JPH0710949B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a thermoplastic resin composition, more specifically, a heat-resistant thermoplastic resin excellent in chemical stability such as chemical resistance and solvent resistance. It relates to a composition.

[Prior Art] In recent years, engineering resins have been used in various fields, and a resin material having strength and elastic modulus at high temperature, heat resistance, and chemical stability is particularly required.

A composition comprising a crystalline polycyanoaryl ether resin and a thermoplastic resin is known (Japanese Patent Laid-Open Nos. 60-28250, 61-85470, 62-116658 and 63-3.
No. 059), it is known to have excellent heat resistance. Among them, compositions with amorphous engineering plastics having a high glass transition temperature such as polysulfone resin, polyetherimide resin, and amorphous polyarylate resin have a relatively low glass transition temperature of crystalline polycyanoaryl ether resin. It is expected to solve problems such as a decrease in elastic modulus at high temperature due to the above and a relatively large molding shrinkage due to crystallinity. However, amorphous heat-resistant engineering plastics such as polysulfone resin have poor chemical resistance and solvent resistance. By adding these, the excellent chemical resistance and solvent resistance of the crystalline polycyanoaryl ether resin can be obtained. There is a problem of being damaged.

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances.

The object of the present invention is to solve the above-mentioned problems, and a composition comprising a crystalline polycyanoaryl ether resin and an amorphous heat-resistant engineering plastic selected from polysulfone resin, polyetherimide resin, and amorphous polyarylate resin. In particular, it is to provide a resin composition which retains excellent chemical resistance such as chemical resistance and solvent resistance of the crystalline polycyanoaryl ether resin and has excellent heat resistance.

[Means for Solving the Problems] As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an amorphous resin selected from polysulfone resin, polyetherimide resin and amorphous polyarylate resin is selected. It was found that a composition containing a polycyanoaryl ether resin having a specific ratio of a specific melt viscosity achieves the above object, and based on this finding, the present invention has been completed.

That is, the present invention comprises (A) 10 to 70% by weight of an amorphous resin selected from polysulfone resin, polyetherimide resin and amorphous polyarylate resin, and (B) at 350 ° C.
The melt viscosity at a shear rate of 1000 sec ^-1 is 500 to 20,000 poise, and the melt viscosity is 350 ° C. of the amorphous material,
A resin composition comprising 30 to 90% by weight of a crystalline polycyanoaryl ether resin having a melt viscosity lower than that at a shear rate of 1000 sec ^-1 is provided.

If the melt viscosity of the crystalline polycyanoaryl ether resin of the component (B) of the present invention is less than 500 poise, the mechanical strength becomes insufficient, and if it exceeds 20,000 poise, the moldability is lowered, which is not preferable. As the crystalline polycyanoaryl ether resin as the component (B), one having a repeating unit represented by the following general formula [I] is preferably used.

(However, Ar ¹ Is. ) Specifically, various polymers having a repeating unit represented by the following formula are preferable.

Further, it is necessary that the melt viscosity of the crystalline polycyanoaryl ether resin as the component (B) is smaller than the melt viscosity of the amorphous resin as the component (A). When the melt viscosity is higher than that of the amorphous resin, the chemical stability such as solvent resistance and chemical resistance becomes insufficient.

As the amorphous resin as the component (A), a resin selected from polysulfone resins, polyether resins, and amorphous polyarylate resins having a higher melt viscosity than the crystalline polycyanoaryl ether resin as the component (B) is used.

As the polysulfone resin, those having a repeating unit represented by the following general formula [II] are preferably used.

Ar ² -SO ₂ -Ar ² -O [II] (However, Ar ² Or Represents ) Specifically, a polysulfone resin having the following repeating unit commercially available from ICI, Further, a polysulfone resin having the following repeating unit commercially available from AMOCO is preferably used.

In addition, various polymers having a repeating unit represented by the following formula are preferably used.

The polyetherimide resin has the following general formula [III]
A polyetherimide resin having a repeating unit represented by is preferably used.

(However, Ar ³ is the same as Ar ^1. ) Specifically, a polyetherimide resin having the following repeating unit marketed by GE under the trade name of Ultem is preferably used.

The amorphous polyarylate resin has the following general formula [IV]
An amorphous polyarylate resin having a repeating unit represented by is preferably used.

CO-Ar ⁴ -COO-Ar-O [IV] and / or Ar ⁴ -COO (However, Ar ⁴ is the same as Ar ^1. ) Specifically, it is commercially available from Unitika under the trade name of U polymer. Copolymers having the following repeating units are preferably used.

