JP2000290477A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in various kinds of processability, capable of providing a molded product having good surface nature, and comprising a rubber-reinforced styrene-based resin and a polyester resin. SOLUTION: This thermoplastic resin composition is obtained by formulating 100 pts.wt. total of (A) 97-10 pts.wt. thermoplastic polyester resin, and (B) 3-90 pts.wt. rubber-reinforced styrene-based resin, with (C) a polytetrafluoroethylene- containing mixed powder comprising polytetrafluoroethylene particles having <=10 μm particle diameters and an organic polymer, so that the amount of the polytetrafluoroethylene component may be 0.0001-20 pts.wt.

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 comprising a rubber-reinforced styrenic resin and a polyester resin, and provides a molding material having excellent moldability which gives a molded article having excellent mechanical properties. is there.

[0002]

2. Description of the Related Art Thermoplastic polyesters represented by polybutylene terephthalate and polyethylene terephthalate have excellent workability, mechanical properties, and other physical and chemical properties, and are therefore used in automobile parts, electric and electronic equipment parts. , Is widely used in the field of precision equipment parts, but has disadvantages such as low impact strength with notch, high molding shrinkage during injection molding, and insufficient dimensional stability. There is a need for improvements. Therefore, in order to improve the impact resistance of these thermoplastic polyesters, a method of blending a rubber-reinforced styrene resin such as an ABS resin (Japanese Patent Publication No. 51-25261), an ABS resin blended with a thermoplastic polyester, and an AS resin To improve the physical properties by introducing a functional group into the
3656, JP-A-1-163249) have been proposed.

However, when the resin composition obtained by the above-described method is processed into various molded articles by blow molding, extrusion molding, foam molding, or the like, characteristics which are the most important in applying these processing methods. In other words, because the melt tension is low,
During blow molding and extrusion molding, the drawdown is severe,
It is very difficult to obtain a molded article of a desired shape by a molding method other than injection molding, for example, uniform cells cannot be obtained during foam molding. Also in injection molding, there are problems such as generation of flow marks and reduction in weld strength due to poor compatibility between the thermoplastic polyester resin and the rubber-reinforced styrene resin.

JP-A-3-183524 discloses an attempt to improve processability by blending polytetrafluoroethylene with various thermoplastic resins. However, polytetrafluoroethylene has poor dispersibility with respect to a general thermoplastic resin containing no halogen atom, and this method requires a large amount of polytetrafluoroethylene to improve processability, There is a disadvantage that the surface properties of the molded article are impaired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition comprising a rubber-reinforced styrene resin and a polyester resin, which gives a molded article having excellent processability and good surface properties. It is in.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer has been used as a rubber. By adding to a thermoplastic resin composition consisting of a reinforced styrenic resin and a polyester resin, the melt tension is remarkably improved, the workability in blow molding, extrusion molding, foam molding, etc. is good, and the weld strength in injection molding is also high. The inventors have found that a molded article having excellent and excellent surface properties can be obtained, and have reached the present invention.

