CA1254343A - Thermosetting resin composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention improves the handlability or operability of a polyamino bismaleimide resin composition by using a vinyl compound containing an epoxy group, and thus provides a non-solvent type polyaminobismaleimide resin composition.
The combined use of the vinyl compound containing an epoxy group with an epoxy resin in the above resin combination reduces its shrinkage upon curing and gives a cured article having good dimensional stability or appearance characteristics.

Description

THERMOSETTING RESIN COMPOSITION

Field of Technolog~
This invention relates to a thermosetting resin composition of the unsaturated bismaleimide compound type, and more specifically to a thermosetting resin composition having excellent handlability (operability) and heat resistance and a sufficiently low shrinkage upon curing.
Prior Art Generally, a thermoset product of an unsaturated bismaleimide compound obtained by reacting an amine with maleic anhydride and by thermosetting the resultant has the advantage that it has excellent heat resistance, and since its curing polymerization reaction, an addition reaction, forms no volatile components during curing and a dense cured product can be formed. However, because the unsaturated bismaleimide compounds has low solubility in general organic solvents, to form a solution Or this compound requires the use Or high-boiling solvents such as dimethylformamide and N-methylpyrrolidone which are highly polar. To compensate for its low solubility, it is also practised to incorporate an epoxy resin or the like in the unsaturated bismaleimide compound, thereby modifying one. Generally, however, some solutions obtained might form precipitates at room temperature, or solventless compositions are too viscous in the practical use.
After all, this type of thermosetting resin composition 3 is difficult to use as a solventless type.
Summar~ Or the Invention It is an object of this invention to provide a thermosetting resin composition of the unsaturated 1~2S4;3~

bismaleimide compound type which can be used as a solventless type.
Another object of this invention is to provide a thermosetting resin composition having excellent handlability (operability) and heat resistance.
Still another object of this invention is to provide a thermosetting resin composition which can be cured in a sufficiently low shrinkage upon curing and being capable of giving a cured product excellent in dimensional stability and appearance.
According to this invention, there is provided a therrnosetting resin composition (I) comprising as essential ingredients (a) a pre-reacted product of a polyamino compound and an unsaturated bismaleimide compound, (b) a vinyl compound containing an epoxy group, (c) an epoxy curing agent, and (d) a radical polymerization initiator, the pre-reacted product (a) being formed by carrying out the pre-reaction in the substantial absence of the vinyl compound (b) containing an epoxy group.
According to this invention, there is also provided a thermosetting resin composition (II) comprising as essential ingredients 5 (a) a pre-reacted product of a polyamino compound andan unsaturated bismaleimide compound, (b) a vinyl compound containing an epoxy group, (b') an aliphatic epoxy compound containing no vinyl group, (c) an epoxy curing agent, and (d) a radical polymerization initiator, the pre-reacted product (a) being formed by carrying out the pre-reaction in the substantial absence of the vinyl -lZ5~3~

compound (b) containing an epoxy group.
Detailed Description Or the Preferred Embodiments There are two embodiments of the thermosetting resin composition of this invention, which will be described below in detai,1,.
Embodiment I
In this embodiment, the following ingredients are used.
In~redient (a) The ingredient (a) is a pre-reacted product Or a polyamino compound and an unsaturated bismaleimide compound.
Examples Or the polyamino compound are those Or the rollowing general rormula R(Nl~2)m (l) wherein R represents an organic group having a valence Or 2 or more, such as an alkylene, cycloalkylene or arylene group and these groups may be bonded to each other either directly or through another bonding group, and m represents an integer of' at least 2.
Speciric examples include 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane,

2,6-diaminopyridine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,

3 2,2-bis(4-aminophenyl)propane, benzidine,

4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, lZS~3~3 bis(4-aminophenyl)methylphosphine, m-xylylenediamine, l,5-diaminonaphthalene, p-xylylenediamine, hexame-thylenediamine, l,4'-diaminobenzophenone, 2,5-bis(m-aminophenyl)-l,3,4-oxadithiazole, 2,5-bis(p-aminophenyl)-1,3,4-oxadithiazole 4,4'-bis(p-aminophenyl)-2,2'-dithiazole, 3, Ll ' -diaminobenzanilide, 2,2'-bis(m-aminophenyl)-5,5'-dibenzimidazole, N,N'-bis(p-aminobenzoyl)-4,4'-diaminodiphenylmethane, l,2,4-triarninobenzene, l,3,5-triaminobenzene, 2,4,6-triaminotoluene, 2,4,6-triamino-l,3,5-trimethylbenzene, l,3,7-triaminonaphthalene, 2, 4, 4'-triaminodiphenyl, 2,4,6-triaminopyridine, 2,4,4'-triaminodiphenylmethane, p-aminophenyl-4,4'-diphenylmethane, tri(4-aminophenyl)methane, 2,4,4'-triaminobenzophenone, 3,5,4'-triaminobenzanilide, melamine-l,2,4,5-tetraaminobenzene, 2,3,6,7-tetraaminonaphthalene, 3,3',4,4'-tetraaminodiphenyl ether, 3,3',4,4'-tetraaminodiphenylmethane, 3,5-bis(3,4'-diaminophenyl)pyridine, and 3 compounds of the folloiwng general formula 12S~3 ~Rl~ L~2 wherein Rl represents anorganic group having l to 8 carbonatoms, and x is O.l to 2.
Examples of the unsaturated bismaleimide compounds sued together with the above polyamino compounds are those Or the following general formula ~ \ C0 / 3~ (3) wherein R2 represents an alkylene, cycloalkylene or arylene group having at least 2 carbon atoms or an organic group composed of a combination of two or more of these groups, and R3 represents a divalent organic group having a carbon-carbon double bond.
Specific examples include reaction products of maleic anhydride with N,N'-phenylenebismaleimide, N,N'-hexamethylene bismaleimide, N,N'-methylene-di-p-phenylene bismaleimide, N,N'-4,4'-benzophenone bismaleimide, N,N'-p-diphenylsulfone bismaleimide, N,N'-(3,3'-dimethyl)-methylene-p-phenylene bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-p-xylylene bismaleimide, N,N'-(3,3'-diethyl)methylene-di-p-phenylene bismaleimide, N,N'-m-toluylene bismaleimide or aniline/formalin reaction product.
These unsaturated bismaleimide compounds may be replaced by monomaleimide compounds such as - l~S~3'~

N-allylmaleimide, N-propylmaleimide, N-hexylmaleimide or N-phenylmaleimide up to about 60% by weight.
Generally, 1 gram-equivalent of the polyamino compound is pre-reacted with about 0.1 to 10 gram-equivalents, preferab]y about 0.5 to 5 gram-equivalents, of the unsaturated bismaleimide compound. The pre-reaction product may be formed by, for example, mixing them in the absence of the vinyl compound containing an epoxy group (ingredient (b)) at a temperature of about 70 to 170 C ror a period Or 2 to 15 minutes by using a roll or the like to form a prepolymer. The softening point of the prepolymer is usually adjusted to 60 to 110 C. The softening point is measured by observing the sample under a microscope while it is heated at a rate of 2 C/min. As a result of this treatment, the amino groups of the polyamino compound add to the unsaturated bond of the bismaleimide compound by the Michael addition reaction whereby a polyaminobismaleimide may be formed .
The ingredient (a) has the advantage that since the curing polymerization reaction is an addition reaction, it forms no volatile component during curing and a dense cured product. In addition, it can dissolve uniformly in the ingredient (b) even at room temperature.
In~redient (b) Examples of the vinyl compound containing epoxy groups as the ingredient (b) include vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and allyl oxide.
3 The epoxy group-containing vinyl compound (b) acts as a diluent for the ingredient (a) and dissolves it even at room temeprature. Accordingly, without using a particular solvent, the curable resin composition is iZS4 formed as a solution of a low viscosity and exerts an improved workability.
Furthermore, an epoxy group contained in the vinyl compound (b), when the resin composition is impregnated in fibers, etc. causes to occur rapid thickening together with a given curing agent, and advantageously this thickening reaction does not induce gelation.
Specifically, since the resulting thickening product does not increase in viscosity with time, molding materials such as SMC or prepregs which must be in the pre-stage of complete curing have an improved storage stability.
'l'he ingredient (b) may contain a styrene-type rnonomer such as styrene, alpha-methylstyrene, vinyltoluene or divinylbenzene in amounts which do not substantially impair its solubilizing power at room temperature on the prepolymer. The upper limi-t Or the amount Or the styrene monomer is set usually at 0.1 to 10 moles, preferably 0.1 to 3 moles, per mole of the ingredient (b). The use of the styrene monomer in the aforesaid ratios is desirable to dissolve (a) component to prepare a lowly viscous solution and, further increases the strength of the cured product.
Ingredient (c) The epoxy curing agent may be any of those known curing agents which do not substantially affect radical polymerization. Specific examples include aliphatic amines, acid anhydrides, dicyandiamide, hydrazines, imidazoles and amine complexes of boron trifluoride.
Ingredient (d) Examples of the radical polymerization initiators are as rOllows:-(l) Compounds resulting from bonding of -0-0-H to lZS43~3 the secondary or tertiary carbon atom Or isopropyl hydroperoxide, tert-butyl hydroperoxide, cumyl hydroperoxide and perbenzoic acid.
(2) Compounds resulting from bonding Or -0-0- to two secondary or tertiary carbon atoms of diisopropyl peroxide, di-tert-butyl peroxide, and dicumyl peroxide.
(3) bis-Peroxides containing 2 peroxy groups per molecule, such as 2,5-dimethyl-2,5-bis(tert-butyl peroxy-(hexane, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)-hexene-3, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexyne-3 and 1,3-bis(tert-butyl peroxy isopropyl)benzene.
These bisperoxides are especially advantageous in regard to peroxy values.
(4) Organic azo compounds containing at least one -C-N-N- bond in the molecular structure, typified by azobisalkanonitriles such as azobisisobutyronitrile, and azobiscarbonamide.
The thermosetting composition tI) Or this invention comprises the ingredients (a) to (d) described above as essential ingredients.
As required, it is possible to incorporate an epoxy curing accelerator such as imidazoles, amine complexes of boron trifluoride, tertiary amines, quaternary ammonium salts or urea compounds, and an internal mold releasing agent such as higher fatty acid metal salts in amounts known per se.
Pre~aration The resin composition of embodiment I generally comprises l to 200 parts by weight, especially 5 to lOO parts by weight, per lOO parts by weight of the ingredient (a), of the ingredient (b), 0.01 to lOO parts by weight, especially 0.05 to 50 . .

l;~S~

g parts by weight, per lO0 parts by weight of the ingredient (a), of the ingredient (c), and 0.01 to lO parts by weight, especially 0.05 to 5 parts by weight, per lO0 parts by weight of the ingredients (a) and (b) combined, of the ingredient (d).
The ingredient (a) is prepared as a solution in the ingredient (b).
The preliminary reaction Or the ingredient (a) is carried out in the substantial absence of the ingredient (b) at a temperature of about 70 to 170 C in a reactor to such an extent that the ingredient (a) dissolves in the ingredient (b) even at room temperature and does not precipitate even when the solution is left to stand at room temperature.
The ingredient (c) and as required, an epoxy curing accelerator or the like are added at room temperature to the resulting uniform solution of the ingredients (a) and (b), and further the ingredient (d) and as required an internal mold releasing agent or the like are added to give the thermosetitng resin composition of embodiment I.
Embodiment II
The thermosetting resin composition of embodiment II contains the ingredient (b'), i.e. the aliphatic epoxy compound containing no vinyl group, as an essential ingredient in addition to the essential ingredients of the resin composition Or embodiment I.
The thermosetting resin composition of embodiment II has a markedly reduced shrinkage upon curing over the resin composition of embodiment I. This brings about 3 the advantage that the dimensional stability and appearance stability of the cured product are not impaired.
Ingredient (b') 1;~5~

Examples of the aliphatic epoxy compound containing no vinyl group used as the ingredient (b') are aliphatic epoxy resins such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether or pentaerythritol polyglycidyl ether, and epoxy resins obtained by the reaction of aliphatic carboxylic acids with epichlorohydrin.
Those epoxy resins which have an epoxy equivalent Or 20 to lO00, especially 50 to 300, and a viscosity at 25 C of l to 30000 cps, especially 5 to lO000 cps, are especially suitably used because they are conductive to the f'ormation Or a resin composition in solution having excellent workability.
~y using the aliphatic epoxy compound containing no vinyl group together with the epoxy group-containing vinyl compound as ingredient (b), the shrinkage of the composition upon curing can be markedly reduced as will be shown by an Example given hereinafter.
Preparation The thermosetting resin composition of embodiment II, generally comprises 2 to 140 parts by weight, especially 5 to 70 parts by weight, per 100 parts by weight of the ingredient (a), of the epoxy group-containing vinyl compound (b), 4 to lO0 parts by weight, especially 8 to 50 parts by weight, per lO0 parts by weight of the ingredient (b), of the epoxy compound (b'), 0.01 to lO0 parts by weight, especially 0.05 to 50 parts by weight, per lO0 parts by weight of the ingredients (a), (b) and (b') combined, of' the epoxy curing agent (c), and 0.01 to lO parts by weight, especially 0.05 to 5 parts by weight, per lO0 parts by weight of the lZS~3~3 resin ingredients (a) to (c), of the radical polymerization initiator (d).
In the preparation of this resin composition, the ingredients (a) and (b) are used in the form of a m:ixture as in emhodiment T.
The thermosetting resin composition of embodiment II can be prepared by adding the aliphatic epoxy colllpound (b'), the epoxy curing agent (c) and as required, an epoxy curing accelerator to the mixture, and further adding thc radical polymerization initiator (d) and as required, an internal mold releasing agent.
The resulting thermosetting resin compositions I
and II of this invention have the following characteristics and advantages.
(1) Since the unsaturated bisimide compound is dissolved as a pre-reacted product with the polyamino compound in the epoxy group-containing vinyl compound of a low viscosity at room temperature, the resulting resin compositions are obtained as a solution Or a low viscosity. Hence, these thermosetting resin compositions have excellent workability or operability.
When these compositions are impregnated in fibers, etc., they rapidly thicken. Since this thickening reaction does not induce gellation, the resulting thickened product does not increase in viscosity with time. As a result, molding materials such as SMC or prepregs which must be in the pre-stage of complete curing have improved storage stability.
(2) As a result of using the radical polymerization initiator, the resin compositions of this invention cure within a short time of less than several minutes even at a temperature of not more than 200 C, and the resulting heat-cured products have excellent mechanical strength lZ~

and good heat resistance.
(3) Since the prepared resin compositions are liquids having a low viscosity, they have a diversity of applications as molding materials for impregnation, casting or lamination. In particular, they can be easily impregnated into reinforcing materials such as glass fibers, aromatic polyamide fibers, aromatic polyester fibers, carbon fibers, silicon carbide fibers and alumina fibers. When they are completely 10 impregnated by using a press or roll at room temperature through a mold-releasing film, molding materials such as a sheet molding compound (SMC) or a prepreg are obtained. l'hese molding materials can be molded into various articles by reacting them under heat and pressure and t~len curing the resin component.
(4) Since the thermosetting resin composition II
has a markedly reduced shrinkage upon curing, it also offers the advantage that the dimensional stability and appearance characteristics of the cured molded articles 20 are not impaired. The following Examples illustrate the invention more specifically. All parts in these examples are by weight.
Example l N,N'-4,4'-diphenylmethane bismaieimide (82 parts) and 18 parts of 4,4'-diaminodiphenylmethane were preliminarily reacted at 130 C for 15 minutes by a roll to obtain 100 parts of a prepolymer. Sixty parts of` the prepolymer and 40 parts of glycidyl methacrylate were mixed in a glass reactor at room temperature for 30 30 minutes to dissolve the prepolymer. Then, 2 parts of dicyandiamide as an epoxy curing agent, 0.5 part Or 2-ethyl-4-methylimidazole as an epoxy curing accelerator, 1 part of dicumyl peroxide as a radical polymerization i'~S~

initiator and 2 parts Or zinc stearate as an internal mold releasing agent were mixed to prepare a thermosetting resin composition.
The thermosetting resin composition was impregnated

5 at roorn tempera-ture into eight layers Or chopped glass fiber mat (chop length 50 mm, basis weight 300 g/m2).
The impregnated mats were pressed at room temperature to prepare an SMC (thickness about 3 mm) having a glass fiber content of about 60 %. A polyethylene film having 10 a thickness of 50 micrometers as a mold releasing film was used as an overcoat. The SMC was left to stand at room temperature f'or several days to render it tack-free, and then cured at 160 C for 3 minutes. It was further cured in an air oven at 200 C ~or 24 hours to 15 obtain a plate-like compression-molded article.
The various properties described below of the SMC
and the article were measured. The results are shown in Table 1.
Viscosity of the thermosetting resin composition:
Measured at 25 C by a E-type viscometer Impregnability of the resin composition in the chopped glass fibermats: Evaluated visually Tackness of SMC: Evaluated visually Drapability of SMC: Evaluated visually 25 Flexural strength and flexural modulus of elasticity of the molded article: Measured in accordance with JIS
K-6911 at 20, 200 and 250 C
Tensile strength Or the molded article: Measured at 20 C
in accordance with JIS K-6911 30 Water absorption Or the molded article: Measured at 20 C
for 24 hours in accordance with JIS K-6911 Storage stability: SMC was stored at 20 C, and the retention of its drapability was evaluated visually.

l~S~3~3 Shrinkage upon curing: SMC was compression-molded by a mold having a marker for measurement of shrinkage upon curing. The shrinkage was calculated from the difference in size between the SMC molded article and the mold.
Example 2 Example 2 was repeated except that the amounts of the prepolymer and glycidyl methacrylate were changed to 70 and 30 parts, respectively.
10 ExamPle 3 Example 1 was repeated except that the amounts of the prepolymer and glycidyl methacrylate were changed both to 50 parts.
Example 4 Example 1 was repeated except that allyl glycidyl ether was used instead of glycidyl methacrylate.
Comparative Example 1 Example 1 was repeated except that styrene was used instead of glycidyl methacrylate, and neither the epoxy 20 curing agent nor the epoxy;curing accelerator were used.
Comparative Example 2 Example 1 was repeated except that bisphenol A-type epoxy resin (epoxy equivalent 185 to 195, viscosity at 25 C 12000 to 15000 cps) was used instead of glycidyl 25 methacrylate, and the radical polymerization agent was not used.
Comparative Example 3 Example 1 was repeated except that glycidyl methacrylate, the epoxy curing agent and the epoxy 3 curing accelerator were not used.
Table 1 also shows the results of evaluation of the various properties of SMCs and molded articles obtained in Examples 2 to 4 and Comparative Examples 1 to 3.

lZ~43~3 Example 5 Example 1 was repeated except that a prepreg and a plate-like compression-molded article were produced by using a glass riber cloth (thickness 0.22 mm, basis 5 weight 300 g/m2) instead Or the chopped glass riber mats. The results of evaluation are shown in Table 2.
Example 6 The thermosetting resin composition obtained in Example 1 was impregnated into a carbon fiber layer 10 (thickness 0.4 mm, basis weight 400 g/m2) in which the flbers were unidirectionally aligned, at room temperature between rolls to prepare a prepreg having a carbon fiber content Or about 65 % by weight. Five plies Or such prepreg were heated in an autoclave under a 15 pressure Or 3 kgr/cm2 to 150 C at a rate Or 2 C/min., and thereafter cured at 150 C rOr 30 minutes to obtain a plate-like compression-molded article. The properties Or the prepreg and the molded article were evaluated as in Example 1, and the results are shown in Table 2.
20 ExamPle 7 The prepolymer (71 parts) prepared in Example 1 and 29 parts of bisphenol A-type epoxy resin (epoxy equivalent 185 - 195, viscosity 12000 - 15000 cps) were reacted at 100 C for 10 minutes while being mixed by a 25 roll. Thus, 100 parts Or a pre-reaction product was obtained. Seventy parts Or the pre-reaction product and 30 parts Or methyl methacrylate were mixed in a glass reactor at 60 C ror 10 minutes to dissolve the pre-reaction product. Then, in the same way as in Example 1, 30 the solution was mixed with the epoxy curing agent, the epoxy curing accelerator, the radical polymerization initiator and the internal mold releasing agent to prepare a thermosetting resin.

i;s~5L'~39~3 Using the thermosetting resin cornposition, SMC and a plate-like compression molded article were produced in the same way as in Example 1, and their properties were evaluated. The results are shown in Table 2.
5 Example 8 N,N'-4,4'-diphenylmethane bismalimide (82 parts) and 18 parts of 4,4'-diaminodiphenylmethane were pre-reacted by heating them at 130 C for 15 minutes by a roll to obtain 100 parts of a prepolymer.
Fifty-five parts of the prepolymer and 35 parts of glycidyl methacrylate were mixed in a glass reactor at room temperature for 30 minutes to dissolve the prepolymer. The solution was then mixed with 10 parts of' ethylene glycol diglycidyl ether as an epoxy 15 compound, 2 parts of dicyandiamide as an epoxy curing agent, ~.5 part of 2-ethyl-4-methylimidazole as an epoxy curing accelerator, 1 part of dicumyl peroxide as a radical polymerization initiator and 2 parts of zinc stearate as an internal mold releasing agent to prepare 20 a thermosetting resin composition.
The resin composition had a viscosity at 25 C of

6,800 cps as measured by an E-type viscometer.
SMC and a plate-like compression-molded article were produced by using the resulting resin composition in 25 the same way as in Example 1, and their properties are shown in Table 2.
Example 9 SMC and a plate-like compression-molded article were produced in the same way as in Example 1 except 3 that the amount Or glycidyl methacrylate was changed to 25 parts, and the amount Or ethylene glycol glycidyl ether was changed to 20 parts.
The properties of SMC and the molded article are iZS~3 ~3 - l7 -sl~wl~ 'clt)l~ 2.
l~xampl e 10 SMC ~nd a plate-like compression-molded article were produced in the same way as in Example 1 except 5 t~lat ti~e amount of glycidyl methacrylate was changed to 1~ parts and the amount of' ethylene glycol glycidyl ether was changed to 30 parts.
'Illc prol)ertics Or~ ~MC and tile molded products are shown in 'I'ahle 2.

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Claims (10)

What is claimed is:

1. A thermosetting resin composition comprising as essential ingredients (a) a pre-reacted product of a polyamino compound and an unsaturated bismaleimide compound, (b) a vinyl compound containing an epoxy group, (c) an epoxy curing agent, and (d) a radical polymerization initiator, the pre-reaction product (a) being formed by carrying out the pre-reaction in the substantial absence of the vinyl compound (b) containing an epoxy group.

2. The composition or claim 1 wherein the vinyl compound (b) containing an epoxy group is at least one compound selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether.

3. The composition of claim 1 wherein the proportion of the ingredient (b) is 1 to 200 parts by weight per 100 parts by weight of the ingredient (a), the proportion of the ingredient (c) is 0.01 to 100 parts by weight per 100 parts by weight of the ingredients (a) and (b) combined, and the proportion of the ingredient (d) is 0.01 to 10 parts by weight per 100 parts by weight of the ingredients (a) and (b) combined.

4. The composition of claim 1 wherein in the ingredient (a), the amount of the unsaturated bismaleimide compound is 0.1 to 10 gram-equivalents per gram-equivalent of the polyamino group.

5. A thermosetting resin composition comprising as essential ingredients (a) a pre-reaction product of a polyamino compound and an unsaturated bismaleimide compound, (b) a vinyl compound containing an epoxy group, (b') an aliphatic epoxy compound containing no vinyl group, (c) an epoxy curing agent, and (d) a radical polymerization initiator, the pre-reaction product (a) being formed by carrying out the pre-reaction in the substantial absence of the vinyl compound (b) containing an epoxy group.

6. The composition of claim 5 wherein the vinyl compound (b) containing an epoxy group is at least one compound selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether.

7. The composition of claim 5 wherein the proportion of the ingredient (b) is 2 to 140 parts by weight per 100 parts by weight of the ingredient (a), the proportion of the ingredient (b') is 4 to 10 parts by weight per 100 parts by weight of the ingredient (b), the proportion or the ingredient (c) is 10 to 100 parts by weight per 100 parts by weight of the ingredients (a), (b) and (b') combined, and the proportion of the ingredient (d) is 0.01 to 10 parts by weight per 100 parts by weight of the ingredients (a), (b) and (b') combined.

8. A sheet molding compound obtained from the composition of claim 1 or 5.

9. The composition of claim 1, 2 or 3, wherein the polyamino compound has the formula:

R(NH2)m (wherein R represents an alkylene, cycloalkylene or arylene group and m represents an integer of 2, 3 or 4);
the bismaleimide has the formula:

(3) (wherein R2 represents an alkylene, cycloalkylene or arylene group having at least 2 carbon atoms or a combination of two or more of these groups, and R3 represents a divalent organic group having a carbon-carbon double bond); and the amount of the unsaturated bismaleimide compound is 0.1 to 10 gram-equivalents per gram-equivalent of the polyamino compound.

10. The composition of claim 5, 6 or 7, wherein the polyamino compound has the formula:
R(NH2)m (wherein R represents an alkylene, cycloalkylene or arylene group and m represents an integer of 2, 3 or 4);
the bismaleimide has the formula:

(3) (wherein R2 represents an alkylene, cycloalkylene or arylene group having at least 2 carbon atoms or a combination of two or more of these groups, and R3 represents a divalent organic group having a carbon-carbon double bond);
the amount of the unsaturated bismaleimide compound is 0.1 to 10 gram-equivalents per gram-equivalent of the polyamino compound; and the aliphatic epoxy compound containing no vinyl group is a member selected from the group consisting of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether and an epoxy resin obtained by the reaction of an aliphatic carboxylic acid with epichlorohydrin.