JPH07258353A - Thermosetting resin composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a novel composition excellent in moisture absorption resistance and electrical properties without impairing the properties of polyimide. [Structure] Represented by the following formula and / or-
^{_{(R 3) n -C 6 H}} 4 -R 4 - bisalkenyl substituted nadimide, the thermosetting resin composition containing a maleimide compound and polymerizable monomer 1-3 hydrogen atoms are substituted with a hydroxyl group in the structure. [Chemical 1] (In the formula, R ¹ and R ² are independently selected hydrogen or a methyl group, n is an integer of 0 or 1, R ³ and R ⁴ may be the same or different, and are alkylene having 1 to 5 carbon atoms. Represents a group or a cycloalkylene group having 5 to 8 carbon atoms.)

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent workability, a cured product is uniform and exhibits excellent mechanical strength, heat resistance and moisture absorption resistance, and electrical characteristics. The present invention relates to a thermosetting resin composition that is useful as a molding material, an adhesive, a coating material, a coating material, and the like, and is also useful as a matrix resin for a composite material containing glass fiber, carbon fiber, or the like as a reinforcing material.

[0002]

2. Description of the Related Art In recent years, with the progress of science and technology, materials used have been required to have higher performance and higher functions, and various resin materials have been developed to meet the demand. Among them, 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.

Among the polyimide raw materials, bisnadiimide having a norbornene ring at both ends and an aromatic group in the molecule has hitherto attracted attention as an addition type polyimide resin raw material having extremely high heat resistance, and a part thereof. Has been put to practical use as a so-called matrix for advanced composite materials, and alkenyl-substituted nadiimide which is a derivative of the bisnadiimide is also known. The alkenyl-substituted nadiimide can improve the drawbacks of polyimide, which has a high curing temperature and has a problem in workability during curing, to a considerable extent, and various thermosetting resin compositions containing the same have been proposed. The present inventors previously synthesized an alkenyl-substituted nadimide having a structure different from these conventionally known alkenyl-substituted nadimides, and the cured product of the alkenyl-substituted nadimide was superior to the conventional cured product of alkenyl-substituted nadimide. Although it was found that it exhibits physical properties (Japanese Patent Application No. 5-22
No. 2258), these alkenyl-substituted nadiimides having a specific structure were insufficient in hygroscopic resistance and electric properties for use in the electric and electronic fields such as printed circuit boards.

[0004]

In view of the above-mentioned conventional techniques, an object of the present invention is to provide a novel composition having excellent moisture absorption resistance and electrical properties without impairing the properties of the polyimide having the specific structure. Especially.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to achieve the above-mentioned object, as a result of the novel specific structure proposed by the present inventors in Japanese Patent Application No. 5-222258. The present invention has been completed by discovering that a composition excellent in moisture absorption resistance and electrical characteristics can be obtained without impairing the characteristics of polyimide by combining a maleimide compound and a polymerizable monomer with an alkenyl-substituted nadiimide.

That is, the gist of the present invention is to provide a thermosetting resin composition containing the following components (A), (B) and (C): (A) General formula [1]

[Chemical 2] (In the formula, R ¹ and R ² are independently selected hydrogen or a methyl group, n is an integer of 0 or 1, R ³ and R ⁴ may be the same or different, and are alkylene having 1 to 5 carbon atoms. Group or a cycloalkylene group having 5 to 8 carbon atoms), and / or -of the bisalkenyl-substituted nadimide.
(R ³ ) _n —C ₆ H ₄ —R ⁴ — Bisalkenyl-substituted nadiimide in which 1 to 3 hydrogen atoms in the structure are substituted with hydroxyl groups (B) Maleimide compound (C) Polymerizable monomer.

The present invention will be described in more detail. Among the components (A) used in the present invention, a bisalkenyl-substituted nadiimide containing no hydroxyl group is disclosed in Japanese Patent Application No. 5-22.
Various bisalkenyl-substituted nadiimides according to No. 2258 can be used. That is, when R ³ or R ⁴ in the general formula [1] is an alkylene group having 1 to 5 carbon atoms, R ³ or R ⁴ is, for example, a methylene group,
Examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, a butylidene group, an s-butylidene group, a 1,2-dimethylethylene group, a 1,1-dimethylethylene group and a pentamethylene group, and R ³ or R ⁴ is a carbon number. When it is a cycloalkylene group of 5 to 8, R ³ or R ⁴ is, for example,
Cyclopentylene group, 2-methylcyclopentylene group,
Dimethylcyclopentylene group, cyclohexylene group, methylcyclohexylene group, ethylcyclohexylene group,
Examples thereof include a cycloheptylene group, a methylcycloheptylene group, and a cyclooctylene group.

An example of such a bisalkenyl-substituted nadiimide is N- [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximidomethyl) phenyl] allylbicyclo. [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- [4- (methallylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximidomethyl) phenyl] methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [4- (allylmethylbicyclo [2]] 1.2.1] hept-5-ene-2,3
-Dicarboximidomethyl) phenyl] allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximidomethyl) phenyl] methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide; N- [4- (allylbicyclo [ 2.2.1]
Hept-5-ene-2,3-dicarboximidoethyl) phenyl] allylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- [4-
(Metallylbicyclo [2.2.1] hept-5-ene-
2,3-Dicarboximidoethyl) phenyl] methallylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N- [4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximidoethyl) phenyl] allylmethylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- [4- (methallylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximidoethyl) phenyl] methallylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide; N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido), N, N′-m-xylylene-bis (methallylbicyclo [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, N'-m-
Xylylene-bis (methallylmethylbicyclo [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 (methallylbicyclo [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'-p
-Xylylene-bis (methallylmethylbicyclo [2.
2.1] hept-5-ene-2,3-dicarboximide) and the like. The component (A) used in the present invention is further a derivative of these bisalkenyl-substituted nadiimides, that is, -in the case of being represented by the general formula [1].
_{^{(R 3) n-C 6}} H 4 -R 4 - can be cited 1 to 3 hydrogen atoms in the structure were substituted with a hydroxyl group. Such bisalkenyl-substituted nadiimides may be used alone or in combination of two or more. Further, the bisalkenyl-substituted nadiimide may be used as an oligomer.

Examples of the maleimide compound as the component (B) used in the present invention include aliphatic maleimide, aromatic maleimide, aliphatic citracone imide, aromatic citracone imide and bismaleimides. Of these, examples of the aliphatic maleimide include maleimide, N-methylmaleimide, N-ethylmaleimide, and N.
-Propylmaleimide, N-laurylmaleimide, N-
Examples thereof include (2-hydroxyethyl) maleimide and N-cyclohexylmaleimide, and examples of the aromatic maleimide include 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
-(4-phenoxyphenyl) maleimide and the like, and examples of the aliphatic citraconic imide include citraconic imide, N-methyl citraconic imide, N-butyl citraconic imide, N-cyclohexyl citraconic imide and the like, and aromatic citraconic imide. Examples of the imide include N-phenylcitraconic imide, N- (3-ethylphenyl) citraconic imide, N- (2,6-dimethylphenyl) citraconic imide, N- (4-chlorophenyl) citraconic imide, and N- (4- Hydroxyphenyl) citraconimide, N- (4-benzylphenyl)
Examples thereof include citraconimide.

Further, as the bismaleimides, for example, bis (4-maleimidophenyl) methane, N, N '
-Phenylene bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidocyclohexyl) methane, N, N'-tolylene bismaleimide, N, N'-dimethylphenylenebis Maleimide, N, N'-xylylene bismaleimide, bis (4-maleimidophenyl) cyclohexane, N, N'-dichlorobiphenylene bismaleimide, bis [4- (methylmaleimido) phenyl]
Methane, bis [4- (methylmaleimide) phenyl] ether, bis [4- (methylmaleimide) phenyl] sulfone, N, N'-ethylene bismaleimide, N, N '
-Hexamethylenebismaleimide, N, N'-hexamethylenebismethylmaleimide and the like are used. In addition, these maleimides may be used alone, or may be used as a mixture of plural kinds, and may be used as an oligomer.