The gist of the present invention is that a particle diameter of 10 μm or less is based on 100 parts by weight of a total of 97 to 10 parts by weight of a thermoplastic polyester resin (A) and 3 to 90 parts by weight of a rubber-reinforced styrene resin (B). Thermoplastic resin in which a polytetrafluoroethylene-containing mixed powder (C) comprising polytetrafluoroethylene particles and an organic polymer is blended such that the polytetrafluoroethylene component becomes 0.0001 to 20 parts by weight. The composition and a master pellet comprising a polytetrafluoroethylene-containing mixed powder (C) comprising a polytetrafluoroethylene particle having a particle diameter of 10 μm or less and an organic polymer and a thermoplastic resin (D) are a thermoplastic polyester resin. (A) 97 to 10 parts by weight and rubber-reinforced styrene resin (B) 3 to 90 parts by weight in total amount 10
The thermoplastic resin composition is blended so that the polytetrafluoroethylene component is 0.0001 to 20 parts by weight with respect to 0 parts by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin (A) used in the present invention includes terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid,
one kind of dicarboxylic acids such as α, β-bis (4-carboxyphenoxy) ethane, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and ester-forming derivatives thereof or Two or more kinds, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4'-hydroxyethoxy Phenyl) propane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, aliphatic polyester oligomers having hydroxyl groups at both ends A polyester resin obtained by a polycondensation reaction with a selected glycol, and may be a homopolyester or a copolyester. Other than the above, as comonomer components for composing the copolyester, glycolic acid, hydroxy acid, hydroxybenzoic acid, hydroxyphenylacetic acid, hydroxycarboxylic acid such as naphthyl glycolic acid, propiolactone, butyrolactone, caprolactone, valerolactone Such a lactone compound can also be used, and a polyfunctional ester-forming component such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid as long as the thermoplasticity can be maintained. And a polyester having a branched or cross-linked structure. In addition, aromatic nuclei such as dibromoterephthalic acid, tetrabromoterephthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, and ethylene or propion oxide adducts of tetrabromobisphenol A have halogens. A polyester copolymer having a halogen using a compound having a compound as a substituent and having an ester-forming group is also included. Further, a polyester elastomer constituting a block copolymer of a high melting point hard segment and a low melting point soft segment can also be used. Examples of the polyester elastomer include a block copolymer of a hard segment mainly composed of an alkylene terephthalate unit and a soft segment composed of an aliphatic polyester or polyether. These thermoplastic polyester resins can be used alone or as a mixture of two or more as the component (A). Particularly preferred thermoplastic polyester resins are polybutylene terephthalate, polyethylene terephthalate and copolymers having these as main repeating units, and the comonomer components forming the copolymer are particularly preferably isophthalic acid, bisphenol A, 2 2,2-bis (β-hydroxyethoxyphenyl) propane, 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane and the like.

The rubber-reinforced styrene resin (B) used in the present invention is obtained by polymerizing an aromatic vinyl monomer and optionally another copolymerizable vinyl monomer in the presence of a rubbery polymer. A copolymer obtained by the method or the copolymer,
It is a mixture with an aromatic vinyl-based monomer and an aromatic vinyl-based polymer obtained by polymerizing another copolymerizable vinyl monomer as required.

[0010] The rubbery polymer mentioned here is a polymer which is rubbery at room temperature, and preferably has a glass transition temperature of -20 ° C or lower. Specifically, polybutadiene, polyisoprene, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, acrylonitrile-butadiene copolymer Polymers, diene-based copolymers such as isoprene-isobutylene copolymer, n-butyl acrylate and acrylate rubber which is a copolymer with an acrylate monomer copolymerizable therewith, and dimethylsiloxane units as main components Silicone rubber, a composite rubber of silicone and acrylate, and the like. Among them, polybutadiene (BR), styrene-butadiene copolymer (SBR), ethylene-propylene-5
-Ethylidene-2-norbornene copolymer (EPDM)
Preferred are diene rubbers such as acrylate rubbers such as poly-n-butyl acrylate, and composite rubbers of silicone and acrylate. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like. The particle size and gel content of the rubbery polymer in the case of production by emulsion polymerization are not particularly limited, but preferably have an average particle size of 0.1 to 1 μm and a gel content of 0 to 95% by weight. .

The aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene. Styrene, dichlorostyrene, bromostyrene, dibromostyrene and the like are exemplified, and one or more kinds can be used. Particularly, styrene and α-methylstyrene are preferred. Other vinyl monomers copolymerizable with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate,
Ethylhexyl acrylate, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, 2-
Examples include unsaturated carboxylic acid alkyl esters such as ethylhexyl methacrylate, and maleimide monomers such as maleimide, N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide.
More than one species can be used. Particularly, acrylonitrile, methyl methacrylate and N-phenylmaleimide are preferred.

As the polymerization method of the component (B), known emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization or a combination thereof can be used. The aromatic vinyl-based monomer and other copolymerizable vinyl-based monomer constituting the aromatic vinyl-based polymer used by mixing with the copolymer include those used for the graft copolymer, respectively. Any one or two or more selected from the same group can be used. In addition, as a polymerization method of the polymer, known emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, or a combination thereof is used.

The composition ratio of the rubbery polymer and the monomer in the rubber-reinforced styrene resin (B) is not limited, but is preferably 15 to 80% by weight of the rubbery polymer and 85% by weight of the monomer.
-20% by weight. If the rubbery polymer content is less than 15% by weight, the resulting resin composition has insufficient impact resistance,
If it exceeds 0% by weight, the affinity with the component (A) is not sufficient. The composition ratio of the aromatic vinyl monomer to the other vinyl monomer in such a monomer is not limited, but is 10 to 100% by weight, particularly 20 to 8% by weight of the aromatic vinyl monomer.
0% by weight, 90 to 0% by weight of other vinyl monomers, especially 8%
0-20% by weight is preferred. These rubber-reinforced styrene resins can be used alone or as a mixture of two or more as the component (B). Particularly preferred rubber-reinforced styrene resins include styrene-acrylonitrile-butadiene copolymer (ABS), styrene-acrylonitrile-ethylene-propylene-ethylidene norbornene copolymer (AES), and hydrogenated products thereof.

The mixing ratio of the thermoplastic polyester resin (A) and the rubber-reinforced styrenic resin (B) can be selected in a wide range, and for example, the thermoplastic polyester resin (A) 97-10
Component (B) is used in an amount of 3 to 90 parts by weight, preferably 95 to 20 parts by weight of component (A) and 5 to 5 parts by weight.
80 parts by weight.

The polytetrafluoroethylene-containing mixed powder (C) used in the present invention is composed of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer. It is necessary that these do not form aggregates. As such a polytetrafluoroethylene-containing mixed powder, an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles are mixed and coagulated or spray-dried. After polymerization of the monomers constituting the organic polymer in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm, or solidification or spray drying In a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles and an aqueous dispersion of organic polymer particles having a particle diameter of 0.05 to 1.0 μm, What is obtained by carrying out emulsion polymerization of the monomer which has a bond, and pulverizing by coagulation or spray drying is preferable. The aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm used for obtaining the polytetrafluoroethylene-containing mixed powder (C) used in the present invention is obtained by emulsion polymerization using a fluorinated surfactant. Obtained by polymerizing a tetrafluoroethylene monomer.

[0016] In the emulsion polymerization of polytetrafluoroethylene particles, a copolymer component such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, or perfluoroalkylvinyl ether is contained as long as the properties of polytetrafluoroethylene are not impaired. Fluorinated olefins and fluorinated alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less based on tetrafluoroethylene.

Commercially available raw materials for the polytetrafluoroethylene particle dispersion include Fluon AD-1 and AD-936 manufactured by Asahi Glass Fluoropolymer Co., Ltd., and Polyflon D-1 and D-2 manufactured by Daikin Industries, and DuPont Mitsui Fluorochemical Co., Ltd. Teflon 30J manufactured by the company can be cited as a representative example.

The organic polymer constituting the polytetrafluoroethylene-containing mixed powder used in the present invention is not particularly limited, but it has a high affinity for a thermoplastic polyester resin from the viewpoint of dispersibility. Preferably, there is.

Specific examples of the monomer for forming the organic polymer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, and p-methylstyrene. Aromatic vinyl monomers such as chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, acrylic Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,
2-ethylhexyl acrylate, methacrylic acid-2-
(Meth) acrylic ester monomers such as ethylhexyl, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate; acrylonitrile, methacrylonitrile Vinyl cyanide monomers such as maleic anhydride; α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide; glycidyl methacrylate Epoxy group-containing monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl ether monomers such as vinyl acetate and vinyl butyrate; ethylene and propylene;
Olefin monomers such as isobutylene; diene monomers such as butadiene, isoprene, and dimethylbutadiene; These monomers can be used alone or in combination of two or more.

Among these monomers, from the viewpoint of affinity with the thermoplastic polyester resin, preferred are aromatic vinyl monomers, (meth) acrylate monomers, and vinyl cyanide monomers. 1 selected from the group consisting of multimers
Monomers containing at least 30% by weight of at least one kind of monomer can be mentioned. Particularly preferred are styrene,
Examples include a monomer containing 30% by weight or more of one or more monomers selected from the group consisting of methyl methacrylate and acrylonitrile.

The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder used in the present invention is preferably 0.1 to 90% by weight.

The polytetrafluoroethylene-containing mixed powder used in the present invention is poured into a hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salted out, solidified, and dried. Alternatively, it can be powderized by spray drying.

Normal polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the step of recovering as a powder from the state of a particle dispersion, and thus it is difficult to uniformly disperse it in a thermoplastic resin. On the other hand, the polytetrafluoroethylene-containing mixed powder used in the present invention is extremely excellent in dispersibility in a thermoplastic resin because polytetrafluoroethylene alone does not form a domain having a particle diameter of more than 10 μm. . As a result, in the thermoplastic resin composition of the present invention, polytetrafluoroethylene is efficiently made into fine fibers in the thermoplastic resin, and various moldability is excellent, and surface property is also excellent.

The thermoplastic resin composition of the present invention is obtained by adding 100 to 100 parts by weight of a total of 97 to 10 parts by weight of the thermoplastic polyester resin (A) and 3 to 90 parts by weight of the rubber-reinforced styrene resin (B). The tetrafluoroethylene-containing mixed powder (C) has a polytetrafluoroethylene component of 0.000.
It is blended so as to be 1 to 20 parts by weight.
If it is less than 0.0001 part, the effect of improving workability is poor, and if it exceeds 20 parts by weight, the fluidity at the time of melting may be too low.

The thermoplastic resin composition of the present invention contains a reinforcing agent or a filler such as pigments and dyes, glass fibers, metal fibers, metal flakes, carbon fibers and the like, as long as the original purpose is not impaired. Di-butyl-4-methylphenol, 4,
Phenolic antioxidants such as 4'-butylidene-bis (3-methyl-6-t-butylphenol), and phosphite antioxidants such as tris (mixed, mono and dinylphenyl) phosphites and diphenyl isodecyl phosphite Agents, sulfur-based antioxidants such as dilaurylthiodipropionate, dimyristylthiodipropionate diasterial thiodipropionate, 2-hydroxy-4-octoxybenzophenone, 2- (2-
Benzotriazole-based ultraviolet absorbers such as hydroxy-5-methylphenyl) benzotriazole;
Light stabilizers such as 2,6,6) -tetramethyl-4-piperidinyl), antistatic agents such as hydroxylalkylamine and sulfonate, ethylenebisstearylamide,
By blending various additives such as a lubricant such as a metal soap and a flame retardant such as tetrabromophenol A, decabromophenol oxide, a TBA epoxy oligomer, a TBA polycarbonate oligomer and antimony trioxide, more desirable physical properties and characteristics can be obtained. Can be adjusted.

Further, the thermoplastic resin composition of the present invention comprises:
If necessary, polyphenylene ether resin, polyamide resin, vinyl polymer such as polymethyl methacrylate (PMMA), polycarbonate resin, vinyl chloride resin, polyolefin resin such as polyethylene and polypropylene, and ethylene / propylene copolymer, ethylene / Butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-
By appropriately blending an olefin rubber such as an ethylidene-2-rubbornene copolymer, an ethylene / propylene / 1,4-hexadiene copolymer, an ethylene / vinyl acetate copolymer, and an ethylene / butyl acrylate copolymer, Desired physical properties and properties Can be adjusted.

A predetermined amount of each of the above essential components and, if desired, optional components is blended and kneaded with a usual kneader such as a roll, a Banbury mixer, a single screw extruder, or a twin screw extruder to prepare a composition. However, usually, it is preferable to form a pellet. Alternatively, the composition of the present invention may be prepared by diluting a master batch containing the polytetrafluoroethylene-containing mixed powder (C) at a high concentration with a thermoplastic resin. The thermoplastic resin (D) used for the master pellet is not particularly limited, and any thermoplastic resin such as a polyolefin resin, a polystyrene resin, a polyester resin, a polyamide resin, a polycarbonate resin, and an ABS resin can be used.

The thermoplastic resin composition of the present invention thus obtained has a high melt tension.
The draw-down resistance in extrusion molding and thermoforming, the uniformity of cells during foam molding, the calender moldability, etc. are improved and the moldability is excellent. In injection molding, there are no problems such as generation of flow marks and reduction in weld strength. In addition, there is no macro-aggregate of polytetrafluoroethylene, and the molded product has excellent surface properties.

The method for processing the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include blow molding, extrusion molding, thermoforming, foam molding, calender molding, injection molding, and melt spinning.

Useful molded articles obtained by using the thermoplastic resin composition of the present invention are not particularly limited, but hollow molded articles, sheets, thermoformed articles, pipes, square bars, irregularly shaped articles, foams, films , Injection molded articles, fibers and the like.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these.

[0032]

EXAMPLES In each description, "parts" indicate parts by weight, and "%" indicates% by weight.
And physical properties are measured by the following methods.

(1) Solid content concentration: 170 ° C. of the particle dispersion
And dried for 30 minutes.

(2) Particle size distribution, weight average particle size: A solution obtained by diluting a particle dispersion with water was used as a sample solution, and a dynamic light scattering method (ELS800 manufactured by Otsuka Electronics Co., Ltd., temperature: 25 ° C., scattering angle: 90) Degree).

(3) Zeta potential: 0.0
An electrophoresis method (ELS800, manufactured by Otsuka Electronics Co., Ltd.)
At a temperature of 25 ° C. and a scattering angle of 10 °).

(4) Melt tension: Examples and comparative examples using a capillary rheometer (Toyo Seiki Capillograph) at a resin temperature of 250 ° C., an orifice L / D = 8 mm / 2 mm, and a piston descending speed of 10 mm / min. Was discharged and the load when the resin composition was taken out at a speed of 4 m / min was measured with a load cell.

(5) Tensile strength and weld tensile strength: Measured according to ASTM D638 using test pieces obtained by injection molding.

(6) Izod impact strength: A test piece obtained by injection molding was measured at 23 ° C. with a notch at 6.4 mm according to ASTM D256.

(7) Flow mark: The gate portion of the injection-molded test piece was visually observed, and judged based on the following criteria.

：: No flow mark ×: With flow mark (6) Appearance: The surface appearance of the injection-molded test piece was visually observed and judged according to the following criteria.

○: No bumps on the surface ×: bumps on the surface Commercially available products were used for the thermoplastic polyester resin, the rubber-reinforced styrene-based resin, and the substances shown in Reference Examples.

Thermoplastic polyester resin (A-1): polybutylene terephthalate resin (Tuffpet PBT, N1000 manufactured by Mitsubishi Rayon) Rubber-reinforced styrene resin (B-1): ABS resin (diapet ABS 1001 manufactured by Mitsubishi Rayon) Example 1 <Polytetrafluoroethylene-containing powder (C-
Production of 1)> In a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, 190 parts of distilled water, 1.5 parts of sodium dodecylbenzenesulfonate, 100 parts of styrene, and 0.5 part of cumene hydroperoxide. And heated to 40 ° C. under a nitrogen stream. Then, iron (II) sulfate 0.001
Parts, disodium ethylenediaminetetraacetate 0.003
, A mixed solution of 0.24 parts of Rongalite salt and 10 parts of distilled water was added to initiate radical polymerization. After the fever ends,
The temperature in the system was maintained at 40 ° C. for 1 hour to complete the polymerization,
A styrene polymer particle dispersion (hereinafter referred to as P-1) was obtained.

The solid concentration of P-1 was 33.3%, the particle size distribution showed a single peak, and the weight average particle size was 96 n.
m, and the surface potential was -32 mV.

