JPH07166028A - Thermosetting resin composition - Google Patents

Abstract

(57) [Structure] Thermosetting containing alkenyl-substituted nadiimide as component (A), compound having at least one vinyl group as component (B) and / or cyclic olefin and phenol resin as component (C) A resin composition having a weight composition ratio (A) / {(B) + (C)} of component (A) to component (B) and component (C) of 20/8.
A thermosetting resin composition, which is 0 or more. [Effect] A composition having excellent compatibility between components, and the cured product thereof has excellent moisture absorption resistance and toughness without impairing heat resistance, electrical characteristics, mechanical strength, and low molding shrinkage. .

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in compatibility between components, moisture absorption resistance and toughness and can be used even without solvent.
Contains an alkenyl-substituted nadiimide useful as a casting material, molding material, coating material, paint, adhesive material, filling material, etc., and also as a matrix resin for composite materials such as glass fiber, carbon fiber, etc. The present invention relates to a thermosetting resin composition.

[0002]

2. Description of the Related Art By introducing an allyl group into nadiimide, which is one of the raw materials for thermosetting resins, the melting point of the raw material imide is lowered, the solubility in a solvent is increased, and the curing temperature can be lowered to some extent. Further, it is known that no volatile component is generated during curing, and that physical properties such as heat resistance, electrical characteristics and mechanical strength of the obtained cured product are not significantly deteriorated. However, thermosetting resins are generally inferior to thermoplastic resins in terms of toughness, and alkenyl-substituted nadiimides are no exception. In recent years, the toughness of alkenyl-substituted nadiimides has been demanded as applications have expanded. Further, in the electronic and electrical fields, moisture absorption resistance is a problem, but in general, polyimide has a drawback that it has a large water absorption rate due to its own imide bond, and alkenyl-substituted nadiimides also have insufficient moisture absorption resistance. there were.

Of these, various studies have been made in the past for improving only the toughness of the thermosetting resin, and recently, polysulfone, polyetherketone, polyetherimide, aromatic polyester and the like have high heat resistance. A method has been proposed in which a thermoplastic resin is added to an epoxy resin to enhance toughness while maintaining heat resistance. There is also an attempt to add a polyetherimide or polyhydantoin to the toughness of a bismaleimide resin which is a thermosetting polyimide {(Int.SAMPE Symp., Vol.33,1546 (1988)}).
These thermoplastic resins have poor compatibility with epoxy resins and bismaleimide resins, and in many cases require the use of a solvent. It has the drawback of being limited to thin films.

Further, a resin composition in which an alkenyl-substituted nadimide and an epoxy resin were combined was developed for the purpose of improving toughness and moisture absorption resistance (Japanese Patent Laid-Open No. 60-124).
No. 619), there was a drawback that the original heat resistance of the alkenyl-substituted nadiimide could not be maintained.

On the other hand, recently, a synthetic resin composition comprising a novolac type phenolic resin excellent in strength and moisture absorption resistance, divinylbenzene and ethylstyrene has been reported (JP-A-5-117337). However, the synthetic resin composition has a drawback that it is still insufficient in heat resistance, mechanical strength at high temperature, and molding shrinkage.

[0006]

Therefore, an object of the present invention is a composition which is free from the above-mentioned drawbacks of the prior art and has excellent compatibility between components, and its cured product has heat resistance and electrical characteristics. Another object of the present invention is to provide a thermosetting resin composition containing an alkenyl-substituted nadiimide, which has excellent moisture absorption resistance and toughness without impairing mechanical strength and low molding shrinkage.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of such circumstances, and found that if an alkenyl-substituted nadiimide is blended with a compound having at least one vinyl group and / or a cyclic olefin and a phenol resin. , A resin composition having good compatibility between components is obtained, and it is found that the cured product has not only excellent heat resistance, electrical characteristics, and mechanical strength but also excellent moisture absorption resistance and toughness, The present invention has been completed.

That is, the present invention is a thermosetting resin containing an alkenyl-substituted nadiimide as the component (A), a compound having at least one vinyl group as the component (B) and / or a cyclic olefin, and a phenol resin as the component (C). A resin composition, comprising (B) component and (C)
Weight composition ratio of component (A) to component (A) / {(B)
+ (C)} is 20/80 or more, and a thermosetting resin composition is provided.

As the alkenyl-substituted nadiimide as the component (A) used in the present invention, those represented by the following general formula (1) are preferable.

[0010]

[Chemical 1]

[In the formula, R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a methyl group, and n represents an integer of 1 or 2. When n is 1, R ³ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 12 carbon atoms.
Or showing a monovalent aromatic group or a benzyl group or a _{group, - {(C q H 2q} O) t (C r H 2r O) u C v H 2v + 1} ( where, q, r, v Each represent an integer of 2 to 6, t represents an integer of 0 or 1, and u represents an integer of 1 to 30) or a group -C ₆ H ₄ -T-C ₆ H ₅ (where T represents Is -CH _{2
-, - C (CH 3)} 2 -, - CO -, - O -, - S -, -
Indicates SO ₂ −. } Is shown.

R ³ has 2 to 2 carbon atoms when n is 2.
0 alkylene group, a cycloalkylene group of 5 to 8 carbon atoms, group _{- {(C x H 2x O} ) y (C z H 2z O) w C b H 2b} -
(Here, x, z, and b each represent an integer of 2 to 6, y represents an integer of 0 or 1, and w represents an integer of 1 to 30). Aromatic group, group -RC
₆ H ₄ — (R ′) _m — (where m represents an integer of 0 or 1, R and R ′ may be the same or different, and have 1 carbon atom (s).
Is an alkylene group having 4 to 4 or a cycloalkylene group having 5 to 8 carbon atoms. ) Or a group —C ₆ H ₄ —A—C ₆ H ₄ —
{Wherein A is _{-CH 2 -, - C (CH} 3) 2 -, - CO
-, - O -, - OC 6 H 4 C (CH 3) 2 C 6 H 4 O -, - S
-, - SO ₂ - shows a. } Is shown.

The hydrogen atom of the R ³ group is 1
It may be substituted with 3 to 3 hydroxyl groups. ]

[0014] The above formula (1) in a group -R-C ₆ represented by R ³ in the case of _{n = 2 H 4 - (R'} ) m - The asymmetrical alkylene phenylene groups contained in, for example, the formula Examples include those represented by (2), (3), (4), (5) and (6).

[0015]

[Chemical 2]

Typical examples of the alkenyl-substituted nadiimide represented by the general formula (1) are shown below.

(Where n is 1) N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N-methyl-methallylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(2-Ethylhexyl) -allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
Allyl-allylmethylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N-allyl-
Methalylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allylbicyclo [2.2.1] hept-5. -Ene-2,3-dicarboximide, N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2] .1] Hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2'-hydroxyethyl)-
Allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (2'-hydroxyethyl) -allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(2 ', 2'-dimethyl-3'-hydroxypropyl)
-Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 ', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2', 3'-dihydroxypropyl) -allyl Methylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (3'-hydroxy-1'-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (4'-hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(4'-hydroxyphenyl) -allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4'-hydroxyphenyl)
-Metallylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (4'-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(3'-Hydroxyphenyl) -allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (p-hydroxybenzyl)-
Allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- [2 '-(2 "-hydroxyethoxy) ethyl] -allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- [2 '-(2 "-hydroxyethoxy) ethyl]-
Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 '-(2 "-
Hydroxyethoxy) ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 '-(2 "-hydroxyethoxy)
Ethyl] -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
[2 ′-[2 ″-(2 ″ ″-hydroxyethoxy) ethoxy] ethyl] -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 ′
-[2 "-(2"'-hydroxyethoxy) ethoxy]
Ethyl] -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 '
-[2 "-(2"'-hydroxyethoxy) ethoxy]
Ethyl] -methallyl bicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- [4'-
(4 "-hydroxyphenyl isopropylidene) phenyl] -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [4 '-(4"-
Hydroxyphenylisopropylidene) phenyl] -allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- [4 '-(4 "-hydroxyphenylisopropylidene) phenyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide.

(Where n is 2) N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), N, N'-ethylene-
Bis (allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), N, N'-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N '
-Hexamethylene-bis (allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ), N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-cyclohexylene-bis (allylbicyclo [2.
2.1] hept-5-ene-2,3-dicarboximide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide), 1,2-bis [3 '-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy] ethane, 1,2-bis [3' -(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy] ethane, 1,2-bis [3 '-(methallylbicyclo [2.2.1]] Hept-5-ene-2,3-dicarboximido) propoxy] ethane, bis [2 '-[3 "-
(Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximido) propoxy] ethyl] ether, bis [2 ′-[3 ″-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy] Ethyl] ether, 1,4-bis [3 '-(allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide) propoxy] butane, 1,4-bis [3 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy ] Butane, N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), N, N'-p
-Phenylene-bis (allylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), N, N'-p
-Xylylene-bis (allylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), N- [4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximidomethyl) phenyl] allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), 2,2-bis [4 '-[4 "-
(Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide) phenoxy] phenyl]
Propane, 2,2-bis [4 '-[4 "-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximido) phenoxy] phenyl] propane, 2,2-bis [4 ′-[4 ″-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy] Phenyl] propane, bis [4
-(Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximido) phenyl] methane, bis [4- (allylmethylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximido) phenyl] methane, bis [4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane, bis [4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane, bis [4- (allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl] ether, bis [4- (allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximido) phenyl] ether, bis [4- (methallylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl] ether, bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] sulfone, bis [4 -(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] sulfone, bis [4- (methallylbicyclo [2.2.1] hept-5-ene -2,3-Dicarboximido) phenyl] sulfone, 1,6-bis (allylbicyclo [2.2.1] hept-5-ene-
2,3-Dicarboximido) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide)
-3,6-Dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis [3 '-(allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximido) propoxy] -3-hydroxy-pentane, 1,4
-Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-
Benzene, 1,4-bis (allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N'-p
-(2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p- (2-hydroxy) xylylene-bis ( Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), N, N'-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), 2,2-bis [4 '-[4 "-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 2 ″-
Hydroxy-phenoxy] phenyl] propane, bis [4- (allylmethylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide) -2-hydroxy-phenyl] methane, bis [3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 4-hydroxy-phenyl] ether, bis [3- (methallylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) -5-hydroxy-phenyl] sulfone.

The alkenyl-substituted nadiimide used in the present invention is not limited to these, and the "alkenyl-substituted nadimide" in the present invention means the above-mentioned monomer or oligomer thereof. Such alkenyl-substituted nadiimides may be used alone or as a mixture thereof.

As the compound having at least one vinyl group, which is one type of the component (B) used in the present invention, a divinyl compound or a monovinyl compound is generally used, and the divinyl compound is, for example, o-divinyl. Benzene, m-divinylbenzene, p-divinylbenzene, divinylnaphthalene, divinyl adipate,
1,5-hexadiene-3,4-diol, 1,3-butadiene, 1,4-pentadiene, 1,3-divinyl-
1,1,3,3-tetramethyldisiloxane, 3,9-
Divinyl-2,4,8,10-tetraoxaspiro [5.5] undecane, di-2-propenyl 1,2-benzenedicarboxylate, di-2-propenyl 1,3-benzenedicarboxylate, N-2- Propenyl-2-propen-1-amine, 1,1′-oxybisethene, 3,3 ′
-Oxybis-1-propene, 1,1'-thiobisethene, 1,1'-sulfonylbisethene, 2,2-dichloro-N, N-di (2-propenyl) acetamide and di-1-propenyl disulfide. And again
Examples of the monovinyl compound include ethylvinylbenzene, styrene, α-methylstyrene, vinylnaphthalene, acrylonitrile, vinyl esters of fatty acids, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and esters of these acids. Can be mentioned.

The cyclic olefin which is another type of the component (B) is, for example, cyclopentene, cyclohexene, 4-vinylcyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclopentadiene,
Dicyclopentadiene, 1,3-cyclohexadiene,
1,3-cycloheptadiene, 1,5-cyclooctadiene, indene and the like can be mentioned.

Among these, divinyl compounds are preferable to monovinyl compounds and cyclic olefins in view of reactivity of the resulting composition and workability of composition preparation. Among the divinyl compounds, o-divinylbenzene and p- Divinylbenzene, m-divinylbenzene, 1,2-benzenedicarboxylic acid di-2-propenyl, 1,3-benzenedicarboxylic acid di-2-propenyl, 3,9-divinyl-
2,4,8,10-Tetraoxaspiro [5.5] undecane is preferred. As the component (B), these compounds may be used alone or as a mixture.

The phenolic resin as the component (C) used in the present invention includes general phenolic resins produced from a phenolic compound and a formaldehyde-supplying substance, as well as aromatic carbons such as xylene and formaldehyde resin. Hydrogen resin, reaction product of xylene resin and phenol,
Also included are phenol alkyl resins synthesized by the reaction of phenol and dimethoxyxylene, phenol / dicyclopentadiene resins obtained by the reaction of phenol and dicyclopentadiene, and resins obtained by polymerizing paravinylphenol, isopropylphenol and the like. Moreover, the thing modified each can also be used, and several kinds may be mixed and used. Further, although the phenol resin can be used as a novolac type or a resol type, the novolac type is preferable from the viewpoint of compatibility with the components (A) and (B). The number average molecular weight of the phenol resin is 200 to 2000, preferably 300 to
900. In addition, as a phenolic compound which is a raw material of a general phenol resin, for example, phenol, cresol, xylenol, ethylphenol, p-ter
t-butylphenol, p-octylphenol, p-
Nonylphenol, p-cumylphenol, p-phenylphenol, hydroquinone, resorcin, catechol, bisphenol A, bisphenol F, benzophenol, methylcatechol, butylcatechol, cresolcin, methylhydroquinone, pyrogallol, dihydroxynaphthalene, trihydroxynaphthalene, or the like. And the like.

At least 1 part of the alkenyl-substituted nadiimide as the component (A) and the vinyl group as the component (B) of the present invention is used.
The mixing ratio of the compound having at least one and / or the cyclic olefin and the phenol resin as the component (C) can be arbitrarily selected, but is generally the sum of the component (B) and the component (C) {(B) When the mixing ratio of + (C)} is increased with respect to the component (A), the mechanical strength of the cured product is slightly lowered, but the moisture absorption resistance and toughness are remarkably improved. Also (A)
Increasing the mixing ratio of the components with respect to {(B) + (C)} tends to increase the mechanical strength and heat resistance of the cured product at high temperatures. Therefore, when the mechanical strength of the cured product is mainly considered, the mixing ratio of the three components is the weight composition ratio (A) / (A) component / (B) component and (C) component weight ratio.
It is appropriate that {(B) + (C)} is 20/80 or more. Also, in consideration of handling workability of the composition, curing speed, physical properties of the final target cured product, etc., the weight ratio (A) /
It is suitable that {(B) + (C)} is in the range of 96/4 to 20/80, preferably 80/20 to 20/80, and the weight ratio of the (B) component to the (C) component (B). ) / (C) is 60
/ 40 to 40/60 is suitable. When {(B) + (C)} is less than 4.0% by weight in the above blending ratio, the toughness and low water absorbency become insufficient. Also,
When the component (B) is 60% by weight or more in the mixing ratio of the component (B) and the component (C), the molding shrinkage ratio increases,
When the content of the component (C) is 60% by weight or more, the mechanical strength at high temperature becomes poor.

One of the components (D) used in the present invention
Examples of the organic peroxide as a seed include di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetyl peroxide, dipropionyl peroxide, di-i-
Butyryl peroxide, benzoyl peroxide, peroxysuccinic acid, t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, 1,1-di-t-butyl peroxycyclohexane. , Di- (t-butylperoxy)
Isophthalate, t-butylperoxymaleate, t
-Butyl peroxyisopropyl carbonate, 2,2
-Di-t-butylperoxybutane and the like can be mentioned.

Other one type of onium salt is, for example, benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium perchlorate, tetraethylammonium. Ammonium compounds such as tetrafluoroborate, m-trifluoromethylphenyltrimethylammonium bromide, tetra-n-butylammonium trifluoromethanesulfonate, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium Bromide, 3-bromopropyltriphenylphosphonium bromide, etc. Sulphonium compounds, benzyltriphenylarsonium chloride, tetraphenylarsonium bromide, arsonium compounds such as tetra-n-butylarsonium chloride, benzyltriphenylstibonium chloride, stebonium compounds such as tetraphenylstibonium bromide, triphenyloxo Oxonium compounds such as aluminum chloride and triphenyloxonium bromide, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-tolyl) sulfonium tetrafluoroborate , Dimethylphenacylsulfonium hexafluorophosphate, dimethylphenacylsulfonium tetra Sulfonium compounds such as luoroborate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroarsenate, triphenylselenonium hexafluoroantimonate, and selenonium such as p- (t-butylphenyl) diphenylselenonium hexafluoroarsenate Compounds, triphenylstannonium chloride, triphenylstannonium bromide, tri-n-butylstannonium bromide, stannonium compounds such as benzyldiphenylstannonium chloride, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium perchlorate, Diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, Diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, (p-methoxyphenyl) phenyliodonium tetrafluoroborate, di (2-nitrophenyl) iodonium hexafluoroarsenate, di (p-tolyl) iodonium hexafluorophosphate, di (P
Examples include iodonium compounds such as -chlorophenyl) iodonium hexafluoroarsenate.

