JPH0551455A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition containing a bismaleimide compound having specific amide ends at a definite ratio and capable of providing a cured product having heat resistance and mechanical characteristics. CONSTITUTION:A thermosetting resin composition containing an (A) amino-ended imidooligomer of formula I (A is divalent aromatic residue; n is 1-20) obtained by reacting biphenyltetracarboxylic acids with an aromatic diamine component and each having an amino group at both ends and imido bond in the inside of the oligomer, and (B) a bismaleimide compound expressed by formula II (R is divalent aromatic residue) such as diphenylalkane-based bismaleimide, at an amount of the component (B) of 1-20 mol, based on 1 mol component (A), and useful for electric and electronic component material, sliding part material, general industrial structural material, etc., as a laminate sheet and molding material.

Description

Detailed Description of the Invention

[0001]

This invention relates to a specific amino-terminated imide oligomer obtained by reacting biphenyltetracarboxylic acids with an excess of an aromatic diamine compound, and a specific bismaleimide compound in a specific ratio. A thermosetting resin composition containing as a component, or a thermosetting composition containing a prepolymer having an unsaturated group obtained by reacting the amino-terminated imide oligomer with a bismaleimide compound as a resin component ..

In the thermosetting resin composition of the present invention, the above-mentioned resin components, that is, the amino-terminated imide oligomer, the bismaleimide compound and the unsaturated prepolymer are soluble in an organic solvent or melted at an appropriately low temperature. It is easy to handle, and when these resin components are thermoset, thermoset products with excellent heat resistance and mechanical properties (particularly toughness) can be formed. As a material, it is useful as an electric / electronic component material, a sliding part material, a general industrial structural material, and the like.

[0003]

2. Description of the Related Art Conventionally, thermosetting resins containing bismaleimide having an unsaturated bond and an imide bond are excellent in electrical properties and coefficient of thermal expansion. Widely used in industry as materials and structural materials.

However, a cured polyimide resin obtained by polymerizing (curing) a bismaleimide compound alone is considerably excellent in thermal properties, but extremely brittle and inferior in mechanical properties. ..

As a solution to the above-mentioned drawbacks, a thermosetting resin composition obtained by reacting an aromatic bismaleimide with an aromatic diamine has been proposed.
No. 23,250, N, N'-
4,4'-diphenylmethane bismaleimide and 4,4 '
-A polyamino bismaleimide resin (manufactured by Rhone-Poulin, trade name: kelimide), which is a reaction product with diaminodiphenylmethane, has been put into practical use.

[0006] However, the known thermosetting resin composition is insufficient in toughness because the thermosetting product has an extremely small elongation, and when the thermosetting product is molded, the thermosetting product is insufficient. It is difficult to obtain a thermosetting product of stable quality with good reproducibility because a large number of microcracks are easily generated.

According to Japanese Patent Laid-Open No. 50-129700, a thermosetting resin obtained from bismaleimide and a cyanate ester has good moldability and the cured product has improved mechanical properties. Have been described. However, the heat-cured product is not sufficient in heat resistance and water resistance.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to solve the above-mentioned problems of the known thermosetting resin, to have a high level of heat resistance and mechanical properties, and to be resistant to water. The object of the present invention is to provide a thermosetting resin composition which has sufficient reproducibility and chemical resistance, and in particular can form a thermosetting product having improved toughness with good reproducibility.

[0009]

The first invention of the present application is the general formula I obtained by reacting biphenyltetracarboxylic acids with an aromatic diamine component.

[0010]

[Chemical 5] (However, A in the formula represents a divalent aromatic residue, and n is 1
-20, preferably 1-10. ), An amino-terminated imide oligomer having an amino group at both ends and an imide bond inside the oligomer, and a general formula II

[0011]

[Chemical 6] (However, R in the formula represents a divalent aromatic residue.) The bismaleimide compound represented by 1 to 20 moles (preferably 2 moles) relative to 1 mole of the amino-terminated imide oligomer.
The present invention relates to a thermosetting resin composition which is uniformly blended and contained as a resin component in a ratio of 10 to 10 mol) of a bismaleimide compound.

The second invention of this application is the above general formula I
1 mol of an amino-terminated imide oligomer represented by: and the bismaleimide compound 1 to 20 represented by the general formula II.
The present invention relates to a thermosetting resin composition containing, as a resin component, a prepolymer having an unsaturated group obtained by reacting a mixture with a mole, preferably 2 to 10 moles.

The prepolymer, which is the resin component in the thermosetting resin composition of the second invention, has a melting point of about 80-
A thermosetting prepolymer having a temperature of 200 ° C., particularly about 100 to 180 ° C., and having at least one carbon-carbon unsaturated group based on bismaleimide is preferable.

In the thermosetting resin composition of the first invention of this application, the resin component consisting of the "homogeneous mixture of the amino-terminated imide oligomer and the bismaleimide" is a lumpy or powdery solid at room temperature. , Its resin component 10
The melting point is preferably about 80 to 2 by reacting by heating at 0 to 200 ° C, particularly about 120 to 180 ° C.
A thermosetting prepolymer having a temperature of 00 ° C., particularly about 100 to 180 ° C. and having at least one unsaturated group based on bismaleimide can be obtained.

The above-mentioned thermosetting prepolymer is the same as the prepolymer which is the resin component in the thermosetting composition of the second invention of this application, for example, the general formula II
I

[Chemical 7] (However, in formula, A and n are the same as the above, and m is 0-40, especially about 0-20.) It has mainly the structural formula etc. which are shown.

The amino-terminated imide oligomer used in the present invention is 3,3 ', 4,4'- or 2,3,3',
An acid derivative such as 4′-biphenyltetracarboxylic acid or an acid dianhydride thereof, or an esterified product or salt of these acids (preferably 2,3,3 ′, 4′-biphenyltetracarboxylic acids alone or 2 , 3,3 ′, 4′- and 3,3 ′, 4,4′-dianhydride biphenyltetracarboxylic acids) and an excess of an aromatic diamine. The obtained low-molecular weight amino-terminated imide oligomer has amino groups at both ends and an imide bond inside the oligomer.

The above amino-terminated imide oligomer has the general formula IV

[Chemical 8] (However, A in the formula represents a divalent aromatic residue.) 40 mol% or more, particularly 45 to 100 mol%, and a general formula V

[0018]

[Chemical 9] (However, A in the formula represents a divalent aromatic residue.) The constituent unit represented by the formula is less than 60 mol%, particularly 0 to 55 mol%.
An amino-terminated imide oligomer having an amino group at both ends and an imide bond inside the oligomer is particularly preferable because it has excellent solubility in an organic polar solvent and compatibility with a bismaleimide.

The above-mentioned amino-terminated imide oligomer preferably has a melting point of about 80 to 260 ° C., particularly about 100 to 250 ° C. Further, it has at least 3 in an organic polar solvent (especially amide solvent, pyrrolidone solvent, etc.). weight%,
Particularly, it is preferable that the compound can be uniformly dissolved at a concentration of about 5 to 40% by weight.

The above-mentioned amino-terminated imide oligomer has an imidation ratio of 90 as measured by infrared absorption spectroscopy.
% Or more, particularly 95% or more, or a high imidation ratio such that an absorption peak related to the amide-acid bond of the polymer is not substantially found in the infrared absorption spectrum analysis and only an absorption peak related to the imide ring bond is observed. Is preferred.

The method for producing the amino-terminated imide oligomer is, for example, 40% by mole or more of 2,3,3 ', 4'-biphenyltetracarboxylic acid and 3,3', 4,4 '.
Biphenyltetracarboxylic acids consisting of less than 60 mol% of biphenyltetracarboxylic acids and aromatic diamine, wherein about 1.05 to 2 mol, particularly 1.1 to 2 mol of aromatic diamine per 1 mol of biphenyltetracarboxylic acids. In the organic polar solvent such as a phenolic solvent or an amide solvent at a high temperature (particularly at a temperature of 140 ° C. or higher), both monomer components are polymerized and imidized. it can.

As the method for producing the amino-terminated imide oligomer, the aromatic tetracarboxylic acid component and the diamine component are polymerized in an organic polar solvent at a low temperature of 0 to 80 ° C. to give an amino-terminated amic acid oligomer. May be produced, and the amino-terminated amic acid oligomer may be imidized by any known method to produce a soluble amino-terminated imide oligomer.

The above-mentioned biphenyltetracarboxylic acids are
A part (for example, 20 mol% or less, particularly 10 mol% or less) of other aromatic tetracarboxylic acids, for example, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid or its acid dianhydride, pyromellitic acid or its acid dianhydride,
2,2-bis (3 ', 4'-dicarboxyphenyl) propane or its acid dianhydride, bis (3', 4'-dicarboxyphenyl) methane or its acid dianhydride, bis (3 ', 4) '-Dicarboxyphenyl) ether or an acid dianhydride thereof, or an aliphatic tetracarboxylic acid,
For example, it may be substituted with butanetetracarboxylic acid or its acid dianhydride.

The aromatic diamine used in the above-mentioned method for producing an amino-terminated imide oligomer is (a) a diamine compound having one benzene ring or one aromatic ring, and examples thereof include phenylenediamines, xylylenediamines, and trialkylbenzenediamines. Kind, etc.

(B) As a diamine compound having two benzene rings or aromatic rings, a benzidine type diamine compound, a diphenyl ether type diamine compound, a diphenyl thioether type diamine compound, a benzophenone type diamine compound, a diphenylsulfine type diamine compound,
Diphenyl sulfide type diamine compound, diphenyl sulfone type diamine compound, diphenyl alkane type diamine compound, etc.

(C) As a diamine compound having three benzene rings or aromatic rings, a bis (phenoxy) benzene-based diamine compound, a bis (phenyl) benzene-based diamine compound, and (d) a benzene ring or aromatic ring. Examples of the diamine compound having four are bis [(phenoxy) phenyl] propane-based diamine compound, bis [(phenoxy) phenyl] sulfone-based diamine compound, and the like, and these can be used alone or as a mixture. ..

As the aromatic diamine, especially 4,
Diphenyl ether-based diamine compounds such as 4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,
Diphenylmethane-based diamine compounds such as 4′-diaminodiphenylmethane and 3,3′-diaminodiphenylmethane,

2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane,
Bis (phenyl) propane-based diamine compounds such as 2,2-bis (4-aminophenyl) hexafluoropropane, diphenylene sulfone-based diamine compounds, 1,3-
Di (4-aminophenoxy) benzene, 1,4-di (4
-Aminophenoxy) benzene and other di (phenoxy)
Benzene-based diamine compound,

Di (phenoxyphenyl) propane-based diamine compounds such as 2,2-di [4- (4-aminophenoxy) phenyl] propane and 2,2-di [4- (3-aminophenoxy) phenyl] propane , Screw [4-
"Aromatic diamine compound having 2 to 4 aromatic rings" such as di (phenoxyphenyl) sulfone-based diamine compound such as (4-aminophenoxy) phenyl] sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone ] Can be mentioned suitably.

The above-mentioned aromatic diamine is a part (about 2
(Less than 0 mol% and less than 10 mol) may be substituted with a polymeric diamine such as diaminopolysiloxane, diaminopolyoxypropylene, diaminopolyethylene glycol.

Examples of the organic polar solvent used in the production of the amino-terminated imide oligomer include acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, N, N-dimethylformamide, N, Formamide-based solvents such as N-diethylformamide, N-methyl-2-pyrrolidone, N-vinyl-2
-Pyrrolidone-based solvents such as pyrrolidone, amide-based solvents such as N-methylcaprolactam, or sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide, and solvents containing sulfur atoms such as dimethyl sulfone, diethyl sulfone, and hexamethyl sulfolamide. ,
Mention may be made of phenolic solvents such as cresol, phenol, xylenol and other solvents such as pyridine, ethylene glycol, tetramethylurea.

The bismaleimide compound represented by the general formula II used in the present invention has a melting point of 1 mol of the aromatic diamine and 2 mol of maleic anhydride similar to those used in the amino-terminated imide oligomer. About 8
The bismaleimide represented by the general formula II having a temperature of 0 to 220 ° C., particularly about 100 to 200 ° C. is preferable.

Examples of the bismaleimide represented by the general formula II include (i) one benzene ring such as N, N'-p-phenylene bismaleimide and N, N'-m-toluylene bismaleimide. Having phenylene bismaleimide, or

(B) N, N'-4,4'-diphenylmethane bismaleimide, N, N'-3,3'-diphenylmethane bismaleimide, N, N'-3,3 '-[3
3′-dimethyldiphenylmethane] bismaleimide,
N, N'-3,3 '-[3,3'-diethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenyl-1,1'-propanebismaleimide, N, N'-
A diphenylalkane-based bismaleimide such as 3,3′-diphenyl-1,1′-propane bismaleimide,

N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenyl ether bismaleimide and other diphenyl ether type bismaleimides, N, N'-4,4'-diphenyl sulfide bis Maleimide, N, N'-3,3'-diphenylsulfide bismaleimide and other diphenylsulfide-based bismaleimides, N, N'-4,4'-diphenylsulfone bismaleimide, N, N'-3,3'-diphenyl Diphenyl sulfone-based bismaleimide such as sulfone bismaleimide,

N, N'-4,4'-diphenylketone bismaleimide, N, N'-3,3'-diphenylketone bismaleimide and other diphenylketone bismaleimides, N, N'-4,4'- Biphenyl bismaleimide,
N, N'-3,3'-biphenyl bismaleimide, N,
Examples include bismaleimide compounds having two or more benzene rings such as biphenyl-based bismaleimides such as N′-3,3 ′-[3,3′-dimethyl-biphenylene] bismaleimide. May be used alone, or two or more of these may be mixed and used.

In the present invention, as the bismaleimide compound, a bismaleimide compound having two benzene rings such as diphenylalkane type bismaleimide and diphenyl ether type bismaleimide is particularly preferable.

As a method for preparing the thermosetting resin composition of the first invention of this application, for example, fine powder of the above-mentioned amino-terminated imide oligomer (average particle diameter: 1 to 100 μm,
2 to 50 μm) and bismaleimide compound powder (average particle diameter: 20 to 200 μm, particularly 50 to 100 μm)
m) may be intimately mixed at a temperature of less than about 80 ° C., in particular at a temperature of 0 to 60 ° C. to prepare a powder mixture, or

The above amino-terminated imide oligomer and bismaleimide compound are uniformly dissolved in an organic polar solvent at the above-mentioned mixing ratio at a temperature of 0 to 120 ° C., particularly 5 to 100 ° C., and then water, methanol, ethanol, etc. In a poor solvent of, the precipitate is dried, and finally, if necessary, by crushing and pulverizing the precipitate,
Powder of thermosetting resin composition (average particle size: 2 to 150 μm)
m, particularly preferably 5 to 100 μm).

As a method for preparing the thermosetting resin composition of the second invention of this application, for example, 1 mol of the amino-terminated imide oligomer represented by the above general formula I and the bis compound represented by the above general formula II are used. A mixture of the maleimide compound and 1 to 20 mol, preferably 2 to 10 mol, prepared by the powder mixing method or the solution method as described above, is preferably about 100 to 220 ° C., particularly preferably 120 to 200.
It is heated to the temperature of ℃ and melted, and the temperature is about 5-40.
After maintaining for 0 minutes, particularly preferably 10 to 350 minutes, the amino group of the amino-terminated imide oligomer is reacted with the unsaturated group of the bismaleimide compound to form a prepolymer having an unsaturated group, and then the mixture is ground. A method for preparing the thermosetting resin composition of the second invention can be mentioned by pulverizing it to obtain a thermosetting resin composition.

Each thermosetting resin composition of the present invention may be used as it is or may be dissolved in an organic solvent and impregnated into glass cloth, carbon cloth, or fibers such as glass fiber and carbon fiber. It is possible to form a prepreg by drying at a temperature of ℃ or lower, and further stack the prepreg to 200 ℃ or higher, especially 200 to 4
At a temperature of 00 ° C, under pressure, for about 5 to 500 minutes, in particular 1
A molded product such as a laminate can be manufactured by heating and curing for 0 to 300 minutes.

Further, each thermosetting resin composition of the present invention is added with short fibers such as glass fiber and carbon fiber, and fine powder such as carbon, molybdenum, silica and silicon carbide, and heat-cured as described above. By doing so, a molding material having improved mechanical properties can be formed.

Further, each thermosetting resin composition of the present invention may further contain various other additives, for example, curing accelerators such as organic peroxides, azo compounds and imidazoles. You may add the additive of.

[0044]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Reference Example 1 [Production of amino-terminated imide oligomer (P1)] In a 1-liter glass flask, (a) 2,3,3'4'-biphenyltetracarboxylic dianhydride (a-BPDA) was added. 29.422 g (0.1 mol), (b) 1,3-bis (4-aminophenoxy) benzene (TPE-R) 58.468 g (0.2 mol), and (c) N-methyl-2. -Pyrrolidone (NMP) (196 g) was charged, and the mixture was stirred at 50 ° C for 1 hour in a nitrogen atmosphere to generate an amino-terminated amic acid oligomer.

Next, the reaction liquid in which the amino-terminated amic acid oligomer was produced was heated to 200 ° C. and stirred at that temperature for 3 hours while removing the condensed water to obtain an amino-terminated imide oligomer having amino groups at both ends. After the reaction is completed, the reaction solution is cooled to room temperature (about 25 ° C.), then poured into water at room temperature to precipitate a powdery amino-terminated imide oligomer, and the amino-terminated imide oligomer is filtered and separated. , Washed twice with 25 ° C. methanol, dried under reduced pressure and dried to obtain a powder of an amino-terminated imide oligomer (P1) having amino groups at both ends (n in the general formula I above).
Is 1, its average molecular weight is 843, and its melting point is 120 ° C. ) Got.

Reference Example 2 [Production of amino-terminated imide oligomer (P2)] 44.14 g (0.15 mol) of (a) 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) ), (B) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) 44.14 g (0.15 mol), (c) 1,3-bis (4-aminophenoxy) ) Benzene (TPE-R) 116.94 g (0.4 mol), and (d) N-methyl-2-pyrrolidone (NMP) 777 g were used in the same manner as in Reference Example 1, except that 777 g was used. A powder of an amino-terminated imide oligomer (P2) having an amino group (n in the above general formula I was 3, the average molecular weight was 1944, and the melting point was 175 ° C.) was obtained.

Reference Example 3 [Production of amino-terminated imide oligomer (P3)] (a) 2,3,3'4'-biphenyltetracarboxylic dianhydride (a-BPDA) 147.11 g (0.5 mol) , (B) 1,3-bis (4-aminophenoxy) benzene (TPE-R) 175.40 g (0.6 mol), and (c) N-methyl-2-pyrrolidone (NMP) 710 g were used. Otherwise, in the same manner as in Reference Example 1, a powder of an amino-terminated imide oligomer (P3) having amino groups at both ends (n in the general formula I is 5, the average molecular weight is 3045, and the melting point is 240 ° C.) was obtained.

