JPH0673290A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic composition excellent in the balance among the heat resistance, the chemical resistance, the moldability and the impact resistance by mixing a specified polyarylethersulfone and a polyarylene sulfide each in a specified amount. CONSTITUTION:This resin composition consists of 95-5 pts.wt. polyarylethersulfone having a structure consisting of repeating units of formula I and those of formula II at a molar ratio of (0 to 70):(30 to 100) and 5-95 pts.wt. polyarylene sulfide (e.g. PPS NR-04, a product of Ube Industries, Ltd.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having an excellent balance of heat resistance, chemical resistance, moldability and impact resistance.

[0002]

2. Description of the Related Art Sulfone polymers such as polysulfone and polyether sulfone are known as engineering plastics having excellent heat resistance.
However, the chemical resistance, moldability and impact resistance are not always good, and their improvement is required. A known method is to blend polyarylene sulfide. For example, JP-A-55-82130 discloses a composite material in which carbon fiber is impregnated with a resin composition containing polysulfone and polyphenylene sulfide as main components. Further, JP-A-62-121761, JP-A-62-119268 and JP-A-62-2.
No. 47755, a block copolymer composed of polysulfone and polyphenylene sulfide, and a polysulfone and / or polyphenylene sulfide composition are disclosed.
Alternatively, a composition in which carbon fibers are impregnated with them, a composition containing a filler, and the like are disclosed. However, in these methods, among the physical properties of the resin composition, for example, although the chemical resistance and the moldability are improved, the impact resistance is insufficient and the balance of the physical properties is not always satisfactory. No, improvement is required.

[0003]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having an excellent balance of heat resistance, chemical resistance, moldability and impact resistance.

[0004]

[Technical Means for Solving the Problems]
It has been found that a thermoplastic resin composition composed of polyarylethersulfone having a specific structure and polyarylene sulfide has an excellent balance of heat resistance, chemical resistance, moldability, and impact resistance. The present invention comprises (A) repeating units of formulas (I) and (II):

Embedded image The ratio of repeating unit (I) to repeating unit (II) is 0.
A thermoplastic resin composition comprising 95 to 5 parts by weight of a polyarylethersulfone having a structure of about 70:30 to 100 (mol%) and 5 to 95 parts by weight of (B) polyarylene sulfide.

The component (A) of the composition of the present invention comprises repeating units of the following formulas (I) and (II):

Embedded image The ratio of repeating unit (I) to repeating unit (II) is 0.
It is a polyaryl ether sulfone having a structure of ˜70: 30 to 100 (mol%).

[0006] As its manufacturing method, in an organic polar solvent,
A polycondensation reaction of a dihalogenodiphenyl sulfone compound and a dihydric phenol compound in the presence of an alkali metal compound,
Alternatively, it can be produced by using hydroquinone and 4,4′-biphenol as the dihydric phenol compound in a predetermined ratio in the polycondensation reaction of the dimetalogen diphenyl sulfone compound and the alkali metal di-salt of the dihydric phenol which are synthesized in advance.

In the dihydric phenol compounds hydroquinone and 4,4'-biphenol, at least one of the hydrogen atoms on the benzene ring of the diphenol compound is a suitable substituent (eg, a lower alkyl group such as a methyl group, an ethyl group or a propyl group), Alternatively, those substituted with a substituent such as a lower alkoxy group such as a methoxy group and an ethoxy group may be used.

The ratio of the repeating unit (I) to the repeating unit (II) can be adjusted by the charging ratio in the polycondensation reaction of hydroquinone and 4,4'-biphenol. In the composition of the present invention, the ratio of the repeating unit (I) to the repeating unit (II) of the polyarylethersulfone is 0 to 70:30 to 100 (mol%), preferably 10 to 60: It is 40 to 90 (mol%).
If it is out of the above range, the balance of the physical properties of the composition is lost, which is not preferable.

In the composition of the present invention, the molecular weight of the polyaryl ether sulfone is not particularly limited, but N-
0.5 g / 100 using methyl-2-pyrrolidone as a solvent
Reduced viscosity (η
sp / c) is preferably 0.2 to 1.0, and 0.
Those of 4 to 0.6 are particularly preferably used.

The component (B) of the composition of the present invention is polyarylene sulfide. The polyarylene sulfide used in the present invention has a repeating unit of the formula

[Chemical 2] The polyphenylene sulfide represented by

In addition to the above repeating unit, as a copolymerization component, a metasulfide bond (IV) represented by the following formula,
Ether bond (V), sulfone bond (VI), biphenyl sulfide (VII) bond, naphthyl sulfide bond (VIII), substituted phenylene sulfide bond (IX)
(Here, R is selected from the group consisting of an alkyl group or an alkoxy group having 12 or less carbon atoms, a phenyl group and nitro),

[0012]

[Chemical 3]

Alternatively, it may contain a trifunctional phenyl sulfido bond or the like. The content of the above copolymerization component,
As long as the physical properties such as heat resistance of the polymer are not impaired, 30
% Or less is preferable. The polyarylene sulfide of the present invention has the above structure and has the structure of ASTM D1
315 with melt indexer defined by 238-74T
Those having a melt flow rate of 5 to 10,000 g / 10 minutes measured under the conditions of ° C and a load of 5 kg are preferably used.

The mixing ratio of the polyaryl ether sulfone and the polyarylene sulfide in the composition of the present invention is 95 to 5 parts by weight with respect to 5 to 95 parts by weight of the polyaryl ether sulfone.
Preferably, polyaryl ether sulfone 20 to 90
It is 80 to 10 parts by weight of polyarylene sulfide with respect to parts by weight.

The mixing ratios are heat resistance, chemical resistance, moldability,
And the balance of properties such as impact resistance,
If the ratio of polyaryl ether sulfone to polyarylene sulfide deviates from the above range, the balance of these properties will be lost. That is, when the ratio of polyarylethersulfone exceeds 95 parts by weight with respect to 100 parts by weight of the composition, the effect of improving chemical resistance and moldability is small, and when the ratio of polyarylethersulfone is less than 5 parts by weight, Heat resistance and impact resistance decrease.

In order to improve the dispersibility of polyaryl ether sulfone and polyarylene sulfide, a compatibilizer may be newly added. Examples of the compatibilizing agent include block copolymers of polyaryl ether sulfone and polyarylene sulfide.

There is no particular limitation on the method of blending the respective components of the present invention, but they can be blended by kneading using an ordinary kneader. For example, it can be obtained as pellets by melt-kneading using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like. The pellets are molded into an arbitrary shape such as a film, a pipe or a tube by injection molding, blow molding, extrusion molding or the like.

Polyethylene, polypropylene, ethylene / vinyl acetate copolymers, ethylene / propylene copolymers, styrene / butadiene copolymers, hydrogenated styrene / butadiene copolymers are further added to the extent that the characteristics of the composition of the present invention are not impaired. Thermoplastic resins such as polymers, polyvinyl chloride resins, polyester resins, polyamide resins and polycarbonates, thermosetting resins such as phenol resins, melamine resins, silicone resins and epoxy resins, glass fibers, carbon fibers, boron Reinforcing agents such as fibers, silicon carbide fibers, asbestos fibers, metal fibers, fillers such as clay, mica, silica, graphite, glass beads, calcium carbonate, talc, etc., antioxidants, heat stabilizers, UV inhibitors, difficult One or more types of flame retardants, pigments, antistatic agents, colorants, etc. It may be added.

[0019]

The composition of the present invention comprising a polyaryl ether sulfone having a specific structural unit and a polyarylene sulfide has improved chemical resistance and moldability,
Further, as compared with a conventionally known composition using a sulfone-based polymer, high impact resistance is obtained, and deterioration of heat resistance is suppressed. That is, the composition of the present invention has chemical resistance,
A thermoplastic resin composition that has an excellent balance of physical properties such as moldability, heat resistance, and impact resistance.
It can be used as a material for electronic and electrical parts, mechanical parts, medical and tableware fields.

[0020]

【Example】

(Method for preparing test piece) A test piece was prepared by pelletizing the composition and then using an injection molding machine Nestal SG100 (mold clamping force 100 ton) manufactured by Sumitomo Heavy Industries, Ltd. (Test method of test piece) (1) Deflection temperature under load Tested according to ASTM D648. (2) Izod impact strength (with notch) It was performed according to ASTM D256. (3) Chemical resistance A test piece (1/8 inch in thickness) was made to have a strain of 1%, kerosene was applied, and 24 hours later, the presence or absence of cracks was visually inspected.

EXAMPLE 1 73.3 g of 4,4'-dichlorodiphenyl sulfone
(0.255 mol), 13.7 g of hydroquinone
(0.124 mol) and 4,4'-biphenol 2
3.2 g (0.124 mol) was added to 30 ml of toluene for azeotropic dehydration and 300 ml of N-methyl-2-pyrrolidone under a nitrogen atmosphere and dissolved, and then 30 g at 70 ° C. in nitrogen.
37.9 g of potassium carbonate which had been heat-treated for 1 minute was reacted under stirring in a nitrogen atmosphere at a temperature of 180 ° C. for 8 hours to obtain a polymerization solution. After completion of the reaction, in order to separate the inorganic substance from the polymerization solution,
A polymer solution was obtained by filtering at a nitrogen pressure of 1.5 kg / cm ² .
300g of polymerization solution was poured into 2000ml of ethanol, and 5
The polymer is precipitated while stirring at 000 rpm, filtered,
After separation, a polymer was obtained. 50 g of this polymer was washed with 500 ml of ethanol and then dried at 90 ° C. to obtain a powder of polyarylethersulfone. The reduced viscosity (ηsp / c) of the obtained polyarylethersulfone was 0.
52, and the ratio of the repeating unit (I) to the repeating unit (II) was 50:50 (mol%).

As the polyarylene sulfide, UB
EPPS NR-04 (manufactured by Ube Industries, Ltd.) was used. The above polyaryl ether sulfone (component A) 7
0 parts by weight and 30 parts by weight of polyarylene sulfide (component B) were mixed, and this mixture was mixed with 30 m
The resin composition of the present invention was obtained by melt-kneading at 330 ° C. using an mφ twin-screw extruder. Each evaluation experiment was conducted using this composition. The results are shown in Table 1.

Examples 2 and 3 A resin composition was obtained in the same manner as in Example 1 except that the mixing ratio of polyaryl ether sulfone and polyarylene sulfide was changed as shown in Table 1.
Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 1.

Comparative Example 1 In Example 2, the polyaryl ether sulfone of the component (A) was replaced with a polysulfone (A
Except that MOCO P-1700) was used.

[Chemical 4] A resin composition was obtained in the same manner as in Example 1. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Comparative Examples 2 and 3 A resin composition was obtained in the same manner as in Example 1 except that the mixing ratio of polyaryl ether sulfone and polyarylene sulfide was changed as shown in Table 1. . Each evaluation experiment was conducted in the same manner as in Comparative Example 1 using this composition. The results are shown in Table 2.

[Table 1]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Doi 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Ltd. Hirakata Research Laboratory

Claims (1)

[Claims] 1. (A) consists of repeating units of the following formulas (I) and (II): The ratio of repeating units (I) to repeating units (II) is 0 to 70:
A thermoplastic resin composition comprising 95 to 5 parts by weight of a polyaryl ether sulfone having a structure of 30 to 100 (mol%) and (B) 5 to 95 parts by weight of a polyarylene sulfide.