JPH07133393A - Resin composition - Google Patents

Abstract

(57) [Summary] [Structure] A resin composition containing the following components (A) and (B). Copolymer of (A) alkenyl-substituted nadiimide (B) (1) vinyl group-substituted aromatic hydrocarbon and / or vinyl group-substituted cyclic hydrocarbon and (2) maleimide compound [Effect] Composition having excellent compatibility The cured product has excellent toughness without impairing heat resistance, electrical characteristics and mechanical strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent toughness, compatibility and heat resistance, can be used without solvent, and is useful as a laminated material, a molding material and a composite material using glass, carbon fiber or the like as a reinforcing material. The present invention relates to a nadiimide resin composition.

[0002]

2. Description of the Related Art With recent advances in science and technology, materials used are required to have higher performance and higher functions, and various resin materials have been developed to meet these requirements. Of these, various high-performance polymers called so-called super engineering plastics (engineering plastics) such as polyetherketone, polyphenylene sulfide, and polyimide are on the market, and expectations for polyimide are particularly high. In particular, bisnadiimide having a norbornene ring at both ends and an aromatic group in the molecule has been attracting attention as an additive type polyimide resin raw material with extremely high heat resistance, and some of them are used for so-called advanced composite materials. It has been put to practical use as a matrix.
However, since the bisnadiimide generally has a high melting point and poor solubility in a solvent, it is difficult to handle and difficult to process.

Further, since the nadimide is poor in reactivity, harsh reaction conditions such as high-temperature molding at 300 ° C. or higher are required for high molecular weight. However, under such reaction conditions, there is a drawback that bubbles (voids) are remarkably generated in the molded body. This is the inverse Diels-Alder of the norbornene ring.
It is said that this is due to the highly volatile cyclopentadiene generated there.

In order to suppress such foaming, a molding method such as an autoclave molding method in which reaction is performed under high temperature and pressure, or an acid anhydride (ester) as a raw material of an imide and a diamine are dissolved in a solvent to form an oligomer, and a varnish is produced. However, the production method and use are considerably limited, and it is not industrially advantageous.

Therefore, in addition to adopting the above-mentioned means to suppress the foaming, the norbornene ring is added to the norbornene ring so that the curing reaction temperature is lowered or a volatile component is not generated even if the reverse Diels-Alder reaction occurs. Various methods for introducing an appropriate substituent have been studied.

As one of them, various methods of introducing an allyl group have been proposed (for example, JP-A-59-80662, JP-A-60-124619 and JP-A-60-1).
78862, JP 61-18761, JP 61-73710, JP 61-19755.
6, JP-A-62-111967, JP-A-6-6
2-253607, JP-A-63-95263, JP-A-63-150311, JP-A-63-1.
70358, JP-A-63-310884,
JP-A-63-317530 and JP-A-1-1975.
No. 16, etc.).

According to these, by introducing an allyl group, the melting point of the raw material imide is lowered, the solubility in the solvent is increased, the curing temperature can be lowered to some extent, and no volatile component is generated during curing, Moreover, it is reported that the physical properties of the obtained cured product were not significantly deteriorated. Such an alkenyl-substituted nadimide has good workability, and its cured product has excellent heat resistance, mechanical properties, electrical properties, and chemical stability. It is useful as a composite material, paint, adhesive, etc.

However, thermosetting resins are generally inferior to thermoplastic resins in terms of toughness, and alkenyl-substituted nadiimides are no exception. Therefore, in recent years, the toughness of alkenyl-substituted nadiimides has been required with the expansion of applications.

In general, various studies have already been conducted for improving the toughness of a thermosetting resin, and recently, a thermoplastic resin having a high heat resistance such as polysulfone, polyetherketone, polyetherimide and aromatic polyester is used as an epoxy resin. A method has been proposed in which the resin is added to a resin to increase the toughness while maintaining heat resistance. There is also an attempt to add polyetherimide or polyhydantoin to the toughness of the bismaleimide resin which is a thermosetting polyimide {In
t. SAMPE Symp. , Vol. 33,1546
(1988)}.

However, these thermoplastic resins have poor compatibility with epoxy resins and bismaleimide resins, and in many cases require the use of a solvent. Therefore, the resin composition is used in a film in which the solvent is easily removed by evaporation. However, there is a drawback that it is limited to thin films such as coating films.

[0011]

Therefore, an object of the present invention is to provide a composition which is free from the above-mentioned drawbacks of the prior art and has excellent compatibility, and the cured product of which has heat resistance, electrical characteristics and mechanical properties. It is to provide a novel resin composition containing an alkenyl-substituted nadiimide as a main component, which has excellent toughness without impairing strength.

[0012]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of such circumstances and found that an alkenyl-substituted nadiimide is blended with a copolymer of a vinyl group-substituted aromatic hydrocarbon and a maleimide compound. If so, a resin composition having good compatibility is obtained, and it is found that the cured product has not only excellent heat resistance and mechanical strength but also excellent toughness,
The present invention has been completed.

That is, the present invention provides a resin composition containing the following components (A) and (B). (A) Alkenyl-Substituted Nadiimide (B) Copolymer of (1) Vinyl Group-Substituted Aromatic Hydrocarbon and / or Vinyl Group-Substituted Cyclic Hydrocarbon and (2) Maleimide Compound

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

[0015]

[Chemical 1]

[Wherein R¹And R²Are the same or different
May represent a hydrogen atom or a methyl group, n is 1 or
Indicates an integer of 2. R³Has 1 carbon when n is 1.
~ 12 alkyl group, C3-6 alkenyl group, charcoal
Cycloalkyl group having 5 to 8 primes, monovalent with 6 to 12 carbon atoms
An aromatic group or a benzyl group of
_qH_2qO)_t(C_rH_2rO)_uC_vH_{2v + 1}] (Where q, r, and v are
Each represents an integer of 2 to 6, and t represents an integer of 0 or 1.
And u represents an integer of 1 to 30) or a group -C₆H_Four-T-C
₆H_Five(Where T is a group -CH₂-, -C (CH₃)₂−, −CO −, −
O-, -S-, -SO₂-Indicates).

R ³ has 2 to 2 carbon atoms when n is 2.
0 alkylene group, a cycloalkylene group of 5 to 8 carbon atoms, the group - _{[(C x H 2x O) y} (C z H 2z O) w C b H 2b ] - (wherein,
x, z, and b each represent an integer of 2 to 6, y represents an integer of 0 or 1, w represents an integer of 1 to 30), a divalent aromatic group having 6 to 12 carbon atoms, group _{-R-C 6 H 4 -R '} - in (wherein, R, R' is at least one of indicates a cycloalkylene group having 5 to 8 alkylene group or a carbon number of 1 to 4 carbon atoms and the other is a single bond, A C1-C4 alkylene group or a C5-C8 cycloalkylene group) or 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
-Indicates).

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

In the above formula (1), the group represented by R ³ may be an asymmetric alkylene / phenylene group, and examples of the group in this case include the following.

[0020]

[Chemical 2]

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

(N = 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) -allylmethylbicyclo [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-dicarboximide, N- (4'-hydroxyphenyl) -methallylbicyclo [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-dicarboximide, 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] -methallylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
{4 '-(4 "-hydroxyphenylisopropylidene) 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 '
-Trimethylene-bis (allylbicyclo [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-dicarboximido) propoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-phenylene-bis (allyl) Methylbicyclo [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 '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [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), 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-dicarboximide)
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- (allyl) Methylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 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-dicarboximide)
Phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -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-dicarboximide) 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-dicarboximido) -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 (allylmethylcyclo [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 "-(allyl Bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximido) -2 "-hydroxy-phenoxy} phenyl] propane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -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-dicarboximide) -5-hydroxy-phenyl} sulfone

The alkenyl-substituted nadimide of the present invention is not limited to these, and in the present invention, the "alkenyl-substituted nadimide" means a monomer having the above structure or an oligomer thereof. Such alkenyl-substituted nadiimides may be used alone or as a mixture thereof. The component (B) used in the present invention is (1) a vinyl group-substituted aromatic hydrocarbon or /
And a vinyl group-substituted cyclic hydrocarbon and (2) a copolymer produced from a maleimide compound, the vinyl group-substituted aromatic hydrocarbon as one component thereof is, for example, styrene, o-, m- or p. -Methyl styrene, o-, m- or p-ethyl styrene, o-, m- or pn-propyl styrene, m- or p-i-propyl styrene, o
-, M- or pn-butylstyrene, o-, m- or pt-butylstyrene, p-chlorostyrene, p-chloromethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-methyl- 6-vinylnaphthalene, 1
-Vinyl anthracene and the like.

Examples of the vinyl group-substituted cyclic hydrocarbon include vinylcyclopentane, vinylcyclohexane, 4-methylvinylcyclohexane, vinylcyclooctane, 3-methylvinylcyclooctane and vinylcyclododecane.

Examples of the maleimide compound used in the present invention include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide and Nn.
-Lauryl maleimide, N- (2-hydroxyethyl)
Maleimides, aliphatic maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, N- (2
-Methylphenyl) maleimide, N- (3-ethylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide,
N- (2,4,6-trimethylphenyl) maleimide,
N- (2-chlorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxymethylphenyl) maleimide, N- (4-carboxyphenyl) maleimide, N -(4-Ethoxycarbonylphenyl) maleimide, N- (4-benzylphenyl) maleimide, N
Examples include aromatic maleimides such as-(4-phenoxyphenyl) maleimide.

The compounds used in the present invention are not limited to the above exemplified compounds. The copolymer of the component (B) is generally obtained by radical polymerization, and the molar composition of (1) vinyl group-substituted aromatic hydrocarbon or / and vinyl group-substituted cyclic hydrocarbon and (2) maleimide compound in the copolymer. Ratio (1) / (2) is 30/70 to 70/3
0, particularly 45/55 to 55-45 is preferable, and the weight average molecular weight of the copolymer is 5,000 to 1,
It is preferably set to, 000,000, particularly 10,000 to 500,000.

The toughness of the cured product of the resin composition according to the present invention is as follows: (A) component alkenyl-substituted nadiimide and (B) component (1) vinyl group-substituted aromatic hydrocarbon or / and vinyl group-substituted ring. It varies depending on the mixing ratio of the formula hydrocarbon and the copolymer composed of the maleimide compound (2), the composition of the component (B), the molecular weight, and the like. Generally, as the mixing ratio of the component (B) to the component (A) increases, the toughness of the composition improves, but the heat resistance and mechanical strength tend to decrease, so that the physical properties of the final cured product, etc. Considering this, it is usually preferable that the weight composition ratio {(A) / (B)} of both components is 99/1 to 70 to 30, and particularly 97/3 to 80/20.

Further, the composition of the present invention containing the components (A) and (B) as essential components cures without using a polymerization catalyst, but the use of the polymerization catalyst can lead to a lower temperature or a shorter time. Harden. The polymerization catalyst used in the present invention includes a cation catalyst and an onium salt. Examples of the cation catalyst include sulfuric acid, dimethyl sulfuric acid, diethyl sulfuric acid, sulfuric acid / pyridine complex, phosphoric acid, phosphorous acid, phenylphosphonic acid, phenylphosphinic acid. , Triethyl phosphate, dimethyl phosphate, diphenyl phosphate, phenyl phosphite, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid / triphenylamine complex, p- Toluenesulfonic acid / pyridine complex, m-nitrobenzenesulfonic acid / pyridine complex, naphthalenesulfonic acid, methyl benzenesulfonate, p-toluenesulfonic acid methyl, p-
An acid or a Bronsted acid that liberates an acid, such as ethyl toluenesulfonate, its ester or amine complex, boron trichloride, boron trifluoride, boron trifluoride / ether complex, boron trifluoride / piperazine complex, iron trichloride , Tin tetrachloride, titanium tetrachloride, aluminum chloride, aluminum chloride / ether complex, aluminum chloride / pyridine complex, aluminum bromide, zinc chloride, antimony pentachloride, etc. Examples include, but are not limited to:

Examples of onium salts include benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltri-n-butylammonium chloride, benzyltri-n-butylammonium bromide, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, Ammonium compounds such as tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate, m-trifluoromethylphenyltrimethylammonium bromide and tetra-n-butylammonium trifluoromethanesulfonate; methyltriphenylphosphonium iodide, methyltriphenylphosphonium Bromide, benzyltriphenylphosphonium chloride, tetraf Sulfonyl bromide, 3-
Phosphonium compounds such as bromopropyltriphenylphosphonium bromide; arsonium compounds such as benzyltriphenylarsonium chloride, tetraphenylarsonium bromide, tetra-n-butylarsonium chloride;

Styvonium compounds such as benzyltriphenylstibonium chloride and tetraphenylstibonium bromide; oxonium compounds such as triphenyloxonium chloride and triphenyloxonium bromide; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarushi , Tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-tolyl) sulfonium tetrafluoroborate, dimethylphenacylsulfonium hexafluorophosphate, dimethylphenacylsulfonium tetrafluoroborate, diphenylphenacylsulfonium tetrafluoroborate, etc. Sulfonium compounds; triphenylselenonium tetrafluoroborate, tri Selenonium compounds such as phenylselenonium hexafluoroarsenate, triphenylselenonium hexafluoroantimonate, p- (t-butylphenyl) diphenylselenonium hexafluoroarsenate; 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,
Examples thereof include iodonium compounds such as di (p-chlorophenyl) iodonium hexafluoroarsenate, but are not limited thereto.

The amount of the cation catalyst or onium salt used as the polymerization catalyst of the present invention is not particularly limited and may be appropriately selected within a wide range, but is usually based on the total amount of the components (A) and (B). 0.005 to 10% by weight, preferably 0.1.
It is used in an amount of 01 to 5% by weight.

The method for mixing the alkenyl-substituted nadiimide as the component (A) and the copolymer as the component (B) is not particularly limited, and both are usually melt-mixed, but the use of a solvent is not hindered. . Since the resin composition of the present invention has excellent compatibility, it is not necessary to use a solvent, and its use is not limited to thin films such as films and coating films. Therefore, it is widely useful as a molding resin, a paint resin, a coating resin, a filling resin, and the like, and is particularly useful as a matrix resin for a composite material. Reinforcement when using the resin composition in a composite material, as the filler, for example, glass fiber, carbon fiber, metal fiber, ceramic fiber, calcium phosphate,
Examples thereof include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder and carbon black, and these are 10 to 500 per 100 parts of the resin composition. Partly mixed and used.

Further, as a usage form of the resin composition,
The component (A) and the component (B) are melt-mixed in the presence or absence of a polymerization catalyst without a solvent, or, if necessary, in the presence of a solvent and then the solvent is removed, and then the composition is melted. Directly into a mold and molded by a molding method such as cast molding, injection molding or compression molding, or the above melt is once cooled to a solid and further pulverized as necessary. A molding method is used in which a finely ground product is charged into a mold, and melting and molding are performed in the mold. Curing molding is 120-280
C., preferably at a temperature of 150 to 260.degree. C., 0.01 to
It is carried out by heating for 5 hours, preferably 0.05 to 2 hours.

As another use form of the resin composition, when it is used as a paint or a coating agent, the mixture is melt-mixed without a solvent, or a mixture obtained by mixing a solution in the presence of a solvent is applied to an adherend, and then 50- 300 ° C, preferably 80-28
At a temperature of 0 ° C., 0.001 to 1 hour, preferably 0.0
It can be polymerized and cured by heating for 05 to 0.5 hours to form a thin film or a coating film. The molded body, thin film, coating film, adhesive body, etc. thus obtained may be further heat-treated at a temperature of 200 to 350 ° C. for 0.1 to 30 hours, if necessary.

[0045]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is a composition having excellent compatibility, and the cured product thereof impairs excellent heat resistance, electrical characteristics and mechanical strength of the cured product of the alkenyl-substituted nadiimide. It has excellent toughness and can be used in a wide range of applications. That is, in a field requiring these excellent various properties, it can be used as a molding resin, a paint resin, a coating resin, a filling resin, and the like,
It is particularly useful as a matrix resin for composite materials. Further, the composition of the present invention has good compatibility of the components, and since it becomes a uniform mixture without using a solvent, the workability is improved, and the form of use is a varnish to form a thin film such as a coating film. The form to be formed is not limited.

[0046]

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 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point 74 ° C) was melted by heating to 200 ° C, and styrene / N-phenylmaleimide alternating co-polymer having a weight average molecular weight of 26,000 obtained by radical polymerization. 5% by weight
The mixture was added and stirring was continued at this temperature for 1 hour to completely dissolve the copolymer. Next, this melt was immediately poured into a simple mold made of two parallel glass plates using a fluororesin as a spacer, and kept under vacuum at a temperature of 200 ° C. for 4 hours to be completely deaerated. Then, put it in an air-circulation type constant temperature bath for 3 hours at 200 ° C., and further 250 hours at 225 ° C.
After curing by holding at 12 ° C for 12 hours, the temperature was lowered to 100 ° C over 6 hours at a constant rate. The mold was taken out from the constant temperature bath and allowed to cool at room temperature, then the test piece was taken out from the mold, ground with sandpaper and shaped into a predetermined size to obtain a test piece.

The glass transition temperature (Tg:
TMA method), fracture toughness value (K _IC : ASTM E399-
90), bending strength (3-point bending test, JIS K7
203), flexural modulus (3-point bending test, JIS
(According to K7203) and the like (the same applies hereinafter). The results are shown below.

Glass transition temperature: 283 (° C.) Fracture toughness value: 0.69 ± 0.02 (MN / m ^3/2 ) Bending strength: 125.5 ± 18.9 (MPa) Bending elastic modulus: 3.47 ± 0.20 (GPa)

Comparative Example 1 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point: 74 ° C) was obtained by the completely same operation as in Example 1 without adding the styrene / N-phenylmaleimide alternating copolymer. When the physical properties of the cured product were tested, the following results were obtained.

Glass transition temperature: 292 (° C.) Fracture toughness value: 0.57 ± 0.03 (MN / m ^3/2 ) Bending strength: 126.1 ± 13.6 (MPa) Bending elastic modulus: 3.44 ± 0.06 (GPa)

Example 2 Instead of adding 5% by weight of the styrene / N-phenylmaleimide alternating copolymer having a weight average molecular weight of 26,000 obtained by radical polymerization in Example 1, a weight obtained by radical polymerization was used. Styrene with an average molecular weight of 85,000 /
A cured product obtained by the completely same operation as in Example 1 except that 5% by weight of the N-phenylmaleimide alternating copolymer was added was subjected to a physical property test, and the following results were obtained. .

Glass transition temperature: 282 (° C.) Fracture toughness value: 0.71 ± 0.02 (MN / m ^3/2 ) Bending strength: 128.0 ± 13.3 (MPa) Bending elastic modulus: 3.39 ± 0.05 (GPa)

Example 3 Instead of adding 5% by weight of the styrene / N-phenylmaleimide alternating copolymer having a weight average molecular weight of 26,000 obtained by radical polymerization in Example 1, the weight obtained by radical polymerization A physical property test was conducted on a cured product obtained by performing the same operation as in Example 1 except that 5% by weight of a styrene / N-phenylmaleimide alternating copolymer having an average molecular weight of 280,000 was added. The result is as follows.

