JPH0770288A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a new resin component capable of producing a thermosetting resin composition excellent in adhesivity to metals, etc., adhesiveness, heat resistance and mechanical properties and useful as a laminating material, etc., by its mixing with an epoxy resin and a curing catalyst. CONSTITUTION:A bisalkenyl-substituted diimide of formula I [R<1> and R<2> are each H, methyl; E is an alkylene or a phenylene group of formula II ((a) is 0 or 1; R<3> and R<3>' are each a 1-4C alkylene, a 5-8C cycloalkylene)], e.g. N,N'-m- xylylene-bis(allylbicyclo[2,2,1] hepto-5-ene-2,3-dicarboxyimide. This compound of formula I can be obtained by reaction of an alkenyl-substituted bicyclo[2,2,1] hepto-5-ene-2,3-dicarboxylic anhydride derivative of formula III with a diamine of the formula H2N-E-NH2.

Description

Detailed Description of the Invention

[0001]

The present invention has excellent workability,
The present invention also relates to a thermosetting resin composition that gives a cured product having excellent mechanical strength and heat resistance. More specifically, it relates to a thermosetting resin composition containing an epoxy resin and a bisalkenyl-substituted nadimide having a specific structure, which is a novel substance, as a resin component. This resin composition is useful as a laminate material, a casting material, a molding material, an adhesive, a paint, a coating agent, and the like, and is also useful as a composite material having glass fiber or carbon fiber as a reinforcing material.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins have been used in considerably large amounts in the electric / electronic fields, aviation / space fields, automobile / vehicle fields and the like. However, with the recent trend toward higher performance, smaller size, and lighter weight of equipment, the materials used in these fields have become thinner, and exposed to high temperatures for a long time. Development of a thermosetting resin having excellent mechanical properties, especially mechanical strength, heat resistance and environment resistance is required.

Conventionally, in the field, epoxy resin,
Maleimide resins, nadiimide resins and polyimide resins have been used. However, the epoxy resin is excellent in mechanical properties and electrical properties, but the heat resistance is not always sufficient, and the condensation type polyimide resin is excellent in heat resistance, but most of them are insoluble, Since it is infusible, molding and processing were difficult. Further, addition type bismaleimide resin and bisnadiimide resin have been developed, but a cured product obtained by thermally polymerizing the bisnadiimide resin has high heat resistance but is extremely brittle.
Cracks are easily generated by thermal shock, and the heat resistance of the cured product of the bisnadiimide resin is as high as that of the bismaleimide resin, but the moldability is extremely poor. None of them is practically usable. It was

As a resin which can improve the above-mentioned drawbacks, can take full advantage of the excellent heat resistance characteristic of the addition type bismaleimide resin and bisnadiimide resin, and can withstand practical use, N, N '-4, 4'
Polyaminobismaleimide, a prepolymer of -diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane, has been developed. However, although the polyamino bismaleimide shows excellent heat resistance, it has a problem that it has a high melt viscosity and is difficult to cast, and that voids are easily generated during curing, which causes deterioration of physical properties. In the system, the raw material acid anhydride (ester) and diamine are dissolved in a solvent to be oligomerized and used as a varnish, or harsh reaction conditions (for example, high temperature molding such as 300 ° C.) are required to obtain a high molecular weight. However, there is a problem that a special curing method must be adopted.

Therefore, a thermosetting resin composition has been proposed which has both excellent mechanical properties and electrical properties of an epoxy resin and excellent heat resistance of an addition type polyimide resin.

For example, a method of blending polyamino bismaleimide with an epoxy resin (Japanese Patent Publication No. 47-42160) is considered to be effective, and several related inventions (Japanese Patent Publication No. 53-34895) have been filed. ing.
However, although the combination of these resins has good compatibility, since polyamino bismaleimide has a relatively high melting point, it requires a high temperature to be mixed with the epoxy resin, and the residual amine and epoxy resin in the imide are required. However, there is a problem in that the stability of the polyaminobismaleimide is poor and the workability is adversely affected.

Also, with respect to a combination of a bismaleimide resin such as N, N'-4,4'-diphenylmethane bismaleimide and an epoxy resin, the compatibility of both components is not good, so that they are made compatible in a solventless system. Requires a high temperature, and after compatibilization, crystals tend to precipitate with a decrease in temperature, which shortens the pot life.

Recently, a bisalkenyl-substituted nadiimide having a lower melting point than that of polyaminobisnadimide and giving a cured product having more excellent heat resistance has been developed. This resin has a very good compatibility with an epoxy resin, and an imidazole catalyst is added to a composition comprising the bisalkenyl-substituted nadiimide and an epoxy resin to cure the resin (JP-A-60-124619). 61-1
8761). Further, the present inventors previously used a composition in which an epoxy resin was combined with the bisalkenyl-substituted nadiimide, and used an onium salt as a catalyst, or a specific catalyst in which an onium salt and a weak reducing agent or copper benzoate were combined. And that the composition can be cured at a relatively low temperature, and the storage stability of the composition is improved, and an alkenyl-substituted nadiimide-
A composition comprising an epoxy resin-onium salt catalyst was proposed (Japanese Patent Application No. 4-136370). These compositions have improved molding and processability, and the cured products obtained have high heat resistance, but their mechanical strength has not yet been sufficiently high.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides an epoxy resin having good adhesiveness and mechanical properties and low cost, heat resistance,
Good flame retardancy and compatibility, low melting point, and by combining a bisalkenyl-substituted nadiimide of a specific structure, which is a novel substance having excellent mechanical properties, by further adding a curing catalyst to the mixed resin composition, An attempt is made to provide a thermosetting resin composition which has a good workability, and in which a curing reaction proceeds at a relatively low temperature for a short time, and which provides a cured product having both excellent properties, particularly excellent mechanical strength. It is a thing.

[0010]

The present inventors have previously found that the cured product thereof exhibits extremely excellent adhesion and adhesion to metals and the like as compared with conventional alkenyl-substituted nadiimides, and also has high heat resistance and mechanical strength. We proposed a novel alkenyl-substituted nadiimide having a specific structure, which is also excellent in properties (filed on August 13, 1993).

Further studies were conducted to apply and develop the unique properties of this novel alkenyl-substituted nadiimide. When a composition was formed by adding an epoxy resin and a curing catalyst to this novel alkenyl-substituted nadiimide, The cured product of this composition exhibits the unique properties of the novel alkenyl-substituted nadiimide, and has a higher adhesiveness to a metal, etc., than the cured product of the composition comprising a conventional alkenyl-substituted nadimide, an epoxy resin and a curing catalyst. The present invention has been completed by finding out that they are excellent in terms of adhesion, heat resistance and mechanical properties, and particularly excellent in mechanical strength.

That is, the gist of the present invention is (A) epoxy resin, (B) general formula [1].

[Chemical 5] {In the formula, R ¹ and R ² are independently selected hydrogen or a methyl group, and E is a general formula [2].

[Chemical 6] (In the formula, a is an integer of 0 or 1, and R ³ and R ^{3 ′} are independently selected C _{1 to} C ₄ alkylene groups or C ₅
It represents a cycloalkylene group -C _8. ) Represents an alkylene-phenylene group. } The thermosetting resin composition characterized by containing the bisalkenyl substituted nadimide represented by these, and (C) hardening catalyst as an essential component.

The thermosetting resin composition of the present invention has good compatibility and workability, causes a curing reaction at a relatively low temperature in a short time, and has a high mechanical strength, heat resistance, adhesiveness,
It gives a cured product having excellent adhesion and flame retardancy, and particularly excellent mechanical strength.

The present invention will be described in more detail. The epoxy resin as the component (A) used in the present invention is not particularly limited, and all known epoxy resins can be used. For example, a bisphenol-type epoxy resin obtained by the reaction of bisphenol and epichlorohydrin, a novolak-type epoxy resin obtained by the reaction of phenol novolak resin or cresol novolak resin and epichlorohydrin, a polyphenol obtained by the reaction of polychlorophenol such as resorcinol or hydroquinone, and epichlorohydrin. Hydroxybenzene type epoxy resin, nitrogen-containing epoxy resin obtained by reaction of aromatic amines such as toluidine and aniline with epichlorohydrin, cyclohexene, vinylcyclohexene,
Cyclopentadiene, alicyclic epoxy resin starting from dicyclopentadiene, butanediol, hexanediol, glycerin, trimethylolpropane,
Examples thereof include, but are not limited to, di- or polyglycidyl ethers such as pentaerythritol, silicon-containing epoxy resins obtained by reacting an epoxy resin with silanol, and epoxy resins having a nitrogen-containing heterocycle obtained from isocyanuric acid. . These epoxy resins are used alone or as a mixture of two or more kinds.

The bisalkenyl-substituted nadiimide having a specific structure, which is the component (B) used in the present invention, has the general formula [1]

[Chemical 7] {In the formula, R ¹ and R ² are independently selected hydrogen or a methyl group, and E is a general formula [2].

[Chemical 8] (In the formula, a is an integer of 0 or 1, and R ³ and R ^{3 ′} are independently selected C _{1 to} C ₄ alkylene groups or C ₅
It represents a cycloalkylene group -C _8. ) Represents an alkylene-phenylene group. } A bisalkenyl-substituted nadimide represented by the general formula [3]

[Chemical 9] (In the formula, R ¹ and R ² each independently represent hydrogen or a methyl group.) Alkenyl-substituted bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid An anhydride derivative (hereinafter abbreviated as “alkenyl-substituted nadic acid anhydride derivative”) and a general formula [4]

[Chemical 10] {In the formula, E is a general formula [2]

[Chemical 11] (In the formula, a is an integer of 0 or 1, and R ³ and R ^{3 ′} are independently selected C _{1 to} C ₄ alkylene groups or C ₅
It represents a cycloalkylene group -C _8. ) Represents an alkylene-phenylene group. } And is synthesize | combined by reaction with the diamine of the specific structure represented.

