JP3213926B2 - 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, and the cured product has high heat resistance and excellent mechanical properties. Therefore, the composition of the present invention is useful as a raw material for molding materials and laminate materials such as electric insulating materials and electric circuit board materials, in various fields where heat resistance and mechanical strength are required. , Lamination, molding,
It can be used by various methods such as sealing and bonding.

[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 provides a polymaleimide-based thermosetting composition which is easy to mold, has no water by-product during curing, has high heat resistance after curing, and has excellent mechanical properties. A curable 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 a resin composition comprising the following three components as a thermosetting resin composition that gives a cured product of a heat resistant resin. Things were found to be suitable. That is, the present invention is a thermosetting resin composition comprising the following component (c) in a thermosetting resin composition comprising the following components (a) and (b). (A) Polymaleimide compound represented by general formula (1)

Embedded image (Z in the formula is any divalent or higher residue of any of aliphatic, aromatic, alicyclic and heterocyclic residues excluding a condensed ring, and n
Is an integer of 2 or more. (B) a methallylphenol-based compound and / or a methallylphenylether-based compound having at least two methallyl groups in one molecule; and (c) any of the following aromatic compounds, alicyclic compounds or acyclic compounds: Compound i) An aromatic compound having at least two amino groups in one molecule and having an amino group in an aromatic ring, in which adjacent carbons are unsubstituted based on the carbon bonded to the amino group. Ii) One molecule. An alicyclic compound having at least two amino groups therein and having an amino group in an aliphatic ring, wherein adjacent carbons are unsubstituted based on the carbon bonded to the amino group; iii) at least two amino groups in one molecule; Hereinafter, the present invention will be described in more detail.

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 general formula (1) is a divalent or higher valent residue, and may be any of an aliphatic group, an aromatic group other than a condensed ring, an alicyclic group and a heterocyclic group. . n is an integer of 2 or more. Specific examples of preferred polymaleimide compounds include, for example, 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 (3,5-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 , 4,4'-dimaleimidobiphenyl, 3,3 '
-Dimaleimidebiphenyl, 3,4'-dimaleimidebiphenyl, 2,5-dimaleimide-1,3-xylene,
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-
Dimaleimidebenzene, 5-ethyl-1,3-dimaleimidebenzene, 4,6-dimethyl-1,3-dimaleimidebenzene, 2,4,6-trimethyl-1,3-dimaleimidebenzene, 2,3 5,6-tetramethyl-1,
Bismaleimides such as 4-dimaleimidobenzene and 4-methyl-1,3-dimaleimidobenzene; trismaleimides such as tris (4-maleimidophenyl) methane; tetrakismaleimides such as bis (3,4-dimaleimidophenyl) methane Poly (4-maleimidostyrene), poly (3-maleimidostyrene), and polymaleimide obtained by maleidizing 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 since a cured product having excellent moldability and heat resistance can be easily obtained.

The polymaleimide compound represented by the general formula (1) can be easily synthesized 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) Component (b) in the present invention is a methallylphenol compound and / or a methallylphenyl ether compound having at least two methallyl groups in one molecule.

Preferred specific examples of the methallyl phenyl ether compound used in the present invention include the following b.
There are compounds described in-to b-. (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, compounds described in the following items b′- to b′-.

(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 methallylphenol compounds 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.

Component (c) Component (c) in the present invention is any of the following aromatic compounds, alicyclic compounds or acyclic compounds. i) an aromatic compound having at least two amino groups in one molecule and having an amino group in an aromatic ring, in which adjacent carbons are unsubstituted based on the carbon bonded to the amino group; ii) An alicyclic compound having at least two amino groups in an aliphatic ring and having an amino group in an aliphatic ring, wherein an adjacent carbon is unsubstituted based on the carbon bonded to the amino group; iii) at least two amino groups in one molecule Acyclic Compound Having Amino Group of Component (c) used in the present invention includes various compounds, and preferred specific examples include the amino compounds listed in the following items c- to c-.

C-: Diamines These are amino compounds having two amino groups in one molecule, and specific compounds include the following. That is,
Isophoronediamine, m-phenylenediamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) methane,
Bis (4-aminophenyl) ether, bis (3-aminophenyl) ether, 4,4'-biphenyldiamine, 3,3'-biphenyldiamine, 3,4'-biphenyldiamine, 5-ethyl-1,3- Phenylenediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, cyclohexylenediamine, 1,8-naphthalenediamine, 1,3-bis (aminomethyl) cyclohexane, 2,6-naphthalenediamine, 1,4-diaminobutane, 2,7-naphthalenediamine, 1,4-diamino-2-butanone, 1,2
-Diaminocyclohexane, bis (4-aminophenyl) sulfone, 1,10-diaminodecane, bis (3-
Aminophenyl) sulfone, 1,12-diaminododecane, 2,7 diaminofluorene, 1,7-diaminoheptane, 3,7-diamino-2-methoxyfluorene,
1,3-diamino-1,2-hydroxypropane, 9.1
0-diaminophenanthrene, diaminomaleonitrile, 3,6-diaminoacridine, 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,
6-diaminoanthraquinone, 2,8-diamino-6
Phenylphenanthridine, 1,2-diamino-2-methylpropane, bis (4-aminocyclohexyl) methane, 1,9-diaminononane, bis (3-aminocyclohexyl) methane, 1,8-diaminooctane, 2,2
-Bis [4- (4-aminophenyloxy) phenyl]
-1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-aminophenyl) -1,1,1,
3,3,3-hexafluoropropane, 1,4-bis (4-aminophenyl) benzene, 1,5-diaminopentane, 1,4-bis (4-aminophenyl) cyclohexane, 1,2-diaminopropane, Bis (4-aminophenyl) diphenylsilane, 1,3-diaminopropane, bis (4-aminophenyl) sulfide, bis (3
-Aminophenyl) sulfide, 2,4-diaminophenol, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfoxide, 2,2-bis (4-aminophenyl) propane, 2,2-bis [ 4-
(4-aminophenyloxy) phenyl] propane,
1,3-adamantanediamine and 1,4-bis (3-
Aminopropyl) piperazine and the like.

C-: Triamines This is an amino compound having three amino groups in one molecule, and specific compounds include tris (2-aminoethyl) amine and the like.

C-: Other amines Specific compounds include triethylenetetramine and tetraethylenepentamine. As the component (c) in the present invention, an aromatic diamine having two amino groups in one molecule is preferable.

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) and (c). Specifically, for example, it is preferable to decrease the component (c) in order to increase heat resistance, while it is preferable to increase the component (c) in order to increase adhesion characteristics and toughness. From such a viewpoint, the preferable mixing ratio of the components (a), (b) and (c) is as follows: component (a) / component (b)
Is from 0.05 to 20, more preferably from 0.1 to 5
And the molar ratio of component (a) / component (c) is 0.05 to
500, more preferably 0.1 to 50. If the proportions of the components (a), (b) and (c) deviate from the above ranges, the heat resistance and / or mechanical strength properties of the obtained cured resin may be reduced.

Component (d) The composition of the present invention may contain, as component (d), 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-
Examples include tetrazen, benzenesulfonyl azide and 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazen.

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

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

Component (e) -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 (e) -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 (e) -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 (e) -4 This component is a component for imparting various properties to the cured resin, and any component conventionally used as a component for modifying certain specific properties is used. Can be used. Preferred specific examples include the following. That is, it is a synthetic resin such as a phenol resin, an alkyd resin, a melamine resin, a fluorine resin, a vinyl chloride resin, an acrylic resin, a silicone resin, and a polyester resin.

The preferable addition amounts of these powdery or fibrous reinforcing materials or fillers, coloring agents, pigments, flame retardants, flame retardant auxiliaries, and synthetic resins are different depending on the application, but are not limited to molding materials or laminating materials. When using the composition of the invention, the total amount of the components (a), (b) and (c) 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 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.

[0035]

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 mol of bis [4-maleimidophenyl] methane as component (a) and 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl as component (b) 1 mol of propane and bis (4-
After 0.1 mol of aminophenyl) methane is uniformly mixed and melted at 100 ° C., 0.12 mol of dicumyl peroxide is added and poured into a Teflon mold.
The plate was cured by heating at 200 ° C. for another 2 hours to obtain a plate-shaped cured product. Table 1 shows the physical properties of the obtained cured product.

Examples 2-4 and Comparative Examples 1-6 Preparation of the compositions listed in Tables 1 and 2 as in Example 1
The curing by heating and the physical properties of the cured product were evaluated. The results are shown in Tables 3 and 4.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

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).

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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As can be seen by comparing the results in Tables 3 and 4, the cured product of the composition of the present invention has a glass transition point of about 240 ° C. or more, hardly decomposes at 400 ° C. or less, and has a high heat resistance. It has excellent mechanical properties such as tensile strength.

[0049]

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 (56) References JP-A-3-139524 (JP, A) JP-A-2-158626 (JP, A) JP-A-62-181335 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08

Claims (1)

(57) [Claims] 1. A thermosetting resin composition comprising the following components (a) and (b), wherein the thermosetting resin composition contains the following component (c). (A) Polymaleimide compound represented by the general formula (1) (Z in the formula is any divalent or higher residue of any of aliphatic, aromatic, alicyclic and heterocyclic residues excluding a condensed ring, and n
Is an integer of 2 or more. (B) a methallylphenol-based compound and / or a methallylphenylether-based compound having at least two methallyl groups in one molecule; and (c) any of the following aromatic compounds, alicyclic compounds or
Acyclic compounds i) aromatic compounds having at least two amino groups in one molecule
When the aromatic ring has an amino group, the carbon bonded to the amino group
An aromatic compound in which adjacent carbons are unsubstituted based on ii) at least two amino groups in one molecule,
When the aromatic ring has an amino group, the carbon bonded to the amino group
Alicyclic compounds in which adjacent carbons are unsubstituted based on iii) non-cyclic compounds having at least two amino groups in one molecule
Formula compound