JP3334176B2 - Thermosetting resin composition - Google Patents

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 for molding, and the cured product has high heat resistance and excellent mechanical properties. Therefore, it is useful as a raw material for molding materials such as electric insulating materials and electric circuit board materials in various fields requiring heat resistance and mechanical strength.

[0002]

2. Description of the Related Art In recent years, the miniaturization and weight reduction of electric equipment and the severer use conditions have been further increased, and accordingly, resin curing of insulating materials and substrate materials used in electric equipment has been accompanied. There is an increasing demand for heat resistance for objects.

A typical heat-resistant resin cured product is polyimide. However, since polyimide is insoluble and insoluble in various solvents, it is difficult to use polyimide as it is as a material for molding or film formation. In general, solution polymerization of an acid dianhydride and a diamine in a polar solvent to obtain a polyamic acid as a polyimide precursor, and then casting the polyamic acid solution or impregnating various fillers and fibers. After removing the solvent, dehydration cyclization prepares a molding material and a film. However, in this production method, there is a problem that water is by-produced during molding.

Further, as a polyimide obtained by the addition reaction, for example, an adduct of bis (4-maleimidophenyl) methane and bis (4-aminophenyl) methane is
It is known as a heat-resistant resin cured product without water by-products during the manufacturing process, but the resulting polyimide is a straight chain with no cross-linking points, so its glass transition point is relatively low and high heat resistance It cannot withstand the usage conditions as a cured 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 a typical example thereof is a mixture of bis (4-maleimidophenyl) methane and 0,0'-diallylbisphenol A. There is a cured product. However, such two-component thermosetting polyimides have insufficient mechanical properties such as tensile strength and Shore hardness, and further improvement is desired to make them practical materials.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a molding resin which is easy to mold, has no water by-product during curing, has high heat resistance after curing, and has excellent mechanical properties. A maleimide-based thermosetting resin composition is provided.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the following four components are used as a thermosetting resin composition for molding to give a cured product of a heat resistant resin. It has been found that a resin composition is suitable. That is,
The present invention is a thermosetting resin composition for molding, characterized by including the following components (c) and (d) in a thermosetting resin composition comprising the following components (a) and (b). (A) a polymaleimide compound (b) a methallylphenol-based compound and / or a methallylphenylether-based compound having at least two methallyl groups in one molecule of a solid at ordinary temperature; and (c) at least two methallylphenyl compounds in one molecule. Epoxy resin having epoxy group (d) Epoxy curing agent The present invention will be described in more detail below.

Component (a) Component (a) in the present invention is a polymaleimide compound, which is a compound represented by the following general formula (1) and having two or more maleimide groups in a molecule.

[0009]

Embedded image

(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 (1)
May be any of aliphatic, aromatic, alicyclic and heterocyclic residues. Specific examples of preferred polymaleimide compounds include, for example, the following compounds. That is, the screw (4
-Maleimidophenyl) methane, bis (3-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 (3,5-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 (4-maleimidophenyl) sulfone, bis (3-maleimidophenyl) sulfone, bis [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-dimaleimide naphthalene, 2,3-dimaleimide naphthalene, 1,5-dimaleimide naphthalene, 1,8-dimaleimide naphthalene, 2,6-dimaleimide naphthalene, 2,7-dimaleimide naphthalene,
4,4′-dimaleimide biphenyl, 3,3′-dimaleimide biphenyl, 3,4′-dimaleimide biphenyl, 2,5-dimaleimide-1,3-xylene, 1,5
-Dimaleimide anthraquinone, 1,2-dimaleimide anthraquinone, 2,7-dimaleimide fluorene,
9,9-bis (4-maleimidophenyl) fluorene,
9,9-bis (4-maleimido-3-methylphenyl)
Fluorene, 9,9-bis (3-ethyl-4-maleimidophenyl) fluorene, 3,7-dimaleimide-2-
Methoxyfluorene, 9,10-dimaleimidophenanthrene, 3,6-dimaleimidoacridine, 1,2-dimaleimidoanthraquinone, 1,5-dimaleimidoanthraquinone, 2,6-dimaleimidoanthraquinone,
3,8-dimaleimide-6-phenylphenanthridine, 1,2-dimaleimidebenzene, 1,3-dimaleimidebenzene, 1,4-dimaleimidebenzene, 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-
Dimaleimide benzene, 5-ethyl-1,3-dimaleimide benzene, 4,6-dimethyl-1,3-dimaleimide benzene, 2,4,6-trimethyl-1,3-dimaleimide benzene, 2,3 5,6-tetramethyl-1,
Bismaleimide such as 4-dimaleimidobenzene and 4-methyl-1,3-dimaleimidobenzene; trismaleimide such as tris (4-maleimidophenyl) methane; tetrakismaleimide such as bis (3,4-dimaleimidophenyl) methane Poly (4-maleimidostyrene), poly (3-maleimidostyrene), and polymaleimide obtained by maleimidating an aromatic polyamine such as an aniline resin obtained by a 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.

The polymaleimide compound represented by the general formula (1) can be easily obtained by reacting a polyamine compound represented by the following general formula (2) with maleic anhydride.

[0012]

Embedded image (In the formula, n is an integer of 2 or more, and Z is a divalent or more polyvalent residue.)

Component (b) The component (b) in the present invention is a methallylphenol-based compound and / or a methallylphenylether-based compound having at least two methallyl groups in one molecule of a solid at ordinary temperature.

Preferred specific examples of the methallylphenyl ether compound used in the present invention include the following b- to
Among the compounds described in item b-, those which are solid at ordinary temperature can be mentioned. (B-): dimethallyl ether compound of biphenyldiol 4,4'-bis (2-methyl-2-propenyloxy)
Biphenyl, 2,2'-bis (2-methyl-2-propenyloxy) biphenyl.

(B-): Dimethallyl ether compound of bisphenol 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- (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.

(B-): Other methallyl ether compounds 1,4-bis (2-methyl-2-propenyloxy) benzene, 1,2,4-tris (2-methyl-2-propenyloxy) benzene, , 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. Preferred methallyl phenyl ether compounds are methallyl phenyl ether compounds having two methallyl groups.

A methallylphenol compound having at least two or more methallyl groups in one molecule can be easily obtained, for example, by heating a methallylphenyl ether compound to cause Claisen rearrangement of the methallyl group. Preferred specific examples of the methallylphenol-based compound having at least two methallyl groups in one molecule used in the present invention include, for example, the compounds described in the following b′- to b′- And a solid one.

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

(B'-): dimethallyl bisphenol compound 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 methallyl phenol compound 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, 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.
Preferred methallyl phenolic compounds are methallyl phenolic compounds having two methallyl groups. Among these methallylphenol-based compounds and methallylphenylether-based compounds, examples of the compound having at least two methallyl groups in one molecule of a solid at normal temperature used in the present invention include the following. Can be 2,2 '
-Bis [4- (2-methyl-2-propenyloxy) phenyl] propane, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfoxide, bis [4-
(2-methyl-2-propenyloxy) phenyl] sulfone (above b-); 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, bis [4-hydroxy- 3- (2-methyl-2-
Propenyl) phenyl] sulfone, 9,9-bis [4-
Hydroxy-3- (2-methyl-2-propenyl) phenyl] fluorene (above b'-); 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, 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 (above b'-).

Component (c) Component (c) in the present invention contains at least 2 components per molecule.
It is an epoxy compound having two epoxy groups. There are various epoxy compounds having at least two epoxy groups in one molecule, and a preferable compound is an epoxy compound having an aromatic ring. Preferred specific examples of the component (c) include, for example, those described in the following c- to c-.

(C-): Diglycidyl ether of bisphenol A As a commercial product, Epikote 827, Epikote 828,
Epicoat 834, Epicoat 1001, Epicoat 1
004, Epicoat 1007, Epicoat 1009 and Epicoat 825 (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite GY250 and Araldite GY6099 (trade names, manufactured by Ciba Geigy), ER
L2774 (trade name, manufactured by Union Carbide), DER
332, DER 331 and DER 661 (both trade names, manufactured by Dow Chemical Company) and the like.

(C-): Epoxy Phenol Novolak As a commercial product, Epikote 152 and Epikote 154
(The above is the product name of Yuka Shell Epoxy Co., Ltd.), DE
N438 and DEN448 (trade names, manufactured by Dow Chemical Co., Ltd.), Araldite EPN1138 and Araldite EPN1139 (trade names, manufactured by Ciba Geigy) and the like.

(C-): epoxy cresol novolac As commercial products, Araldite ECN1235, Araldite ECN1273 and Araldite ECN1280
(The above is a product name of Ciba-Geigy).

(C-): Brominated epoxy resin Commercially available products include Epicoat 5050 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) and BREN (trade name, manufactured by Nippon Kayaku Co., Ltd.).

(C-): 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 or the like with peracetic acid or the like; -1,4-butanediol diglycidyl ether. -1,6-hexanediol diglycidyl ether.・ Epicoat 604 (product name made by Yuka Shell Epoxy Co., Ltd.)

Component (d) Component (d) in the present invention is an epoxy resin curing agent, and any of those known as curing agents for epoxy compounds can be used. Preferred epoxy resin curing agents include, for example, the following compounds d- to d-.

(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
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-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-): polyphenolic acid bisphenol F, bisphenol A, novolak phenol resin and p-hydroxystyrene resin.

(D-): imidazole compound Boron trifluoride complex of amine, dicyandiamide, organic acid hydrazide and polymercaptan. 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 properties of the thermosetting resin composition of the present invention are determined according to the method of use, the required performance and the intended use.
It can be controlled appropriately by changing the mixing ratio of (b), (c) and (d). Specifically, for example, it is preferable to decrease the component (c) in order to increase the heat resistance, while it is preferable to increase the component (c) in order to increase the adhesive property and the low viscosity property. From such a viewpoint, the preferable mixing ratio of the components (a), (b), (c) and (d) is such that the molar ratio of the component (a) / the component (b) is 0.05 to 2
0, more preferably 0.1 to 5, the molar ratio of component (a) / component (c) is 0.05 to 500, more preferably 0.1 to 50, and component (c) / component ( The molar ratio of d) is from 0.05 to 500, more preferably from 0.1 to 50, even more preferably from 0.1 to 25. If the proportions of the components (a), (b), (c) and (d) deviate from the above ranges, in the properties of the obtained cured resin, heat resistance and / or mechanical strength properties deteriorate. There is fear.

Component (e) The composition of the present invention may contain, as a component (e), a radical initiator for curing the composition by heating.
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, 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 formate, tert-butyl perphenylacetate, tert-butyl per-4-methoxyacetate, perN- (3- Toluyl) carbamic acid
peroxides such as tert-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'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, stannic chloride per part by weight of 2,2'-azobisisobutyronitrile 21.5 parts by weight of the mixture, 2,2'-
Methyl azobis-2-methylpropionate, 2,2'-
18. stannic chloride per part by weight of dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate; 53 parts by weight of a mixture of 1,1′-azobis (1-methylbutyronitrile-
Sodium 3-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-arylmalonodinitrile, 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-
There are tetrazen, benzenesulfonyl azide, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazen and the like.

The preferred amount of these radical initiators varies depending on the application, but is preferably 0 to 50 parts by weight, more preferably 0 to 10 parts by weight, per 100 parts by weight of the total of components (a) and (b). is there.

Component (f) The following components (f) -1 to (f) -4 can be added to the thermosetting resin composition of the present invention, if necessary.

Component (f) -1 This component is a component for increasing the mechanical strength of the cured resin, and any of those conventionally used can be used. There is something.
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; , Quartz powder, fused silica, crystalline silica; kaolin,
Talc; carbon black; antimony trioxide; fine powdered mica; graphite; molybdenum disulfide; carbon fiber; glass fiber; rock wool; ceramic fiber; inorganic fibers such as asbestos; paper, pulp, wood, polyamide fiber, aramid fiber, and boron. Synthetic fibers such as fibers.

Component (f) -2 This component is a component for coloring the cured resin, and any of those conventionally used can be used.
Preferred specific examples include the following. That is, titanium dioxide, graphite carbon black, iron black, molybdenum red,
Navy blue, ultramarine, cadmium yellow, cadmium red and boron nitride.

Component (f) -3 This component is a component for imparting flame retardancy to the cured resin, and any of those conventionally used can be used. Preferred specific examples include the following. That is, a dimethacrylate reactant of tetrabromobisphenol A, tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-
Brominated flame retardants such as 3,5-dibromophenyl) propane and decabromodiphenyl ether; antimony trichloride;
Inorganic flame retardants such as zirconium hydroxide, magnesium hydroxide, tin oxide, etc., triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, phenylene bis (phenylcresyl phosphate), xylenyl diphenyl Phosphate, phenylene bis (dicresyl phosphate)
Such as aromatic phosphate ester flame retardants and polycondensates thereof,
Tris (2-chloroethyl) phosphate, bis (2-
(Halo) alkyl phosphate flame retardants such as (chloroethyl) vinyl phosphate; polycondensates thereof; and inorganic phosphorus flame retardants such as red phosphorus.

Component (f) -4 This component is a component for imparting various desired properties to the cured resin, and those conventionally used as components for modifying certain specific properties include: Any of them can be used as long as the properties of the composition of the present invention are not impaired. Preferred specific examples include the following. That is,
Synthetic resins such as phenolic resins, alkyd resins, melamine resins, fluorine resins, vinyl chloride resins, acrylic resins, silicone resins and polyester resins.

The preferable addition amounts of these powdery or fibrous reinforcing materials or fillers, coloring agents, pigments, flame retardants, flame retardant auxiliaries and synthetic resins differ depending on the application, but are not limited to molding materials or laminates. When using the composition of the invention, the total amount of the components (a), (b), (c) and (d) is up to 500 parts by weight based on 100 parts by weight in total.

The resin composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components at a temperature not reaching the curing temperature of the composition. By heating at a temperature for 1 to 20 hours, the composition is easily cured, and a cured product having excellent heat resistance and mechanical properties can be obtained.

[0042]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. The various physical property values evaluated in Examples and Comparative Examples were measured as follows. -Tensile strength Measured according to JIS K7113.シ ョ Shore D hardness Measured according to JISZ2246. ○ Weight loss temperature 5%, 10%, 20% Using a thermogravimetric differential heating method (TG.
DTA), the temperature at which 5%, 10% and 20% weight loss was measured. -Decomposition temperature The temperature at which the rate of temperature rise was 20 ° C / min and the temperature at which rapid heat generation and weight loss were caused by TG / DTA was defined as the decomposition temperature. ○ Glass transition point The temperature at which the dielectric loss tangent was the maximum value in the viscoelastic spectrum (VES) was defined as the glass transition point.

Example 1 1 mole of bis [4-maleimidophenyl] methane as component (a) and 1 mole of 2,2-bis [4-hydroxy-3- (2-methyl-2-) as component (b) Propenyl) phenyl] propane (melting point 71 ° C.), 0.1 mol of Epicoat 604 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) as component (c) and 0.04 mol of bis (4-amino) as component (d) After phenyl) methane was uniformly mixed and melted at 100 ° C., it was poured into a Teflon mold, and
For 2 hours, and further cured by heating at 200 ° C. for 2 hours.
A plate-like cured product was obtained. Table 1 shows the physical properties of the obtained cured product.

Examples 2 to 25 and Comparative Examples 1 to 4 Preparation of the compositions listed in Tables 1 to 3 in the same manner as in Example 1
Curing by heating and evaluation of physical properties of the cured product were performed. Tables 4 to 6 show these results.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

However, the symbols in the table showing the types of the compounds are as follows:
The following compounds are shown (the symbols shown immediately below the compounds are the symbols in the table).

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

As can be seen by comparing the results in Tables 4 and 5 with Table 6, most of the cured product of the composition of the present invention hardly decomposes at 400 ° C. or lower, and even if the decomposition temperature is relatively low, 350 It hardly decomposes below ℃, has high heat resistance, and also has excellent mechanical properties such as tensile strength.

[0074]

The thermosetting resin composition of the present invention is easy to mold, does not produce water as a by-product during curing, has high heat resistance after curing, and has excellent mechanical properties.

Continuation of the front page (72) Inventor Masao Takei 1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi Examiner, Nagoya Research Institute, Toagosei Chemical Industry Co., Ltd. Naoto Kaga (56) References JP-A-4-122719 (JP) JP-A-3-128908 (JP, A) JP-A-54-68899 (JP, A) JP-A-3-281521 (JP, A) JP-A-2-185517 (JP, A) 2-185516 (JP, A) JP-A-50-12198 (JP, A) JP-A-5-222164 (JP, A) JP-A-5-105741 (JP, A) JP-A-4-175334 (JP, A A) JP-A-3-70729 (JP, A) JP-A-2-92918 (JP, A) JP-A-53-134099 (JP, A) JP-A-54-116096 (JP, A) -108859 (JP, A) JP-A-6-93047 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/40-59/66

Claims (1)

(57) [Claims] 1. A thermosetting resin composition for molding , characterized by comprising the following components (c) and (d) in a thermosetting resin composition comprising the following components (a) and (b): (A) a polymaleimide compound (b) a methallylphenol-based compound and / or a methallylphenylether-based compound having at least two methallyl groups in one molecule of a solid at ordinary temperature; and (c) at least two methallylphenyl compounds in one molecule. Epoxy resin having epoxy group (d) Epoxy resin curing agent