JPH04100855A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in moldability, high-temp. strengths, elastic modulus, heat resistance, etc., by mixing a specific crystalline polycyanoaryl ether with a thermoplastic polyimide in a specified wt. ratio. CONSTITUTION:10-90wt.% crystalline polycyanoaryl ether having repeating units of formula I (wherein Ar is a group of formula II, III, or IV) is mixed with 90-10wt.% thermoplastic polyimide having repeating units of formula V, VI, or VII (wherein X is -CH2-, -CO-, a group of formula VIII, etc.; and Y<1>, Y<2>, and Y<3> are each -O-, -CO-, -SO2-, etc.) to give the title compsn. If necessary, a fibrous reinforcement (e.g. a glass fiber), a non-fibrous reinforcement (e.g. silica), etc., may be further added to the compsn. The resulting compsn. is suitably used as the material of an electric or electronic part, a machine part, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition suitably used as a material for parts and the like in fields such as electrical and electronic equipment and machinery.

[Conventional technology]

In recent years, so-called engineering resins have been used in a wide range of fields. Among these resins, aromatic polyether resins are attracting attention as materials for mechanical parts and parts of electrical and electronic equipment because they have excellent heat resistance and moldability. By the way, as the field of use expands, the required characteristics are also becoming stricter, and materials with even higher heat resistance are desired.

Among these aromatic polyether resins, crystalline polycyanoaryl ether has excellent heat resistance, mechanical strength, flame retardance, and chemical stability, but conventional crystalline polycyanoaryl Ether could not withstand use under extremely harsh conditions. For this reason, attempts have been made to further improve its properties (Japanese Unexamined Patent Publication No. 60-2
58250, JP-A No. 61-85470, and JP-A No. 62-116658), crystalline polycyanoarylethers having sufficiently high heat resistance are not necessarily obtained.

Furthermore, polyimides having various structures are known. However, all of these polyimides have high melt viscosity and have difficulty in molding processability.

[Problem to be solved by the invention]

The present invention aims to provide a thermoplastic resin composition that has low melt viscosity, good moldability, high mechanical strength at high temperatures, high elastic modulus, and excellent heat resistance.

[Means to solve the problem]

As a result of extensive research in order to solve the above problem, the present inventor discovered that the object could be achieved by a combination of a crystalline polycyanoaryl ether having a specific repeating unit and a thermoplastic polyimide, and based on this knowledge, Based on this, the present invention has been completed.

That is, the present invention is based on the general formula (in which X has the same meaning as above, Yl is a direct bond,
-O--CO-1-502--C(CH2)Z- or-
C (Ch)! - indicates. ) or 10 to 90% by weight of a crystalline polycyanoaryl ether having repeating units, and the general formula (wherein X has the same meaning as above, Y2 and Y3 are Y
It has the same meaning as l. ) The present invention provides a thermoplastic resin composition comprising 10 to 90% by weight of a thermoplastic polyimide having repeating units represented by:

Specifically, the crystalline polyline anoarylether having a repeating unit represented by the general formula [A] used in the present invention is 1ls CF.

C.N. C.N. You can.

The repeating units that can be contained in the copolymer are as follows: CN CN mother SO□0000→ mother CO@-0@0乎, +@SO□00(×public0+ pe◇co＠o℃Xhakai, monoga Can be mentioned.

The crystalline polycyanoaryl ether used in the present invention is a copolymer containing the above-mentioned homopolymer as well as the following repeating units in addition to the above-mentioned repeating units within a range that does not lose crystallinity. Single grain type C
Specific examples of the thermoplastic polyimide having a repeating unit represented by B') include the following.

Specifically, the thermoplastic polyimide having a repeating unit represented by the general formula [B2] used in the present invention is CH.

Examples include.

Specific examples of the thermoplastic polyimide having a repeating unit represented by the general formula [B3] used in the present invention include 0@0@SO, @O@O@, and the like.

In the thermoplastic resin composition of the present invention, a crystalline polycyanoaryl ether having a repeating unit represented by the above general formula (A) and the above general formula (B'), (B'') or [
The composition ratio of the thermoplastic polyimide having the repeating unit represented by [B3] is 10 to 90% by weight of the former: 9
0 to 10% by weight. If the blending ratio of thermoplastic polyimide is less than 10% by weight, the improvement in mechanical strength at high temperatures will be insufficient. When the overlap exceeds 90%, melt moldability decreases.

The method for producing the thermoplastic resin composition of the present invention includes kneading the crystalline polycyanoaryl ether and thermoplastic polyimide using a commonly used method such as a hot roll, a kneader, or a Banbury mixer 1 melt molding machine. is preferred. The kneading temperature in this case is 300 to 450
The temperature is preferably 350 to 400°C, particularly 350 to 400°C.

The thermoplastic resin composition of the present invention obtained as described above has a low melt viscosity and good moldability. Therefore, it is possible to obtain a desired molded product by injection molding. Also,
It has a high heat distortion temperature, high mechanical strength at high temperatures, and a high elastic modulus. Therefore, it can be used as a material for mechanical parts that require high heat resistance.

Additionally, additives such as fibrous reinforcing materials and non-fibrous fillers may be added to the thermoplastic resin composition of the present invention as desired during manufacture or use.

Suitable fibrous reinforcement materials include glass fiber, carbon fiber,
Examples include titanate whiskers, wollastonite, and ceramic fibers (SiC).

Suitable non-fibrous fillers include calcium carbonate, mica, titania, silica, alumina, silicon carbide, silicon nitride, boron nitride, and the like.

These additives can be used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the resin composition. By blending these, the heat resistance of the thermoplastic resin composition is further improved.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

W Exception 1 (Production of crystalline polycyanoal ether) Dichlorobenzonitrile 5 5
．． 211 kg, resorcinol 3.30 kg, potassium carbonate 4.27 kg, lithium carbonate 430 g, N as a solvent
-Methylpyrrolidone 4.31! , add toluene 21,
The mixture was stirred at room temperature for 1 hour while blowing argon gas therein, and then the temperature was raised to 195°C and the reaction was carried out for 3.5 hours. After the reaction is completed, the reaction product is poured into methanol to precipitate a polymer, and the precipitated polymer is pulverized using a high-speed mixer (manufactured by Fukae Kogyo), and then mixed with 100% water.
42 times 3 times, methanol 100! The product was washed twice with water and dried to obtain 6.15 kg (yield: 95%) of crystalline polycyanoaryl ether containing the following repeating units.

N When the thermal properties of this polymer were measured, the melting point was 340°C and the thermal decomposition onset temperature was 490°C.

Production Example 2 (Production of crystalline polycyanoarylether copolymer) Internal volume 200I equipped with stirring device, rectification device, and argon gas blowing pipe! 1.548 kg of dichlorohenzonitrile, 5.58 kg of 4,4'-dihydroxybiphenyl, 4.975 kg of potassium carbonate, and 501 N-methylpyrrolidone as a solvent were placed in a reactor, and the mixture was heated for 1 hour while blowing argon gas into the reactor. 195° from room temperature
The temperature was raised to C. After raising the temperature, a small amount of toluene was added and the generated water was removed from the reaction system by azeotropy. and 195°
The reaction was carried out for 30 minutes at a temperature of C. Then 4.4'-
4.5822 kg of difluorobenzophenone to 70 N-methylpyrrolidone! A solution dissolved in was added and the reaction was further carried out for 1 hour. After the reaction is completed, the reaction product is pulverized using a high-speed mixer (manufactured by Fukae Kogyo), and then mixed with 1 part of water.
Wash with 001 5 times and dry to form 3 repeating units below.
10.20 kg (yield: 100%) of a crystalline polycyanoaryl ether copolymer having a ratio of 0 to 0 was obtained.

N When the thermal properties of this polymer were measured, the melting point was 379°C and the thermal decomposition onset temperature was 562°C.

Production Example 3 (Production of thermoplastic polyimide) Internal volume 10 equipped with a stirring device, reflux condenser and argon gas blowing pipe
0I! In a reactor, 6.17 kg of bis(4-(4-(4-aminophenoxy)phenoxy)phenyl)sulfone was added.
(10 mol) and 30 mol of N,N-dimethylacetamide as the solvent. 2.14 kg (9.8 mol) of pyromellitic dianhydride was added over 1 hour while blowing argon gas into the mixture, and the mixture was further stirred at room temperature for 12 hours to obtain a polyamic acid solution. Continuing, 4.08kg
(40 mol) of triethylamine, 6.03 kg (60
mol) of acetic anhydride was added dropwise, and the mixture was stirred at room temperature for 12 hours.

After the reaction is completed, the reaction product is poured into water to precipitate a polymer, and the precipitated polymer is washed with methanol and dried to obtain a thermoplastic polyimide 7 containing the following repeating units.
5 kg (yield 95%) was obtained.

When the thermal properties of this polymer were measured, the glass transition temperature was 285°C and the thermal decomposition temperature was 530°C.

Example 1 Crystalline polycyanoaryl ether obtained in Production Example 1,
The thermoplastic polyimide obtained in Production Example 3 was
The mixture was blended in a ratio of 0:80 (wt%), and this mixture was melt-kneaded at 350°C for 3 minutes using a twin-screw extruder to obtain a thermoplastic resin composition.

Next, the pellet of this resin composition was molded with an injection molding machine using a spiral flow mold (mold temperature 220°C, thickness 1 mm) at an injection pressure of 9 MPa and an injection temperature of 350''C. The flow length during injection molding was measured, and the moldability of the resin composition was evaluated based on the fluidity.

In addition, in order to check the heat resistance of this resin composition, ASTM
The heat distortion temperature was measured in accordance with D-648.

The results of these measurements are shown in Table 1.

Example 2 The crystalline polyline aryl ether obtained in Production Example 1,
The procedure was the same as in Example 1, except that the blending ratio of the thermoplastic polyimide obtained in Production Example 3 was 50:50 (wt%).

The measurement results are shown in Table 1.

Example 3 Crystalline polycyanoaryl ether obtained in Production Example 1,
Example 1 except that the blending ratio of the thermoplastic polyimide obtained in Production Example 3 was 20:80 (wt%) of the former:the latter fXZr, and the injection molding temperature was 380°C.
I did the same thing. The measurement results are shown in Table 1.

Table 1 Example 4 The mixing ratio of the crystalline polycyanoarylether copolymer obtained in Production Example 2 and the thermoplastic polyimide obtained in Production Example 3 was 50:50 (weight%) of the former:the latter. The same procedure as in Example 1 was carried out except that the following values were set. The measurement results are shown in Table 1.

Example 5 30 parts by weight of glass fiber was blended with 100 parts by weight of the thermoplastic resin composition obtained in Example 1, and the mixture was melt-kneaded at 350°C using a two-wheel mixer to form pellets of the resin composition. Manufactured. Using this resin composition, fluidity and heat resistance were evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a thermoplastic resin composition that has a low melt viscosity, good moldability, high mechanical strength at high temperatures, high elastic modulus, and excellent heat resistance.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A] (Ar in the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
Indicates either ▼ There are mathematical formulas, chemical formulas, tables, etc. or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ) 10 to 90% by weight of crystalline polycyanoarylether having a repeating unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [B^1] (X in the formula is -CH_2-, -CO-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas , chemical formulas, tables, etc. ▼ ), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [B^2] (X in the formula has the same meaning as above, Y^1 indicates a direct bond, - O-, -CO-, -SO_2, -C(CH_3)_
2- or -C(CF_3)_2-. ) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [B^3] (X in the formula has the same meaning as above, and Y^2 and Y^3
has the same meaning as Y^1. ) A thermoplastic resin composition comprising 90 to 10% by weight of a thermoplastic polyimide having repeating units represented by: