JPH0680116B2 - Thermosetting resin composition - Google Patents

Description

The present invention relates to a novel thermosetting resin composition having excellent impact resistance and flexibility.

[Conventional technology]

BACKGROUND ART Conventionally, a thermosetting resin having an imide structure has been widely used in industry because it has excellent electrical insulation properties, heat resistance, and dimensional stability of molded products.

However, the thermosetting resin using the aromatic bismaleide is a material that is insoluble and infusible and has excellent heat resistance, but has a drawback that it is poor in impact resistance and flexibility.

Therefore, as a method for improving the impact resistance and flexibility of the aromatic bismaleide, there is an attempt to use an aromatic diamine as the aromatic bismaleimide. For example, N, N '-(4,
4'-methylenediphenylene) bismaleimide and 4,4'-
Polyamino bismaleimide resin (made by Rhone-Poulin, trade name Kelimide) consisting of diaminodiphenylmethane is superior in impact resistance and flexibility to aromatic bismaleide alone, so it is impregnated varnish, laminated board, molded Widely used in products.

However, these thermosetting resins have not been satisfactory in terms of impact resistance and flexibility.

[Problems that the invention is trying to solve]

It is an object of the present invention to provide a thermosetting resin that maintains conventional heat resistance, is excellent in impact resistance and flexibility, and has toughness.

[Means for solving problems]

As a result of intensive studies to achieve the above objects, the present inventors have found that a thermosetting resin composition comprising a novel bismaleimide compound and a specific amount of a diamine compound is particularly effective, and Completed the invention.

That is, the thermosetting resin composition of the present invention has the formula (I) N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide represented by the general formula (II) (In the formula, R is Represents a divalent group consisting of, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group or an oxide. Represents a group selected from the group. ) Is a thermosetting resin composition consisting of a diamine compound.

The novel N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide represented by the formula (I) is converted to 4,4-bis (4-aminophenoxy) biphenyl by a generally known method. It can be easily produced by condensing and dehydrating maleic anhydride.

The diamine compound used in the present invention is specifically 1,3-
Bis (3-aminophenoxy) benzene, bis (3-aminophenoxy) methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) Phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3 -Aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl]
Sulfone, bis [4- (3-aminophenoxy) phenyl]
Examples thereof include ethers, which may be used alone or in combination of two or more.

These diamine compounds can be industrially advantageously produced with high purity and high yield by condensing the corresponding bisphenols and m-dinitrobenzene in an aprotic polar solvent in the presence of a base and then reducing the condensation. (Japanese Patent Application Sho 60-325
68, Japanese Patent Application 60-59560).

N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide represented by the above formula (I) and the formula (II)
A thermosetting resin composition is obtained from the diamine compound represented by the formula (1). In this case, various methods described below can be used.

(1) Bismaleimide and diamine are pulverized and mixed in a solid state, or this is heat-treated into a prepolymer and then pulverized into pellets or powder. In this case, the heating condition is preferably such that the prepolymer stage is partially cured. Generally, the temperature is 70 to 220 ° C. for 5 to 240 minutes, and the temperature is preferably 80 to 200 ° C. for 10 to 180 minutes. Is.

(2) Bismaleimide and diamine are dissolved in an organic solvent, then discharged into a poor solvent and the precipitated crystals are filtered and dried to give pellets or powder, or after dissolving in an organic solvent, pretreatment by heat treatment is performed. After the polymer is partially cured to the stage, it is discharged into a poor solvent and the precipitated crystals are filtered and dried to obtain pellets or powder. The condition in this case is also (1)
According to. The usable organic solvent is limited in that it does not substantially react with both components, but it is desirable that it is a good solvent for both reaction components. Usually, the reaction solvent used is methylene chloride, dichloroethane, halogenated hydrocarbons such as trichloroethylene, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diisopropyl ketone, tetrahydrofuran, dioxane, ethers such as methyl cellosolve,
Aromatic compounds such as benzene, toluene, chlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-
Examples include aprotic polar solvents such as dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

In addition, in the composition consisting of bismaleimide and diamine according to the present invention, an antioxidant and a heat stabilizer, an ultraviolet absorber, a flame retardant aid, an antistatic agent, a lubricant, and a colorant within a range that does not impair the object of the present invention. One or more of the usual additives such as can be added.

In addition, other thermosetting resins (for example, phenol resin, epoxy resin, etc.), thermoplastic resins (for example, polyethylene, polypropylene, polyamide, polycarbonate,
Polysulfone, polyethersulfone, polyetheretherketone, modified polyphenylene oxide, polyphenylene sulfide, etc.) or reinforcing materials such as glass fiber, carbon fiber, aromatic polyamide fiber, alumina fiber, potassium titanate fiber, clay, mica, silica Fillers such as graphite, glass beads, alumina, and calcium carbonate can also be added in appropriate amounts according to the purpose.

The molar ratio of N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide represented by the formula (I) to the diamine compound represented by the formula (II) is 10: 1 to 1: 1. .
It is preferably used in the range of 2. If the diamine compound is used in a small proportion, it will not be possible to obtain a cured product having good impact resistance and flexibility. On the contrary, if the amount is too large, the heat resistance of the cured product is adversely affected.

