JPH072842B2 - 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 bismaleimide 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 bismaleimide, there is an attempt to use an aromatic diamine for the aromatic bismaleimide. For example, N, N′−
(4,4'-methylenediphenylene) bismaleimide and 4,
Polyamino bismaleimide resin consisting of 4'-diaminodiphenylmethane (Rhone Poulenc Company, trade name
Kelimide) is more widely used for impregnating varnishes, laminates, molded products, etc., because it is superior in impact resistance and flexibility to aromatic bismaleimide alone.

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

[Problems to be solved by the invention]

It is an object of the present invention to provide a thermosetting resin that maintains the 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 general formula (I) (In the formula, 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 comprising a bismaleimide compound and 4,4'-diaminodiphenylmethane.

The novel bismaleimide compound represented by the general formula (I) can be prepared by the conventional method using the general formula (II) (In the formula, 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. ) Can be easily produced by condensation and dehydration reaction of the diamine compound and maleic anhydride, specifically, 1,3-
Bis (3-maleimidophenoxy) benzene, bis [4
(3-maleimidophenoxy) phenyl] methane, 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) phenyl] butane, 2,
2-bis [4- (3-maleimidophenoxy) phenyl-1,1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-maleimidophenoxy) biphenyl, bis [4-
(3-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenor] sulfide, bis [4 (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone , Bis [4- (3-maleimidophenoxy) phenyl] ether and the like, and these may be used alone or in admixture of two or more.

The 4,4'-diaminodiphenylmethane used in the present invention is industrially advantageously produced from aniline and formaldehyde.

A bismaleimide compound represented by the above formula (I) and 4,
A thermosetting resin composition is obtained from 4'-diaminodiphenylmethane, and in this case, various methods shown 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 into 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 portions. Usually, the reaction solvent used is methylene chloride, dichloroethane, halogenated hydrocarbons such as trichloroethylene, acetone, ketones such as methyl ethyl ketone, cyclohexanone, diisopropyl ketone, tetrahydrofuran, dioxane, ethers such as methyl cellosolve,
Aromatic compounds such as benzene, toluene, chlorobenzene, acetonitrile, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethyl sulfoxide, N-
Examples include aprotic polar solvents such as 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.

Bismaleimide compound represented by formula (1) and 4,4′-
The molar ratio of diaminodiphenylmethane used is 10: 1 to 1: 1.
It is preferably used in the range of 1.2. When the proportion of the diamine compound used is small, a cured product cannot have 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.

[Examples] 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 43.2 g (0.44 mol) of maleic anhydride and 130 g of acetone and dissolved. A solution of 73.6 g (0.2 mol) of 4,4'-bis (3-aminophenoxy) biphenyl dissolved in 515 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 110.6g (Yield 98.0%), mp183-185 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 1720 (carbonyl group), 1255 (ether bond) 112 g of the bismaleamic acid thus obtained was suspended in 300 g of acetone, 9.6 g of triethylamine was added, and the mixture was stirred at room temperature for 30 minutes. To do.

Magnesium oxide (II) 0.4g, cobalt acetate (II) · 4H
After adding 0.04 g of ₂ O, 52.0 g of acetic anhydride is added dropwise at 25 ° C. over 30 minutes, and the mixture is further stirred for 3 hours. After the reaction was completed, the formed crystals were filtered, washed and dried to obtain 4,4'-bis (3-maleimidophenoxy) biphenyl as pale yellow crystals.

Yield 84.5g (Yield 80.0%), mp207-209 ℃ 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): 459 ° C Example-2 A reaction flask equipped with a stirrer and a thermometer was charged with 10.8 g (0.11 mol) of maleic anhydride and 32 g of acetone and dissolved. 2,2-bis [4- (3-aminophenoxy)]
A solution prepared by dissolving 20.5 g (0.05 mol) of phenyl] propane in 41 g of acetone was added dropwise 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 29.7g (Yield 98.0%), mp169-171 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 3280 and 3220 (NH), 1700 (carboxyl group), 1580 and 1550 (amide bond) MS (FD method): m / e608 (M + 2), 510, 491, 411 38 g of the bismaleamic acid thus obtained is suspended in 92 g of acetone, 3 g of triethylamine is added, and the mixture is stirred at room temperature for 30 minutes.

Magnesium oxide (II) 0.13 g, cobalt acetate (II) -4
After adding 0.013 g of H ₂ O, 16 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 produced crystals were filtered, washed with methanol, and dried under reduced pressure at 40 ° C for 2,2
-Bis [4- (3-aminophenoxy) phenyl] propane was obtained as pale yellow crystals.

Yield 30g (Yield 83.9%), mp161-164 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 1775 and 1715 (imide bond) 1255 (ether bond) MS (FD method, m / e): 571 (M + 1) 5% weight loss temperature (in air): 447 ° C Synthesis example- 3 To a reaction flask equipped with a stirrer and a thermometer, 37.8 g (0.385 mol) of maleic anhydride and 113 g of acetone are charged and dissolved. A solution of 70 g (0.175 mol) of bis [4- (3-aminophenoxy) phenyl] sulfide dissolved in 140 g of acetone was added dropwise thereto at room temperature, and the mixture was further stirred at 25 ° C. for 3 hours. The produced crystals were filtered, washed, and dried to obtain bismaleamic acid as pale yellow crystals.

Yield 104g (Yield 99.6%), mp202-204 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 3280 (NH), 1690 (carbonyl group), 1
In a reaction flask equipped with 240 (ether bond), MS (FD method, m / e): 596, 400 stirrer and thermometer, 104 g of the bismaleamic acid thus obtained is suspended in 300 g of acetone.

After adding 8.4 g of triethylamine, the mixture is stirred at 25 ° C for 30 minutes.

Magnesium oxide (II) 0.35 g, cobalt acetate (II) -4
After adding 0.035 g of H ₂ O, 45.5 g of acetic anhydride was added dropwise, and further 25
Stir for 2 hours at ° C.

After completion of the reaction, the reaction solution is dropped into water 1 with stirring. The formed crystals are filtered, washed with water, dried and then bis [4-
(3-Maleimidophenoxy) phenyl] sulfide was obtained as pale yellow crystals.

Yield 92 g (yield 93.8%). This crystal was recrystallized from acetone to obtain a pure product.

mp: 64-67 ℃ Elemental analysis (%) IR (KBr, cm ^-1 ): 1770sh and 1730 (imide bond) 1260 (ether bond), MS (FD method, m / e): 560 5% weight reduction temperature (in air): 434 ° C Example-1 4 In a stainless steel container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 4,4′-bis (3-maleimidophenoxy) biphenyl and 4,4′-diaminodiphenylmethane were charged in the molar ratios shown in Table 1, respectively. Charge at 20 ° C at 180 ° C
Minute heating and melting reaction occurred. Then, it was cooled to room temperature, the reaction product solidified into a brown transparent glass was crushed and taken out,
Further, it was ground in a mortar and passed through a 60-mesh sieve to obtain a partially cured polyamino bismaleimide type thermosetting resin composition.

The composition was filled in a mold (10 × 80 × 4 mm) heated to 180 ° C. while being heated and melted, and then filled at a pressure of 50 Kg / cm ² and 200 ° 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 4,1'-bis (3-maleimidophenoxy) biphenyl and 4,4'-diaminodiphenylmethane are shown in Table 1 in a stainless steel container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. After charging in a charged molar ratio and injecting N-methyl-2-pyrrolidone in an amount such that the resin concentration becomes 55% by weight to dissolve both components, a heating reaction was carried out 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. This was dried at 110 ° C. for 20 minutes and further at 130 ° C. for 20 minutes, then crushed in a mortar and passed through a 60-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 in Table 1, the thermosetting resin composition according to the present invention is a material having a high Izod impact value, a high bending strength and a high bending elastic modulus, and excellent impact resistance and flexibility.
It also has excellent heat resistance with a% weight loss temperature of 400 ° C or higher.

〔The invention's effect〕

INDUSTRIAL APPLICABILITY The thermosetting resin of the present invention has excellent heat resistance, impact resistance and flexibility, and is expected to be widely used in electric, electronic parts, various structural members, sliding parts, etc. The effect is great.

Claims (2)

[Claims] 1. A general formula (I) (In the formula, 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 bismaleimide compound represented by the formula (4) and 4,4'-diaminodiphenylmethane. 2. A thermosetting material as claimed in claim 1, wherein the bismaleimide compound (I) and 4,4'-diaminodiphenylmethane are used in a molar ratio of 10: 1 to 1: 1.2. Resin composition.