JPH03172325A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat resistance, impact resistance, toughness and flexibility and useful as electrical and electronic parts, various structural members, sliding parts, etc., by compounding a specific polymaleimide compound and a diamine compound at a specific ratio. CONSTITUTION:The objective composition is composed of 100 pts.wt. of a polymaleimide compound of formula I ((n) is 0-50) and 5-100 pts.wt. (preferably 10-80 pts.wt.) of a diamine compound of formula II [R is group of formula III or formula IV (X is direct bond, 1-10C bivalent hydrocarbon group, hexafluorinated isopropylidene, carbonyl, thio, sulfinyl, sufonyl or oxide)] [e.g. 1,3-bis(3-aminophenoxy)benzene]. The compound of formula I can be produced by the condensation and dehydration reaction of an aromatic amine resin of formula V with maleic anhydride.

Description

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

(Prior Art) Thermosetting resins having an imide structure have been widely used in industry since they have excellent electrical insulation properties, heat resistance, 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, attempts have been made to use aromatic diamines in aromatic bismaleimide. For example, N,
N'-4,4'-diphenylmethane bismaleimide and
There is a polyamino bismaleimide resin (manufactured by Loos-Boulin, trade name: Kelimide) consisting of 4.4'-diaminodiphenylmethane, but it has not yet been satisfactory in terms of impact resistance and toughness.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a new thermosetting resin composition that maintains conventional heat resistance and has excellent impact resistance and toughness.

[Means for solving problems]

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

That is, the thermosetting resin composition of the present invention comprises 1 part of the polymaleimide compound toofflff represented by the general formula (1) (where n is -0 representing an integer of O to 50) and the general formula (
■) Represents a divalent group consisting of
A diamine compound represented by (representing a group selected from the group consisting of a divalent hydrocarbon group of IO, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide) It is a thermosetting resin composition consisting of 5 to 100 parts by weight.

The polymaleimide compound represented by the above - binding margin (1) is a condensation of an aromatic amine resin represented by the general formula (III) (m) (wherein n is an integer of θ to 50) and maleic anhydride. - Can be easily produced by dehydration reaction.

- The aromatic amine resin represented by Ill is the one previously filed by the present applicant (Japanese Patent Application Laid-Open No. 0F-9512
5, JP-A-123828), for example, aniline and the general formula (IV) (wherein, Y represents a halogen, a hydroxyl group, an alkoxy group,
) It can be produced from an aralkyl derivative represented by

In addition, the other component, diamine compound (n), specifically includes 1.3-bis(3-aminophenoxy)benzene, bis(4-(3-aminophenoxy)phenyltumethane, 1.1-bis(3-aminophenoxy)benzene, -bis(4-(3-aminophenoxy)phenyl)ethane, 1,2-bis(4-(3-aminophenoxy)nophenoxy)phenyl]propaz,
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-
Examples include aminophenoxy) phenyl ether, which may be used alone or in combination of two or more.

Polymaleimide compound 2 represented by the above-mentioned binding margin (1)
- A thermosetting resin composition is obtained from the diamine compound represented by the binding margin (II). In this case, various methods shown below can be used.

■ A solid-solid mixture of a polymaleimide compound and a diamine compound, a solid-liquid mixture,
Alternatively, this may be added to produce a prepolymer, which is then crushed to form pellets or casseroles4. Make it II'. In this case, the heating conditions are preferably those that partially cure the prepolymer stage, and for -m, the temperature is 70 to 220°C for 5 to 240 minutes, preferably 80 to 200°C for 10 to 180 minutes. is appropriate.

■ A polymaleimide compound and a diamine compound are dissolved in an Ia solvent, then discharged into a poor solvent, and the precipitated crystals are filtered and dried to form a pellet or powder, or alternatively, dissolved in an organic solvent and then heated. After being partially cured to the prepolymer stage through treatment, it is discharged into a poor solvent, and the precipitated crystals are filtered and dried to form pellets or powder. The conditions in this case also comply with (2).

The organic solvent that can be used is limited in that it does not substantially react with both components, but it is desirable that it is a good solvent for both components.

Usually, the solvents used are halogenated hydrocarbons such as methylene chloride, dichloroethane, and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisopropyl ketone, tetrahydrofuran,
Ethers such as dioxane and methyl cellosolve, aromatic compounds such as benzene, toluene, and chlorobenzene,
Acetonitrile, N, N-dimethylformamide, N,
N-dimethylacetamide, dimethyl sulfoxide, N
-Aprotic polar solvents such as -methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone.

The amount of the diamine compound represented by the general formula (Il) is -10
It is used in a proportion of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, based on parts of Off[ffi.

If the diamine compound is less than 5 parts by weight, the cured product will be extremely brittle and will not have satisfactory bending strength;
If the amount is 100 parts by weight or more, the heat resistance of the cured product will deteriorate.

If necessary, the following components can be added to the thermosetting resin composition of the present invention within a range that does not impair the object of the present invention.

(a) f! For example, radical polymerization initiators such as azo metals and organic peroxides, ionic catalysts such as tertiary amines, quaternary ammonium salts, imidazoles, and boron trifluoride/amine salts.

(b) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, These include basic magnesium silicate, fired ray, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, graphite, asbestos, molybdenum disulfide, and antimony trioxide.

Further, fibrous reinforcing agents and fillers include inorganic fibers such as glass fiber, rock wool, ceramic fiber, alumina fiber, and potassium titanate fiber, and organic fibers such as carbon fiber and aromatic polyamide.

(c) Various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, phenol resin, epoxy resin, melamine resin, silicone resin, etc. thermosetting resins, polyamides, polycarbonates, polysulfones, polyethersulfones, polyetheretherketones, modified polyphenylene oxides, polyphenylene sulfides, polyetherimides, fluororesins, etc.

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〕

Hereinafter, the present invention will be explained in detail with reference to Synthesis Examples, Examples, and Comparative Examples.

In addition, in these examples, the physical properties of the thermosetting resin composition and the like were measured by the following methods.

- GPC analysis: Use Shimadzu LC-6^.

- Softening point: According to JIS K-2548 (ring and ball softening point measurement method).

・Izotsu impact strength (without notch): AS-D M-D-
256.

- Bending strength 9 Flexural modulus: ^ According to STM-D-790.

・Thermal decomposition start temperature rTGA method in air, heating rate l
The onset temperature of severe ffi reduction is measured in 0° C./sin.

Synthesis Example 1 1490 g of aniline (16
aol), α, α゛-dichloro-p-xylene 280.
2 g (1,6+*ol) and 35% aqueous hydrochloric acid solution 1
75.2 g (4.8 s+ol) was charged, and the temperature was raised while stirring while passing nitrogen gas. During the course of the reaction, distilled water was removed using a moisture vessel, and the temperature was raised to the reflux point of aniline.

The reaction was completed by aging in this state for 15 hours.

Next, this reaction solution was cooled to 140°C and poured into 1600 g of 18% caustic soda aqueous solution. While stirring FA, 1000 g of toluene was added to complete neutralization.

When it was allowed to stand still, it separated into two layers, so the lower layer was removed by liquid separation, and water washing and liquid separation were repeated. The obtained oil layer was concentrated in vacuo to recover unreacted aniline with toluene, and a pale yellow, transparent, oily aromatic amine resin was obtained as the residue.

・Yield ii1: 442g ・N value of composition knee binding margin (1) by GPC analysis n-0 near 6%, n-1: 19% n=2: 4%,
n≧3: 1%・Average molecular weight: 350・Amine value: 0.65 eq/100g Next,
A polymaleimide compound was produced using this aromatic amine resin.

P-) toluenesulfonic acid 20 in a reactor equipped with a water separator
Next, 380 g (3.88 mol) of maleic anhydride was charged into the reactor and 800 g of toluene was charged, and water was removed by azeotropic dehydration under heating and reflux. The above-mentioned aromatic amine resin 400
A solution prepared by dissolving 100 g in 400 g of toluene was added dropwise over 12 hours. During the process, water distilled out azeotropically was removed from the system, and toluene was refluxed.

After the dropwise addition was completed, aging was performed for 3 hours to complete the reaction. The total amount of distilled water was 50 g. The reaction solution was cooled to 70°C, and a small amount of insoluble matter was removed by filtration.

Next, 600 g of water was added and kept under reflux for 30 minutes. When the mixture was allowed to stand still, it was separated into two layers, and the lower layer was removed, 1000 g of water was added, and the water washing and separation process was repeated twice. The oil layer was concentrated in vacuo to 150°C to obtain a maleimide compound as a residue.

This was discharged while hot, and after cooling, it was crushed to obtain a yellow powdery polymaleimide compound.

・Yield: 620 g, ・Softening point: 94°C Synthesis Example 2 558 g (6 mol) of aniline was placed in a reactor equipped with a water separator.
), and the temperature was raised while passing nitrogen gas. Internal temperature 1
When the temperature reached 50°C, 350.2 g (2 mol) of α,α-dichloro-p-xylene was charged in portions to prevent the internal temperature from rising rapidly. After charging, the internal temperature was kept at 210°C and the reaction was completed by aging for 10 hours. Post-treatment after the reaction was the same as in Synthesis Example 1, including neutralization, washing with water, separation, and concentration, resulting in a pale yellow color. A transparent aromatic amine resin was obtained.

・Yield: 460g ・N value n=o of composition knee binding margin (1) by GPC analysis:
36%, n...1:22%, n-2:14%.

n=3:9%, n-4:6%9 n≧5=13%・Average molecular weight: SSO,・Softening point=56°C・Amine value=
0.61 eq/100g Next, a polymaleimide compound was produced using this aromatic amine resin.

A perfluoroalkanesulfonic acid type ion exchange IA resin (trade name Nafi) as a catalyst was placed in a reactor equipped with a water separator.
on-H: 80 g (manufactured by DuPont) and 800 g of toluene were charged, and further 297.6 g of maleic anhydride (3,
2 mol) was added and kept at reflux.

Next, 400 g of the aromatic amine resin was added in advance to N,
A solution dissolved in 200 g of N-dimethylformamide was added dropwise over 10 hours. After 0 dropwise addition, the reaction was completed by aging under reflux for 5 hours. ￥1 The total amount of water was 48g. The reaction solution was cooled to 70°C, filtered, and Naf
ion-H was excluded.

Next, this filtrate is vacuum i! By condensing the solvent toluene and N,
The N-dimethylformamide was collected and the product was discharged hot. After cooling, it was pulverized to obtain a crude polymaleimide compound powder. This powder was slushed in water 2I2 at 40°C overnight, filtered and washed with water to obtain a yellow powdery polymaleimide compound.

・Amount: 580g, ・Softening point:
110°C Examples 1 to 4 The polymaleimide compound obtained in Synthesis Example 1 and 4.4°-bis(3-aminophenoxy)biphenyl were placed in a stainless steel reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube. Each, the first. Charge the parts by weight shown in * and heat to 180°C.
Melt by heating for 20 minutes at 150°C and under reduced pressure (1
0~15m5+lIg), after degassing for 30 minutes,
The resin composition was cooled to room temperature and solidified into a transparent brown glass.

After filling the composition into a mold heated to 180°C while melting it, 50kg/cIi, 3 at 200°C.
The molded product was held for 0 minutes, compression molded, taken out, and post-cured for 4 hours in an open environment at 250°C to form a test piece of the cured product (length: 27 m, width: 12.7 m, thickness: 6.5 m).
4m) was obtained.

Izot impact strength (without notch) for this test piece
, flexural strength, flexural modulus, and thermal decomposition onset temperature were measured, and the results are shown in Table 1.

Examples 5 to 11 and Comparative Examples 1 and 2 The same operations as in Examples 1 to 4 were carried out using the polymaleimide compounds and diamine compounds shown in Table 1 in the parts by weight shown in Table 1, respectively. The results shown in Table 1 were obtained.

Comparative Example 3 N,N'-4,4°-diphenylmethane bismaleimide and 4,4°-diaminodiphenylmethane were each added to the first
Using the parts by weight shown in the table, the same operations as in Examples 1 to 4 were carried out to obtain the results shown in Table 1.

Comparative Example 4 Using Kelimide-1050 (manufactured by Nippon Polyimide ■) as a thermosetting resin composition, the same operations as in Examples 1 to 4 were carried out to obtain the results shown in Table 1.

〔Effect of the invention〕

The thermosetting resin of the present invention has excellent heat resistance, impact resistance, and flexibility, and can be used for electrical/electronic parts, various structural members, etc.
It is expected to be used in a wide range of applications such as sliding parts, and has great industrial effects.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, n represents an integer from 0 to 50.) 100 parts by weight of a polymaleimide compound represented by the general formula (II) ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R represents a divalent group consisting of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.) X is a direct bond, carbon number 1~
It represents a group selected from the group consisting of 10 divalent hydrocarbon groups, hexafluorinated isopropylidene groups, carbonyl groups, thio groups, sulfinyl groups, sulfonyl groups, or oxides. ) A thermosetting resin composition comprising 5 to 100 parts by weight of a diamine compound represented by: