JPH0668024B2 - 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 that the invention is trying to solve]

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 is (1) the general formula (I) (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. ) And a bismaleimide compound 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. ) And the molar ratio of the bismaleimide compound (I) and the diamine compound (II) is 1
A thermosetting resin composition having a composition ratio in the range of 0: 1 to 1: 1.2.

The novel bismaleimide compound represented by the general formula (I) can be easily produced by subjecting a diamine compound represented by the general formula (II) and maleic anhydride to a condensation / dehydration reaction by a generally known method. Is 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] 1,1,1,3,3,
3-hexafluoropropane, 4,4'-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-
Maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl ether and the like. These may be used alone or in admixture of two or more.

The diamine compound used in the present invention is specifically 1,3
-Bis (3-aminophenoxy) benzene, bis [4-
(3-aminophenoxy) phenyl] 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-amino) Phenoxy) 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] ether and the like can be mentioned, and these can be used alone or in admixture of two or more.

These diamine compounds can be industrially advantageously produced in 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).

The bismaleimide compound represented by the above formula (I) and the formula (I
A thermosetting resin composition is obtained from the diamine compound represented by I). 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) dissolving bismaleimide and diamine in an organic solvent,
Next, the crystals that have been discharged and precipitated in a poor solvent are filtered and dried into pellets or powder, or after being dissolved in an organic solvent,
After partially curing to the prepolymer stage by heat treatment, the crystals are discharged into a poor solvent and precipitated to dry them into pellets or powder. The conditions in this case also conform to (1). 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, 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, toluene and chlorobenzene. Aprotic polar solvents such as aromatic compounds, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone And so on.

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 the bismaleimide compound 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 1: 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.

〔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 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 ℃ 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 (II) oxide 0.4g, Cobalt (II) acetate ・ 4H ₂ O
After adding 0.04 g, 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 ℃ 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 Synthesis 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)]
Phenyl] propane 20.5 g (0.05 mol) with acetone 41 g
The solution dissolved in was added dropwise at room temperature, and at 3
Stir for 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 ℃ IR (KBr, cm ^-1 ): 3280 and 3220 (NH), 1700 (carboxyl group), 1580 and 1550 (amide bond) MS (FD method, m / e): 608 (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 (II) oxide 0.13g, cobalt (II) acetate ・ 4H ₂ O
After adding 0.013 g, 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 formed crystals were filtered, washed with methanol, and dried under reduced pressure at 40 ° C. for 2,2-
Bis [4- (3-maleimidophenoxy) phenyl] propane was obtained as pale yellow crystals.

Yield 30g (Yield 83.9%), mp 161-164 ℃ 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 A reaction flask equipped with a stirrer and a thermometer was charged with 37.8 g (0.385 mol) of maleic anhydride and 113 g of acetone and dissolved. 70 g (0.175 mol) of bis [4- (3-aminophenoxy) phenyl] sulfide was added to 140 g of acetone.
The solution dissolved in is added dropwise at room temperature and 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 ℃ IR (KBr, cm ^-1 ): 3280 (NH), 1690 (carbonyl group), 1240
(Ether bond) MS (FD method, m / e): 596, 400 In a reaction flask equipped with a stirrer and a 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 (II) oxide 0.35g, Cobalt (II) acetate ・ 4H ₂ O
After adding 0.035 g, add 45.5 g of acetic anhydride dropwise and further at 25 ° C.
Stir for 2 hours.

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 ℃ IR (KBr, cm ⁻¹ ): 1770sh and 1730 (imide bond 1260 (ether bond), MS (FD method, m / e): 560 5% weight loss temperature (in air): 434 ° C. Examples-1 to 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'-bis (3-aminophenoxy) biphenyl are shown in Table-1. The charged molar ratio shown was charged, and the mixture was heated and melted for 20 minutes at 180 ° C. Then, 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.

The composition was charged while being heated and melted in a mold (10 × 80 × 4 mm) heated to 180 ° C., and then the pressure was 50 kg / cm ₂ , and the temperature was 3 at 200 ° C.
It was held for 0 minutes and compression molded. Then, after cooling to room temperature, the primary molded product was taken out from the mold and post-cured for 4 hours in a hot air gear 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 AST
According to MD-790, the 5% weight loss temperature of the molded test piece was also measured and the results shown in Table-1 were obtained.

Example-5 4,4'-bis (3-maleimidophenoxy) biphenyl and 4,4'-bis (3-aminophenoxy) biphenyl were placed in a stainless steel container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, respectively. After charging with the charging molar ratio shown in Table-1, and injecting N-methyl-2-pyrrolidone in an amount such that the resin concentration becomes 55% by weight to dissolve both components, 13
The reaction was carried out by heating at 0 ° 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. 20 minutes at 110 ℃,
After further drying at 130 ° C. for 20 minutes, it was ground 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 20 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 390 ° 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 (1)

[Claims] 1. A general formula (I) (In the formula, R is Represents a divalent group consisting of, X is a direct bond, 2 having 1 to 10 carbon atoms
Valent hydrocarbon group, hexafluorinated isopylidene group,
It represents a group selected from the group consisting of a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group and an oxide. ) And a bismaleimide compound represented by the general formula (II) (In the formula, R is Represents a divalent group consisting of, X is a direct bond, 2 having 1 to 10 carbon atoms
Valent hydrocarbon group, hexafluorinated isopylidene group,
It represents a group selected from the group consisting of a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group and an oxide. ) And the molar ratio of the bismaleimide compound (I) and the diamine compound (II) is 10:
A thermosetting resin composition having a composition ratio in the range of 1 to 1: 1.2.