JPH07268074A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting polymaleimide resin composition which can be easily molded, does not form water as a by-product in curing and can give a cured resin product having high thermal aging resistance and excellent chemical stability and mechanical properties when cured. CONSTITUTION:This resin composition is the one comprising a polymaleimide compound (a), an alkenylphenol compound and/or an alkenylphenyl ether compound (b) each of which has at least two alkenyl groups in the molecule, a high-molecular epoxy resin (c) having at least two epoxy groups in the molecule and having a number-average molecular weight of 1000 or above and an epoxy resin curing agent (d) and having 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, the cured product of which has high heat aging resistance and chemical stability and mechanical properties even after being exposed to high temperature for a long time. It is excellent. Therefore, it is useful as a raw material for various fields where heat resistance and mechanical strength are required, for example, resins for multilayer laminates, sliding materials, 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. 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, a cured resin obtained by simply thermally polymerizing a bismaleimide resin is extremely brittle, and cracks easily occur due to thermal shock such as cooling and heating, and it is not practical. 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. Let
After removing the solvent, a molding material or a film is prepared by dehydration cyclization. However, this manufacturing method has a problem that water is by-produced during molding.

[0003]

According to the present invention, molding is easy, water is not generated as a by-product during curing, heat aging resistance is high due to curing, and chemical stability and mechanical properties are excellent. It is intended to provide a polymaleimide-based thermosetting resin composition capable of obtaining a resin cured product.

[0004]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that as a thermosetting resin composition giving a heat-resistant resin cured product, a polymer type epoxy resin and an epoxy resin are used. The present invention was completed by finding that a thermosetting resin composition containing a resin curing agent in a specific ratio is suitable. That is, the present invention provides the following component (a),
It is composed of component (b), component (c) and component (d), and the total amount of component (c) and component (d) is component (a), component (b), component (c) and component (d). In a ratio of 0.5 to 60 parts by weight per 100 parts by weight in total, the thermosetting resin composition is characterized. (A) Polymaleimide compound (b) Alkenylphenol compound and / or alkenylphenyl ether compound having at least two alkenyl groups in one molecule (c) Polymeric epoxy resin having a number average molecular weight of 1000 or more (d) Epoxy resin curing agent

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 and / or alkenylphenyl ether compound having at least two alkenyl groups in one molecule. At least 2 in one molecule used in the present invention
Specific preferred examples of the alkenylphenol compound having one or more alkenyl groups include, for example, the following b- to
There is a compound according to item b-.

(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.

Preferred specific examples of the alkenyl phenyl ether compound used in the present invention include the compounds described in the following items b- 'to b-'. (B- '): dimethallyl ether compound of biphenyldiol 4,4'-bis (2-propenyloxy) biphenyl,
4,4'-bis (2-methyl-2-propenyloxy)
Biphenyl, 2,2'-bis (2-methyl-2-propenyloxy) biphenyl.

(B- '): dialkenyl ether compound of bisphenol 2,2'-bis [4- (2-propenyloxy) phenyl] propane, 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, 1,1-bis [4- (2-methyl-2-propenyloxy) phenyl] cyclohexane, 1,1,1,3
3,3-hexafluoro-2,2-bis [4- (2methyl-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.

(B- '): Other alkenyl ether compound 1,4-bis (2-propenyloxy) benzene, 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, tris [4- (2-methyl-2-propenyloxy) phenyl] methane, 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, 1,2-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. The preferred alkenyl phenyl ether compound is a methallyl phenyl ether compound having two methallyl groups because a resin cured product having excellent heat aging resistance can be easily obtained. The preferred component (b) in the present invention 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 a polymer type epoxy resin having a number average molecular weight of 1,000 or more having one epoxy group. Specific preferred examples of the polymer type epoxy resin include, for example, the following c- and c-
Are listed in. The preferred component (c) in the present invention is a novolac type epoxy resin because a cured product having excellent heat aging resistance can be easily obtained.

(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 As commercially available products, OXIRON 1000 and Phenoxy P
KHS (above, UCC brand name), Oxylac E-
1081 (trade name of Nippon Shokubai Co., Ltd.), epoxy polybutadiene PB-EP (trade name of Nippon Soda Kogyo Co., Ltd.), Araldite 488 (trade name of Ciba-Geigy Co., Ltd.), DER684 (trade name of Dow Chemical Co., Ltd.), and Eponor 55. (Yukaka Shell Epoxy Co., Ltd. product name).

Component (d) The component (d) in the present invention is an epoxy resin curing agent, and any known curing agent for epoxy compounds can be used. Examples of preferable epoxy resin curing agents include compounds described in d- to d- below.

(D-): 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- Aminoethylpiperidine, 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.

(D-): Acid anhydride Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

(D-): Polyhydric phenol Bisphenol F, bisphenol A, novolac phenol resin and p-hydroxystyrene resin.

(D-): Imidazole compound As commercially available products, Cureazole 2MZ and Cureazole 2E
Z, Curezol 2E4MZ, Curezol 2IZ, Curezol 2MZ-CMS, Curezol 2E4MZ-
CMS (above, trade name by Shikoku Kasei Co., Ltd.) and the like.
These epoxy resin curing agents may be used alone or in combination of two or more. The preferred epoxy resin curing agent in the present invention is an aromatic diamine.

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 ratios of (b), (c) and (d), but in order to obtain a cured resin product excellent in heat aging resistance, the components (c) and (d) are combined. The total amount is the total of 1 of the components (a), (b), (c) and (d).
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.
The weight ratio of component (a) / component (b) is 0.05 to 2
It is preferably 0, more preferably 0.1 to 5, and the weight ratio of component (c) / component (d) is 0.1 to 100, more preferably 0.2 to 50. If component (a),
If the compounding ratios of (b), (c) and (d) deviate from the above range, the heat-aging property of the resin cured product obtained may deteriorate.

If desired, the following components (e) and (f) can be added to the composition of the present invention.

Component (e) Component (e) is a component for promoting heat curing of the composition, and any of those conventionally used as a radical initiator can be used. The following are preferred specific examples. That is, cumyl peroxide, tert-butyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,2 peroxide. 4-dichlorobenzoyl, 4-bromomethylbenzoyl peroxide, lauroyl peroxide,
Diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroxyperoxide, tert-butyl pertriphenylacetate, tert-butyl peracetate, tert-butyl hydroperoxide, tert-butyl perbenzoate, perbenzoate. Tert-butyl formate,
Tert-butyl perphenylacetate, tert-methoxy 4-peroxy
-Butyl, per N- (3-toluyl) carbamic acid tert-
Peroxides such as butyl; 2,2'-azobispropane,
2,2'-dichloro-2,2'-azobispropane,
1,1′-azo (methylethyl) diacetate, 2,
2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile,
Methyl 2,2'-azobis-2-methylpropionate,
2,2'-dichloro-2,2'-azobisbutane, 2,
2'-azobis-2-methylbutyronitrile, 2,2 '
-Dimethyl 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 ' 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 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, per 100 parts by weight of the components (a) and (b).

Component (f) Specific examples of the preferred component (f) include the following f- to f-
There are ingredients.

Component (f-) This component is a component for increasing the mechanical strength of the cured resin 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 (f-) 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 (f-) 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 (f-) This component is a component for imparting various desired properties to the cured resin product, 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.

Component (f-)-powder or fibrous reinforcing materials or fillers exemplified as component (f-), colorants, pigments, flame retardants, flame retardant aids and synthetic resins are preferably added in respective amounts. Varies depending on the use, but when the composition of the present invention is used as a molding material or a laminate, it is 500 per 100 parts by weight of the total amount of the components (a), (b), (c) and (d). Up to parts by weight.

The resin composition of the present invention can be easily prepared by uniformly mixing the above 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 properties 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.

[0034]

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. ○ 5% weight loss temperature Thermogravimetric differential thermal method (TG ·
The temperature at which the weight loss was 5% 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.

Example 1 27.74 g of bis (4-maleimidophenyl) methane as component (a) and 21.74 g of 2,2-bis [4-hydroxy-3- (2-methyl-) as component (b). Two
-Propenyl) phenyl] propane, 0.30 g of ESCN-100T as a component (c) (trade name of Sumitomo Chemical Co., Ltd., having the structure shown in the following Chemical Formula 2), and 0.19 g as a component (d). Bis (4-aminophenyl) sulfone of No. 1 was uniformly melted at 100 ° C., 0.77 g of dicumyl peroxide was further added as the component (e), and the mixture was poured into a Teflon mold and kept at 120 ° C. for 2 hours. Further, it was heated at 160 ° C. for 2 hours for curing to obtain a plate-shaped cured product.

[0036]

[Chemical 2]

The obtained cured product was exposed at 250 ° C. for 7 days, and the bending strength of the molded product and the heat aging resistance against the weight loss temperature were examined. As a result, the bending strength is 9.61k.
It was gw / mm ² .

Examples 2 to 5 As in Example 1, the compositions listed in Table 1 were tested 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 Component (c) and component (d) were not blended, but 28.05 g of bis (4-maleimidophenyl) methane as component (a) and 21.95 g of 2,2 as component (b). -Bis [4
-Hydroxy-3- (2-methyl-2-propenyl) phenyl] propane was uniformly mixed and melted at 100 ° C., and 0.77 g of dicumyl peroxide was further added as the component (e), and then a Teflon mold was used. And heated at 120 ° C. for 2 hours and 160 ° C. for another 2 hours to cure. However, the obtained cured product was brittle and a molded product could not be obtained.

Comparative Examples 2 to 5 As in Example 1, the compositions listed in Table 1 were prepared at 120 ° C. for 2 hours.
The obtained cured product was exposed for 7 days at 250 ° C., and the physical properties of the molded product were evaluated. The results are shown in Table 2. In each of Comparative Examples 2 to 5, the mechanical strength of the molded body was almost zero after exposure at a high temperature of 250 ° C.

Comparative Example 6 Without blending the components (a) and (b), 30.77 g of ESCN-100T (trade name of Sumitomo Chemical Co., Ltd.) as the component (c) and 19. as the component (d). 23 g of bis (4-aminophenyl) sulfone was uniformly melted at 100 ° C., then poured into a Teflon mold and cured by heating at 120 ° C. for 2 hours and at 160 ° C. for another 2 hours to cure into a plate. I got a thing. The obtained cured product was exposed at 250 ° C. for 7 days, and the bending strength of the molded body was examined. as a result,
It was found that there was almost no bending strength.

As is clear from Tables 1 and 2, the total amount of the component (c) and the component (d) per 100 parts by weight of the total of the components (a), (b), (c) and (d). In the case where the ratio is less than 0.5 wt%, a strong cured product could not be obtained under this curing condition, whereas the ratio of the total amount of the component (c) and the component (d) was 0.5 to. 60 wt
In the range of%, even if exposed at 250 ° C for 7 days,
Its bending strength is maintained at 4 kgw / mm ² or more,
It has high heat aging resistance and excellent mechanical properties such as bending strength.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention is easy to mold and does not produce a low molecular weight compound such as water as a by-product during curing. The cured resin product obtained has high heat aging resistance and excellent chemical stability and mechanical properties even after being exposed to high temperature for a long time.

Front page continued (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. The following component (a), component (b), component (c):
And component (d), and component (c) and component (d)
Of the total amount of component (a), component (b), component (c)
And 0.5 to 60 per 100 parts by weight of the total of the component (d).
A thermosetting resin composition, characterized in that the thermosetting resin composition is contained in a proportion of parts by weight. (A) Polymaleimide compound (b) Alkenylphenol compound and / or alkenylphenyl ether compound having at least two alkenyl groups in one molecule (c) Number average having at least two epoxy groups in one molecule Polymer type epoxy resin having a molecular weight of 1000 or more (d) Epoxy resin curing agent