JPH02272028A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful as electrical parts, electronic parts, various structural members, sliding members, etc., having excellent heat resistance, impact resistance and toughness, comprising a specific bismaleimide compound and a specific diamine compound. CONSTITUTION:The aimed composition comprising (A) a bismaleimide compound [e.g.1,3-bis(3-maleimidophenoxy)benzene, etc.] shown by formula I (R bifunctional group shown by formula II or formula III; X is direct bond, 1-10 deg.C bifunctional hydrocarbon group, hexafluorinated isopropylidene, carbonyl, thio, sulffnyl, sulfonyl or oxide) and a diamine compound {e.g. 4,4'-bis[4-(4amino-alpha,alpha- dimethylbenzyl)phenoxy]-diphenylsulfone, etc.} shown by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel thermosetting resin composition that has excellent mechanical strength without impairing heat resistance.

[Conventional technology]

Thermosetting resins having an imide structure have been widely used in industry due to their excellent electrical insulation, heat resistance, and dimensional stability of molded products.

However, the thermosetting resin obtained by thermally polymerizing aromatic bismaleimide alone is a material with excellent heat resistance, but has the disadvantage of being extremely brittle and lacking in toughness. As a method to improve this drawback, there have been attempts to use thermosetting resin compositions consisting of aromatic bismaleimide and aromatic diamine. For example, N,N'-4,4'-diphenylmethane bismaleimide and 4 Polyamino bismaleimide resin (manufactured by Loos-Boulin, trade name Kelimide) consisting of .4°-diaminodiphenylmethane has been put into practical use and is widely used in impregnated varnishes, laminates, molded products, etc. (Japanese Patent Publication No. 46-23250) ).

However, these thermosetting resin compositions did not have sufficient heat resistance, and their impact resistance and toughness were also unsatisfactory.

[Problem to be solved by the invention]

An object of the present invention is to provide a thermosetting resin composition having excellent mechanical strength and heat resistance.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors found that a thermosetting resin composition comprising a novel bismaleimide compound and a specific aromatic diamine compound is particularly effective, and the present invention completed.

That is, the thermosetting resin composition of the present invention essentially has the following characteristics:
Represents a divalent group consisting of general formula (1), where X is a direct bond and has 1 to 1 carbon atoms.
bismaleimide, which represents a group selected from the group consisting of 10 divalent hydrocarbon groups, hexafluorinated isopropylidene groups, carbonyl groups, thio groups, sulfinyl groups, sulfonyl groups, or oxides Compound and formula (n)C)1
This is a thermosetting resin composition comprising an aromatic diamine compound represented by 3.

The novel bismaleimide compound represented by the general formula (1) is usually expressed by a known method to represent a divalent group represented by the general formula (II), where X is a direct bond, and the number of carbon atoms is 1 to 1.
10 divalent hydrocarbon groups, hexafluorinated isopropylidene groups, carbonyl groups, thio groups, sulfinyl groups, sulfonyl groups, or oxides; Condensation of maleic anhydride
It can be easily produced by dehydration reaction, specifically, 1,3-bis(3-maleimidophenoxy)benzene, bis(4-
(3-maleimidophenoxy)phenylcomethane, 1.
1-bis(4-(3-maleimidophenoxy)phenyl]ethane, 1.2-bis(4-(3-maleimidophenoxy)phenyl)ethane, 2.2-bis(4-(3-maleimidophenoxy)phenyl) Propane, 2.2-bis[4-(3-maleimidophenoxy)phenylcobutane, 2.2-bis(4-(3-maleimidophenoxy)
phenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4°-bis(3-maleimidophenoxy)biphenyl, bis(4-(3-maleimidophenoxy)phenylkoketone, bis( 4-(3-71-imidophenoxy)phenyl sulfide, bis(4-(3-maleimidophenoxy)phenyl) sulfoxide, bis(
Examples include 4-(3-maleimidophenoxy)phenyl]sulfone, bis(4-(3-maleimidophenoxy)phenyl ether), and these may be used alone or in combination of two or more.

The diamine compound used in the present invention is 4,4'-bis(4-(4-amino-α) represented by formula (n).
α-dimethylbenzyl)phenoxy]-diphenylsulfone, 2-<4'-aminophenyl/) -
2-(4”-hydroxyphenyl)propane and 4,4
It can be synthesized in the presence of dichlorodiphenyl sulfone and a more basic compound in an organic solvent.

A thermosetting resin composition is obtained from the bismaleimide compound of the above general formula (1) and the diamine compound represented by the formula (■). In this case, various methods shown below can be used.

(1) Bismaleimide and diamine are pulverized and mixed in solid form, or this is heat-treated to form a prepolymer, which is then pulverized into pellets or powder. The heating conditions in this case are preferably those that partially cure the prepolymer stage, and for -i, the temperature is 70 to 220'C and the temperature is 5 to 240'C.
10-180 minutes, preferably at a temperature of 80-200°C.
It is appropriate to set the number of minutes.

(2) Dissolve bismaleimide and diamine in an organic solvent, then discharge into a poor solvent and dry the precipitated crystals to form pellets or powder, or dissolve them in an organic solvent and heat-process to preform. After partially curing to the polymer stage, it is discharged into a poor solvent and the precipitated crystals are dried to form a pellet or powder. The conditions in this case also conform to (1).

The organic solvent that can be used is limited in that it does not substantially react with the image components, but it is also desirable that it be a good solvent for the re-reactive components. Usually, reaction solvents used are halogenated hydrocarbons such as methylene chloride, dichloroethane, and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisopropyl ketone, ethers such as tetrahydrofuran, dioxane, and methyl cellosolve, benzene, etc.
・Aromatic compounds such as toluene and chlorobenzene, aprotic polar compounds such as acetonitrile, N,N-dimethylformamide, NN-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidabridinone such as solvents.

-IG The ratio of the bismaleimide compound of formula (1) and the diamine compound represented by formula (TI) is 0.1 to 1.2 per mol of the bismaleimide compound.
The amount used is preferably 0.2 to 0.8 mole, and if the proportion of the diamine compound used is small, a cured product will not have good impact resistance and toughness. On the other hand, if the amount is too high, it will adversely affect the heat resistance of the cured product.

If necessary, the following components can be added to the thermosetting resin composition of the present invention within a range that does not impair the object of the present invention.

(b) Curing accelerators, such as radical polymerization initiators such as azo compounds and organic peroxides, ionic catalysts such as tertiary amines, quaternary ammonium salts, imidazoles, and boron trifluoride/amine salts. .

(iv) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, and bases. Magnesium silicate, fired clay, fine powder silica, fused silica, crystalline silica, carbon black, kaolin, fine powder mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, dioxide Antimony, as well as fibrous reinforcing agents and fillers, such as glass fibers, ronfural, ceramic fibers, amina fibers, potassium titanate l! These include inorganic fibers such as fiber, carbon fibers, and organic fibers such as aromatic polyamide.

(c) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, thermosetting resins such as phenol resin, epoxy resin, melamine resin, silicone resin, polyamide, polycarbonate, polysulfone, polyether sulfone, polyether ether ketone, modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, fluororesin, etc. It is.

The thermosetting resin composition of the present invention is molded by a known molding method such as a compression molding method, a transfer molding method, an extrusion molding method, or an injection molding method, and is put into practical use.

(Example〕 The present invention will be explained below using examples.

Examples 1 to 3 4,4°-bis(4-(4-amino-α, α-
dimethylbenzyl) phenoxyfudiphenyl sulfone (
AHP-3 (hereinafter abbreviated as AHP-3) and 1,3-bis(3-maleimidophenoxy)benzene were mixed in advance at the molar ratio shown in Table 1.
The mixture was heated for 1 minute to undergo a melting reaction.

Thereafter, the mixture was cooled to room temperature, and the reaction product solidified into a brown transparent glass was pulverized to obtain a yellow fine powder of a partially cured thermosetting resin composition.

The composition was heated to 180°C in a mold (10 x 80 x 4
m) while heating and melting, the pressure is 50 kg/
CD, held at 200°C for 30 minutes, and compression molded. After cooling to room temperature, the molded product is removed from the mold.
Further, post-curing was performed in a hot air oven at 250° C. for 4 hours to obtain an Izot impact test piece and a bending test piece.

Isotsu impact test (no notch) bending test is JIS
The thermal decomposition initiation temperature was measured in air at a temperature increase rate of 10'C/l1in, and the results shown in Table 1 were obtained.

Example-4 AHP-3 and 1,3-bis(3-maleimidophenoxy)benzene were charged into a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube at the molar ratio shown in Table 1. Then, after injecting N-methyl-2-pyrrolidone in an amount to make the resin concentration 55% by weight and dissolving both components,
A heating reaction was carried out at 130°C for 50 minutes. The resulting brown transparent varnish was dropped into stirring water, and the precipitate was filtered, washed with water, and dried with hot air at 80'C for 15 hours.

This was dried at 110'C for 20 minutes and then at 130'C for 20 minutes, and then ground to obtain a thermosetting resin composition.

Thereafter, the same operations as in Examples 1 to 3 were carried out to obtain the results shown in Table 1.

Examples 5 to 8 and Comparative Examples 1 to 2 The diamine compounds and bismaleimide compounds shown in Table 1 were mixed at the molar ratio shown in Table 1, and then the same procedure as in Examples 1 to 3 was carried out. The results shown in Table 1 were obtained through the operation.

[Effects of the Invention] The thermosetting resin composition of the present invention has euoxide heat resistance, impact resistance, and toughness, and is widely used in electrical and electronic parts, various structural members, sliding parts, etc. is expected, and the effects of industrial use are significant.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) Essentially, formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a divalent group consisting of
Represents a group selected from the group consisting of 10 divalent hydrocarbon groups, hexafluorinated isopropylidene groups, carbonyl groups, thio groups, sulfinyl groups, sulfonyl groups, or oxides. ) A thermosetting resin composition consisting of a bismaleimide compound represented by the formula (II) ▲Formula, chemical formula, table, etc.▼(II).