Glass transition temperature: 284 (° C.) Fracture toughness value: 0.71 ± 0.02 (MN / m ^3/2 ) Bending strength: 126.1 ± 11.5 (MPa) Bending elastic modulus: 3.46 ± 0.04 (GPa)

Example 4 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point: 74 ° C) was melted by heating to 200 ° C, and styrene / N-phenylmaleimide.N- having a weight average molecular weight of 197,000, which was obtained by radical polymerization. 5% by weight of cyclohexylmaleimide (90:10 mol ratio) alternating copolymer was added, and the cured product obtained by the completely same operation as in Example 1 was subjected to a physical property test. was gotten.

Fracture toughness value: 0.67 ± 0.02 (MN /
m ^3/2 ) Flexural strength: 98.2 ± 7.5 (MPa) Flexural modulus: 3.587 ± 0.113 (GPa)

Example 5 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point: 74 ° C) was melted by heating to 200 ° C, and styrene / N-phenylmaleimide.N- having a weight average molecular weight of 197,000, which was obtained by radical polymerization. 8% by weight of an alternating copolymer of cyclohexylmaleimide (90:10 mol ratio) was added, and stirring was continued at this temperature for 1 hour to completely dissolve the copolymer. Then, under vacuum, at a temperature of 200 ° C., 2
Hold for a while to completely degas. The solid obtained by cooling to room temperature is roughly crushed and packed into a simple mold made of two parallel glass plates using a fluororesin as a spacer,
It was melted by heating under vacuum at a temperature of 200 ° C. and kept at that temperature for 2 hours to be completely degassed. After that, it was put in an air circulation type thermostatic bath, and was held at 200 ° C. for 3 hours, 225 ° C. for 3 hours, and 250 ° C. for 12 hours to be cured, and then at a constant rate of 6
It took time and the temperature was lowered to 100 ° C. After taking out the mold from the constant temperature bath and allowing it to cool at room temperature, take out the test piece from the mold and polish it with sandpaper to shape it to the specified dimensions.
A physical property test showed that the fracture toughness value was 0.69 ±
It was 0.02 (MN / m ^3/2 ).

Example 6 In Example 5, styrene / N-phenylmaleimide.N-cyclohexylmaleimide (90:10 mol) obtained by radical polymerization and having a weight average molecular weight of 197,000.
Ratio) Instead of adding 8% by weight of the alternating copolymer, styrene / N-phenylmaleimide.N-cyclohexylmaleimide (9
(0:10 mol ratio) A physical property test was conducted on a cured product obtained by the same operation as in Example 5, except that 8% by weight of the alternating copolymer was added. The glass transition temperatures thereof were 298 and 209. (° C.), fracture toughness value is 0.67 ± 0.
It was 01 (MN / m ^3/2 ).

Example 7 In Example 1, instead of the styrene / N-phenylmaleimide alternating copolymer, styrene / N-phenylmaleimide.N-cyclohexylmaleimide (having a weight average molecular weight of 300,000 obtained by radical polymerization was used. 90:10
(Mole ratio) A cured product obtained by performing the same operation as in Example 1 except that 5% by weight of the alternating copolymer was added was subjected to a physical property test, and the following results were obtained.

Glass transition temperature: 294 and 214 (broad) (° C.) Fracture toughness value: 0.63 ± 0.01 (MN / m ^3/2 ) Bending strength: 112.2 ± 8.6 (MPa) Bending elasticity Rate: 3.535 ± 0.047 (GPa)

Example 8 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point 74 ° C) was melted by heating to 200 ° C, and styrene / N-phenylmaleimide.N- having a weight average molecular weight of 291,000 was obtained by radical polymerization. 6% by weight of cyclohexylmaleimide (80:20 mol ratio) alternating copolymer was added, and the cured product obtained by the completely same operation as in Example 1 was tested for physical properties. was gotten.