In addition, a polymer having the following repeating unit, A copolymer or the like having a repeating unit represented by the following formula is preferably used.

If the compounding amount of the crystalline polycyanoaryl ether resin in the resin composition of the present invention exceeds 90% by weight, there is no effect of improving heat resistance, and if it is less than 30% by weight, chemical resistance, solvent resistance and the like decrease.

Next, the mechanical strength of the molded article obtained from the composition containing 60 to 95% by weight of the resin composition and 5 to 40% by weight of the inorganic filler is further improved.

Examples of the inorganic filler include glass fiber, carbon fiber,
Examples thereof include fibrous substances such as potassium titanate / whiskers and wollastonite, and non-fibrous substances such as silicon carbide, titania, mica, calcium carbonate and calcium sulfate. If the content of the inorganic filler is less than 5% by weight, the effect of addition as a reinforcing material is insufficient, and if it exceeds 40% by weight, the moldability is deteriorated.

The resin composition of the present invention, when used in the production or processing thereof, if necessary, within a range not impairing the object of the present invention, other additive components other than the above respective components, for example, Various additives such as a stabilizer such as an antioxidant and an anti-UV agent, an antistatic agent, a lubricant, a coloring agent and a release agent may be contained.

The method for producing the resin composition of the present invention is not particularly limited, and can be produced by various methods such as known methods.

Usually, for example, after mixing the above predetermined components (in some cases, further additional components) in the predetermined ratio,
It can be obtained by melt-kneading using a hot roll, a kneader, a Banbury mixer, and a melt extruder. The kneading temperature at that time is usually 300 to 400 ° C, preferably 340 to 3
It is suitable to set within the range of 60 ℃.

The resin composition thus obtained, if necessary,
It is molded into various molded products such as pellets, and is further molded into a desired shape by compression molding, extrusion molding, injection molding or the like.

[Examples] Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto.

Production Example 1 2,6-dichlorobenzonitrile 5.2 was placed in a reactor having an inner volume of 10 equipped with a stirrer, a rectification unit and an argon gas blowing tube.
11 kg, resorcin 3.32 kg, calcium carbonate 4.27 kg, and N-methylpyrrolidone 4.5 and toluene 2 as solvents
Was charged, and the mixture was stirred at room temperature for 1 hour while blowing argon gas therein, and then heated to 197 ° C. and reacted for 2.5 hours.

After completion of the reaction, the reaction product was put into methanol to precipitate the polymer, and the high speed mixer (Fukae Industry Co., Ltd.)
Crushed with water) and then with water 100 three times, methanol 100
6.26 kg of polymer (yield 95%) after washing twice with
Got

The resulting polymer has the following repeating units and has a melting point
The temperature was 340 ° C and the thermal decomposition initiation temperature was 490 ° C. The melt viscosity of this polymer at 350 ° C. and a shear rate of 1000 sec ⁻¹ was measured using a Capillograph manufactured by Toyo Seizo Seisakusho, and found to be 3,800 poises.

Production Example 2 2,6-dichlorobenzonitrile 5.2 was added to a reactor having an inner volume of 10 equipped with a stirrer, a rectification unit and an argon gas blowing tube.
11 kg, resorcin 3.30 kg, potassium carbonate 4.17 kg, and N-methylpyrrolidone 4.3 and toluene 2 as a solvent are charged, and argon gas is blown thereinto at room temperature for 1 hour.
After stirring for an hour, the temperature was raised to 193 ° C. and the reaction was performed for 4.5 hours.

After completion of the reaction, the reaction product was put into ethanol to precipitate the polymer, and the high speed mixer (Fukae Industry Co., Ltd.)
After crushing with water), water 100 times 3 times, methano 100
It was washed twice with, and dried to obtain 6.15 kg of polymer (yield 95%).

The resulting polymer has the following repeating units and has a melting point
The temperature was 340 ° C and the thermal decomposition initiation temperature was 490 ° C. The melt viscosity of this polymer at 350 ° C. and a shear rate of 1000 sec ⁻¹ was measured using a Capillograph manufactured by Toyo Seiki Seisakusho, and it was 9,500 poise.

Measurement example 1 3 of polyether sulfone (ICI, VICTRX PES 4800G)
When the melt viscosity at 50 ° C and a shear rate of 1000 sec ^-1 was measured using a Toyo Seiki Seisakusho Capillograph, it was 5,200.
It was a poise.

Measurement Example 2 Polyetherimide (GE, Ultem 1000) at 350 ° C,
When the melt viscosity at a shear rate of 1000 sec ^-1 was measured using a Capillograph manufactured by Toyo Seizo Seisakusho, it was 4,100 poise.

Measurement Example 3 Amorphous polyarylate (Unitika Co., U-100) 350
When the melt viscosity at a shear rate of 1000 sec ^{-1 at} ℃ was measured using a Capillograph manufactured by Toyo Seiki Seisakusho, it was 6,7,000 poise.

Examples 1 to 3 Polycyanoaryl ethers and polyether sulfones (ICT, VICTREX PES 4800G) obtained in Production Example 1 have the composition shown in Table 1 (numerical values in the table represent% by weight) and are biaxial. Kneading was performed for 2 minutes at 350 ° C. using an extruder. The obtained composition was injection molded and subjected to a bending test and a chemical resistance test. Bending tests were performed at 25 ° C and 180 ° C according to ASTM-D-790. The chemical resistance test was indexed by the rate of weight increase after immersion in N-methylpyrrolidone for 8 hours at 25 ° C.

Examples 4 to 6 The polycyanoaryl ether obtained in Production Example 1 and polyetherimide (GE, Ultem 1000) were kneaded with the composition shown in Table 1 at 350 ° C. for 2 minutes using a twin-screw extruder. The composition obtained was injection molded and subjected to a bending test and a chemical resistance test.

Examples 7 to 9 Polycyanoaryl ether obtained in Production Example 1 and amorphous polyarylate (U-100, Unitika Ltd.) were used in the composition shown in Table 1 at 350 ° C. for 2 minutes using a twin-screw extruder. Kneaded
The composition obtained was injection molded and subjected to a bending test and a chemical resistance test.

Examples 10 to 12 Polycyanoaryl ether obtained in Production Example 1, polyether sulfone (ICT VICTREX PES 4800G) and glass fiber were kneaded in the same manner as in Example 1 with the composition shown in Table 1, and Example 1 The same experiment was performed.

Comparative Examples 1 to 9 In Examples 1 to 9, the same experiments as in Examples 1 to 9 were performed, except that the polymer obtained in Production Example 2 was used as the polycyanoaryl ether in the proportions shown in Table 2.

Comparative Example 10 In Example 1, 10 parts by weight of the polycyanoaryl ether obtained in Preparation Example 1 and polyether sulfone (ICI V
The same experiment as in Example 1 was conducted except that 90 parts by weight of ICTREX PES 4800G) was used.

Reference Example 11 Only the crystalline polycyanoaryl ether of Production Example 1 was molded and the properties were measured.

Reference Example 12 Only the crystalline polycyanoaryl ether of Production Example 2 was molded and the properties were measured.

Reference Example 13 Only a polyether sulfone (ICI VICTREX PES 4800G) was molded and the characteristics were measured.

Reference Example 14 Only polyetherimide (Ultem 1000) was molded and the properties were measured.

Reference Example 15 Only amorphous polyarylate (U-100) was molded and the properties were measured.

Table 3 shows the measurement results of the characteristics in the above Examples, Comparative Examples and Reference Examples.

As is clear from the results shown in Table 3, a polymer having a melt viscosity outside the scope of the present invention is used as the polycyanoaryl ether, and when the composition range of the composition is outside the scope of the present invention, it is sufficient. No chemical resistance can be obtained.

[Effect of the Invention] The resin composition of the crystalline polycyanoaryl ether resin of the present invention and the amorphous resin selected from the polysulfone resin, the polyetherimide resin and the amorphous polyarylate resin has the former chemical resistance. It retains chemical stability such as solvent resistance and solvent resistance, and has the latter heat resistance, and its industrial value is extremely large.

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Claims (2)

[Claims] 1. To (A) 10 to 70% by weight of an amorphous resin selected from a polysulfone resin, a polyetherimide resin and an amorphous polyarylate resin, (B) at 350 ° C. and a shear rate of 1000 sec ⁻¹ . Melt viscosity is 500
30 to 90% by weight of a crystalline polycyanoaryl ether resin having a melt viscosity of less than 20,000 poise and a melt viscosity lower than that of the amorphous resin at 350 ° C. and a shear rate of 1000 sec ^-1 . Resin composition. 2. A resin composition comprising 60 to 95% by weight of the resin composition according to claim 1 and 5 to 40% by weight of an inorganic filler.