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, and an injection molding method, and put into practical use.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Synthesis Example-1 A reaction flask equipped with a stirrer and a thermometer is charged with 21.6 g (0.22 mol) of maleic anhydride and 65 g of acetone and dissolved. A solution of 36.8 g (0.1 mol) of 4,4'-bis (3-aminophenoxy) biphenyl dissolved in 294 g of acetone was added dropwise thereto at room temperature, and the mixture was further stirred at 23 to 27 ° C for 3 hours.
After the reaction was completed, the generated crystals were filtered, washed with acetone, and dried to obtain bismaleamic acid as yellow crystals.

Yield 56.3g (Yield 99.6%), mp205-208 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 1740 (carbonyl group), 1700 (amide bond), 1255 (ether bond) 28.2 g of the bismaleamic acid thus obtained was suspended in 56 g of acetone, and 2.4 g of triethylamine was added. Then
Stir for 30 minutes at room temperature.

Magnesium oxide (II) 0.1g, cobalt acetate (II) · 4H
After adding 0.01 g of ₂ O, 13.0 g of acetic anhydride is added dropwise at 25 ° C. over 30 minutes, and the mixture is further stirred for 4 hours. After the reaction was completed, the formed crystals were filtered, washed, and dried to obtain N, N'-4,4'-bis (4-
Aminophenoxy) biphenyl bismaleimide was obtained as pale yellow crystals.

Yield 24.4g (Yield 92.3%), mp218-220 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 1720 and 1710 (imide bond) 1250 (ether bond) MS (FD method, m / e): 528 (M ⁺ ) 5% weight loss temperature (in air): 453 ℃ Examples-1 to 4 N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide and 4,4'-bis were placed in a stainless steel container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. (3-Aminophenoxy) biphenyl was charged at the charging molar ratio shown in Table 1, and the mixture was heated and melted at 180 ° C. for 20 minutes for reaction. Then, it was cooled to room temperature, the reaction product solidified into a brown transparent glass was crushed and taken out, and further crushed in a mortar to 60
It was passed through a mesh screen to obtain a partially cured polyamino bismaleimide type thermosetting resin composition.

After filling the composition while heating and melting it in a mold (10 × 80 × 4t) heated to 180 ° C., the pressure was 50 Kg / cm ² , and the temperature was 30 ° C. at 30 ° C.
Hold for minutes and compression molding. After cooling to room temperature,
The primary molded product was taken out of the mold and post-cured for 4 hours in a hot air gar oven at 250 ° C. to obtain an Izod impact test piece and a bending test piece. Izod impact test (without notch) is ASTM D-256, bending test is ASTM D-7
According to 90, the 5% weight loss temperature of the molded test piece was also measured and the results shown in Table-1 were obtained.

Example-5 A N, N'-4,4'-bis (4-aminophenoxy) biphenylbismaleimide and 4,4'-bis (were added to a stainless steel container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. 3-Aminophenoxy) biphenyl was charged at the charging molar ratios shown in Table-1, and the amount of the resin concentration was 55% by weight.
After injecting N-methyl-2-pyrrolidone to dissolve both components, the mixture was heated and reacted at 130 ° C for 50 minutes. The brown transparent varnish obtained was dropped into water with stirring, and the deposited precipitate was filtered, washed with water, and dried with hot air at 80 ° C. for 15 hours. 2 at 110 ℃
After drying for 0 minutes and further at 130 ° C. for 20 minutes, it was ground in a mortar and passed through a mesh sieve to obtain a partially cured polyamino bismaleimide type thermosetting resin composition.

Then, the same operation as in Examples-1 to 4 was performed to obtain the results shown in Table-1.

Examples-6 to 8 and Comparative Examples-1 to 2 Using bismaleimide and diamine shown in Table-1, the same operation as in Examples-1 to 4 was carried out at the charged molar ratio shown in Table-1. The results shown in Table-1 were obtained.

From the results shown in Table-1, the thermosetting resin composition according to the present invention has a high Izod impact value, a high bending strength and a high bending elastic modulus, and is a material excellent in impact resistance and flexibility.
It also has excellent heat resistance with a% weight loss temperature of 400 ° C or higher.

[Advantages of the Invention] The thermosetting resin of the present invention has excellent heat resistance, impact resistance and flexibility, and is expected to be widely used for electric, electronic parts, various structural members, sliding parts and the like. The industrial use effect is great.

Claims (2)

[Claims] 1. A formula (I) N, N'-4,4'-bis (4-aminophenoxy) biphenyl bismaleimide represented by the formula (II) (In the formula, R is Represents a divalent group consisting of, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group or an oxide. Represents a group selected from the group. ) A thermosetting resin composition comprising a diamine compound represented by: 2. A thermosetting resin composition according to claim 1, wherein the bismaleimide compound (I) and the diamine compound (II) are used in a molar ratio of 10: 1 to 1: 1.2. object.