Reference Example 4 [Production of amino-terminated polyimide (P4)] (a) 88.266 g (0.30 mol) of 2,3,3'4'-biphenyltetracarboxylic dianhydride (a-BPDA), (B) 1,3-bis (4-aminophenoxy) benzene (TPE-R) 90.625 g (0.31 mol), and (c) N-methyl-2-pyrrolidone (NMP) 672 g Is a powder of amino-terminated polyimide (P4) having amino groups at both ends (n in the general formula I is 30, the average molecular weight is 16800, and melting is performed in the same manner as in Reference Example 1. Thermal decomposition did not occur up to 450 ° C).

Example 1 [Preparation of thermosetting resin composition] 1 mol of the amino-terminated imide oligomer (P1) prepared in Reference Example 1 and N, N'-
2 mol of 4,4′-diphenylmethane bismaleimide and N-methyl-2-pyrrolidone (NMP) at 80 ° C.
To prepare a solution containing 20% by weight of a resin component, cooled to room temperature (about 25 ° C.), and then poured into water at room temperature to precipitate a powdery precipitate, which is filtered and separated, Further, it was dried under reduced pressure to obtain a powdery thermosetting resin composition (having an average particle diameter of 15 μm and a melting point of 136 ° C.).

[Production of Thermosetting Molded Product] The powdery thermosetting resin composition obtained as described above is heated to 180 ° C. to be melted, sufficiently mixed and degassed to 200 ° C. After being poured into a heated mold, the pressure was maintained at 10 kg / cm ² and the temperature was 230 ° C. for 2 hours to form a thin plate (150 mm in length × 150 mm in width × 2 mm in thickness). Remove the sheet from the mold and further at 250 ° C. for 2 hours and 27
Post-curing was performed in a hot air oven at 0 ° C. for 2 hours to prepare a tensile test piece. The tensile test is ASTM-D6
No. 38, and the thermal decomposition temperature of the test piece was measured in air at a heating rate of 10 ° C./min. The results are shown in Table 1.

Example 2 A powdery thermosetting resin composition (average) was prepared in the same manner as in Example 1 except that the amount of N, N'-4,4'-diphenylmethane bismaleimide used was changed to 4 mol. Particle size is 25μ
m, and the melting point is 120 ° C. ) Got.

A thin plate-shaped tensile test piece was prepared in the same manner as in Example 1 except that the thermosetting resin composition obtained as described above was used, and the tensile test and the thermal decomposition temperature were measured. The results are shown in Table 1.

Example 3 The amino-terminated imide oligomer (P
2) In the same manner as in Example 1 except that 1 mol and 2 mol of N, N'-4,4'-diphenylmethane bismaleimide were used, a powdery thermosetting resin composition (having an average particle diameter of 20 μm and a melting point of 147 ° C.).

A thin plate-shaped tensile test piece was prepared in the same manner as in Example 1 except that the thermosetting resin composition obtained as described above was used, and the tensile test and the thermal decomposition temperature were measured. The results are shown in Table 1.

Examples 4 to 5 N, N'-4,4'-diphenylmethane bismaleimide was used in an amount of 4 mol (Example 4) or 6 mol (Example 5).
In the same manner as in Example 3 except that the thermosetting resin composition was in the form of powder (Example 4: Average particle size is 27 μm, melting point is 143 ° C. Example 5: Average particle size) Is 3
It has a melting point of 140 ° C. ) Respectively.

Thin plate-like tensile test pieces were prepared in the same manner as in Example 1 except that the thermosetting resin compositions obtained as described above were used, and the tensile test and the thermal decomposition temperature were measured. The results are shown in Table 1.

Example 6 The amino-terminated imide oligomer (P
3) In the same manner as in Example 1 except that 1 mol and 4 mol of N, N′-4,4′-diphenylmethane bismaleimide were used, a powdery thermosetting resin composition (having an average particle diameter of 30 μm and a melting point of 150 ° C.).

A thin plate-shaped tensile test piece was prepared in the same manner as in Example 1 except that the thermosetting resin composition obtained as described above was used, and the tensile test and the thermal decomposition temperature were measured. The results are shown in Table 1.

Example 7 [Production of unsaturated prepolymer] 1 mol of the amino-terminated imide oligomer (P2) produced in Reference Example 2 and N, N'-
6 mol of 4,4′-diphenylmethane bismaleimide was used as a powder and mixed, and the mixture was heated at 180 ° C. for 30 minutes to react to form an unsaturated prepolymer. The polymer was pulverized and pulverized to obtain a thermosetting resin composition composed of a powdery unsaturated prepolymer (having an average particle diameter of 60 μm and a melting point of 141 ° C.).

A thin plate-shaped tensile test piece was prepared in the same manner as in Example 1 except that the thermosetting resin composition obtained as described above was used, and the tensile test and the thermal decomposition temperature were measured. The results are shown in Table 1.

Comparative Examples 1 to 2 1 mol of 4,4'-diaminodiphenylmethane (Comparative Example 1) or 1 mol of 1,3-bis (4-aminophenoxy) benzene (Comparative Example 2) and N, N'-4 , 4'-diphenylmethane bismaleimide and 2 mol were used,
In the same manner as in Example 1, a powdery thermosetting resin composition (Comparative Example 1: average particle diameter 30 μm, melting point 83
℃. Comparative Example 2: The average particle diameter is 35 μm and the melting point is 120 ° C. or lower. ) Were prepared respectively.

Thin plate-like tensile test pieces were prepared in the same manner as in Example 1 except that each thermosetting resin composition obtained as described above was used. Each measurement is performed and those results are
Shown in the table.

Comparative Example 3 In the same manner as in Example 1 except that 1 mol of the amino-terminated polyimide (P4) prepared in Reference Example 4 and 4 mol of N, N'-4,4'-diphenylmethane bismaleimide were used. , Powdery thermosetting resin composition (average particle size 50 μm
m, and the melting point is 300 ° C. or higher. ) Got. The thermosetting resin composition obtained as described above had an extremely high melting point, and therefore could not be molded under the molding conditions of Example 1.

[0065]

[Table 1]

[0066]

The thermosetting resin composition of the present invention has a resin composition in which the amino-terminated imide oligomer, the bismaleimide compound and the unsaturated prepolymer, which are the above-mentioned resin components, are soluble in an organic solvent or have a relatively low temperature. It is extremely easy to handle because it melts at 100 ° C., and when a thermosetting resin composition mainly containing those resin components is heat-cured, it has excellent heat resistance and mechanical properties (particularly toughness). So that it can form a laminated board,
It is useful as a molding material for electric / electronic component materials, sliding part materials, general industrial structural materials, and the like.

Claims (2)

[Claims] 1. A general formula I obtained by reacting biphenyltetracarboxylic acids with an aromatic diamine component. (However, A in the formula represents a divalent aromatic residue, and n is 1
~ 20. ), An amino-terminated imide oligomer having an amino group at both ends and an imide bond inside the oligomer, and a compound represented by the general formula II: (However, R in the formula represents a divalent aromatic residue.) The bismaleimide compound represented by the formula (1) is used at a ratio of 1 to 20 mol of the bismaleimide compound to 1 mol of the amino-terminated imide oligomer. A thermosetting resin composition contained as a component. 2. A general formula I obtained by reacting biphenyltetracarboxylic acids with an aromatic diamine component. (However, A in the formula represents a divalent aromatic residue, and n is 1
~ 20. 1 mol of an amino-terminated imide oligomer having an amino group at both ends and an imide bond inside the oligomer, represented by the general formula II: (However, R in the formula represents a divalent aromatic residue.) A prepolymer having an unsaturated group obtained by reacting a mixture with 1 to 20 mol of a bismaleimide compound represented by A thermosetting resin composition containing.