JP2673855B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Sulfone polymers such as polysulfone and polyethersulfone are known as engineering plastics having excellent heat resistance.
However, the impact resistance is not necessarily large, and as a method for improving the impact resistance, it is known to blend a rubber-grafted styrene copolymer such as acrylonitrile-butadiene-styrene resin (hereinafter abbreviated as ABS resin). For example,
JP-B-46-37896, JP-B-49-2766
No. 8, or JP-A-56-167752, a composition of an ABS resin and polyether sulfone; JP-A-56-16552, a composition of an ABS resin, a polysulfone, and an organosilicon compound; JP-A-56-
Japanese Patent No. 16552 discloses a composition with an ABS resin, polyarylene polysulfone, and polycarbonate, and Japanese Patent Laid-Open No. 63-305152 discloses a composition with an ABS resin, polysulfone, and polyetherimide. However, in these compositions of ABS resin and sulfone-based polymer, it is necessary to increase the addition amount of the rubber-like polymer in order to improve the impact resistance, and therefore it is unavoidable that the heat resistance is lowered. That is, the balance of physical properties such as heat resistance and impact resistance is not always satisfactory, and improvement is required.

[0003]

It is an object of the present invention to provide a thermoplastic resin having an excellent balance of physical properties such as heat resistance and impact resistance.

[0004]

[Technical means for solving the problems]
It has been found that a thermoplastic resin composed of a polyarylethersulfone having a specific structure and a rubber-grafted styrene copolymer has an excellent balance of physical properties such as heat resistance and impact resistance. The present invention comprises (A) repeating units of formulas (I) and (II):

Embedded image The ratio of repeating units (I) to repeating units (II) is 0 to 70:
A thermoplastic resin composition comprising 5 to 95 parts by weight of a polyaryl ether sulfone having a structure of 30 to 100 (mol%) and (B) 95 to 5 parts by weight of a rubber-grafted styrene copolymer. Regarding

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 units (I) to repeating units (II) is 0 to 70:
It is a polyarylethersulfone having a structure of 30 to 100 (mol%).

[0006] The production method is as follows:
In the presence of an alkali metal compound, a polycondensation reaction between a dihalogenodiphenyl sulfone compound and a dihydric phenol compound,
Alternatively, it can be produced by using hydroquinone and 4,4′-biphenol as a dihydric phenol compound in a predetermined ratio in a polycondensation reaction between a previously synthesized alkali metal disalt of dihydric phenol and a dihalogenodiphenyl sulfone compound.

In the dihydric phenol compounds hydroquinone and 4,4'-biphenol, at least one of the hydrogen atoms on the benzene ring is replaced with a suitable substituent (for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, etc.). 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 the ratio is out of the above range, the balance of the physical properties of the composition is lost, which is not preferable.

[0009] In the composition of the present invention, the molecular weight of the polyarylethersulfone is not particularly limited.
0.5 g / 100 using methyl-2-pyrrolidone as a solvent
reduced viscosity (η) measured at 30 ° C.
(sp / c) is preferably from 0.2 to 1.0.
Those having 4-0.6 are particularly preferably used.

The component (B) of the composition is a rubber-grafted styrene copolymer. As the rubber-grafted styrene copolymer, ABS composed of vinyl cyanide compound, conjugated diene compound, and aromatic vinyl compound in various ratios is used.
Resins can be mentioned.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Examples of the conjugated diene compound include butadiene and isoprene. As the aromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene,
Examples thereof include dimethyl styrene and chlorostyrene. In addition, unsaturated carboxylic acid alkyl ester compounds such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate, maleimide,
N-methylmaleimide, N-phenylmaleimide, N-
A maleimide compound such as cyclohexylmaleimide and a carboxylic acid anhydride such as maleic anhydride, methylmaleic anhydride and phenylmaleic anhydride may be contained as the fourth component.

The ABS resin is, for example, a graft copolymer obtained by grafting styrene and / or acrylonitrile onto polybutadiene rubber, styrene-butadiene copolymer rubber or acrylonitrile-butadiene copolymer rubber,
It may be in the form of a blend of styrene-butadiene copolymer rubber and styrene-acrylonitrile resin, or a combination thereof.

As the manufacturing method thereof, a known manufacturing method,
For example, an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method and the like can be mentioned.

As the rubber-grafted styrene copolymer, in addition to the above ABS resin, acrylic rubber is used as a rubber component (AAS resin), chlorinated polyethylene is used (ACS resin), ethylene-propylene-diene type. Examples thereof include those using rubber (AES resin) and those using polybutadiene rubber.

The ratio of the polyaryl ether sulfone to the rubber-grafted styrene copolymer in the composition of the present invention is 95 to 5 parts by weight of the rubber-grafted styrene copolymer with respect to 5 to 95 parts by weight of the polyaryl ether sulfone. . Preferably, polyaryl ether sulfone 20-
Rubber-grafted styrene copolymer 80 to 90 parts by weight
To 10 parts by weight. The mixing ratio is related to the balance of properties such as impact resistance and heat resistance, and if the ratio of the polyarylethersulfone and the rubber-grafted styrene copolymer deviates from the above range, the balance of these properties is lost.

In order to improve the dispersibility of the polyaryl ether sulfone and the rubber-grafted styrene copolymer, a compatibilizer may be newly added. Examples of the compatibilizer include a block copolymer of polyarylethersulfone and a styrene copolymer, a graft copolymer, and a functional group-containing styrene copolymer.

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 formed into an arbitrary shape such as a film, a pipe, and 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. Polymers, polyvinyl chloride resins, polyamide resins, thermoplastic resins such as polycarbonates, thermosetting resins such as phenol resins, melamine resins, silicone resins, epoxy resins, glass fibers, carbon fibers,
Reinforcing agent such as boron fiber, silicon carbide fiber, asbestos fiber, metal fiber, filler such as clay, mica, silica, graphite, glass beads, calcium carbonate, talc, or antioxidant, heat stabilizer, ultraviolet ray inhibitor, One or more of a flame retardant, a pigment, an antistatic agent, a colorant and the like may be added.

[0019]

The composition of the present invention comprising a polyaryl ether sulfone having a specific structural unit and a rubber-grafted styrene copolymer is a composition using a conventionally known sulfone polymer such as polysulfone or polyether sulfone. Compared with the product, even if the amount of the rubber component is small, high impact resistance can be obtained, and deterioration of heat resistance can be suppressed. That is, the composition of the present invention is a thermoplastic resin having an excellent balance of physical properties such as heat resistance and impact resistance,
It can be used as a material for various automobile parts, electronic and electrical parts, mechanical parts, medical and tableware fields.

[0020]

【Example】

(Method of preparing test piece) The test piece was prepared by pelletizing the composition and then using a Nestal SG100 (mold clamping force: 100 ton) injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. (Test method of test piece) (1) Heat distortion temperature It was performed according to ASTM D648. (2) Izod impact strength (with notch) This was performed according to ASTM D256.

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 and dissolved in 30 ml of toluene for azeotropic dehydration and 300 ml of N-methyl-2-pyrrolidone under a nitrogen atmosphere.
37.9 g of potassium carbonate heat-treated for 1 minute was stirred and reacted at 180 ° C. for 8 hours in a nitrogen atmosphere to obtain a polymerization solution. After the reaction, to separate the inorganic substances from the polymerization solution,
Filtration was performed under a nitrogen pressure of 1.5 kg / cm ² to obtain a polymerization solution.
300 g of the polymerization solution was poured into 2000 ml of ethanol, and 5
The polymer was precipitated while stirring at 000 rpm, filtered,
After separation, a polymer was obtained. After washing 50 g of this polymer with 500 ml of ethanol, it was dried at 90 ° C. to obtain polyarylethersulfone powder. The reduced viscosity (ηsp / c) of the obtained polyarylether sulfone is 0.5
2, and the ratio of the repeating unit (I) to the repeating unit (II) was 50:50 (mol%).

As the ABS resin, Psycolak T (trade name: manufactured by Ube Saikon) was used. 90 parts by weight of the polyarylethersulfone (component A) and 10 parts by weight of ABS resin (component B) were mixed, and this mixture was melt-kneaded at 280 ° C. using a 30 mmφ twin screw extruder manufactured by Nakatani Machinery Co. A resin composition of the invention was obtained. Each evaluation experiment was performed using this composition. The results are shown in Table 1.

Examples 2 to 4 A resin composition was prepared in the same manner as in Example 1 except that the mixing ratio of the polyaryl ether sulfone and the rubber grafted styrene copolymer was changed as shown in Table 1. Obtained. 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 1, except that the polyaryl ether sulfone of the component (A) was replaced with a polysulfone having a structure consisting of repeating units of the following formula (P-1700 manufactured by AMOCO).

Embedded image 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 to 4 Resin compositions were obtained in the same manner as in Comparative Example 1 except that the mixing ratio of polysulfone and rubber graft styrene copolymer was changed as shown in Table 1. . Each evaluation experiment was performed in the same manner as in Comparative Example 1 using this composition. The results are shown in Table 2.

[Table 1]

[Table 2]

Claims (1)

(57) [Claims] (A) A repeating unit 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 5 to 95 parts by weight of a polyaryl ether sulfone having a structure of 30 to 100 (mol%) and (B) 95 to 5 parts by weight of a rubber-grafted styrene copolymer. .