Fracture toughness value: 0.77 ± 0.02 (MN /
m ^3/2 ) Flexural strength: 73.3 ± 2.6 (MPa) Flexural modulus: 3.46 ± 0.10 (GPa)

Example 9 In Example 5, styrene / N-phenylmaleimide.N-cyclohexylmaleimide (90:10 mol ratio)
Instead of the alternating copolymer, styrene / N-phenylmaleimide / N-cyclohexylmaleimide (80:20) having a weight average molecular weight of 291,000 obtained by radical polymerization.
(Mole ratio) A cured product obtained by the completely same operation as in Example 5 except that 7% by weight of the alternating copolymer was added was subjected to a physical property test, and its glass transition temperatures were 301 and 209 (broad). ) (° C), fracture toughness value is 0.89 ±
It was 0.03 (MN / m ^3/2 ).

Example 10 In Example 9, styrene / N-phenylmaleimide.N-cyclohexylmaleimide (80:20 mol) obtained by radical polymerization and having a weight average molecular weight of 291,000 was used.
The ratio of the alternating copolymer was increased from 6% by weight to 7% by weight, except that the cured product obtained by the same operation as in Example 9 was subjected to a physical property test. The results were obtained.

Glass transition temperature: 303 and 206 (° C.) Fracture toughness value: 1.09 ± 0.03 (MN / m ^3/2 ) Bending strength: 69.2 ± 2.3 (MPa) Bending elastic modulus: 3 .584 ± 0.073 (GPa)

Example 11 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane (melting point: 74 ° C) was melted by heating to 200 ° C, and styrene / N-phenylmaleimide. 5% by weight of cyclohexylmaleimide (90:10 mol ratio) alternating copolymer was added, and stirring was continued for 1 hour at this temperature to completely dissolve the copolymer, and then the mixture was kept under vacuum at a temperature of 200 ° C. for 2 hours. And completely degassed. Next, the melt is heated to 180 ° C.
After lowering the temperature to 1% by weight of diphenyliodonium hexafluorophosphate and stirring to completely dissolve it, pour it into a simple mold made of two parallel glass plates using a fluororesin as a spacer, and lightly After degassing, put it in an air circulation type thermostat, hold it at 180 ° C for 3 hours, 200 ° C for 3 hours and 250 ° C for 10 hours to cure it, and then cool it to 100 ° C at a constant rate for 6 hours. did. The mold was taken out from the constant temperature bath and allowed to cool at room temperature, then the test piece was taken out from the mold, ground with sandpaper and shaped into a predetermined size to obtain a test piece. When the physical properties of this test piece were tested, the following results were obtained.

Fracture toughness value: 0.73 ± 0.03 (MN /
m ^3/2 ) Bending strength: 71.2 ± 1.3 (MPa) Bending elastic modulus: 3.51 ± 0.11 (GPa)

Example 12 The same as Example 11 except that 1% by weight of methyl p-toluenesulfonate was added instead of 1% by weight of diphenyliodonium hexafluorophosphate as a curing catalyst. When the cured product obtained by the operation was subjected to a physical property test, the following results were obtained.

Fracture toughness value: 0.69 ± 0.02 (MN /
m ^3/2 ) Bending strength: 69.3 ± 1.1 (MPa) Bending elastic modulus: 3.48 ± 0.12 (GPa)

Claims (3)

[Claims] 1. A resin composition containing the following components (A) and (B). (A) Alkenyl-Substituted Nadiimide (B) Copolymer of (1) Vinyl Group-Substituted Aromatic Hydrocarbon and / or Vinyl Group-Substituted Cyclic Hydrocarbon and (2) Maleimide Compound 2. The resin composition according to claim 1, further comprising a cation catalyst or an onium salt as a polymerization catalyst. 3. The weight composition ratio (A) / (B) of the component (A) and the component (B) is 99/1 to 70/30.
Or the resin composition according to 2.