Examples of the polymerizable monomer which is the component (C) used in the present invention include styrene derivatives, unsaturated carboxylic acid esters or unsaturated carboxylic acid esters, bisphenols having unsaturated side chains, and triallyl isocyanurate. And triallyl cyanurate and the like. Examples of the styrene derivative include styrene, divinyl styrene, chlorostyrene, bromostyrene, tolyl styrene, and examples of the carboxylic acid unsaturated ester include o-, m-, p-diallyl phthalate, o-, m-,
p-phthalic acid dibutylene, o-, m-, p-phthalic acid dipentylene, o-, m-, p-phthalic acid dioctylene,
phthalic acid dialkenyl ester such as o-, m-, p-phthalic acid didecanylene, trimellitic acid trialkenyl ester such as trimellitic acid triallyl, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, Examples of the bisphenols having an unsaturated side chain include acrylic acid esters or methacrylic acid esters such as diethylene glycol dimethacrylate and hydroxyethyl methacrylate, and diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, dimethallyl bisphenol A, and dimethyl ester. Examples thereof include taryl bisphenol F and dimethallyl bisphenol S.

The mixing ratios of the above-mentioned component (A), component (B) and component (C) can be arbitrarily selected, but in general, the component ( It is the sum of the component (B) and the component (C) of A) {(B)
+ (C)} is mixed in a weight ratio (A) /
{(B) + (C)} is 96/4 to 10/90, preferably 80/20 to 20/80, and the weight ratio (B) / (C) of the component (B) to the component (C) is 80. / 20 to 20/8
0, preferably 70/30 to 30/70 is suitable.

Further, the composition of the present invention containing the components (A), (B) and (C) as essential components cures without using a polymerization catalyst, but a curing catalyst is used as the component (D). It will cure at a lower temperature or in a shorter time.
As the component (D), an organic peroxide, an onium salt,
Examples include cation catalysts and organic group-containing metal compounds.

Examples of the organic peroxide include di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetyl peroxide, dipropionyl peroxide and di-t-butyl peroxide.
i-butyryl peroxide, benzoyl peroxide,
Peroxysuccinic acid, t-butyl hydroperoxide,
Cyclohexyl hydroperoxide, cumene hydroperoxide, t-butylperoxybenzoate, t-butylperoxypivalate, 1,1-di-t-butylperoxycyclohexane, di- (t-butylperoxy) isophthalate, t-butylperoxymaleate , T-butylperoxyisopropyl carbonate,
2,2-di-t-butylperoxybutane and the like can be mentioned.

Examples of onium salts include ammonium compounds, phosphonium compounds, arsonium compounds, stibonium compounds, oxonium compounds, sulfonium compounds, selenonium compounds, stannonium compounds, and iodonium compounds. Examples of the ammonium compound include benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate, m-trifluoromethylphenyltrimethyl. Ammonium bromide, tetra-n
-Butyl ammonium trifluoromethane sulfonate, etc., as phosphonium compounds, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, 3-bromopropyltriphenylphosphonium bromide, etc., as arsonium compounds Is benzyltriphenylarsonium chloride, tetraphenylarsonium bromide, tetra-n-butylarsonium chloride, etc., as the stibonium compound, benzyltriphenylstibonium chloride, tetraphenylstibonium bromide, etc., and the oxonium compound, Sulfonation of triphenyloxonium chloride, triphenyloxonium bromide, etc. The objects, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, tri (p- methoxyphenyl) sulfonium hexafluorophosphate,
Tri (p-tolyl) sulfonium tetrafluoroborate, dimethylphenacylsulfonium hexafluorophosphate, dimethylphenacylsulfonium tetrafluoroborate, and the like. Examples of the selenonium compound include triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroarsenate, Triphenylselenonium hexafluoroantimonate,
Examples of stannonium compounds such as p- (t-butylphenyl) diphenylselenonium hexafluoroarsenate include triphenylstannonium chloride, triphenylstannonium bromide, tri-n-butylstannonium bromide and benzyldiphenylstanno. Examples of iodonium compounds such as aluminum chloride include 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- chlorophenyl) iodonium hexafluoroarsenate and the like.

As the cation catalyst, for example, sulfuric acid, dimethyl sulfuric acid, diethyl sulfuric acid, 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 sulfonic acid, ethyl p-toluene sulfonic acid, etc., or Bronsted acid that releases an acid, or its ester, amine complex; boron trichloride, boron trifluoride , Boron trifluoride / ether complex, iron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, aluminum chloride / pyridine complex, aluminum bromide, zinc chloride, antimony pentachloride, etc. Examples thereof include a complex with a base.

Typical examples of the organic group-containing metal compound are magnesium, zinc, titanium, vanadium,
Acetylacetone such as chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, lanthanum, cerium, hafnium, tantalum or tungsten, preferably magnesium, zinc, vanadium, manganese, iron or cerium. Mention may be made of salts, carboxylates, metallocenes, alcoholates, chelate compounds or organometallic compounds, more preferably acetylacetone salts or carboxylates of magnesium, zinc, vanadium, manganese, iron or cerium.

The amount of the component (D) as described above is not particularly limited and may be appropriately selected within a wide range, but with respect to the total amount of the component (A), the component (B) and the component (C). , Usually 0.005 to 10% by weight, preferably 0.01
~ 5 wt% is used.

The cured product of the composition of the present invention having the above-mentioned components has excellent workability similar to that of the polyimide having the specific structure, and the cured product is uniform and has excellent mechanical strength.
Since it exhibits heat resistance and further excellent moisture absorption resistance and electrical characteristics, it is useful in a wider field including the electric and electronic fields as compared with the polyimide.

The curing conditions of the thermosetting resin composition of the present invention differ depending on the form of use. For example, when used as a molding material, the component (A), the component (B) and the component (C) are used.
After melt-mixing the three components or component (A), component (B), component (C) and component (D), a molding method such as cast molding, injection molding or compression molding is applied to the composition. Then do. Curing molding is 50 to 260 ° C., preferably 80 to 25
0.5 to 20 hours at a temperature of 0 ° C., preferably 1 to 10
It is performed by heating for a time.

As another use form, when it is used as a paint or coating material, it is melt-mixed without a solvent, or a mixture made into a solution with a solvent is applied to an object, and if necessary, the solvent is removed and dried. The coating produced by
0.01-at a temperature of 60 ° C, preferably 80-220 ° C
It can be polymerized and cured by heating for 5 hours, preferably 0.05 to 2 hours to form a thin film or coating film.

By utilizing such curing and polymerization methods, the composition can be used as an adhesive or a filler.

The molded body, thin film, coating film, and adhesive body thus obtained may be further heat-treated at a temperature of 150 to 350 ° C. for 0.5 to 30 hours, if necessary.

Further, the composition is also useful as a matrix of a composite material, and upon polymerization and curing, various fillers such as glass fiber, carbon fiber, metal fiber, ceramic fiber, calcium phosphate, calcium carbonate are added if necessary. , Magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder, carbon black, etc., the total amount of component (A), component (B) and component (C) 10
There is no problem even if 10 to 500 parts by weight are mixed with 0 parts by weight.

[0025]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the contents of the present invention are not limited to these. In the following, "parts" means "parts by weight".

Examples 1 to 5 N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 as component (A)
-Dicarboximide) (hereinafter abbreviated as "BANI-X"), bis (4-maleimidophenyl) methane (hereinafter abbreviated as "BMI") as the component (B), and triallyl isocyanurate as the component (C). (Hereafter, "TA
Abbreviated as "IC". ) Is melt-mixed in the composition ratio shown in Table 1, and 1
It was placed on a hot plate exposed to 60 ° C. air, stirred while maintaining the temperature, and the gelation time was measured. The results are shown in Table 1.

Comparative Examples 1 and 2 In Examples 4 and 5, the component (A), BANI-X, was used.
Instead of bis [4- (allylbicyclo [2.2.1]]
Gelation time was measured by the same method as in Examples 4 and 5 except that hept-5-ene-2,3-dicarboximido) phenyl] methane (hereinafter abbreviated as "BANI-M") was used. did. The results are shown in Table 1.

[0028]

[Table 1]

Examples 6 to 10 Examples 1 to 5 except that diallyl m-phthalate (hereinafter abbreviated as "DAP") was used as the component (C) in place of TAIC. The gelation time was measured in the same manner as in. The results are shown in Table 2.

Comparative Examples 3 and 4 In Examples 9 and 10, the component (A) BANI-
Example 9 except that BANI-M was used instead of X
The gelation time was measured by the same method as described in 10 and 10. The results are shown in Table 2.

[0031]

[Table 2]

Examples 11 to 15 In Examples 1 to 5, as component (D), dicumyl peroxide (hereinafter referred to as "DCP"), which is an organic peroxide, is further used.
Abbreviated as "O". 1) was melt-mixed, placed on a hot plate exposed to air at 160 ° C., stirred while maintaining the temperature, and the gelation time was measured. The results are shown in Table 3.

[0033]

[Table 3]

Examples 16 to 20 Examples 11 to 15 are the same as Examples 11 to 15 except that the component (D) is changed to an onium salt of diphenyliodonium hexafluorophosphate (hereinafter abbreviated as "DPIHFP"). Gelation time was measured by the same method. The results are shown in Table 4.

[0035]

[Table 4]

Examples 21 to 25 Examples 11 to 15 except that the component (D) in Example 11 to 15 was changed to pyridine sulfate as a cation catalyst.
The gelation time was measured in the same manner as in. The results are shown in Table 5.

[0037]

[Table 5]

Examples 26 to 30 In Examples 11 to 15, component (D) was replaced with iron (III) acetylacetone salt (hereinafter referred to as metal group-containing metal compound).
Abbreviated as “FeAcAc”. ) Example 11 except that
The gelation time was measured in the same manner as in -15. The results are shown in Table 6.

[0039]

[Table 6]

Examples 31 to 35 In Examples 6 to 10, DC was further added as the component (D).
One part of PO was added, melt-mixed, placed on a hot plate exposed to air at 160 ° C., stirred while maintaining the temperature, and the gelation time was measured. The results are shown in Table 7.

[0041]

[Table 7]

Examples 36 to 40 In Examples 31 to 35, component (D) was added to DPIHFP.
The gelling time was measured by the same method as in Examples 31 to 35 except that the gelation time was changed to. The results are shown in Table 8.

[0043]

[Table 8]

Examples 41 to 45 In Examples 31 to 35, the gelling time was measured in the same manner as in Examples 31 to 35 except that the component (D) was changed to pyridine sulfate. The results are shown in Table 9.

[0045]

[Table 9]

Examples 46 to 50 In Examples 31 to 35, the component (D) was replaced with FeAcAc.
The gelling time was measured by the same method as in Examples 31 to 35 except that the gelation time was changed to. The results are shown in Table 10.

[0047]

[Table 10]

Examples 51-55 BANI-X as component (A) of various compositions, component (C)
As a component (B), BMI was added to the solution after adding TAIC as the component and heating at 160 ° C. to form a uniform solution.
The obtained uniform mixture was poured into a mold and cured under the following conditions.

First stage 160 ° C. for 2 hours Second stage 200 ° C. for 2 hours Third stage 250 ° C. for 5 hours

A test piece was prepared using this cured product, and the glass transition temperature (based on the TMA method, temperature at the inflection point of the coefficient of thermal expansion at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere), bending strength ( 3-point bending test, conforming to JIS K7203), flexural modulus (3-point bending test, conforming to JIS K7203),
Water absorption rate (according to JIS K7209), thermogravimetric reduction rate (according to TGA method, under nitrogen atmosphere, heating rate 10 ° C /
Minute 5% decrease in temperature), dielectric constant (JIS K6
911, measurement frequency 1MHz, dielectric loss tangent (JI
According to SK6911, measurement frequency 1 MHz) and the like were measured (the same applies hereinafter). The results are shown in Table 11.

Comparative Examples 5 and 6 In Examples 54 and 55, the BANI of component (A)
Thermoforming was performed in the same manner as in Examples 54 and 55 except that BANI-M was used instead of -X, and the physical properties of the obtained cured product were evaluated. The results are shown in Table 11.

Comparative Example 7 In Example 51, the component (C) and the component (B) were not used, but the component (A), BANI-X alone, was heat-molded,
The physical properties of the obtained cured product were evaluated. The results are shown in Table 11.

Comparative Example 8 In Example 51, the BMI of the component (B) alone was heat-molded without using the components (A) and (C), and the physical properties of the obtained cured product were evaluated. The results are shown in Table 11.

Comparative Example 9 Physical properties of a cured product obtained by heat molding in the same manner as in Comparative Example 7 except that BANI-M was used in place of BANI-X as the component (A) in Comparative Example 7. An evaluation was made. The results are shown in Table 11.

[0055]

[Table 11]

Examples 56 to 60 In Examples 51 to 55, TAIC was used as the component (C).
Examples 51-5 except that DAP was used in place of
Heat molding was performed in the same manner as in No. 5, and the physical properties of the obtained cured product were evaluated. The results are shown in Table 12.

Comparative Examples 10 and 11 In Examples 59 and 60, the BANI of component (A)
The thermosetting was performed in the same manner as in Examples 59 and 60 except that BANI-M was used instead of -X, and the physical properties of the obtained cured product were evaluated. The results are shown in Table 12.

[0058]

[Table 12]

[0059]

The thermosetting resin composition of the present invention has excellent workability similar to that of the polyimide having the above-mentioned specific structure, and the cured product shows uniform and excellent mechanical strength and heat resistance. Since it exhibits moisture absorption resistance and electric characteristics superior to those of the polyimide, it is useful in a wide range of fields including electric and electronic fields such as printed circuit boards.

Claims (3)

[Claims] 1. A thermosetting resin composition containing the following components (A), (B) and (C). (A) General formula [1] (In the formula, R ¹ and R ² are independently selected hydrogen or a methyl group, n is an integer of 0 or 1, R ³ and R ⁴ may be the same or different, and are alkylene having 1 to 5 carbon atoms. Group or a cycloalkylene group having 5 to 8 carbon atoms), and / or -of the bisalkenyl-substituted nadimide.
(R ³ ) _n -C ₆ H ₄ -R ⁴ -Bisalkenyl-substituted nadiimide in which 1 to 3 hydrogen atoms in the structure are substituted with hydroxyl groups (B) maleimide compound (C) polymerizable monomer 2. The thermosetting resin composition according to claim 1, which further contains, as the component (D), at least one curing catalyst selected from organic peroxides, onium salts, cation catalysts and organic group-containing metal compounds. object. 3. The weight composition ratio (A) / {(B) + (C)} of the component (A) to the component (B) and the component (C) is 9.
6/4 to 10/90, and the weight composition ratio (B) / (C) of the component (B) to the component (C) is 80/20 to.
The thermosetting resin composition according to claim 1 or 2, which is 20/80.