As the other one type of cation catalyst, for example, sulfuric acid, dimethylsulfate, diethylsulfate, pyridine sulfate, phosphoric acid, phosphorous acid, phenylphosphonic acid,
Phenylphosphinic acid, triethyl phosphate, dimethyl phosphate, phenyl phosphite, methanesulfonic acid, trifluoromethanesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, benzenesulfonic acid, p- Toluenesulfonic acid, p-toluenesulfonic acid / triphenylamine complex, p-toluenesulfonic acid /
Pyridine complex, m-nitrobenzene sulfonic acid / pyridine complex, naphthalene sulfonic acid, methyl benzene sulfonate, p-toluene sulfonic acid ethyl etc. Acid or Bronsted acid releasing acid, or its ester, amine complex; boron trichloride, tri Halogen showing Lewis acidity such as boron fluoride, boron trifluoride / ether complex, iron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, aluminum chloride / pyridine complex, aluminum bromide, zinc chloride, antimony pentachloride. However, the compounds are not limited to these.

The amount of the organic peroxide, onium salt or cation catalyst which is the component (D) of the present invention is not particularly limited and may be appropriately selected within a wide range.
It is usually 0.005 to 10% by weight, preferably 0.01 to 5% by weight, based on the total amount of the components (A), (B) and (C).

Since the thermosetting resin composition of the present invention has excellent compatibility, it is not necessary to use a solvent. Therefore, the application is not limited to the application in the form of a varnish dissolved in a solvent. It is applicable to various uses. That is,
It is useful as a laminated material, a casting material, a molding material, a coating material, a paint, an adhesive material, a filling material, and the like, and is also useful as a matrix resin such as a composite material having glass fiber, carbon fiber, or the like as a reinforcing material. Examples of reinforcing and fillers when the resin composition is used in a composite material include glass fiber, carbon fiber, metal fiber, ceramic fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide. , Gypsum, silica, alumina, clay, talc, quartz powder, carbon black and the like, and these are used by mixing 10 to 500 parts with respect to 100 parts of the thermosetting resin composition.

Curing of the thermosetting resin composition of the present invention is generally carried out by heating at 50 to 260 ° C. for 0.01 to 20 hours. The curing conditions vary depending on the form of use, for example, when used as a molding material,
Three components of (A), (B) and (C) or (A),
After the four components (B), (C) and (D) are melt-mixed, a molding method such as cast molding, injection molding, compression molding or the like is adopted, and the curing temperature is 50 to 260 ° C., preferably 80 to 2
50 ° C., curing time 0.5 to 20 hours, preferably 1 to 1
It's 0 hours. In addition, as another usage form, when it is used as a paint or coating material, it is melt-mixed without a solvent,
Alternatively, the mixture obtained by mixing the solutions in the presence of a solvent is applied to an adherend, and then the solvent is removed if necessary,
0.01-5 at a temperature of 80 ° C, preferably 80-220 ° C.
It can be polymerized and cured by heating for a time, preferably 0.05 to 2 hours, to form a thin film or a coating film.

If necessary, the molded body, composite material, thin film, coating film, adhesive body, etc. obtained under the above-mentioned curing conditions may be used.
Further heat treatment may be performed at a temperature of 0 to 350 ° C. for 0.5 to 30 hours.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited to these.

Example 1 As the component (A), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-
90 parts by weight of 2,3-dicarboximide) (hereinafter referred to as BANI-H) and 5 parts by weight of a mixture of 81% divinylbenzene and 19% ethylstyrene (manufactured by Sankyo Kasei Co., Ltd.) as the component (B). Novolak type phenolic resin (trade name: Praiofen TD-20)
93: 5 parts by weight of Dainippon Ink and Chemicals, Inc. and 3 parts by weight of a 30% phenol solution of xylene sulfonic acid as component (D) were added, and the mixture was stirred at 80 ° C. to obtain a solution. This solution was treated as follows and cast-molded. 1st stage 150 ° C for 3 hours 2nd stage 200 ° C for 2 hours 3rd stage 225 ° C for 2 hours 4th stage 250 ° C for 10 hours

A test piece was prepared using this cured product, and the thermogravimetric reduction rate (the temperature at the time of 5% reduction at a temperature rising rate of 5 ° C./min in a nitrogen atmosphere according to the TGA method) and fracture toughness value ( K
_IC : ASTM D5045-91A), molding shrinkage (JIS K6911), tensile strength (JIS)
Conforms to K7113, type 1 test piece is used), water absorption (J
IS K7209), bending strength (3-point bending test,
JIS K7203), flexural modulus (3-point bending test, JIS K7203), etc. were measured (the same applies hereinafter). The results are shown in Table 1.

Example 2 Example 1 was repeated except that the amounts of component (A), component (B) and component (C) were changed to 50 parts by weight, 25 parts by weight and 25 parts by weight, respectively. Heat molding was carried out in the same manner, and physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Example 3 In Example 2, the component (A), BANI-H, was replaced with N,
N'-m-xylylene-bis (allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide) (hereinafter referred to as BANI-X), except that the resin was heat-molded in the same manner as in Example 2 to obtain a cured resin product. The physical properties were evaluated. The results are shown in Table 1.

Example 4 In Example 2, the component (A) BANI-H was replaced with bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl]. Example 2 except that methane (hereinafter referred to as BANI-M) was used.
Heat molding was performed in the same manner as above, and physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Example 5 Example 4 was repeated except that the amounts of component (A), component (B) and component (C) were changed to 80 parts by weight, 10 parts by weight and 10 parts by weight, respectively. Heat molding was performed in the same manner as above, and physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Example 6 Example 4 was the same as Example 4 except that the amounts of component (A), component (B) and component (C) were 20 parts by weight, 40 parts by weight and 40 parts by weight, respectively. Heat molding was carried out in the same manner, and physical properties of the obtained resin cured product were evaluated.
The results are shown in Table 1.

Example 7 In the same manner as in Example 2 except that the compounding amount of the component (D) was changed to 1 part by weight, heat molding was carried out in the same manner as in Example 2, and the physical properties of the obtained resin cured product were evaluated. It was The results are shown in Table 1.

Example 8 In Example 2, the xylene sulfonic acid 3 of the component (D) was used.
Heat-molding was carried out in the same manner as in Example 2 except that the 0% phenol solution was changed to di (p-chlorophenyl) iodonium hexafluoroarsenate, and the physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Example 9 In Example 2, the xylene sulfonic acid 3 of the component (D) was used.
Heat-molding was performed in the same manner as in Example 2 except that the 0% phenol solution was changed to p-toluenesulfonic acid / pyridine complex, and the physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Example 10 In Example 2, the novolac type phenol resin of the component (C) was replaced with a resol type phenol resin (trade name: Sumicon P
R-175: manufactured by Sumitomo Bakelite Co., Ltd., and heat-molded in the same manner as in Example 2 except that the component (D) was not added, and physical properties of the obtained resin cured product were evaluated. . The results are shown in Table 1.

Comparative Example 1 Comparative Example 1 was the same as Example 1 except that the amount of the component (A), BANI-H, was 100 parts by weight, and the components (B) and (C) were not added. Heat molding was carried out in the same manner, and physical properties of the obtained resin cured product were evaluated.
The results are shown in Table 1.

Comparative Example 2 In Comparative Example 1, the component (A), BANI-H, was replaced with BAN.
The cured resin was heat-molded in the same manner as in Comparative Example 1 except that it was changed to IX, and the physical properties of the obtained cured resin were evaluated. The results are shown in Table 1.

Comparative Example 3 In Comparative Example 1, the component (A), BANI-H, was replaced with BAN.
Heat-molding was carried out in the same manner as in Comparative Example 1 except for changing to IM, and the physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Comparative Example 4 In Example 1, the component (A) was not blended, but the component (B) was used.
Heat-molding was carried out in the same manner as in Example 1 except that the compounding amounts of the component (C) and the component (C) were each 50 parts by weight, and the physical properties of the resulting cured resin product were evaluated. The results are shown in Table 1.

Comparative Example 5 In Example 1, the component (C) was not added, but the component (A) was used.
Heat-molding was carried out in the same manner as in Example 1 except that the compounding amounts of the component (B) and the component (B) were each 50 parts by weight, and the physical properties of the obtained resin cured product were evaluated. The results are shown in Table 1.

Comparative Example 6 In Example 1, the component (B) was not added, but the component (A) was used.
Heat-molding was carried out in the same manner as in Example 1 except that the compounding amounts of the component (C) and the component (C) were each 50 parts by weight, and the physical properties of the resulting cured resin product were evaluated. The results are shown in Table 1.

[0050]

[Table 1]

Notes to Table 1 1) N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 2) N, N'-m -Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 3) bis [4- (allylbicyclo [2.2.1] hept-5-ene- 2,3-Dicarboximido) phenyl]
Methane 4) Mixture of 81% divinylbenzene and 19% ethylstyrene (manufactured by Sankyo Kasei Co., Ltd.) 5) Novolac type phenol resin (trade name Praiofen TD-2093: manufactured by Dainippon Ink and Chemicals, Inc.) 6) Resol type phenol resin (trade name: Sumicon PR-
175: Sumitomo Bakelite Co., Ltd.) 7) Xylenesulfonic acid 30% phenol solution 8) Di (p-chlorophenyl) iodonium hexafluoroarsenate 9) p-toluenesulfonic acid / pyridine complex

Comparing Examples 1 to 10 with Comparative Examples 1 to 6, Comparative Example 1 using only the component (A) and the component (D)
In the case of 3, the water absorption rate is high and the moisture absorption resistance is insufficient. In the case of Comparative Example 4 in which the component (B), the component (C) and the component (D) were used, the thermal weight loss point of 5% was low, the heat resistance was insufficient, the molding shrinkage ratio was high, and further at 200 ° C. Bending strength is also low. Component (A), component (B) and component (D)
In the case of Comparative Example 5 in which No. 1 was used, the molding shrinkage rate is high and the bending strength at 200 ° C. is also low. In the case of Comparative Example 6 using the component (A), the component (C) and the component (D),
The thermal weight loss point of 5% is low and the heat resistance is insufficient.
The bending strength at 0 ° C is also low.

[0053]

EFFECT OF THE INVENTION The thermosetting resin composition of the present invention is a composition having excellent compatibility between the respective components, and the cured product thereof has excellent heat resistance and electrical characteristics of the alkenyl-substituted nadiimide cured product. Since it has excellent moisture absorption resistance and toughness without impairing mechanical strength and low molding shrinkage, it can be used in a wide range of fields including electronic and electrical fields, for laminated materials, casting materials,
It is useful as a molding material, a coating material, a paint, an adhesive material, a filling material and the like, and also as a matrix resin such as a composite material having glass fiber, carbon fiber or the like as a reinforcing material. Further, the composition of the present invention has good compatibility between components, and becomes a uniform mixture without the use of a solvent, so that workability is improved and a varnish is used as a film, a thin film such as a coating film. The composition is not limited to the above-mentioned form, and the mixing ratio of the components can be largely changed according to the purpose, and a uniform cured product can be provided.

Claims (3)

[Claims] 1. A thermosetting resin composition comprising an alkenyl-substituted nadimide as the component (A), a compound having at least one vinyl group as the component (B) and / or a cyclic olefin, and a phenol resin as the component (C). There is (A) for component (B) and component (C)
The weight composition ratio (A) / {(B) + (C)} of the components is 20 /
80 or more, The thermosetting resin composition characterized by the above-mentioned. 2. An organic peroxide as component (D),
The thermosetting resin composition according to claim 1, which contains at least one type of polymerization catalyst selected from an onium salt and a cationic catalyst. 3. The weight composition ratio (A) / {(B) + (C)} of component (A) to component (B) and component (C) is 96/4 to 20/80, and the weight ratio is (B) /
(C) is 60 / 40-40 / 60, The thermosetting resin composition of Claim 1 or 2.