JPS6232207B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent heat resistance.

Conventionally, three-dimensional polymaleimide, which is made by heating and polymerizing polymaleimides alone, has been known as a heat-resistant resin, but this three-dimensional polyimide has the disadvantage of being extremely brittle, making it unsuitable for practical use. Ta.

A method of producing heat-resistant maleimide amine resin by reacting polymaleimides with polyamines has also been proposed, but in this case, if aliphatic polyamines are used, the reaction proceeds rapidly, making molding difficult. In addition, there was a problem of poor heat resistance.

On the other hand, when an aromatic polyamine is used, a resin with good heat resistance can be obtained, but in this case, the curing reaction must be carried out under fairly severe conditions even with the melt method, such as 160%
The drawback was that it required several hours to several tens of hours at ~250°C.

Furthermore, various methods have been proposed for blending epoxy resins with these maleimide resins, but there is a problem that the compatibility between polymaleimides and epoxy resins is poor, and mixtures of maleimide amine resins and epoxy resins are difficult to blend with maleimide resins. The remaining amine in the amine resin easily reacts with the epoxy resin, resulting in poor stability and workability.

The present invention was made in view of the above circumstances, and
The object is to provide a thermosetting resin composition that has excellent heat resistance, stability, and workability.

That is, the thermosetting resin composition of the present invention comprises: (a) 10 to 90% by weight of the total resin composition; (In the formula, R ₁ is a divalent organic group, and X ₁ and X ₂ each represent the same or different monovalent atoms or groups selected from a hydrogen atom, a halogen atom, or an organic group.) Maleimides and (b) General formula (In the formula, R ₂ is a monovalent atom or group selected from a hydrogen atom, a halogen atom, or an organic group, and m represents an integer of 1 to 5, respectively.) Addition reaction product with aminophenols represented by and (b) maleimide group 1 of the bismaleimides mentioned in (a) above.
Furfuryl alcohol in an amount of 0.01 to 0.5 mol% based on the equivalent, and (c) 5 to 250 parts by weight based on 100 parts by weight of the total amount of the addition reaction product in (a) above and the furfuryl alcohol in (b) above.
parts by weight of a polyfunctional epoxy compound.

Examples of the polymaleimide (a) used in the present invention include ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide, 4,4'-diphenylmethane bismaleimide, 4,4' -diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4'-diphenylcyclohexane bismaleimide, 4・4′-diphenylene bismaleimide, etc.

In addition, N-3-chlorophenylmaleimide, N-4
- A monomaleimide such as nitrophenylmaleimide can also be used in combination.

Examples of aminophenols in (b) include o-, m-, p-, isomer aminophenol and aminocresol, aminoxylenol containing various substituent isomers, aminochlorophenol, aminobromophenol, amino These include catechol, aminoresorcin, aminobis(hydroxyphenyl)propane, and aminooxybenzoic acid.

One type or two or more types of each of the above-mentioned polymaleimides and aminophenols can be selected and subjected to the addition reaction. The amount of aminophenols used at this time is preferably 0.1 to 1 mol, preferably 0.15 to 0.9 mol, per equivalent of the maleimide group of the polymaleimide.

If the amount of aminophenols is less than 0.1 mol, the compatibility between the adduct and the epoxy resin described below will deteriorate, and if it exceeds 1 mol%, the stability of the resin composition will be lowered due to residual amine, and the desired heat resistance will be lowered. It becomes difficult to obtain.

The reaction temperature of the addition reaction is generally in the range of 50 to 200°C, preferably 80 to 180°C, and the reaction time can be arbitrarily selected, usually from several minutes to several tens of hours. The raw material mixture may be melt-reacted without a solvent or may be reacted in the presence of a solvent. Solvents that can be used in the latter reaction include polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, as well as acetone, methyl ethyl ketone, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Low boiling solvents such as cyclohexane can also be used.

The resin composition of the present invention can be obtained by mixing the thus synthesized polymaleimide/aminophenol adduct, furfuryl alcohol, and a polyfunctional epoxy compound.

As the polyfunctional epoxy compound (c), a wide variety of compounds generally known as epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polyglycidyl ester of polycarboxylic acid, polyglycidyl ether of polyol, epoxy resin obtained by glycidylation of amine, epoxidized unsaturated compound. Resin group or alicyclic polyepoxides, epoxy resins having heterocycles, epoxy resins having heterocyclic rings, etc. can also be used.

The above-mentioned epoxy resins can be used alone or in combination of two or more.

The blending ratio of the polymaleimide/aminophenol adduct, polyfunctional epoxy compound, and furfuryl alcohol can be varied over a wide range depending on the application, but in general, the following blending ratio is appropriate.

In other words, the proportion of the polymaleimide/aminophenol adduct in the total resin composition is 10% by weight.
~90%, preferably 20-80%. If it is less than 10%, the heat resistance of the resin composition will decrease, and if it exceeds 90%, the mechanical strength will decrease. Further, the blending ratio of furfuryl alcohol is 0.01 to 0.5 mol per equivalent of maleimide group of the polymaleimide, preferably 0.05 to 0.5 mol.
Use 0.4 mol. By using furfuryl alcohol, workability and curing properties are improved.

Furthermore, the polyfunctional epoxy compound is suitably 5 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the polymaleimide/aminophenol adduct and the furfuryl alcohol composition. If the amount is less than 250 parts by weight, the adhesion and curing properties will be insufficient, and if it exceeds 250 parts by weight, the heat resistance will decrease.

The resin composition of the present invention is thermosetting and hardens by heating. A curing temperature of 150 to 250°C is generally desirable.

Furthermore, in the present invention, various additives may be added as necessary. For example, in order to improve curability, a curing catalyst selected from known acid anhydrides, boron fluoride complexes, tertiary amines, imidazoles, quaternary ammonium salts, peroxides, etc. can be added. In addition, talc, alumina,
Fillers such as silicone, zircon, quartz glass powder, and glass fiber, colorants such as carbon black and red iron, coupling agents such as glycidoxypropyltriethoxysilane, and mold release agents such as stearic acid may also be added as appropriate. .

The thermosetting resin composition of the present invention has thermal shock resistance,
It has excellent heat aging resistance and high temperature mechanical properties.
It can be used for a wide range of purposes such as impregnation, lamination, molding, and adhesion.

Next, examples of the present invention will be described. In addition, in the following, "parts" are "parts by weight" unless otherwise specified.
shows.

Example 1 4,4'-diphenylmethane bismaleimide 179
(equivalent to 1 equivalent of maleimide group) and 54.5 g (0.5 mol) of p-aminophenol were mixed and reacted at 150°C for 30 minutes. In addition, furfuryl alcohol
Add 9.8g (0.1mol) and hold for 5 minutes to determine the softening point.
A composition of a polymaleimide/aminophenol adduct and furfuryl alcohol was obtained at 68°C.

100 parts of this composition was mixed with 100 parts of bisphenol A epoxy resin (epoxy equivalent: 480), 3 parts of triethylamine, 3 parts of stearic acid, and 350 parts of quartz glass powder (passed through 325 mesh) at 90 to 100°C using a mixing roll. The mixture was kneaded for 10 minutes, cooled, and then ground to obtain a molded powder.

Next, using this molding powder, 180℃, 3 minutes, 60℃
Transfer molding was carried out at Kg/cm ² . The obtained molded product has a glass transition point of 215℃, and a bending strength (JIS-K-6911) of 11.8Kg/mm ² at room temperature and 200℃.
It was 11.4Kg/ ^mm2 .

Example 2 134 g of m-phenylene bismaleimide (corresponding to 1 equivalent of maleimide group) and m-aminophenol
32.7g (0.3mol) were mixed and reacted at 150°C for 30 minutes. Furthermore, 9.8 g (0.1 mol) of furfuryl alcohol was added and held for 5 minutes to obtain a polymaleimide/aminophenol adduct and furfuryl alcohol composition with a softening point of 78°C. 100 parts of this composition,
50 parts of phenol novolak type epoxy resin (epoxy equivalent: 180) and 0.1 part of 2-ethyl-4-methylimidazole were dissolved in dioxane to remove the resin content.
A 50% by weight resin solution was prepared.

Next, this resin solution was applied and impregnated onto a glass cloth (250 x 250 x 0.18 mm) treated with aminosilane.
A prepreg was produced by drying at 100°C for 10 minutes and then at 150°C for 10 minutes. Nine sheets of this prepreg were stacked and pressure-molded using a press machine at 170° C. and 45 kg/cm ² for 30 minutes to obtain a laminate with a thickness of 1.6 mm.

This laminate was further after-cured at 200°C for 5 hours and its bending strength (JIS-C-648) was measured. It obtained excellent values of 60Kg/mm ² at room temperature, 48Kg/mm ² at 200°C, and 500Kg/mm 2 at 250°C. 55Kg/ ^mm2 even after heating for hours
An excellent value was obtained.

Example 3 4,4'-diphenylmethane bismaleimide 179
(equivalent to 1 equivalent of maleimide group) and 43.6 g (0.4 mol) of m-aminophenol were mixed and heated at 150°C for 30
Let it react for a minute. More furfuryl alcohol
19.6 g (0.2 mol) was added and held for 5 minutes to obtain a polymaleimide/aminophenol adduct and furfuryl alcohol composition with a softening point of 72°C.

100 parts of this composition, 100 parts of alicyclic epoxy resin (epoxy equivalent: 140) and benzyldimethylamine.
0.1 was mixed and heated to 80°C to prepare a uniform liquid composition.

Such a liquid composition has fluidity even at room temperature and has a viscosity of 1 poise at 70°C, making it suitable for impregnation treatment. This liquid composition was poured into a mold and heated and cured at 150°C for 5 hours and then at 200°C for 15 hours to make a 1 mm thick test piece.The dielectric loss tangent of the test piece was measured: 0.003 at room temperature and 0.018 at 200°C. It showed excellent characteristics. Moreover, the weight loss after heating at 250°C for 500 hours was only 5.0%.

Example 4 4,4'-diphenylmethane bismaleimide 179
(equivalent to 1 equivalent of maleimide group), 43.6 g (0.4 mol) of m-aminophenol, and 100 g of ethylene glycol monomethyl ether were heated to 120-130°C and reacted for 3 hours, and further 19.6 g (0.2 mol) of furfuryl alcohol was added. The mixture was added and held for 30 minutes to obtain a viscous resin solution.

Next, 50 parts of bisphenol A type epoxy resin (epoxy equivalent: 480) and 0.1 part of boron fluoride monoethanolamine were added to 100 parts of this resin solution, and the resin content was further adjusted to 50% by weight with ethylene glycol monomethyl ether.

Next, this resin solution was applied and impregnated onto a glass cloth (250 x 250 x 0.18 mm) treated with aminosilane.
A prepreg was produced by drying at 100°C for 10 minutes and then at 150°C for 10 minutes. Nine sheets of this prepreg were stacked and pressure-molded using a press at 170° C. and 4.5 kg/cm ² for 30 minutes to obtain a laminate with a thickness of 1.6 mm.

This laminate was further after-cured at 200°C for 5 hours and its bending strength (JIS-C-6481) was measured. It obtained excellent values of 55Kg/mm ² at room temperature, 47Kg/mm ² at 200°C, and 500Kg/mm 2 at 250°C. 51Kg/ ^mm2 even after heating for hours
An excellent value was obtained.

Comparative example 1 4,4'-diphenylmethane bismaleimide 179
(corresponding to 1 equivalent of maleimide group) and 79.2 g (0.4 mol) of 4,4'-diaminodiphenylmethane were mixed and reacted at 150°C for 30 minutes to obtain a polymaleimide amine resin composition.

100 parts of this composition was dissolved in N-methyl-2-pyrrolidone together with 50 parts of bisphenol A type epoxy resin (epoxy equivalent: 480) to prepare a resin solution having a resin content of 50% by weight.

Next, in the same manner as in Example 2, this resin solution was treated with a glass cloth (250 x 250 x 0.18
A prepreg was prepared by coating and impregnating the material (mm) and drying it at 150°C for 10 minutes. Nine sheets of this prepreg were stacked and pressure-molded in a press at 170° C. and 45 kg/cm ² for 30 minutes to obtain a laminate with a thickness of 1.6 mm.

This laminate was further after-cured at 200℃ for 5 hours and the bending strength (JIS-C-6481) was measured: 54Kg/mm ² at room temperature, 32Kg/mm ² at 200℃, 250℃
After heating for 500 hours, the value was 38Kg/ ^mm2 .

Claims (1)

[Scope of Claims] 1 (a) 10 to 90% by weight of the total resin composition, (a) General formula (In the formula, R ₁ is a divalent organic group, and X ₁ and X ₂ each represent the same or different monovalent atoms or groups selected from a hydrogen atom, a halogen atom, or an organic group. The same applies hereinafter.) Bismaleimides represented and (b) general formula (In the formula, R ₂ is a monovalent atom or group selected from a hydrogen atom, a halogen atom, or an organic group, and m represents an integer of 1 to 5. The same applies hereinafter.) an addition reaction product, and (b) the maleimide group 1 of the bismaleimide of (a) above.
Furfuryl alcohol in an amount of 0.01 to 0.5 mol% based on the equivalent, and (c) 5 to 250 parts by weight based on 100 parts by weight of the total amount of the addition reaction product in (a) above and the furfuryl alcohol in (b) above.
parts by weight of a polyfunctional epoxy compound.