Representative examples of the alkenyl-substituted nadic acid anhydride derivative represented by the general formula [3] include, for example, allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboxylic anhydride, methallylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, allylmethylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboxylic anhydride and methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-
An example is a dicarboxylic acid anhydride.

As the diamine represented by the general formula [4], E is a phenylene-alkylene structure, for example, a phenylene-methylene group (wherein phenylene is
Any of o-, m- or p-bonding forms may be used, and the same applies hereinafter. ), Phenylene / ethylene group, phenylene / trimethylene group, phenylene / tetramethylene group,
Phenylene ・ butylidene group, phenylene ・ s-butylidene group, phenylene ・ 1,2-dimethylethylene group, phenylene ・ 1,1-dimethylethylene group, phenylene ・
1,2-cyclopentenylene group, phenylene-1,3-
Cyclopentenylene group, phenylene-1,4-cyclopentenylene group, phenylene-2-methyl-1,4-cyclopentenylene group, phenylene-2,3-dimethyl-
1,4-cyclopentenylene group, phenylene-1,2-
Cyclohexenylene group, phenylene / 1,4-cyclohexenylene group, phenylene-2-methyl-1,3-cyclohexenylene group, phenylene-3-methyl-1,4-
Cyclohexenylene group, phenylene-3-ethyl-1,
4-cyclohexenylene group, phenylene / 1,3-cycloheptenylene group, phenylene-3-methyl-1,4-
Cycloheptenylene group, phenylene-4-methyl-1,
3-cycloheptenylene group, phenylene / 1,3-cyclooctenylene group, phenylene / 1,4-cyclooctenylene group, etc., and also alkylene / phenylene / alkylene structure such as o-, m- or p-xylylene Base,
Methylene / phenylene / ethylene group, ethylene / phenylene / ethylene group, methylene / phenylene / trimethylene group, methylene / phenylene / 1,2-dimethylethylene group, methylene / phenylene / 1,4-cyclopentenylene group, ethylene / phenylene -Butylidene group, ethylene-phenylene-ethylene group, ethylene-phenylene-
1,3-cyclopentenylene group, butylidene / phenylene / butylidene group, trimethylene / phenylene / s-butylidene group, trimethylene / phenylene / 1,3-cyclooctenylene group, 1,4-cyclopentenylene / phenylene / 1,4-cyclopentenylene group, 1,3-cyclopentenylene / phenylene / 3-ethyl-1,4-cyclohexenylene group, 1,3-cyclooctenylene / phenylene / 1,3-cyclooctene Examples thereof include, but are not limited to, a nylene group and a 1,4-cyclohexenylene / phenylene / 1,3-cyclooctenylene group.

The bisalkenyl-substituted nadimide represented by the general formula [1] used in the present invention may be synthesized by a conventional synthesis method of bisalkenyl-substituted nadimide. That is, the above alkenyl-substituted nadic acid anhydride derivative and diamine are added in the presence or absence of a solvent to 80 to 2
By holding at a temperature of 20 ° C. for 0.5 to 20 hours, both components react stoichiometrically to synthesize the bisalkenyl-substituted nadimide of the present invention. As the solvent when synthesized in the presence of a solvent, benzene, toluene, xylene, methylnaphthalene, tetralin, chloroform, trichlene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, Examples thereof include N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.

In the bisalkenyl-substituted nadiimide of the present invention, individual compounds belonging to the category may be used singly, or two or more kinds may be mixed and used as an oligomer. it can.

Further, the (A) component epoxy resin and (B)
Since it has good compatibility with the bisalkenyl-substituted nadiimide as a component, it can be mixed in any proportion, but in consideration of the balance between workability of the composition and physical properties after curing, particularly heat resistance and mechanical strength (A It is suitable to use the component (B) in an amount of 10 to 500 parts by weight, preferably 20 to 300 parts by weight, relative to 100 parts by weight of the component).

Among the 1) heterocyclic amines or tertiary amines which are one of the curing catalyst systems of the component (C) used in the present invention, the heterocyclic amines include, for example, imidazole and its alkyl. Groups, alkenyl groups, phenyl groups or benzyl groups substituted imidazoles, eg 1
-Methylimidazole, 2-ethyl-4-methylimidazole, 2-vinylimidazole, 2-phenylimidazole, 1-propenyl-2-phenylimidazole,
1-propenyl-4-phenylimidazole, 2-phenyl-4-methylimidazole, 1- (3-aminopropyl) -imidazole, N-acyl-substituted imidazole, for example 1- (2,4,6-trimethylbenzoyl)- 2-phenylimidazole, 1- (2,6-dichlorobenzoyl) -2-methylimidazole, 1-
(2,6-Dichlorobenzoyl) -phenylimidazole, 1- (2,6-dichlorobenzoyl) -2-ethyl-4-methylimidazole, 1- (2,6-dichlorobenzoyl) -4-phenylimidazole, 1- (2-chloro-6-nitrobenzoyl) -2-ethylimidazole, 1-pentachlorobenzoyl-2-methylimidazole, 1-pentachlorobenzoyl-2-phenylimidazole, etc., or pyridine, dimethylaminopyridine, piperidine, piperazine, etc. Examples of the tertiary amine include triethylamine, diethylaminopropylamine, diethylaminoethylamine,
Dimethylaminobenzylamine, 1,6-bis- (dimethylamino) -hexane, triethanolamine, N,
Examples thereof include, but are not limited to, N-dimethylaniline, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylaminobenzaldehyde and tris (dimethylaminomethyl) phenol.

Examples of the Lewis acid of the Lewis acid complex of 2) heterocyclic amine or tertiary amine, which is one of the curing catalyst system of the component (C) used in the present invention, include B.
Examples thereof include, but are not limited to, F ₃ , BCl ₃ , AlCl ₃ , FeCl ₃ , TiCl ₄ and SnCl _{4 and the} like, preferably BF ₃ and BCl ₃ .

The 3) onium salt, which is one of the curing catalyst systems of the component (C) used in the present invention, includes ammonium compounds [R ₄ N] ⁺ X ⁻ , (R is a substituted or unsubstituted aromatic group). Or, it represents a straight chain or branched chain alkyl or alkenyl group, which are each independently selected.
X ⁻ represents an anion having weak or no nucleophilicity. The same applies below. ), Phosphonium compound [R ₄ P]
⁺ X ⁻ , an arsonium compound [R ₄ As] ⁺ X ⁻ , a stibonium compound [R ₄ Sb] ⁺ X ⁻ , an oxonium compound [R ₃
O] ⁺ X ⁻ , sulfonium compound [R ₃ S] ⁺ X ⁻ , selenonium compound [R ₃ Se] ⁺ X ⁻ , stannonium compound [R ₃ Sn] ⁺ X ⁻ , and iodonium compound [R ₂ I].
⁺ X ^{− and the} like, and preferably an iodonium compound [R
₂ I] ⁺ X ⁻ . As typical iodonium compounds, for example, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium perchlorate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, (P-Methoxyphenyl) phenyliodonium tetrafluoroborate, di (2-
Examples include, but are not limited to, nitrophenyl) iodonium hexafluoroarsenate, di (p-tolyl) iodonium hexafluorophosphate, and di (p-chlorophenyl) iodonium hexafluoroarsenate.

Among the curing catalyst systems of component (C) used in the present invention, 4) onium salt and weak reducing agent or copper benzoate, the weak reducing agent is represented by the general formula [5].

[Chemical 12] The α-hydroxyketones represented by or an endiol which is a tautomer thereof are exemplified, and typical examples thereof include ascorbic acid, benzoin, anisoin,
Examples thereof include, but are not limited to, 4,4′-dichlorobenzoin, furoin and α-pyridoin. As the copper benzoate, mono- or divalent copper benzoate is used. The amount of the weak reducing agent or copper benzoate used is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, relative to 1 part by weight of the onium salt.

In the present invention, the addition amount of the curing catalyst as the component (C) is not particularly limited and may be appropriately selected within a wide range. Usually, the total amount of the components (A) and (B) is 100.
0.1-8 parts by weight, preferably 0.2-
Use 5 parts by weight.

The composition of the present invention can be prepared by a conventional preparation method. For example, a method of melt-mixing the respective components in the absence of a solvent, a method of dissolving and mixing the respective components in the presence of the solvent, and then removing the solvent if necessary, etc. are adopted.
The solvent used in the preparation in the presence of a solvent is the same as that used in the synthesis of the bisalkenyl-substituted nadiimide.

The composition of the present invention can be used for various purposes. For example, when the composition of the present invention is used as a molded product, the composition is subjected to a molding method such as cast molding, injection molding or compression molding at 120 to 280 ° C., preferably 1
It can be cured by heating at a temperature of 50 to 260 ° C. for 0.01 to 10 hours, preferably 0.05 to 8 hours to obtain a molded product. When used as a coating agent or paint, the composition is applied to a substrate such as metal, glass, ceramic or plastic,
After removing the solvent if necessary, at a temperature of 120 to 300 ° C, preferably 150 to 280 ° C, 0.005 to 10
It can be cured by heating for a time, preferably 0.01 to 8 hours, to form a thin film or a coating film.

The molded product, thin film and coating film obtained as described above may be further heat-treated at a temperature of 200 to 280 ° C. for 0.5 to 30 hours, if necessary.

The composition of the present invention can also be used as an adhesive, a filler, a binder for organic or inorganic substances.

The composition of the present invention is also useful as a matrix resin for composite materials, and various fillers such as 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 are used as the composition 100 of the present invention.
10 to 500 parts may be mixed with respect to parts by weight.

[0031]

The present invention will be described in more detail with reference to the following examples, but the contents of the present invention are not limited to these.

Examples 1 to 5 N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) (hereinafter abbreviated as BANI-mX). ) 50 parts by weight and 50 parts by weight of an epoxy resin (EP 828; Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd., the same applies hereinafter) are added to a mixture of heterocyclic amines or tertiary amines shown in Table 1 or Lewis acid complexes thereof. When 2 parts by weight were mixed uniformly, 1 part of the mixture was placed on a hot plate exposed to air at 200 ° C., stirring was performed while maintaining the temperature, and the gelation time was measured. The results shown in Table 1 were obtained. It was

Table 1 Heterocyclic amines or tertiary amines, or Lewis acid complexes thereof Gelation time Example 1 Imidazole 1 minute 30 seconds Example 2 2-Methylimidazole 2 minutes 00 seconds Example 3 2-Phenylimidazole 4 Min 00 sec Example 4 N, N-dimethylaniline 8 min 00 sec Example 5 piperidine · BF ₃ complex 7 min 00 sec

Examples 6 to 7 To a mixture of 50 parts by weight of BANI-mX and 50 parts by weight of the epoxy resin (produced by Yuka Shell Epoxy Co., Ltd.) shown in Table 2, 2 parts by weight of 2-phenylimidazole was uniformly mixed. When 1 part was placed on a hot plate exposed to air at 200 ° C., stirring was performed while maintaining the temperature, and the gelation time was measured, the results shown in Table 2 were obtained.

Table 2 Epoxy resin Gelation time Example 6 EP180S65 (Epicoat 180S65, same below) 2 minutes 00 seconds Example 7 EP1001 (Epicoat 1001, same below) 3 minutes 10 seconds

Examples 8-9 50 parts by weight of BANI-mX and epoxy resin (EP8
28) A mixture of 50 parts by weight was uniformly mixed with an onium salt shown in Table 3 and a catalyst obtained by adding a weak reducing agent to the onium salt, and 1 part of the mixture was placed on a hot plate exposed to air at 200 ° C., When the gelation time was measured while stirring while maintaining the temperature, the results shown in Table 3 were obtained.

Table 3 Onium salt Weak reducing agent Gelation time Example 8 Diphenyliodonium tetrafluoroborate 2 parts by weight-4 minutes 00 seconds Example 9 Diphenyliodonium tetrafluoroborate benzoin 1.6 parts by weight 0.4 parts by weight 3 minutes 50 seconds

Examples 10 to 11 A mixture of 50 parts by weight of BANI-mX and 50 parts by weight of the epoxy resin shown in Table 4 was uniformly mixed with 2 parts by weight of diphenyliodonium tetrafluoroborate, and 1 part of the mixture was heated at 200 ° C. in air. When the gelation time was measured by placing the sample on a hot plate exposed to, stirring while maintaining the temperature, the results shown in Table 4 were obtained.

Table 4 Epoxy resin Gelation time Example 10 EP180S65 2 minutes 00 seconds Example 11 EP1001 3 minutes 30 seconds

Examples 12 to 13 A mixture of 50 parts by weight of BANI-mX and 50 parts by weight of the epoxy resin shown in Table 5 was uniformly mixed with 1.6 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of benzoin. Then, 1 part thereof was placed on a hot plate exposed to air at 200 ° C., stirred while maintaining the temperature, and the gelation time was measured.
The result is as follows.

Table 5 Epoxy resin Gelation time Example 12 EP180S65 1 minute 00 seconds Example 13 EP1001 5 minutes 30 seconds

Examples 14 to 16 A mixture of 50 parts by weight of an epoxy resin (EP828) and 50 parts by weight of an alkenyl-substituted nadimide shown in Table 6 was added to 0.8 parts by weight of diphenyliodonium hexafluorophosphate and 0.1 part of diphenyliodonium tetrafluoroborate. 8 parts by weight and 0.4 parts by weight of benzoin were uniformly mixed, 1 part of the mixture was placed on a hot plate exposed to air at 200 ° C., stirring was performed while maintaining the temperature, and gelling time was measured. The result is as follows.

Table 6 Alkenyl-Substituted Nadiimide Gel Time Example 14 BANI-mX 4 min 00 sec Example 15 N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide) 3 minutes 50 seconds Example 16 N, N '-(p-phenylene) .ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximide) 4 minutes 20 seconds

Examples 17 to 18 A mixture of 50 parts by weight of BANI-mX and 50 parts by weight of the epoxy resin shown in Table 7 was added to 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of benzoin are mixed uniformly, and 1 part thereof is placed on a hot plate exposed to air at 200 ° C.,
When stirring the mixture while maintaining the temperature and measuring the gelation time, the results shown in Table 7 were obtained.

Table 7 Epoxy resin Gelation time Example 17 EP180S65 2 minutes 50 seconds Example 18 EP1001 4:00 minutes

Example 19 70 parts by weight of BANI-mX and epoxy resin (EP8)
28) To a mixture of 30 parts by weight, 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of ascorbic acid are uniformly mixed,
One part thereof was placed on a hot plate exposed to air at 200 ° C., stirring was performed while maintaining the temperature, and the gelation time was measured and found to be 18 minutes and 00 seconds.

Example 20 30 parts by weight of BANI-mX and epoxy resin (EP8)
28) To a mixture of 70 parts by weight, 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of benzoin are uniformly mixed, and 1 part of the mixture is heated to 200 ° C. It was placed on a hot plate exposed to the air, stirred while keeping the temperature, and the gelation time was measured, and it was 3 minutes and 50 seconds.

Example 21 70 parts by weight of BANI-mX and epoxy resin (EP8)
28) A mixture of 30 parts by weight was uniformly mixed with 0.8 part by weight of diphenyliodonium hexafluorophosphate, 0.8 part by weight of diphenyliodonium tetrafluoroborate and 0.4 part by weight of copper (II) benzoate, One part was placed on a hot plate exposed to air at 200 ° C., and the mixture was stirred while maintaining the temperature, and the gelation time was measured, and it was 4 minutes 00 seconds.

Example 22 30 parts by weight of BANI-mX and an epoxy resin (EP8)
28) 70 parts by weight was heated and melted in an oil bath at 150 ° C., 2 parts by weight of 2-phenylimidazole was added thereto, and the mixture was stirred uniformly. Next, it was degassed under reduced pressure, poured into a mold, and heat-cured in the air at 200 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 131 ° C., bending strength: 1
The elastic modulus was 7.4 Kg / mm ² , and the flexural modulus was 287 Kg / mm ² .

Example 23 The cured product obtained in Example 22 was further exposed to air,
After heat treatment at 250 ° C. for 2 hours, a test piece was cut out and subjected to a physical property test, and the glass transition temperature (Tg, TMA
Method): 142 ° C., bending strength: 18.7 Kg / mm ² , bending elastic modulus: 312 Kg / mm ² .

Comparative Example 1 Bis {4- (allylbicyclo [2.2.1] hept-5
30 parts by weight of -ene-2,3-dicarboximido) phenyl} methane (melting point 92 ° C) and epoxy resin (EP
828) 70 parts by weight was heated and melted in an oil bath at 150 ° C., 2 parts by weight of 2-phenylimidazole was added thereto, and the mixture was stirred uniformly. Next, it was degassed under reduced pressure, poured into a mold, and heat-cured in the air at 200 ° C. for 2 hours.
When a test piece was cut out from the cured product and tested for physical properties, the glass transition temperature (Tg, TMA method): 130 ° C., bending strength:
13.2 Kg / mm ² , flexural modulus: 313 Kg / mm ²
Met.

Example 24 30 parts by weight of BANI-mX and epoxy resin (EP1
001) 70 parts by weight are heated and melted in an oil bath at 150 ° C., and 1- (2,6-dichlorobenzoyl) -2 is added thereto.
-2 parts by weight of ethyl imidazole was added and the mixture was stirred uniformly. Then, it was degassed under reduced pressure, poured into a mold, and heat-cured in the air at 200 ° C. for 2 hours and further at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 116 ° C., bending strength: 16.0 Kg / mm ² , bending elastic modulus: 294 K
It was g / mm ² .

Example 25 30 parts by weight of BANI-mX and epoxy resin (EP8
28) 70 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 of benzoin are added thereto.
Parts by weight were added and stirred uniformly. Next, it was degassed under reduced pressure, poured into a mold, and heat-cured in the air at 200 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, a glass transition temperature (Tg, TMA method): 90 ° C.,
Flexural strength: 15.9 Kg / mm ² , flexural modulus: 341
Kg / mm ² , 5% weight loss temperature: 326 ° C (TGA
Method, in a nitrogen stream, the temperature rising rate was 10 ° C./min).

Example 26 Example 25 except that the curing conditions in Example 25 were 200 ° C. for 12 hours instead of 200 ° C. for 2 hours.
When a physical property test of a cured product obtained by performing the same operation as above was conducted, a glass transition temperature (Tg, TMA method): 1
The temperature was 07 ° C., the bending strength was 15.6 Kg / mm ² , and the bending elastic modulus was 330 Kg / mm ² .

Example 27 The same operation as in Example 25 was carried out except that the curing conditions in Example 25 were changed to 200 ° C. for 2 hours and then 250 ° C. for 2 hours instead of 200 ° C. for 2 hours. When the physical property test of the cured product obtained by applying was performed, glass transition temperature (Tg, TMA method): 141 ° C., bending strength: 16.
0 Kg / mm ² , flexural modulus: 315 Kg / mm ² , 5%
The weight reduction temperature was 357 ° C. (TGA method, nitrogen stream, temperature rising rate: 10 ° C./min).

Comparative Example 2 Bis {4- (allylbicyclo [2.2.1] hept-5
30 parts by weight of -ene-2,3-dicarboximido) phenyl} methane (melting point 75 ° C) and epoxy resin (EP
828) 70 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 part by weight of diphenyliodonium hexafluorophosphate, 0.8 part by weight of diphenyliodonium tetrafluoroborate and 0.
4 parts by weight was added and stirred uniformly. Then, it was degassed under reduced pressure, poured into a mold, and heat-cured in the atmosphere at 200 ° C. for 2 hours and subsequently at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 144 ° C., bending strength: 12.
It was 0 Kg / mm ² and flexural modulus: 380 Kg / mm ² .

Example 28 50 parts by weight of BANI-mX and epoxy resin (EP8
28) 50 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts of benzoin are added thereto.
Parts by weight were added and stirred uniformly. Next, after degassing it under reduced pressure, it was poured into a mold and kept in the air at 200 ° C. for 2 hours.
Subsequently, it was cured by heating at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, the glass transition temperature (Tg, TMA method): 141 ° C., bending strength: 16.8K
g / mm ² , flexural modulus: 373 kg / mm ² , 5% weight loss temperature: 372 ° C. (TGA method, in nitrogen stream, temperature rising rate: 10 ° C./min).

Example 29 30 parts by weight of BANI-mX and epoxy resin (EP1
80S65) 70 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of benzoin are added to homogenize. Stir it. Next, after degassing it under reduced pressure, it was poured into a mold and kept at 200 ° C. in the atmosphere for 2
It was cured by heating for 2 hours and subsequently at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 125 ° C., bending strength: 1
3.5 Kg / mm ² , flexural modulus: 356 Kg / mm ² ,
5% weight loss temperature: 378 ° C. (TGA method, in nitrogen stream,
The temperature rising rate was 10 ° C./min).

Example 30 70 parts by weight of BANI-mX and epoxy resin (EP1)
80S65) 30 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 parts by weight of diphenyliodonium hexafluorophosphate, 0.8 parts by weight of diphenyliodonium tetrafluoroborate and 0.4 parts by weight of benzoin are added to obtain a uniform mixture. Stir it. Next, after degassing it under reduced pressure, it was poured into a mold and kept at 200 ° C. in the atmosphere for 2
It was cured by heating for 2 hours and subsequently at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 140 ° C., bending strength: 1
0.0 Kg / mm ² , flexural modulus: 403 Kg / mm ² ,
5% weight loss temperature: 386 ° C. (TGA method, in nitrogen stream,
The temperature rising rate was 10 ° C./min).

Example 31 30 parts by weight of BANI-mX and an epoxy resin (EP1
001) 70 parts by weight are heated and melted in an oil bath at 150 ° C., and 0.8 part by weight of diphenyliodonium hexafluorophosphate, 0.8 part by weight of diphenyliodonium tetrafluoroborate and 0.
4 parts by weight was added and stirred uniformly. Then, it was degassed under reduced pressure, poured into a mold, and heated at 200 ° C. for 2 hours in the air, and subsequently heat-cured at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, glass transition temperature (Tg, TMA method): 100 ° C., deflection temperature under load: 1
18 ° C., bending strength: 17.1 Kg / mm ² , bending elastic modulus: 295 Kg / mm ² , 5% weight loss temperature: 393 ° C.
(TGA method, nitrogen flow, temperature rising rate: 10 ° C / min)
Met.

Example 32 N, N '-(p-phenylene) .ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
30 parts by weight of dicarboximide and 70 parts by weight of an epoxy resin (EP1001) were heated and melted in an oil bath at 150 ° C., and 2 parts by weight of diphenyliodonium tetrafluoroborate was added thereto and stirred uniformly. Next, after degassing it under reduced pressure, pour it into a mold and let
It was cured by heating at 00 ° C. for 2 hours and subsequently at 250 ° C. for 2 hours. When a test piece was cut out from the cured product and tested for physical properties, the glass transition temperature (Tg, TMA method): 138 ° C., bending strength: 16.3 Kg / mm ² , bending elastic modulus: 310 K
It was g / mm ² .

[0062]

EFFECT OF THE INVENTION The thermosetting resin composition of the present invention is excellent in compatibility of each component and storage stability, and is cured at a relatively low temperature in a short time, so that it is workable in various applications. Is excellent. Moreover, it gives a cured product having excellent adhesiveness to metal, adhesion, heat resistance, and mechanical properties, especially mechanical strength, as compared with conventional epoxy resin-bisalkenyl-substituted nadiimide resin compositions.

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[Procedure amendment]

[Submission date] October 26, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

As the diamine represented by the general formula [4], E is a phenylene alkylene structure, for example, a phenylene methylene group (wherein phenylene is
Any of o-, m- or p-bonding forms may be used, and the same applies hereinafter. ), Phenylene / ethylene group, phenylene / trimethylene group, phenylene / tetramethylene group,
Phenylene ・ butylidene group, phenylene ・ s-butylidene group, phenylene ・ 1,2-dimethylethylene group, phenylene ・ 1,1-dimethylethylene group, phenylene ・
1,2 Shikuropen Ji Ren group, phenylene 1,3 Shikuropen Chi alkylene group, phenylene-1,4 Shikuropen Chi <br/> alkylene group, phenylene 2-methyl-1,4-Shikuropen
Ji Ren group, phenylene 2,3-dimethyl-1,4 Shikuropen Ji Ren group, phenylene 1,2-cyclohexylene <br/> alkylene group, phenylene-1,4-cyclohexylene alkylene group, phenylene 2 - methyl-1,3-cyclohexylene alkylene group,
Phenylene 3-methyl-1,4-cyclohexylene alkylene group, phenylene 3-ethyl-1,4-cyclohexylene les <br/> down group, phenylene 1,3 Shikurohepu Chi alkylene group, phenylene 3- methyl-1,4-Shikurohepu Ji Ren group, phenylene 4-methyl-1,3-Shikurohepu Ji Ren group,
Phenylene 1,3 Shikurooku Chi alkylene group, phenylene-1,4 Shikurooku Chi alkylene group, also of alkylene phenylene alkylene structure, for example o-, m- or p- xylylene group, methylene phenylene-ethylene group , Ethylene / phenylene / ethylene group, methylene / phenylene / trimethylene group, methylene / phenylene /
1,2-dimethylethylene group, methylene phenylene
1,4 Shikuropen Ji Ren, ethylene-phenylene
Butylidene, ethylene-phenylene-ethylene, ethylene-phenylene-1,3 Shikuropen Chi alkylene group, butylidene phenylene butylidene, trimethylene
Phenylene s-butylidene group, trimethylene phenylene 1,3 Shikurooku Chi alkylene group, 1,4-cyclopentyl <br/> emissions Chi Len phenylene 1,4 Shikuropen Chi Ren group,
1,3 Shikuropen Ji Ren-phenylene-3-ethyl -
1,4-cyclohexylene alkylene group, 1,3 Shikurooku Chi les <br/> down-phenylene 1,3 Shikurooku Chi alkylene group, 1,4
- cyclohexylene Len phenylene-1,3-Shikurooku
Chi Ren group and the like, but not limited thereto.

Claims (3)

[Claims] 1. An epoxy resin (A), a general formula [1]: {In the formula, R ¹ and R ² are each independently selected hydrogen or a methyl group, and E is represented by the general formula [2] (In the formula, a is an integer of 0 or 1, and R ³ and R ^{3 ′} are independently selected C _{1 to} C ₄ alkylene groups or C ₅
It represents a cycloalkylene group -C _8. ) Represents an alkylene-phenylene group. } The thermosetting resin composition characterized by containing the bisalkenyl substituted nadiimide represented by these, and (C) curing catalyst as an essential component. 2. The curing catalyst is 1) a heterocyclic amine or a tertiary amine, 2) a Lewis acid complex of a heterocyclic amine or a tertiary amine, 3) an onium salt, or 4) an onium salt and a weak reduction. The thermosetting resin composition according to claim 1, which is an agent or copper benzoate. 3. (A) 100 parts by weight of epoxy resin, (B) general formula [1] {In the formula, R ¹ and R ² are each independently selected hydrogen or a methyl group, and E is represented by the general formula [2] (In the formula, a is an integer of 0 or 1, and R ³ and R ^{3 ′} are independently selected C _{1 to} C ₄ alkylene groups or C ₅
It represents a cycloalkylene group -C _8. ) Represents an alkylene-phenylene group. } The thermosetting resin composition of Claim 1 or 2 which mix | blends 10-500 weight part of bis alkenyl substituted nadimide represented by these.