JPH07268075A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which is free from any epoxy resin curing agent, can be easily molded, does not form water as a by-product when cured, and can give a cured product having high thermal aging resistance and excellent chemical stability and mechanical properties when cured. CONSTITUTION:This resin composition is one which is free from any epoxy resin curing agent, comprises a polymaleimide compound (a), an alkenylphneol compound (b) having at least two alkenyl groups in the molecule and an epoxy resin (c) having at least two epoxy groups in the molecule and has a total content of components (c) and (d) of 0.5-60wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, which has a high heat aging resistance and an excellent mechanical property even after being exposed to high temperature for a long time. . Therefore, various fields requiring heat resistance with respect to mechanical strength, for example, resins for multilayer laminates, sliding materials,
It is useful as a raw material for sealing materials, electrical insulating materials, molding materials, paints and adhesives.

[0002]

2. Description of the Related Art In recent years, in electric and electronic fields, transportation fields such as airplanes and vehicles, performance improvement, downsizing and weight reduction of devices have been promoted, and accordingly, development of materials having higher heat resistance. Is desired. Conventionally, epoxy resins, polyimide resins, and maleimide resins have been used in each of the above fields. However, although the epoxy resin is excellent in electrical characteristics and mechanical characteristics, it is not sufficiently satisfactory in heat resistance. In addition, when an epoxy resin is used, generally, an epoxy resin curing agent is often used in combination, and the use of the epoxy resin curing agent causes a problem that heat resistance is lowered. Further, although the polyimide resin has excellent heat resistance, it is insoluble and infusible in various solvents, so that it is difficult to use it as a molding or film forming material as it is. An addition type bismaleimide resin is known as a polyimide having improved moldability. However, the cured resin obtained by simply thermally polymerizing the bismaleimide resin is extremely brittle,
Cracks easily occur due to thermal shock such as cooling and heating, which is not practical. Polyaminobismaleimide resin, which is a prepolymer of bis (4-maleimidophenyl) methane and bis (4-aminophenyl) methane, has been put to practical use as a resin that can improve such drawbacks and sufficiently withstand practically. However, even this resin cannot be said to have sufficient heat resistance. In general, 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.

[0003]

DISCLOSURE OF THE INVENTION The present invention is easy to mold, does not produce a low molecular weight compound such as water as a by-product during curing, has high heat aging resistance due to curing, and is exposed to high temperature for a long time. The present invention provides a polymaleimide-based thermosetting resin composition capable of obtaining a cured resin product having excellent mechanical properties even after being cured.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy resin curing agent is used as a component of a thermosetting resin composition which gives a cured product of a heat resistant resin. The inventors have found that a resin composition composed of the following three components having a specific composition can be an excellent resin cured product without containing any of the above, and have completed the present invention.
That is, the present invention does not contain an epoxy resin curing agent and is composed of the following components (a), (b) and (c), and the component (c) is replaced by the components (a), (b) and ( It is a thermosetting resin composition characterized by containing 0.5 to 60 parts by weight per 100 parts by weight of c) in total. (A) Polymaleimide compound (b) Alkenylphenol compound having at least two alkenyl groups in one molecule (c) Epoxy resin having at least two epoxy groups in one molecule

The present invention will be described in more detail below. Component (a) The component (a) in the present invention is a polymaleimide compound, which is a compound having at least two maleimide groups represented by the following general formula (1) in the molecule.

[0006]

[Chemical 1]

