JPH02272027A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title new composition useful as electrical parts, electronic parts, various structural members, sliding members, etc., having excellent heat resistance, impact resistance and rigidity, comprising a specific diamine compound and a bismaleimide compound. CONSTITUTION:The aimed composition comprising (A) a diamine compound shown by formula I and (B) a bismaleimide compound shown by II [R<1> is group shown by formula III or formula IV (R<2> to R<4> are H or methyl; X is direct bond, CH2, O, S, SO2, CO or group shown by formula V)].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel thermosetting resin composition having excellent IT resistance and toughness.

[Conventional technology]

Conventionally, thermosetting resins having an imide structure have been widely used in industry because they have excellent electrical insulation properties, heat resistance 1, and dimensional stability of molded products.

However, although thermosetting resins made using aromatic bismaleimide are insoluble and infusible materials and have excellent heat resistance, they have the disadvantage of poor impact resistance and toughness.

Therefore, as a method for improving the impact resistance and toughness of aromatic bismaleimide, aromatic bismaleimide and 4,4'
- There is a polyamino bismaleimide resin consisting of diaminodiphenylmethane (Japanese Patent Publication No. 46-23250),
The results were still unsatisfactory in terms of impact resistance and toughness. Furthermore, since 4,4'-diaminodiphenylmethane is harmful to the human body, there are also problems in handling hygiene.

[Problems to be Solved by the Invention] The purpose of the present invention is to maintain the conventional heat resistance and also improve the SIl resistance.
The object of the present invention is to obtain a new thermosetting resin composition having excellent properties and toughness.

[Means for solving problems]

The present inventors conducted extensive research to achieve the above object, and as a result, completed the present invention.

That is, the thermosetting resin composition of the present invention has the following properties:
A diamine compound of formula (1) and a bismaleimide having a monocatalytic formula (n), R3, R3 and R4 are hydrogen atoms or methyl groups, X is a direct bond, C11s, oxygen atom, sulfur atom It is a thermosetting resin composition made of a compound.

The diamine compound used in the present invention is 4,4゛-bis(4-(4-amino-α,
α-dimethylbenzyl)phenoxy]-diphenylsulfone, which is 2-(4′-aminophenyl)-2-(4″-hydroxyphenyl)propane and 4,4′-dichlorodiphenylsulfone in the presence of a more basic compound. , can be synthesized in organic solvents.

The bismaleimide compound (n) used in the present invention includes N,N'-p-phenylenebismaleimide, N
, N″-m-phenylene bismaleimide, N, N′-2
,4-toluylenebismaleimide, N,N'-2,6
-) Louisene bismaleimide, NJ'-4,4' -
diphenylmethane bismaleimide, N,)l'-3,
3'-diphenylmethane bismaleimide, N, N'
-4,4'-diphenyl ether bismaleimide,
N,N'-3,3'-diphenyl ether bismaleimide, N,N'-4°4'-diphenyl sulfide bismaleimide, N,N'-3,3'-diphenyl sulfide bismaleimide, N,N'-4 , 4'-diphenylsulfone bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4'-diphenylketone bismaleimide, N, N'-3,3'-
diphenylketone bismaleimide, 11. N'-4,4
”-biphenyl bismaleimide, NIN'-3,3'-
biphenyl bismaleimide, N, N'-4゜4'-diphenyl-1,1-propane bismaleimide, kidney, N'-
3,3°-diphenyl-1,1-propane bismaleimide, 3,31-dimethyl-N, N'-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-N,
Examples include N'-4,4'-biphenyl bisla 1/imide, which may be used alone or in a mixture of two or more.

A thermosetting resin composition is obtained from the diamine compound of the above formula (1) and the bismaleimide compound represented by the formula (II). 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 generally the temperature is 70 to 220°C and the temperature is 5 to 240°C.
It is appropriate to set the temperature to 10 to 180 minutes, preferably at a temperature of 80 to 200°C.

(2) Dissolve bismaleimide and diamine in an organic solvent, then discharge into a poor solvent, and dry the precipitated crystals to form a pellet or powder, or dissolve them in an organic solvent and heat-process to form Brevolima After being partially cured to the 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 solvents that can be used are limited by the fact that they do not substantially react with both components, but it is also desirable that they are good solvents for both reaction components.The reaction solvents that are usually used are methylene chloride and dichloroethane. , halogenated hydrocarbons such as trichlorethylene, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, diisopropyl ketone, ethers such as tetrahydrofuran, dioxane, methyl cellosolve, benzene,
Aromatic compounds such as toluene and chlorobenzene, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. These include aprotic radial solvents.

The ratio of the diamine compound of formula (1) and the bismaleimide compound represented by formula (II) is 0.1 to 1.2 mol, preferably 0.2 to 0.8 mol, of the diamine compound per 1 mol of the bismaleimide compound. If the proportion of the diamine compound used is small, it will not be possible to obtain a cured product with good impact resistance and toughness, and if it is too large, it will adversely affect the heat resistance of the cured product.

Although the resin composition of the present invention can be easily cured without a catalyst, it can also be thermally cured using a polymerization initiator such as an organic peroxide or an azo compound. Examples of such polymerization initiators include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, tertiary amines, quaternary ammonium salts, and imidazoles.

In addition, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardant aids, antistatic agents, lubricants, and colorants may be added to the composition comprising bismaleimide and diamine according to the present invention, within a range that does not impair the purpose of the present invention. One or more types of conventional additives such as can be added.

In addition, other thermosetting resins (for example, phenolic resins, epoxy resins, etc.), thermoplastic resins (for example, polyethylene, polypropylene, polyamide, polycarbonate, polysulfone, polyethersulfone, polyetheretherketone, modified polyphenylene oxide) , polyphenylene sulfide, etc.) or glass fiber,
Reinforcing agents such as carbon fiber, aromatic polyamide fiber, alumina fiber, potassium titanate fiber, and fillers such as clay, mica, silica, graphite, glass beads, alumina, and calcium carbonate are also blended in appropriate amounts depending on the purpose. It is also possible to do so.

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 (
ARP-3 (hereinafter abbreviated as ARP-3) and N,N-4,4°-diphenylmethane bismaleimide were mixed in advance at the molar ratio shown in Table 1. Powders were charged and heated and melted at 180°C for 20 minutes. . 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 (10X80X4
mm) while heating and melting, and then pressurized to 50k.
g/ej, held at 200°C for 30 minutes, and compression molded. Thereafter, after cooling to room temperature, the molded product was taken out from the mold and further post-cured for 4 hours in a 250'C hot air oven to obtain an Izot impact test piece and a bending test piece. The Izotsu II test (no notch) bending test was conducted in accordance with JIS-6911, and the thermal decomposition onset temperature was measured in air at a heating rate of 10°C/in. The results shown in Table 1 were obtained. .

Example 4 AHP-3 and N,N'-4,4'-diphenylmethane bismaleimide were charged at the molar ratio shown in Table 1 into a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube. N-methyl-2-pyrrolidone was injected in an amount to give a resin concentration of 55% by weight, and after dissolving both components, a heating reaction was carried out at 130° C. for 50 minutes. The resulting brown transparent face 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 11 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.

〔Effect of the invention〕

The thermosetting resin composition of the present invention has excellent heat resistance, impact resistance, and toughness, and is expected to be widely used in electrical and electronic parts, various structural members, sliding parts, etc., and is suitable for industrial applications. The effects of its use are great.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) Essentially, the diamine compound of formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼The diamine compound of (I) and general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 has ▲mathematical formulas, chemical formulas, tables, etc.▼,
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where R^2, R^3 and R^4 are hydrogen atoms or methyl groups, X is a direct bond, CH_2, oxygen atom, sulfur atom, SO_2, CO, Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A thermosetting resin composition comprising a bismaleimide compound represented by: