JPS6348334A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition excellent in heat resistance, impact resistance and flexibility and suitable for use in electronic components, etc., by reacting, by heating, N,N'-4,4'-diphenylmethane-bismaleimide with a specified diamine compound. CONSTITUTION:N,N'-4,4'-Diphenylmethanebismaleimide (A) reprented by formula I is mixed with a diamine compound (B) represented by formula II (wherein R is a group of formula III or IV, X is a direct bond, a 1-10C bivalent hydrocarbon, hexafluorinated isopropylidene, carbonyl, thio, sulfinyl, sulfonyl or oxide group), e.g., 4,4'-bis(3-aminophenoxy) biphenyl in a molar ratio of 10:1-1:1.2, and the mixture is reacted by heating to obtain the purpose thermosetting resin composition. Component A can be obtained by condensing 4,4'-diamine- diphenylmethane with maleic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel thermosetting resin composition having excellent impact resistance and flexibility.

[Conventional technology]

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

However, although thermosetting resins made from aromatic bismaleides are insoluble and infusible and have excellent heat resistance, they have the disadvantage of poor impact resistance and rotational speed.

For this reason, as a method for improving the impact resistance, support and flexibility of aromatic bismaleimide, attempts have been made to use aromatic diamines in aromatic bismaleimide.

Polyamino bismaleimide resin (manufactured by Loos-Boulin, trade name: Kelimide) consisting of f, N, N'-(4,4'-methylene diphenylene) bismaleimide and 4,4°-diaminodiphenylmethane is Since its impact resistance and flexibility are superior to those of aromatic bismaleide alone, it is widely used in metal festivals, laminates, molded products, etc.

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

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a thermosetting resin that maintains the conventional heat resistance, has excellent impact resistance and flexibility, and has toughness. be.

[Means for solving problems]

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

That is, the thermosetting resin composition of the present invention comprises N,N24,4°-diphenylmethane-bismaleimide represented by formula (1) and general formula (n) (wherein R is -) - or ( 2 consisting of 3-x-Q-
represents a valent group, and X represents 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 a cyclic group consisting of an oxide. Represents a discovered group. ) This is a thermosetting resin composition made of a diamine compound represented by:

N,N-4,4''-diphenylmethane-bismaleimide represented by the above formula (1) is prepared by a commonly known method.
．． It can be easily produced by condensing and dehydrating 4'-diaminodiphenylmethane and maleic anhydride.

Specifically, the diamine compound used in the present invention is 1,
3-bis(3-aminophenoquino)benzene, bis(3
-aminophenoquine)methane, 1.1-bis[4-(3
-aminophenoquino)phenyl]ethane, 1゜2-bis(4-(3-aminophenoxy)phenyl]ethane, 2
42-bis(4-(3-aminophenoxy)phenyl)
Propane, 2,2-bis(4-(3-aminophenoquine)phenylbutane, 2,2-bis(4-(3-ami7)
'Phenoxy)phenyl]-1゜1.1.3.3.3-
Hexafluoropropane, 4.4°-bis(3-aminophenoquine)biphenyl, bis(4-(3-aminophenoquine)phenyltaketone, bis(4-(3-aminophenoquino)phenyl)sulfide, bis (4-(3-aminophenoxy)phenyl) sulfoxide, bis(4-
(3-7minophenoxy)phenyl]sulfone, bis(4-(3-aminophenoquine)phenyl)ether, etc., and these may be used alone or in combination of two or more.

These diamine compounds are industrially advantageous with high purity and high yield by condensing the corresponding bisphenols and m-dinitrohenzene in an aprotic polar solvent in the presence of a base and then converting the compounds into quinary compounds. Manufacturer Techil (vF Kansho 1960)
-32568, patent application Sho 6O-59560).

A thermosetting resin composition is obtained from the N,mer 4.4°-diphenylmethane-bismaleimide represented by the above formula (1) and the diamine compound represented by K (II), and in this case, various methods shown below can be used. can be used.

(1) Bismaleimide and diamine are mixed in solid form by FA, or this is heat-treated to form a prepolymer, which is then ground into pellets or powder. The heating conditions in this case are preferably those that partially cure the prepolymer stage, generally at a temperature of 70 to 220°C.
0 minutes, preferably at a temperature of 80-200'C for 10-18
It is appropriate to set it to 0 minutes.

(2) Bismaleimide and diamine are dissolved in an organic solvent, then discharged into a poor solvent, and the precipitated crystals are dried to form bereft or powder, or dissolved in an organic solvent.
After 3 solutions, the solution is partially cured to a prepolymer stage by heat treatment, and then discharged into a poor solvent and the precipitated crystals are dried to form a pellet or powder. The conditions in this case are also (
Conforms to 1). ``The organic solvent that can be used is limited in that it does not substantially react with both components, but it is also desirable that it be a good solvent for both reaction components. Usually, reaction solvents used include 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 chlorohenzene. aromatic compounds, aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, N,lf-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidabridinone, etc. be.

It should be noted that an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant aid, an antistatic agent, a lubricant, and a coloring agent may be added to the composition comprising bismaleimide and diamine according to the present invention to the extent that the object of the present invention is not impaired. It is possible to add one or more kinds of ordinary additives such as.

In addition, other thermosetting resins (e.g., phenolic resins, epoxy resins, etc.), thermoplastic resins (e.g., 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, etc. , graphite, glass peas, alumina, calcium carbonate, and other fillers can also be blended in appropriate amounts depending on the purpose.

The molar ratio of N,N24,4-diphenylmethane-bismaleimide represented by formula (1) and the diamine compound represented by ff is within the range of 10.1 to 1:1.2. is preferred. If the proportion of the diamine compound used is low, a cured product cannot have good impact resistance and flexibility. On the other hand, if the amount is too high, it will adversely affect the heat resistance of the cured product.

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 with reference to Examples.

Examples 1 to 4 N,N'-4,4°-diphenylmethane-
Bismaleimide and 4,4'-bis(3-aminophenoquine)biphenyl were charged at the molar ratio shown in Table 1, and heated and melted at 180 DEG C. for 20 minutes.

Thereafter, it was cooled to room temperature, and the reaction product solidified into a brown transparent glass was crushed and taken out. It was further crushed in a mortar and passed through a 60 sieve sieve to obtain a partially cured polyamino bismaleimide type thermosetting resin composition. Obtained.

A mold (10X80X4L) in which the composition was heated to 180°C
Heated to? 8 After filling while melting, the pressure is 50Kg/
cd, held at 200°C for 30 minutes, and compression molded. 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 Izot impact test piece and a bending test piece. Izotsu impact test (no notch) is ASTM
D-256, a bending test was conducted according to ASTM D-790, and the 5-Hrr reduction temperature of the molded test piece was measured, and the results shown in Table 1 were obtained.

Example-5 In a stainless steel container equipped with a stirrer, a reflux condenser, and a nitrogen tube, N,N"-4,4"-diphenylmecune-bismaleimide and 4,4'-bis(3-aminophenoxy) were added. Biphenyl was charged at the molar ratio shown in Table 1, and N-methyl-2-pyrrolidone was injected in an amount to give a resin concentration of 55% by weight. After dissolving both components, the mixture was heated at 130°C. The mixture was heated and reacted 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 heated to 110℃ for 20 minutes, then 130℃ for 2 minutes.
After drying for 0 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.

Thereafter, the same operations as in Examples 1 to 4 were carried out to obtain the results shown in Table 1.

Examples 6 to 8 and Comparative Examples 1 to 2 Using the bismaleimide and diamine shown in Table 1, the same operations as in Examples 1 to 4 were carried out at the charging molar ratios 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 Izot impact value, high bending strength and bending modulus, and is a material with excellent impact resistance and flexibility.
It has excellent heat resistance with a percent weight loss of 390°C or higher.

〔Effect 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 in electrical and electronic parts, various structural members, sliding parts, etc., and has industrial applications. The effect is great.

Claims (2)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼N,N'-4,4'-diphenylmethane- represented by (I)
Bismaleimide and general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R consists of ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a divalent group, where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group,
Represents a group selected from the group consisting of a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide. ) A thermosetting resin composition comprising a diamine compound represented by: (2) The 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. thing.