(In the formula, Z is a divalent or higher valent residue, and n is an integer of 2 or more.) Z in the general formula (1) is aliphatic, aromatic, alicyclic or It may be any of heterocyclic residues. Specific examples of preferable polymaleimide compounds include the following compounds. That is, bis (4-maleimidophenyl) methane, bis (3-maleimidophenyl) methane, bis (4-maleimidocyclohexyl) methane, bis (3-
Maleimidocyclohexyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-
Ethyl-4-maleimidophenyl) methane, bis (3,3
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, bis (3-ethyl-4-maleimido-5)
Methylphenyl) 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, 2,2-bis (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] Propane, bis (4-
Maleimidophenyl) ether, bis (3-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, bis (3-maleimidophenyl) ketone, bis (4-maleimidophenyl) sulfone, bis (3-maleimidophenyl) sulfone, Screw [4-
(4-Maleimidophenyloxy) phenyl] sulfone, bis (4-maleimidophenyl) sulfide, bis (3-maleimidophenyl) sulfide, bis (4
-Maleimidophenyl) sulfoxide, bis (3-maleimidophenyl) sulfoxide, bis (4-maleimidophenyl) diphenylsilane, 1,4-bis (4-
Maleimidophenyl) cyclohexane, 1,4-dimaleimidonaphthalene, 2,3-dimaleimidonaphthalene,
1,5-dimaleimidonaphthalene, 1,8-dimaleimidonaphthalene, 2,6-dimaleimidonaphthalene, 2,
7-dimaleimidonaphthalene, 4,4′-dimaleimidobiphenyl, 3,3′-dimaleimidobiphenyl, 3,
4'-dimaleimidobiphenyl, 2,5-dimaleimido-1,3-xylene, 1,5-dimaleimidoanthraquinone, 1,2-dimaleimidoanthraquinone, 2,7-
Dimaleimidofluorene, 9,9-bis (4-maleimidophenyl) fluorene, 9,9-bis (4-maleimido-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-4-maleimidophenyl) fluorene ,
3,7-dimaleimido-2-methoxyfluorene, 9,
10-dimaleimidophenanthrene, 1,2-dimaleimidoanthraquinone, 1,5-dimaleimidoanthraquinone, 2,6-dimaleimidoanthraquinone, 1,2-
Dimaleimidobenzene, 1,3-dimaleimidobenzene, 1,4-dimaleimidobenzene, 1,4-bis (4
-Maleimidophenyl) benzene, 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 -Bismaleimides such as dimaleimidobenzene and 4-methyl-1,3-dimaleimidobenzene; trismaleimides such as tris (4-maleimidophenyl) methane; bis (3,4
-Tetrakismaleimides such as dimaleimidophenyl) methane; poly (4-maleimidostyrene) and poly (3-
Maleimide styrene) and polymaleimide obtained by maleimidating an aromatic polyamine such as an aniline resin obtained by the reaction of aniline and formaldehyde. As the component (a) in the present invention, an aromatic bismaleimide compound is particularly preferable because a cured product excellent in moldability and heat resistance can be easily obtained.

Component (b) Component (b) in the present invention is an alkenylphenol compound having at least two alkenyl groups in one molecule, and at least two or more in one molecule used in the present invention. Specific preferred examples of the alkenylphenol-based compound having an alkenyl group are:
To b-items.

(B-): dialkenylbiphenyldiol compound 3,3'-bis (2-propenyl) -4,4'-biphenyldiol, 3,3'-bis (2-propenyl)-
2,2'-biphenyldiol, 3,3'-bis (2-
Methyl-2-propenyl) -4,4'-biphenyldiol, 3,3'-bis (2-methyl-2-propenyl)
-2,2'-biphenyldiol.

(B-): dialkenyl bisphenol compound 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-propenyl) phenyl] -1-phenylethane, 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, 2,2-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, 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 and 2-
Hydroxy-3- (2-methyl-2-propenyl) phenyl 4-hydroxy-3- (2-methyl-2-propenyl) phenyl ketone.

(B-): Other alkenylphenol compounds 2,3-bis (2-propenyl) -1,4-benzenediol, 2,5-bis (2-propenyl) -1,4-benzenediol, 3,5,6-Tris (2-propenyl) -1,2,5-benzenetriol, 2,4-dihydroxy-3,5-bis (2-propenyl) acetophenone, 2,5-dihydroxy-3,4- Bis (2-propenyl) acetophenone, 2,5-dihydroxy-3,
6-bis (2-propenyl) acetophenone, 2,6-
Dihydroxy-3,5-bis (2-propenyl) acetophenone, 3,5-dihydroxy-2,4-bis (2-
Propenyl) acetophenone, 3,5-dihydroxy-
2,6-bis (2-propenyl) acetophenone, 1,
8-dihydroxy-2,7-bis (2-propenyl) anthraquinone, 2,4-dihydroxy-3,4-bis (2-propenyl) benzaldehyde, 2,5-dihydroxy-3,4-bis (2-propenyl) Benzaldehyde, 2,5-dihydroxy-3,6-bis (2-propenyl) benzaldehyde, 3,4-dihydroxy-
2,5-bis (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-bis (2-propenyl) naphthalene, 1,4-dihydroxy-2,3-bis (2-propenyl) naphthalene, 1,5-dihydroxy-2,6-bis (2-propenyl) naphthalene, 1,6- Dihydroxy-2,5-bis (2-propenyl) naphthalene, 1,6-dihydroxy-2,7-bis (2-propenyl) naphthalene, 2,
6-dihydroxy-1,5-bis (2-propenyl) naphthalene, 2,6-dihydroxy-1,7-bis (2-
Propenyl) naphthalene, 2,6-dihydroxy-3,
7-bis (2-propenyl) naphthalene, 2,6-dihydroxy-3,5-bis (2-propenyl) naphthalene, 2,7-dihydroxy-3,6-bis (2-propenyl) naphthalene, 2,7- Dihydroxy-1,6-bis (2-propenyl) naphthalene, 2,7-dihydroxy-1,8-bis (2-propenyl) naphthalene, 1,
4-dihydroxy-2,3-bis (2-propenyl) anthraquinone, 1,5-dihydroxy-2,6-bis (2-propenyl) anthraquinone, 1,8-dihydroxy-2,7-bis (2-propenyl) Anthraquinone, 5,8-dihydroxy-6,7-bis (2-propenyl) -1,4-naphthoquinone, 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-3,5-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, 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-2,3-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 and 5,8-dihydroxy-6,7-bis (2-methyl-2)
-Propenyl) -1,4-naphthoquinone. The preferred alkenylphenol-based compound is an alkenylphenol-based compound having two methallyl groups, because a resin cured product having excellent heat aging resistance can be easily obtained.

Component (c) The component (c) in the present invention contains at least 2 in one molecule.
It is an epoxy resin having one epoxy group, and is preferably a polymer type epoxy resin having a number average molecular weight of 1,000 or more. There are various types of polymer type epoxy resins, and specific examples thereof include those described in the following c- and c-.

(C-): Novolac type epoxy resin As commercially available products, Epicoat 152 and Epicoat 154
(These are the product names of Yuka Shell Epoxy Co., Ltd.), DE
N431 and DEN438 (above, trade name of Dow Chemical Co., Ltd.), EPN1138, EPN1139, ECN12
35, ECN1275, ECN1280, ECN129
9 and ERE 1359 (above, trade name manufactured by Ciba-Geigy), ESCN-100T (trade name manufactured by Sumitomo Chemical Co., Ltd.) and the like.

(C-): Other polymer type epoxy resin Commercially available products, OXIRON 1000 and Phenoxy P
KHS (above, UCC brand name), Oxylac E-
1081 (trade name manufactured by Nippon Shokubai Kogyo Co., Ltd.), epoxy polybutadiene PB-EP (trade name manufactured by Nippon Soda Kogyo Co., Ltd.), Araldite 488 (trade name manufactured by Ciba-Geigy Co., Ltd.), DER684 (trade name manufactured by Dow Chemical Co., Ltd.) and Eponor 55. (Yukaka Shell Epoxy Co., Ltd. product name).

The characteristics of the thermosetting resin composition of the present invention are the above-mentioned component (a), depending on the method of use, required performance and application.
It can be appropriately controlled by changing the blending ratio of (b) and (c), but in order to obtain a resin cured product having excellent heat aging resistance, the total of components (a), (b) and (c) is required. 1
The amount should be 0.5 to 60 parts by weight per 00 parts by weight. If less than 0.5 parts by weight or more than 60 parts by weight,
There is a problem that the heat aging resistance of the cured resin is reduced.
Further, the weight ratio of component (a) / component (b) is 0.05 to 2
It is preferably 0, more preferably 0.1 to 5. If the blending ratios of the components (a), (b) and (c) deviate from the above range, the heat-aging resistance of the resulting cured resin product may deteriorate.

Component (d) In the composition of the present invention, a radical initiator for heating and curing the composition may be added as the component (d),
Any of the conventionally used radical initiators can be used. As a preferred specific example,
For example: That is, cumyl peroxide, peroxide
tert-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, diisopropyl peroxycarbonate , Tetralin hydroperoxide,
1-phenyl-2-methylpropyl-1-hydroxyperoxide, tert-butyl pertriphenylacetate, peracetic acid
tert-butyl, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl formate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate,
Peroxides such as tert-butyl perN- (3-toluyl) carbamate; 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (Methylethyl) diacetate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2,
2'-azobisisobutyronitrile, 2,2'-methyl azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-
2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5- Dihydroxymethylphenylazo-
2-methylmalonodinitrile, 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'-
Azobis-1,2-diphenylmethane, poly (bisphenol A-4,4'-azobis-4-cyanopentaate) and poly (tetraethylene glycol-2,2'-
Azo compounds such as azobisisobutyrate); 1,4-bis (pentaethylene 1-2-tetrazene, benzenesulfonyl azide and 1,4-dimethoxycarbonyl-1,
4-diphenyl-2-tetrazene and the like. The preferred addition amount of these radical initiators varies depending on the use, but is 0 to 50 parts by weight, and more preferably 0 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b).

Component (e) In the thermosetting resin composition of the present invention, the following e-
~ E-components can be added.

Component (e-) This component is a curing catalyst for promoting the reaction of the epoxy group, and is a component that participates in the reaction only at the initiation of the reaction of the epoxy group and does not participate in the reaction in the subsequent polymerization process. However, any of those conventionally used can be used, and preferable specific examples include the following. That is,
Aliphatic tertiary amine represented by triethanolamine,
N, N'-dimethylpiperazine, alicyclic tertiary amine represented by 1,4-diazabicyclo [2.2.2] octane, represented by 1,8-diazabicyclo [5.4.0] -7-undecene Heterocyclic tertiary amines, N, N'-dimethylbenzylamine, 2- (dimethylaminomethyl)
Aromatic tertiary amines represented by phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2-methyl-4-methylimidazole, imidazoles represented by 2-ethyl-4-methylimidazole, tri Phosphorus compounds typified by phenylphosphine, Lewis acids typified by monoethylamine of boron trifluoride, and the like.

Component (e-) This component is a component for increasing the mechanical strength of the resin cured product, and any of those conventionally used can be used. Preferred specific examples are as follows. There is.
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 (e-) 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 (e-) This component is a component for imparting flame retardancy to the resin cured 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 (e-) This component is a component for imparting various desired properties to the cured resin, and the component conventionally used as a component for modifying certain specific properties is Any of them can be used as long as the characteristics of the composition of the invention are not impaired. 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 preferable addition amount of the e-curing catalyst varies depending on the use, but when the composition of the present invention is used as a molding material or a laminate, the component (a), the component (b) and the component (c) are used. 0.5 to 5 parts by weight per 100 parts by weight of the total total amount of the above).

The preferable addition amounts of these powdery or fibrous reinforcing materials or fillers, coloring agents, pigments, flame retardants, flame retarding aids and synthetic resins shown in e- to e- differ depending on the use. When the composition of the present invention is used as a molding material or a laminate, it is up to 500 parts by weight based on 100 parts by weight of the total of the components (a), (b) and (c).

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

By curing the composition of the present invention, a cured resin product having excellent heat aging resistance can be easily obtained. Therefore, it is useful in various applications where these characteristics are required. Insulation material, electric circuit board material,
It is useful as a raw material for molding materials, laminated materials, encapsulants, heat-resistant adhesives, heat-resistant fillers and the like.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. The various physical property values evaluated in the examples and comparative examples are measured as follows. Bending strength Measured according to JIS K7203. Example 1 25.26 g of bis (4-maleimidophenyl) methane as component (a) and 19.75 g of 2,2-bis [4-hydroxy-3- (2-methyl-2) as component (b).
-Propenyl) phenyl] propane and 4.95 g of ESCN-100T (trade name of Sumitomo Chemical Co., Ltd., having the structure of the following chemical formula 2) as component (c) 10
It is uniformly mixed and melted at 0 ° C., and further 0.07 as the component (d).
After adding 6 g of triphenylphosphine and 0.70 g of dicumyl peroxide, the mixture was poured into a Teflon mold and heated at 120 ° C. for 2 hours and then at 160 ° C. for another 2 hours to be cured to obtain a plate-shaped cured product. Got

[0027]

[Chemical 2]

The obtained cured product was exposed at 250 ° C. for 7 days, and the heat aging resistance against bending strength of the molded product was examined. As a result, the bending strength was 14.16 kgw / mm ² .

Examples 2-5 As in Example 1, the compositions listed in Table 1 were prepared at 120 ° C. for 2 hours.
The resulting cured product was exposed for 7 days at 250 ° C., and the bending strength of the molded product was measured. The results are shown in Table 2.

Comparative Example 1 28.05 g of bis (4-maleimidophenyl) methane as component (a) and 21.95 g of 2,2-bis [4-hydroxy-3- (2-methyl-) as component (b). Two
-Propenyl) phenyl] propane was uniformly mixed and melted at 100 ° C, 0.77 g of dicumyl peroxide was further added as the component (d), and the mixture was poured into a Teflon mold and heated at 120 ° C for 2 hours at 160 ° C. Then, it was heated for 2 hours for curing. However, the obtained cured product is brittle,
It was not possible to obtain a molded body.

Comparative Example 2 8.43 g of bis (4-maleimidophenyl) methane as the component (a) and 6.60 g of 2,2 as the component (b).
-Bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane and 3 as component (c)
5.13 g of ESCN-100T (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was uniformly mixed and melted at 100 ° C., and 0.073 g of triphenylphosphine as the component (e-) and 0. After adding 23 g of dicumyl peroxide, pour into a Teflon mold and
Cured by heating at 0 ° C. for 2 hours and 160 ° C. for another 2 hours. However, the obtained cured product was brittle and a molded product could not be obtained.

Comparative Example 3 As component (c), 32.1 g of ESCN-100T (trade name of Sumitomo Chemical Co., Ltd.)
After 18 Gg of phenol novolac, which is usually used as a curing agent, is uniformly melted, 0.032 g of triphenylphosphine is further added as the component (e-), and then the mixture is poured into a Teflon mold for 2 hours at 120 ° C. ,
It was heated at 160 ° C. for 2 hours and further heated at 200 ° C. for 2 hours to be cured, and the obtained cured product was exposed at 250 ° C. for 7 days, and the bending strength of the molded body was measured. As a result, the bending strength was 3.62 kgw / mm ² .

As is clear from Tables 1 and 2, when the ratio of the component (c) per 100 parts by weight of the components (a), (b) and (c) is less than 0.5% by weight, While a cured product having excellent mechanical properties cannot be obtained, when the ratio of the component (c) is in the range of 0.5 to 60% by weight,
Even if exposed at 250 ° C for 7 days, its bending strength is 11k.
It is confirmed that the resin has gw / mm ² or more and has high heat aging resistance.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

EFFECTS OF THE INVENTION The heat-resistant resin composition of the present invention is easy to mold, does not form a low molecular weight compound such as water as a by-product during curing, and is obtained from the thermosetting resin composition of the present invention. The resin cured product obtained has high heat aging resistance and excellent mechanical properties even after being exposed to a high temperature for a long time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Kimura 1-1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (1)

[Claims] 1. An epoxy resin curing agent-free composition comprising components (a), (b) and (c). Component (c) is replaced with component (a), component (b) and component (c). The thermosetting resin composition contains 0.5 to 60 parts by weight per 100 parts by weight in total. (A) Polymaleimide compound (b) Alkenylphenol compound having at least two alkenyl groups in one molecule (c) Epoxy resin having at least two epoxy groups in one molecule