and a polymaleimide compound has excellent heat resistance and mechanical properties. That is, the present invention is a thermosetting resin composition comprising a trialkenyl ether represented by the following general formula (a) and this compound and a polymaleimide compound.

[0009]

[Chemical 2]

(However, R ¹ , R ² and R ³ in the formula all represent a hydrogen atom or a methyl group and may be the same or different from each other.) The present invention will be described in detail below. .

R ¹ , R ² and R ³ in the above general formula (a) representing the compound of the present invention are each a hydrogen atom or a methyl group, and the compound of the present invention [hereinafter simply referred to as compound (a)
Say. ] Is specifically 1- [1-methyl-1-
(4- (2-Methyl-2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene, 1- [1- Methyl-1- (4- (2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4-
(2-Methyl-2-propenyloxy) phenyl) ethyl] benzene, 1- [1-methyl-1- (4- (2-methyl-2-propenyloxy) phenyl) ethyl] -4
-[1- (4- (2-propenyloxy) phenyl)-
1- (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene, 1- [1-methyl-1- (4
-(2-Methyl-2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4- (2-propenyloxy) phenyl) ethyl] benzene, 1- [1-methyl-1- (4 -(2-Propenyloxy) phenyl) ethyl] -4- [1- (4- (2-propenyloxy) phenyl) -1- (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene and 1- [1-methyl-1- (4- (2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4- (2-propenyloxy) phenyl) ethyl] benzene.

The compound (a) is, for example, a reaction represented by the following formula (1) [hereinafter referred to simply as reaction (1). ], It can be easily obtained. The raw material in this reaction is trisphenol, 1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1-methyl- (4-hydroxyphenyl) ethyl] benzene (shown in Chemical Formula 4 below. A compound, abbreviated as S1), 3-halopropene (a compound represented by the following chemical formula 5 and abbreviated as S2) and / or 3-halo-2-methylpropene (a compound represented by the following chemical formula 6) And is abbreviated as S3).

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

To carry out the reaction (1), preferably a temperature of 1 is used.
S1 as a starting material is stirred at a temperature of 00 ° C. or lower, more preferably 30 to 80 ° C. in a solvent in which an equivalent or excess equivalent of a base is present with respect to S1, while stirring S1.
1.05 to 1.20 per equivalent of phenolic hydroxyl group
S2 and / or S3 may be added so that the proportion of halogen atoms is equivalent. In reaction (1), S2 and S
Since the halogen atom of 3 has the same reactivity, when S2 and S3 are used in combination, a compound (a) in which R ¹ , R ² and R ³ in the general formula (a) are hydrogen or a methyl group can be produced depending on the ratio. Obtainable.

Preferred solvents include dichloromethane, chloroform, tetrahydrofuran, N, N-dimethylformamide, benzene, toluene, dimethylsulfoxide, pyridine, organic solvents such as methanol and ethanol, water, or a mixed solvent of organic solvent and water. A mixed solvent of water, water and methanol is particularly preferable.

As a preferred base, triethylamine,
Tributylamine, picoline, N, N-dimethyl-p-
There are tertiary amines such as toluidine, sodium hydroxide and potassium hydroxide.

When the reaction (1) is started, S1 and S2 and / or S3 react quantitatively, and S1 almost disappears within about 20 hours. In order to clearly understand the end point of the reaction, it is desirable to trace the residual amount of S1 by thin layer chromatography, ¹ H-nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum and the like.

After a lapse of a predetermined time from the start of the reaction (1) and the residual amount of S1 is almost eliminated, the reaction solution is extracted with an organic solvent such as diethyl ether, ethyl acetate, dichloromethane, chloroform, benzene or toluene. To do. The extract is first washed with an aqueous alkaline solution and then with water. After sufficient washing by repeating washing with an alkaline aqueous solution and water in this way, a drying agent such as anhydrous sodium sulfate, anhydrous magnesium sulfate or calcium chloride is added to the reaction solution to remove water in the reaction solution. . Then, the organic solvent is removed by distillation under normal pressure or reduced pressure from the reaction solution obtained by filtering off the desiccant, whereby the desired compound (a) can be isolated.

Since this reaction proceeds relatively easily and there are almost no by-products, the reaction product can be used as a thermosetting resin composition or a raw material for polymer synthesis in various industrial fields without going through a purification step. Can be used as it is, and if necessary, purification can be performed using a conventionally used purification means such as column chromatography.

Since the compound (a) has three alkenyl groups in the molecule, it has high polymerizability and is useful as a cross-linking agent in various polymer synthesis reactions.

Next, the thermosetting resin composition containing the compound (a) will be described in detail. By reacting the polymaleimide compound with the compound (a), a cured resin product having excellent heat resistance and mechanical properties can be obtained. The polymaleimide compound [referred to as component (b)] used in the thermosetting resin composition of the present invention is a widely known and used substance, and is represented by the following general formula (b). , A compound having two or more maleimide groups in the molecule.

[0025]

[Chemical 7]

(Z in the formula is a divalent or higher valent residue, and n is an integer of 2 or more.) Z in the general formula (b).
May be any of aliphatic, aromatic, alicyclic and heterocyclic residues. As the component (b) in the present invention, an aromatic bismaleimide is particularly preferable because a cured product excellent in moldability, mechanical properties and heat resistance can be easily obtained. Specific preferred examples of the component (b) include the following compounds. That is, bis (4-maleimidophenyl) methane, 1,2-dimaleimidobenzene, bis (3
-Maleimidophenyl) methane, 1,3-dimaleimidobenzene, bis (4-maleimidophenyl) ether,
1,4-dimaleimidobenzene, bis (3-maleimidophenyl) ether, 1,4-dimaleimidonaphthalene, 2,3-dimaleimidonaphthalene, 1,5-dimaleimidonaphthalene, 4,4′-dimaleimidobiphenyl, 1,8-dimaleimidonaphthalene, 3,3′-dimaleimidobiphenyl, 2,6-dimaleimidonaphthalene, 3,4′-dimaleimidobiphenyl, 2,7-dimaleimidonaphthalene, 2,2′-bis [4 -(4-maleimidophenyloxy) phenyl] sulfone, 2,5-
Dimaleimide-1,3-xylene, bis (4-maleimidophenyl) ketone, bis (4-maleimidophenyl)
Sulfone, 1,5-dimaleimidoanthraquinone, bis (3-maleimidophenyl) sulfone, 1,2-dimaleimidoanthraquinone, 2,7-dimaleimidofluorene, 9,9-bis (4-maleimidophenyl) fluorene, 3, 7-dimaleimido-2-methoxyfluorene,
9,9-bis (4-maleimido-3-methylphenyl)
Fluorene, 9,10-dimaleimidophenanthrene,
9,9-bis (3-ethyl-4-maleimidophenyl)
Fluorene, 3,6-dimaleimidoacridine, 1,2
-Dimaleimide anthraquinone, 1,5-dimaleimide anthraquinone, 2,6-dimaleimide anthraquinone, 3,8-dimaleimide-6-phenylphenanthridine, bis (4-maleimidocyclohexyl) methane, bis (3-maleimidocyclohexyl) methane,
1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenyloxy) phenyl]
Propane, 1,1,1,3,3,3-hexafluoro-
2,2-bis (4-maleimidophenyl) propane,
1,4-bis (4-maleimidophenyl) benzene,
1,4-bis (4-maleimidophenyl) cyclohexane, bis (4-maleimidophenyl) diphenylsilane, bis (4-maleimidophenyl) sulfide, bis (3-maleimidophenyl) sulfide, bis (4-maleimidophenyl) sulfoxide, Bis (3-maleimidophenyl) sulfoxide, 2,2-bis (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, bis (3-methyl-4-maleimide) Phenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, isophorone dimaleimide, 1,2-dimaleimidoethane, 1,4-dimaleimidobutane, 1,6-dimaleimidohexane, 1,3 -Bis (maleimidomethyl) cyclohexane, 1,4-di Reimido-2-butanone,
1,2-dimaleimidocyclohexane, 1,10-dimaleimidodecane, 1,12-dimaleimidodecane, 1,
7-dimaleimidoheptane, 2,5-dimaleimidopyridine, 1,3-dimaleimido-2-hydroxypropane, 1,8-dimaleimido-p-menthane, 2,3-dimaleimidonaphthalene, 1,2-dimaleimide-2 -Methylpropane, 1,9-dimaleimidononane, 1,8-
Dimaleimidooctane, 1,5-dimaleimidopentane, 1,3-dimaleimidopropane, 2,4 dimaleimidophenol, 3,4-dimaleimidobenzophenone,
2,6-dimaleimide toluene, 3,4-dimaleimide toluene, adamantane-1,3-dimaleimide, 2,
3-dimaleimidopyridine, 1,4-bis (3-maleimidopropyl) piperazine, 4,5-dimaleimidopyridine 2,6-dimaleimidopyridine, 3,4-dimaleimidopyridine bis (3-ethyl-4-maleimide) Phenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, bis (3-propyl-4-maleimidophenyl) methane, bis (3,5-dipropyl-4-)
Maleimidophenyl) methane, bis (3-butyl-4-)
Maleimidophenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl) methane, 2-methyl-1,
4-dimaleimidobenzene, 2,3-dimethyl-1,4
-Dimaleimidobenzene, 2,5-dimethyl-1,4-
Dimaleimidobenzene, 2,6-dimethyl-1,4-dimaleimidobenzene, 4-ethyl-1,3-dimaleimidobenzene, 5-ethyl-1,3-dimaleimidobenzene, 4,6-dimethyl-1, 3-dimaleimidobenzene, 2,4,6-trimethyl-1,3-dimaleimidobenzene, 2,3,5,6-tetramethyl-1,4-dimaleimidobenzene, bis (3-ethyl-4-maleimide) -5-methylphenyl) methane, 4-methyl-1,3-
Bismaleimide such as dimaleimidebenzene; Tris (4
-Maleimidophenyl) trismaleimide such as methane;
Tetrakismaleimides such as bis (3,4-dimaleimidophenyl) methane; poly (4-maleimidostyrene) and poly (3-maleimidostyrene), and aromatic polyamines such as aniline resins obtained by the reaction of aniline with formaldehyde are maleimidized. And polymaleimide compounds.

The component (b) can be easily synthesized, for example, by reacting maleic anhydride with a polyamine compound represented by the following general formula (c).

[0028]

[Chemical 8] (N in the formula is an integer of 2 or more, and Z is a divalent or higher polyvalent residue.)

The performance of the composition of the present invention can be variously changed by changing the compounding ratio of the compound (a) and the component (b). Specifically, the composition may be adjusted according to the method of use, the required performance and the intended use. In order to obtain a cured product having excellent heat resistance, the molar ratio [compound (a) / component (b)] is set to 0. 05-20, more preferably 0.1-
5, and more preferably 0.5 to 2.

The following components can be added to the thermosetting resin composition of the present invention, if necessary. (C) Alkenyl phenyl ether This compound is an ether in which an alkenyl group and a benzene ring are bonded via oxygen, and the following compounds are preferred specific examples. That is, 4,4'-bis (2-methyl-2-propenyloxy) biphenyl, 2'2'-bis (2-methyl-2-propenyloxy) biphenyl,
4,4'-bis (2-propenyloxy) biphenyl,
2,2'-bis (2-propenyloxy) biphenyl,
2,2-bis [4- (2-methyl-2-propenyloxy) phenyl] propane, bis [4- (2-methyl-2)
-Propenyloxy) phenyl] methane, bis [4-
(2-methyl-2-propenyloxy) phenyl] sulfoxide, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfide, bis [4- (2-methyl-2-propenyloxy) phenyl] ether, Bis [4- (2-methyl-2-propenyloxy) phenyl] sulfone, 1,1-bis [4- (2-methyl-2-
Propenyloxy) phenyl] ethylbenzene, 2,2
-Bis [4- (2-propenyloxy) phenyl] propane, bis [4- (2-propenyloxy) phenyl]
Methane, bis [4- (2-propenyloxy) phenyl] sulfoxide, bis [4- (2-propenyloxy) phenyl] sulfide, bis [4- (2-propenyloxy) phenyl] ether, bis [4- (2 -Propenyloxy) phenyl] sulfone, 1,1-bis [4
-(2-Methyl-2-propenyloxy) phenyl] cyclohexane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2-methyl-2-propenyloxy) phenyl] Propane, bis [4- (2-methyl-2-propenyloxy) phenyl] ketone, 9,9-
Bis [4- (2-methyl-2-propenyloxy) phenyl] fluorene, 3,3-bis [4- (2-methyl-
2-propenyloxy) phenyl] phthalide, bis [2
-(2-Methyl-2-propenyloxy) phenyl] methane, 2,2-bis [3-methyl-4- (2-methyl-
2-propenyloxy) phenyl] propane, bis [2
-(2-Methyl-2-propenyloxy) phenyl] ketone, 2- (2-methyl-2-propenyloxy) phenyl 4- (2-methyl-2-propenyloxy) phenyl ketone, 1,1-bis [4 -(2-Propenyloxy) phenyl] ethylbenzene, 1,1-bis [4-
(2-propenyloxy) phenyl] cyclohexane,
1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2-propenyloxy) phenyl] propane, bis [4- (2-propenyloxy) phenyl] ketone, 9,9 -Bis [4- (2-propenyloxy) phenyl] fluorene, 3,3-bis [4- (2-propenyloxy) phenyl] phthalide, bis [2- (2-propenyloxy) phenyl] methane, 2,2 -Bis [3
-Methyl-4- (2-propenyloxy) phenyl] propane, bis [2- (2-propenyloxy) phenyl] ketone, 2- (2-propenyloxy) phenyl
4- (2-propenyloxy) phenyl ketone, 1,4
-Bis (2-propenyloxy) benzene, 1,2,4
-Tris (2-propenyloxy) benzene, 2,4-
Bis (2-propenyloxy) acetophenone, 2,5
-Bis (2-propenyloxy) acetophenone, 2,
6-bis (2-propenyloxy) acetophenone,
3,5-bis (2-propenyloxy) acetophenone, 1,8-bis (2-propenyloxy) anthraquinone, 1,4-bis (2-methyl-2-propenyloxy) benzene, 1,2,4-tris (2-methyl-2-
Propenyloxy) benzene, 2,4-bis (2-methyl-2-propenyloxy) acetophenone, 2,5-
Bis (2-methyl-2-propenyloxy) acetophenone, 2,6-bis (2-methyl-2-propenyloxy) acetophenone, 3,5-bis (2-methyl-2-)
Propenyloxy) acetophenone, 1,8-bis (2
-Methyl-2-propenyloxy) anthraquinone,
2,3-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,4-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,5-bis (2-
Methyl-2-propenyloxy) benzaldehyde,
3,4-bis (2-methyl-2-propenyloxy) benzaldehyde, 1,1,1-tris [4- (2-methyl-2-propenyloxy) phenyl] ethane, 1-
[1-Methyl-1- (4- (2-methyl-2-propenyloxy) phenyl) ethyl, 4- [1,1-bis (4
-(2-Methyl-2-propenyloxy) phenyl) ethyl] benzene, 1- [1-methyl-1- (4- (2-
Propenyloxy) phenyl) ethyl-4- [1,1-
Bis (4- (2-propenyloxy) phenyl) ethyl] benzene, 2,3-bis (2-propenyloxy)
Benzaldehyde, 2,4-bis (2-propenyloxy) benzaldehyde, 2,5-bis (2-propenyloxy) benzaldehyde, 3,4-bis (2-propenyloxy) benzaldehyde, 1,1,1-tris [4 -(2-propenyloxy) phenyl] ethane, 1
-[1-Methyl-1- (4- (2-propenyloxy))
Phenyl) ethyl] -4- [1,1-bis (4- (2-
Propenyloxy) phenyl) ethyl] benzene, 1,
2-bis (2-propenyloxy) naphthalene, 1,2
-Bis (2-propenyloxy) anthraquinone, 1,
3-bis (2-propenyloxy) naphthalene, 1,4
-Bis (2-propenyloxy) anthraquinone, 1,
4-bis (2-propenyloxy) naphthalene, 1,5
-Bis (2-propenyloxy) anthraquinone, 1,
5-bis (2-propenyloxy) naphthalene, 1,8
-Bis (2-propenyloxy) anthraquinone, 1,
6-bis (2-propenyloxy) naphthalene, 2,2
-Bis (2-propenyloxy) azobenzene, 2,3
-Bis (2-propenyloxy) naphthalene, 2,6-
Bis (2-propenyloxy) naphthalene, 2,7-bis (2-propenyloxy) naphthalene, 5,8-bis (2-propenyloxy) -1,4-naphthoquinone,
1,2-bis (2-methyl-2-propenyloxy) naphthalene, 1,3-bis (2-methyl-2-propenyloxy) naphthalene, 1,4-bis (2-methyl-2-)
Propenyloxy) naphthalene, 1,5-bis (2-methyl-2-propenyloxy) naphthalene, 1,6-bis (2-methyl-2-propenyloxy) naphthalene,
2,3-bis (2-methyl-2-propenyloxy) naphthalene, 2,6-bis (2-methyl-2-propenyloxy) naphthalene, 2,7-bis (2-methyl-2-)
Propenyloxy) naphthalene, 1,2-bis (2-methyl-2-propenyloxy) anthraquinone, 1,4
-Bis (2-methyl-2-propenyloxy) anthraquinone, 1,5-bis (2-methyl-2-propenyloxy) anthraquinone, 1,8-bis (2-methyl-2)
-Propenyloxy) anthraquinone, 2,2'-bis (2-methyl-2-propenyloxy) azobenzene and 5,8-bis (2-methyl-2-propenyloxy)
-1,4-naphthoquinone and the like. Of these, alkenyl phenyl ethers having two methallyl groups are preferred compounds.

The preferred amount of the alkenyl phenyl ether added varies depending on the application, but is 1 part by weight or less based on 1 part by weight of the total amount of the compound (a) and the component (b).

(D) Alkenylphenol This compound is a phenol in which an alkenyl group is bonded to a benzene ring, and preferable specific examples thereof include the following compounds. That is, 3,3'-bis (2-methyl-2-propenyl) -4,4'-biphenyldiol, 3,3'-bis (2-methyl-2-propenyl) -2,2'-biphenyldiol, 3,3'-di (2-propenyl) -4,
4'-biphenyldiol, 3,3'-di (2-propenyl) -4,4'-biphenyldiol, 2,2'-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] Propane, bis [4-hydroxy-3-
(2-Methyl-2-propenyl) phenyl] methane, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-
3- (2-methyl-2-propenyl) phenyl] sulfide, bis [4-hydroxy-3- (2-methyl-2-)
Propenyl) phenyl] ether, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfone, 2,2-bis [4-hydroxy-3- (2-propenyl) phenyl] propane, bis [ 4-hydroxy-3- (2-propenyl) phenyl] methane, bis [4
-Hydroxy-3- (2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfide, bis [4-hydroxy-3
-(2-Propenyl) phenyl] ether, bis [4-
Hydroxy-3- (2-propenyl) phenyl] sulfone, 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] ethylbenzene, 1,1
-Bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane, 1,1,1,3
3,3-hexafluoro-2,2-bis- [4-hydroxy-3- (2-methyl-2-propenyl) phenyl]
Propane, bis [4-hydroxy-3- (2-methyl-
2-propenyl) phenyl] ketone, 9,9-bis [4
-Hydroxy-3- (2-methyl-2-propenyl) phenyl] fluorene, 3,3-bis [4-hydroxy-
3- (2-methyl-2-propenyl) phenyl] phthalide, bis [2-hydroxy-3- (2-methyl-2-propenyl) phenyl] methane, 2,2-bis [4-hydroxy-3-methyl- 5- (2-methyl-2-propenyl) phenyl] propane, bis [2-hydroxy-3-
(2-Methyl-2-propenyl) phenyl] ketone, 2
-Hydroxy-3- (2-methyl-2-propenyl) phenyl 4-hydroxy-3- (2-methyl-2-propenyl) phenyl ketone, 1,1-bis [4-hydroxy-3- (2-propenyl) Phenyl] ethylbenzene, 1,1-bis [4-hydroxy-3- (2-propenyl) phenyl] cyclohexane, 1,1,1,3
3,3-hexafluoro-2,2-bis- [4-hydroxy-3- (2-propenyl) phenyl] propane, bis [4-hydroxy-3- (2-propenyl) phenyl] ketone, 9,9- Bis [4-hydroxy-3- (2
-Propenyl) phenyl] fluorene, 3,3-bis [4-hydroxy-3- (2-propenyl) phenyl]
Phthalide, bis [2-hydroxy-3- (2-propenyl) phenyl] methane, 2,2-bis [4-hydroxy-3-methyl-5- (2-propenyl) phenyl] propane, bis [2-hydroxy- 3- (2-propenyl)
Phenyl] ketone, 2-hydroxy-3- (2-propenyl) phenyl 4-hydroxy-3- (2-propenyl) phenyl ketone, 2,3-di (2-propenyl)
-1,4-benzenediol, 2,5-di (2-propenyl) -1,4-benzenediol, 3,5,6-tri (2-propenyl) -1,2,5-benzenetriol, 2, 4-dihydroxy-3,5-di (2-propenyl) acetophenone, 2,5-dihydroxy-3,4-
Di (2-propenyl) acetophenone, 2,5-dihydroxy-3,6-di (2-propenyl) acetophenone, 2,6-dihydroxy-3,5-di (2-propenyl) acetophenone, 2,3-bis ( 2-methyl-2-
Propenyl) -1,4-benzenediol, 2,5-bis (2-methyl-2-propenyl) -1,4-benzenediol, 3,5,6-tris (2-methyl-2-propenyl) -1 , 2,5-benzenetriol, 2,4-
Dihydroxy-3,5-bis (2-methyl-2-propenyl) acetophenone, 2,5-dihydroxy-3,4
-Bis (2-methyl-2-propenyl) acetophenone, 2,5-dihydroxy-3,6-bis (2-methyl-2-propenyl) acetophenone, 2,6-dihydroxy-3,5-bis (2-methyl) -2-propenyl) acetophenone, 3,5-dihydroxy-2,4-bis (2-methyl-2-propenyl) acetophenone, 3,
5-dihydroxy-2,6-bis (2-methyl-2-propenyl) acetophenone, 1,8-dihydroxy-
2,7-bis (2-methyl-2-propenyl) anthraquinone, 2,4-dihydroxy-3,4-bis (2-methyl-2-propenyl) benzaldehyde, 2,5-dihydroxy-3,4-bis ( 2-Methyl-2-propenyl) benzaldehyde, 2,5-dihydroxy-3,6
-Bis (2-methyl-2-propenyl) benzaldehyde, 3,4-dihydroxy-2,5-bis (2-methyl-2-propenyl) benzaldehyde, tris [4-hydroxy-3- (2-methyl-2-) Propenyl) phenyl] methane, 1,1,1-tris [4-hydroxy-3]
-(2-methyl-2-propenyl) phenyl] ethane,
2,2'-dihydroxy-3,3 '-(2-methyl-2
-Propenyl) azobenzene, 3,5-dihydroxy-
2,4-di (2-propenyl) acetophenone, 3,5
-Dihydroxy-2,6-di (2-propenyl) acetophenone, 1,8-dihydroxy-2,7-di (2-propenyl) anthraquinone, 2,4-dihydroxy-
3,4-di (2-propenyl) benzaldehyde, 2,
5-dihydroxy-3,4-di (2-propenyl) benzaldehyde, 3,4-dihydroxy-2,5-di (2
-Propenyl) benzaldehyde, tris [4-hydroxy-3- (2-propenyl) phenyl] methane, 1,
1,1-tris [4-hydroxy-3- (2-propenyl) phenyl] ethane, 2,2′-dihydroxy-3,
3 '-(2-propenyl) azobenzene, 1- [1-methyl-1- (4-hydroxy-3- (2-propenyl))
Phenyl) ethyl] -4- [1,1-bis (4-hydroxy-3- (2-propenyl) phenyl) ethyl] benzene, 1,3-dihydroxy-2,4-di (2-propenyl) naphthalene, 1 , 4-dihydroxy-2,3-di (2-propenyl) naphthalene, 1,5-dihydroxy-2,6-di (2-propenyl) naphthalene, 1,6-
Dihydroxy-2,5-di (2-propenyl) naphthalene, 1,6-dihydroxy-2,7-di (2-propenyl) naphthalene, 2,6-dihydroxy-1,5-di (2-propenyl) naphthalene, 1- [1-methyl-1
-(4-Hydroxy-3- (2-methyl-2-propenyl) phenyl) ethyl, 4- [1,1-bis (4-hydroxy-3- (2-methyl-2-propenyl) phenyl) ethyl] benzene , 1,3-dihydroxy-2,4
-Bis (2-methyl-2-propenyl) naphthalene,
1,4-dihydroxy-2,3-bis (2-methyl-2)
-Propenyl) naphthalene, 1,5-dihydroxy-
2,6-bis (2-methyl-2-propenyl) naphthalene, 1,6-dihydroxy-2,5-bis (2-methyl-2-propenyl) naphthalene, 1,6-dihydroxy-2,7-bis ( 2-Methyl-2-propenyl) naphthalene, 2,6-dihydroxy-1,5-bis (2-methyl-2-propenyl) naphthalene, 2,6-dihydroxy-1,7-bis (2-methyl-2-) Propenyl) naphthalene, 2,6-dihydroxy-3,7-bis (2-methyl-2-propenyl) naphthalene, 2,6-dihydroxy-3,5-bis (2-methyl-2-propenyl) naphthalene, 2, 7-dihydroxy-3,6-bis (2-
Methyl-2-propenyl) naphthalene, 2,7-dihydroxy-1,6-bis (2-methyl-2-propenyl)
Naphthalene, 2,7-dihydroxy-1,8-bis (2
-Methyl-2-propenyl) naphthalene, 1,4-dihydroxy-7,3-bis (2-methyl-2-propenyl) anthraquinone, 1,5-dihydroxy-2,6-
Bis (2-methyl-2-propenyl) anthraquinone,
1,8-dihydroxy-2,7-bis (2-methyl-2)
-Propenyl) anthraquinone, 5,8-dihydroxy-6,7- (2-methyl-2-propenyl) -1,4-
Naphthoquinone, 2,6-dihydroxy-1,7-di (2
-Propenyl) naphthalene, 2,6-dihydroxy-
3,7-di (2-propenyl) naphthalene, 2,6-dihydroxy-3,5-di (2-propenyl) naphthalene, 2,7-dihydroxy-3,6-di (2-propenyl) naphthalene, 2, 7-dihydroxy-1,6-di (2-propenyl) naphthalene, 2,7-dihydroxy-1,8-di (2-propenyl) naphthalene, 1,4-
Dihydroxy-2,3-di (2-propenyl) anthraquinone, 1,5-dihydroxy-2,6-di (2-propenyl) anthraquinone, 1,8-dihydroxy-2,
7-di (2-propenyl) anthraquinone and 5,8-
Dihydroxy-6,7-di (2-propenyl) -1,4
-Naphthoquinone and the like. Of these, alkenylphenols having two methallyl groups are preferred compounds.

The preferred addition amount of these alkenylphenols varies depending on the use, but is 1 part by weight or less based on 1 part by weight of the total amount of the compound (a) and the component (b).

(E) Epoxy resin This compound is an epoxy compound having at least two epoxy groups in one molecule. At least 2 in one molecule
There are various epoxy compounds having individual epoxy groups, and any known epoxy resin for molding can be used. A preferred compound is an epoxy compound having an aromatic ring. Specific preferred compounds of the component (e) include, for example, those described in e- to e- below.

E-: Diglycidyl ether of bisphenol A As commercially available products, Epicoat 827, Epicoat 828,
Epicoat 834, Epicoat 1001, Epicoat 1
004, Epicoat 1007, Epicoat 1009, and Epicoat 825 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite GY250 and Araldite GY6099 (all manufactured by Ciba Geigy), ER
L2774 (trade name of Union Carbide), DER
332, DER331 and DER661 (above, trade name by Dow Chemical Co.).

E-: Epoxyphenol novolak Commercially available Epicoat 152 and Epicoat 154
(These are the product names of Yuka Shell Epoxy Co., Ltd.), DE
N438 and DEN448 (these are product names manufactured by Dow Chemical Co., Ltd.), Araldite EPN1138, and Araldite EPN1139 (the product names manufactured by Ciba-Geigy Co., Ltd.).

E-: Epoxycresol novolak As commercial products, Araldite ECN1235, Araldite ECN1273 and Araldite ECN1280.
(These are product names manufactured by Ciba-Geigy).

E-: Brominated Epoxy Resin Commercially available products include Epicoat 5050 (trade name of Yuka Shell Epoxy Co., Ltd.) and BREN (trade name of Nippon Kayaku Co., Ltd.).

E-: Others For example, there are the following compounds. -Diglycidyl ether of bisphenol F A diglycidyl ester compound obtained by reacting a dibasic acid such as phthalic acid, dihydrophthalic acid and tetrahydrophthalic acid with epihalohydrin. An epoxy compound obtained by reacting an aromatic amine such as aminophenol or bis (4-aminophenyl) methane with epihalohydrin. * 1,1,1,3,3,3-hexafluoro-2,2-
[4- (2,3-epoxypropoxy) phenyl] propane. -A cycloaliphatic epoxy compound obtained by the reaction of dicyclopentadiene and the like with peracetic acid and the like. -1,4-butanediol diglycidyl ether. -1,6-hexanediol diglycidyl ether. Epicoat 604 (trade name of Yuka Shell Epoxy Co., Ltd.) The preferable addition amount of these epoxy resins varies depending on the use, but is 1 part by weight or less based on 1 part by weight of the total amount of the compound (a) and the component (b). Is.

(F) Epoxy Resin Curing Agent This compound is a curing agent for epoxy resin and is an effective component when an epoxy resin is added to the composition, and is known as a curing agent for epoxy resin. Any of can be used. Examples of preferable epoxy resin curing agents include the compounds described in f- to f- below. f-: amines triethylenetetramine, bis (4-amino-3,5-
Diethylphenyl) methane, tetraethylenepentamine, bis (4-amino-3-propylphenyl) methane, bis (4-aminophenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane, N- Aminoethylpiperazine, bis (4-amino-3-butylphenyl) methane, isophoronediamine, bis (4-amino-3,5-dibutylphenyl) methane, metaphenylenediamine, 2-methyl-1,4-phenylenediamine, Bis (4-aminophenyl) sulfone, 2,3-dimethyl-1,4-phenylenediamine, bis (3-aminophenyl) methane, 2,5-dimethyl-1,4-phenylenediamine, bis (4-aminophenyl) ) Ether, 2,6-dimethyl-1,4-phenylenediamine,
Bis (3-aminophenyl) ether, 4-ethyl-
1,3-phenylenediamine, 4,4′-biphenyldiamine, 5-ethyl-1,3-phenylenediamine,
3,3'-diphenyldiamine, 4,6-dimethyl-
1,3-phenylenediamine, 3,4′-diphenyldiamine, 2,4,6-trimethyl-1,3-phenylenediamine, 1,2′-phenylenediamine, 2,3,3
5,6-tetramethyl-1,4-phenylenediamine,
1,3-phenylenediamine, bis (4-amino-3-
Ethyl-5-methylphenyl) methane, 1,4-phenylenediamine, 4-methyl-1,3-phenylenediamine, 1,4-naphthalenediamine, benzyldimethylamine, 1,5-naphthalenediamine, 1,8-naphthalene Diamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,5-diamino-1,3-xylene, bis (4-aminophenyl) sulfone, bis (3-
Aminophenyl) sulfone, 2,7-diaminofluorene, 3,7-diamino-2-methoxyfluorene, 9,
10-diaminophenanthrene, 3,6-diaminoacridine, 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, 2,8-diamino-6-phenylphenanthridine, bis (4- Aminocyclohexyl) methane, bis (3-aminocyclohexyl) methane, 2,2-bis [4- (4-aminophenyloxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (4-aminophenyl) -1,1,1,3,3,3
3-hexafluoropropane, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenyl) cyclohexane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) sulfide , Bis (3-aminophenyl) sulfide, bis (4
-Aminophenyl) sulfoxide, bis (3-aminophenyl) sulfoxide, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenyloxy) phenyl] propane, bis (4 -Amino-
3-methylphenyl) methane, bis (4-amino-3,
5-dimethylphenyl) methane, bis (4-amino-3)
-Ethylphenyl) methane, 2,4,6-tris (dimethylaminomethyl) phenol and DBU.

F-: Acid anhydride Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

F-: Polyphenolic acid Bisphenol F, bisphenol A, novolac phenol resin and p-hydroxystyrene resin.

F-: Imidazole type compounds Boron trifluoride complexes of amines, dicyandiamides, organic acid hydrazides and polymercaptans. The preferred component (f) is an aromatic diamine.

The preferable addition amount of the component (f) varies depending on the use, but an amount which is commonly used as a curing agent for epoxy resin may be used.

(G) Room-Temperature Liquid Alkenyl Compound Component (g) is a room-temperature liquid alkenyl compound having at least one alkenyl group in one molecule, and does not impair the heat resistance of the cured resin product of the resin composition. It is a component that can lower the viscosity. Specific preferred examples include the following compounds. That is, allylbenzene, 1,9-decadiene, 1-decene, trans-5
-Decene, 2,3-dimethyl-1,3-butadiene,
2,3-dimethyl-1-butene, 2,3-dimethyl-2
-Butene, 3,3-dimethyl-1-butene, 2,5-dimethyl-1,5-hexadiene, 2,5-dimethyl-
2,4-hexadiene, trans, cis-2,6-dimethyl-2,4,6-octatriene, trans, trans-
2,6-dimethyl-2,4,6-octatriene, 2,
4-dimethyl-1,3-pentadiene, 1,1-diphenylethylene, dipentene, 1,4-difernyl-
1,3-Butadiene, trans-4,4'-difernylstilbene, divinylbenzene, 1-dodecene, 2-ethyl-1-butene, cis-9-heneicosene, 1-heptadecene, 1,6-heptadiene, 1- Heptene, cis
-2-heptene, trans-2-heptene, cis-3-heptene, 1-hexadecene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, cis-
2, trans-4-hexadiene, trans-2, trans-
4-hexadiene, 2,4-hexadiene, 1-hexene, trans-2-hexene, trans-3-hexene, isoprene, limonene, 3-methyl-1,2-butadiene, 2-methyl-1-butene, 2- Methyl-2-butene, 3-methyl-1-butene, 2-methyl-1-heptene, 1-methyl-1,5-hexadiene, 3-methyl-
1,5-hexadiene, 2-methyl-1-hexene, 3
-Methyl-1-hexene, trans-2-methyl-1,3
-Pentadiene, 2-methyl-1,3-pentadiene,
2-methyl-1,3-pentadiene, 2-methyl-1,
4-pentadiene, 3-methyl-1,3-pentadiene, 3-methyl-1,4-pentadiene, 2-methyl-
1-pentene, 2-methyl-2-pentene, 3-methyl-1-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, cis-4-methyl-2-pentene,
2-methyl-1-phenyl-1-propene, 2-methylpropene, α-methylstyrene, trans-β-methylstyrene, β-methylstyrene, 4-methylstyrene, 2
-Methyl-1-undecene, 1-nonadecene, 1,8-
Nonadiene, 1-nonene, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, allyl isocyanate, allyl isothiocyanate, allyl mercaptan,
Allyl methacrylate, 2-allyl-2-methyl-1,
3-cyclopentanedione, 4-allyl-1,2- (methyldioxy) benzene, 2-allyl-6-methylphenol, allylmethyl sulfide, 3-allyloxy-
1,2-propanediol, allyloxytrinaphthylsilane, allylpentafluorobenzene, 2-allylphenol, 1- (2-allylphenoxy) -3- (isopropylamino) -2-propanol, allylphenyl ether, allylphenyl sulfone , Allyl propyl ether, diallyl sulfide, diallyl amine, diallyl carbonate, diallyl malate, diallyl phenylphosphine, diallyl phthalate, diallyl succinate, 1,3 diallyl urea, methallyl alcohol, 1-
Methallyl-3-methyl-2-thiourea, 2-methyl-
2-propenyl phenyl ether, 1-allyloxy-
4-tert-butylbenzene, 2-allyl-4-tert-butylphenol, 2-allylphenol, 2-methallylphenol, 1-octadecene, 1,7-octadiene, 1-octene, trans-2-octene, trans- Four
-Octene, 1-pentadecene, 1,4-pentadiene, 1-pentene, cis-2-pentene, trans-2-
Pentene, 2-pentene, cis-piperylene, trans-
Piperylene, squalene, styrene, 1-tetradecene, 7-tetradecene, 1,1,4,4-tetraphenyl-1,3-butadiene, cis-9-tricosene, 1-
Tridecene, 2,3,3-trimethyl-1-butene,
2,4,4-trimethyl-1-pentene, 2,4,4-
Trimethyl-2-pentene, 1,2,4-trivinylcyclohexane, noundecene, vinylcyclohexane, 4-vinyl-1-cyclohexene, vinylcyclooctane, vinylcyclopentane, allyl acetate, allyl alcohol, allylamine, N-allylaniline,
4-allylanisole, allyl-1-benzotriazolyl carbonate, allyl butyl ether, allyl butyrate, allyl cyclohexylamine, allyl cyclopentane, 4-allyl-1,2-dimethoxybenzene, 4-allyl-2,6-dimethoxy Phenol, allylcyphenylphosphine, diallyl sulfide, diallyl ether, allyl ethyl ether, allyl glycidyl ether, 4-tert-butyl-1-methallyloxybenzene,
4-tert-butyl-2-methallylphenol, 2- (4
-Allyloxyphenyl) -2-phenylpropane, 2
-(4-methallyloxyphenyl) -2-phenylpropane, 2- (4-hydroxy-3-allylphenyl)-
2-phenylpropane, 2- (4-hydroxy-3-methallylphenyl) -2-phenylpropane, 2,4,6
-Tris [2- (2-propenyl) phenyloxy]-
1,3,5-triazine and 2,4,6-tris [2-
(2-Methyl-2-propenyl) phenyloxy]-
1,3,5-triazine and the like. Among these, preferred compounds include compounds containing an aromatic allyl group or an aromatic methallyl group because a cured product having excellent heat resistance can be easily obtained. The preferred addition amount of the component (g) varies depending on the use, but it is up to 1 part by weight based on 1 part by weight of the total amount of the compound (a) and the component (b).

(H) Amino compound having at least two amino groups in one molecule Component (h) is an amino compound having at least two amino groups in one molecule, and preferred specific compounds are as follows. There is.

H-: Diamine This is an amino compound having two amino groups in one molecule, and specific compounds include the following. That is,
Isophoronediamine, m-phenylenediamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) methane,
Bis (4-aminophenyl) ether, bis (3-aminophenyl) ether, 4,4'-biphenyldiamine, 3,3'-biphenyldiamine, 3,4'-biphenyldiamine, bis (4-amino-3, 5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane, bis (4-amino-3-butylphenyl) methane, bis (4-amino-3,5-dibutylphenyl) methane, 2-methyl-1,4-phenylenediamine, 2,3-dimethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine ,
2,6-dimethyl-1,4-phenylenediamine, 4-
Ethyl-1,3-phenylenediamine, 5-ethyl-
1,3-phenylenediamine, 4,6-dimethyl-1,
3-phenylenediamine, 2,4,6-trimethyl-
1,3-phenylenediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2
-Phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 1,3-phenylenediamine, bis (4-amino-3-ethyl-5-methylphenyl) methane, 1,4- Phenylenediamine, 4-methyl-1,3-phenylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, cyclohexylenediamine, 1,8-naphthalenediamine, 1,3
-Bis (aminomethyl) cyclohexane, 2,6-naphthalenediamine, 1,4-diaminobutane, 2,7-naphthalenediamine, 1,4-diamino-2-butanone,
2,5-diamino-1,3-xylene, 1,2-diaminocyclohexane, bis (4-aminophenyl) sulfone, 1,10-diaminodecane, bis (3-aminophenyl) sulfone, 1,12-diaminododecane , 2, 7
Diaminofluorene, 1,7-diaminoheptane, 2,
5-diaminopyridine, 3,7-diamino-2-methoxyfluorene, 1,3-diamino1,2-hydroxypropane, 9,10-diaminophenanthrene, diaminomaleonitrile, 3,6-diaminoacridine, 1,8
-Diamino-p-menthane, 1,2-diaminoanthraquinone, 2,3-naphthalenediamine, 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone,
2,8-diamino-6-phenylphenanthridine,
1,2-diamino-2-methylpropane, bis (4-aminocyclohexyl) methane, 1,9-diaminononane, bis (3-aminocyclohexyl) methane, 1,8
-Diaminooctane, 2,2-bis [4- (4-aminophenyloxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,4-bis (4-aminophenyl) benzene, 1,5- Diaminopentane, 1,4-bis (4-aminophenyl) cyclohexane, 1,2-diaminopropane, bis (4-aminophenyl) diphenylsilane,
1,3-diaminopropane, bis (4-aminophenyl) sulfide, 3,4-diaminobenzophenone, bis (3-aminophenyl) sulfide, 2,4-diaminophenol, bis (4-aminophenyl) sulfoxide, 2, 4-diaminotoluene, bis (3-aminophenyl) sulfoxide, 2,6-diaminotoluene, 2,
2-bis (4-aminophenyl) propane, 3,4-diaminotoluene, 2,2-bis [4- (4-aminophenyloxy) phenyl] propane, bis (4-amino-)
3-methylphenyl) methane, 1,3-adamantanediamine, bis (4-amino-3,5-dimethylphenyl) methane, 1,4-bis (3-aminopropyl) piperazine, bis (4-amino-3-). Ethylphenyl) methane, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 4,5-diaminopyrididine and the like.

H-: triamines This is an amino compound having three amino groups in one molecule, and specific compounds include the following. That is,
Tris (2-aminoethyl) amine, melamine and 2,
4,6-triaminopyrimidine and the like.

H-: Other amines Specific compounds include triethylenetetramine and tetraethylenepentamine. As the component (h), an aromatic diamine having two amino groups in one molecule is preferable. Since the component (h) has no reactivity with the compound (a) and has reactivity with the component (b), the amount of the component (h) added is the amount of the component (b) blended. It is desirable to adjust based on the amount.
The preferred addition amount of the component (h) varies depending on various uses, but up to 1 part by weight can be used per 1 part by weight of the component (b).

Component (i) Component (i) is a radical initiator for heating and curing the composition. The composition of the present invention is easily cured even in the absence of an initiator for the curing reaction, but in some cases, any of those conventionally used as a radical initiator can be used. The following are preferred specific examples. That is, cumyl peroxide, tert peroxide
-Butyl, acetyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1.
-Hydroxyperoxide, pertriphenylacetic acid tert-
Butyl, tert-butyl peracetate, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl performate, tert-butyl perphenylacetate, per-4-methoxyacetic acid
tert-butyl, per-N- (3-toluyl) carbamic acid te
Peroxides such as rt-butyl; 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate,
2,2′-azobis (2-amidinopropane) hydrochloride,
2,2'-azobis (2-amidinopropane) nitrate,
2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile per part by weight of stannic chloride 21.5 parts by weight of mixture, 2,2'-
Methyl azobis-2-methylpropionate, 2,2'-
Dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, stannic chloride per 1 part by weight of dimethyl 2,2'-azobisisobutyrate 19. 53 parts by weight of the mixture, 1,1'-azobis (1-methylbutyronitrile-
3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalono Dinitrile, 2,
2'-azobis-2-methylvaleronitrile, 2- (4
-Bromophenylazo) -2-allylmalonodinitrile, dimethyl 4,4-azobis-4-cyanovalerate,
2,2, -azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,
2'-azobis-2-propylbutyronitrile, 1,
1'-azobis-1-chlorophenylethane, 1,1 '
-Azobis-1-cyclohexanecarbonitrile, 1,
1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1 ' Azo compounds such as azobis-1,2-diphenylmethane, poly (bisphenol A-4,4′-azobis-4-cyanopentaate) and poly (tetraethylene glycol-2,2′-azobisisobutyrate); 1,4-bis (pentaethylene 1-2
Examples include tetrazene, benzenesulfonyl azide, and 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene.

The preferable addition amount of these radical initiators depends on the use, but it depends on the compound (a) and the component (b).
The total amount is up to 5 parts by weight based on 100 parts by weight.

Component (j) As the component (j), the following components (j) -1 to
(J) -4 can be added.

Component (j) -1: Reinforcing material or filler This component is a component for increasing the mechanical strength of the cured resin, and any of those conventionally used can be used. The following are preferred specific examples.
That is, metal oxides such as aluminum oxide and magnesium oxide; metal hydroxides such as aluminum hydroxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder; basic magnesium silicate; calcined clay; fine powder silica. , Quartz powder, fused silica, crystalline silica; kaolin,
Talc; carbon black; antimony trioxide; finely powdered mica; graphite; molybdenum disulfide; carbon fiber; glass fiber; rock wool; ceramic fiber; inorganic fibers such as asbestos; paper, pulp, wood materials; polyamide fiber, aramid fiber, boron It is a synthetic fiber such as a fiber.

Component (j) -2; Colorant This component is a component for coloring the resin cured product, and any of those conventionally used can be used.
The following are preferred specific examples. That is, titanium dioxide, yellow lead carbon black, iron black, molybdenum red,
Examples include dark blue, ultramarine, cadmium yellow, cadmium red, and boron nitride.

Component (j) -3; flame retardant This component is a component for imparting flame retardancy to the cured resin product, and any of those conventionally used can be used. The following are preferred specific examples. That is, a dimethacrylate reaction product of tetrabromobisphenol A, tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-).
3,5-dibromophenyl) propane, decabromodiphenyl ether and other brominated flame retardants, antimony trichloride,
Inorganic flame retardants such as zirconium hydroxide, magnesium hydroxide, tin oxide, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, phenylene bis (phenyl cresyl phosphate), xylenyl diphenyl Phosphate, phenylene bis (dicresyl phosphate)
Aromatic phosphate ester flame retardants such as and polycondensates thereof,
Tris (2-chloroethyl) phosphate, bis (2-
Examples include (halo) alkyl phosphate ester-based flame retardants such as chloroethyl) vinyl phosphate, polycondensates thereof, and inorganic phosphorus-based flame retardants such as red phosphorus.

Component (j) -4: Synthetic resin This component is a component for imparting various properties to a cured resin product, and has been conventionally used as a component for modifying certain specific properties. Are all available. The following are preferred specific examples. That is, it is a synthetic resin such as a phenol resin, an alkyd resin, a melamine resin, a fluororesin, a vinyl chloride resin, an acrylic resin, a silicone resin and a polyester resin.

The preferred amounts of these powdery or fibrous reinforcing materials or fillers, colorants, flame retardants, flame retardant aids, and synthetic resins to be added differ depending on the intended use.
And 100 per 100 parts by weight of the total of the component (b)
Up to parts by weight.

The resin composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components at a temperature which does not reach the curing temperature of the composition, and this can be prepared at an appropriate temperature, for example, 120 to 300 ° C. By heating at a temperature for 1 to 20 hours, it can be easily cured, and a cured product having excellent heat resistance and mechanical properties can be obtained.

[0059]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. Example 1 Trisphenol 1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1- (4-hydroxyphenyl) -1- (methyl) ethyl] benzene 212
g (0.5 mol) was placed in a 1-liter three-necked flask, and 200 ml of methanol was poured. 75 g (1.8 mol) of 96% sodium hydroxide while stirring with a mechanical stirrer (about 200 rpm) in a cloudy white state while heating.
Was dissolved in 150 ml of water and slowly added dropwise through the dropping funnel. After a while, the reaction liquid turns light pink and then light purple, and becomes almost transparent. Next, 163 g (1.8 mol) of 3-chloro-2-methylpropene was slowly added dropwise. After completion of dropping, the temperature of the reaction solution was raised to 60 ° C., and the temperature was raised for 6.5 hours.
Further stirring was continued. After the reaction, the reaction product was extracted with toluene (800 ml), and the extracted toluene solution was sufficiently washed with a 5% aqueous sodium carbonate solution and water in this order, and dried overnight in the presence of anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure with a rotary evaporator to obtain 297 g of a concentrate (yield was about 1
It is 00%. ). The ¹ H-NMR spectrum and IR spectrum of the obtained compound are as shown in Table 1 and Table 2, respectively, and this compound was 1- [1-methyl-1- (4-
(2-Methyl-2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene.

[0060]

Table 1 Chemical shift value of ¹ H-nuclear magnetic resonance spectrum of the product obtained by synthesis in Example 1 and its assignment (C
DCI ₃ , 100MHz, tetramethylsilane)

[0061]

[Chemical 9]

[0062]

[Table 2] IR spectrum of the product obtained by synthesis in Example 1

Example 2 The compound (a) obtained in Example 1 and bis (4-maleimidophenyl) methane were mixed at an equimolar ratio of 140 to 150.
The mixture was uniformly mixed and melted at a temperature of ℃, and 3 mol% of dicumyl peroxide [compound (a) and component (b)
Based on the total number of moles of the above], the mixture was quickly poured into a molding die for 2 hours at 120 ° C., then 200
It heated at 2 degreeC for 2 hours, and obtained the resin hardened | cured material. The physical properties of this cured product were measured by the following methods, and the results are shown in the table below. ○ Tensile strength Measured according to JIS K7113. ○ Shore D hardness Measured according to JIS Z2246. Weight loss temperature 5%, 10%, 20% Thermogravimetric differential thermal method (TG.
The temperature at which the weight loss of 5%, 10% and 20% was measured by DTA). Decomposition temperature The temperature at which the temperature rise rate was 20 ° C./minute, and the temperature at which abrupt heat generation and weight loss occurred due to TG / DTA was taken as the decomposition temperature. Glass transition point The temperature at which the dielectric loss tangent has the maximum value in the viscoelastic spectrum (VES) was taken as the glass transition point.

[0064]

[Table 3]

[0065]

INDUSTRIAL APPLICABILITY The trialkenyl ether of the present invention has three alkenyl groups which are polymerization-reactive functional groups in one molecule and is useful as a raw material for polymer synthesis in various industrial fields. It is particularly useful as a raw material compound for obtaining a polyimide having processability and excellent heat resistance and mechanical properties. Further, the polymaleimide compound-based thermosetting resin composition containing the novel compound of the present invention is a cured resin product having excellent heat resistance and mechanical properties, and is useful as an electrical insulating material, a laminate-forming material, or the like. .

Front Page Continuation (72) Inventor Masao Takei 1-1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (2)

[Claims] 1. A trialkenyl ether represented by the following general formula (a). [Chemical 1] (However, R ¹ , R ² and R ³ in the formula all represent a hydrogen atom or a methyl group and may be the same or different from each other.) 2. A thermosetting resin composition comprising the trialkenyl ether according to claim 1 and a polymaleimide compound.