On the other hand, as a polytetrafluoroethylene-based particle dispersion, Fluon AD manufactured by Asahi Glass Fluoropolymers Co., Ltd.
936 was used. AD936 has a solid content of 63.0%
And containing 5 parts of polyoxyethylene alkylphenyl ether per 100 parts of polytetrafluoroethylene. The particle size distribution of AD936 shows a single peak, the weight average particle size is 290 nm, and the surface potential is −
20 mV.

To 833 parts of AD936, 1167 parts of distilled water was added to obtain a polytetrafluoroethylene particle dispersion F-1 having a solid content of 26.2%. F-1 contains 25% of polytetrafluoroethylene particles and 1.2% of polyoxyethylene nonylphenyl ether.

Separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet was prepared by mixing 160 parts of F-1 (40 parts of polytetrafluoroethylene) and 181.8 parts of P-1 (60 parts of polystyrene). And stirred at room temperature for 1 hour under a nitrogen stream. Then the temperature inside the system was raised to 80 ° C,
Hold for 1 hour. No solid matter was separated through a series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion was 29.3%, the particle size distribution was relatively broad, and the weight average particle size was 168 nm.

341.8 parts of this particle dispersion was poured into 700 parts of 85 ° C. hot water containing 5 parts of calcium chloride to separate a solid, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene (C). -1) 98 parts were obtained.

After C-1 was shaped into a strip shape at 250 ° C. by a press molding machine, ultrathin sections were observed with a microtome and observed under a transmission electron microscope without staining. Although polytetrafluoroethylene is observed as a dark area, 10 μm
No aggregates larger than m were observed.

Reference Example 2 <Production of mixed powder (C-2) containing polytetrafluoroethylene> A separable flask equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel was used in Reference Example 1. F
-1 to 160 parts (polytetrafluoroethylene 40
Parts), 1.0 part of dodecylbenzenesulfonic acid, 7 parts of distilled water
0 parts were charged, and the temperature was raised to 80 ° C. under a nitrogen stream. Next, 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 of Rongalit salt
, A mixture of 18 parts of acrylonitrile, 42 parts of styrene, and 0.3 part of tertiary butyl peroxide was added dropwise from a dropping funnel for 90 minutes to allow radical polymerization to proceed. After dropping, the internal temperature is set to 8
It was kept at 0 ° C. for 1 hour. No solid matter was separated through a series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion was 33.2%, the particle size distribution was relatively broad, and the weight average particle size was 249 nm.

301.5 parts of this particle dispersion is poured into 700 parts by weight of 85 ° C. hot water containing 5 parts of calcium chloride, and the solid is separated, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene ( C-2) 97 parts were obtained.

After C-2 was shaped into a strip at 250 ° C. by a press molding machine, ultrathin sections were observed with a microtome without staining using a transmission electron microscope. Although polytetrafluoroethylene is observed as a dark area, 10 μm
No aggregates larger than m were observed.

Reference Example 3 <Production of mixed powder containing polytetrafluoroethylene (C-3)> A mixture of 70 parts of dodecyl methacrylate and 30 parts of methyl methacrylate was added to 2,2'-azobis (2,4-dimethylvaleronitrile). ) 0.1 parts were dissolved. 2.0 parts of sodium dodecylbenzenesulfonate and 3 parts of distilled water
Add 00 parts of the mixed solution, and mix
After stirring for 4 minutes at rpm, 30MP was added to the homogenizer.
2 times at the pressure of a, stable dodecyl methacrylate /
A methyl methacrylate preliminary dispersion was obtained. This was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, the internal temperature was raised to 80 ° C. under a nitrogen stream, and the mixture was stirred for 3 hours to undergo radical polymerization, and dodecyl methacrylate / methyl A methacrylate copolymer particle dispersion (hereinafter referred to as P-2) was obtained.

The solid content concentration of P-2 was 25.1%, the particle size distribution showed a single peak, and the weight average particle size was 190.
nm, and the surface potential was -39 mV.

80 parts (20 parts of polytetrafluoroethylene) of F-1 used in Reference Example 1 and 239.0 parts of P-2
(60 parts of dodecyl methacrylate / methyl methacrylate copolymer) was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel, and stirred at room temperature for 1 hour under a nitrogen stream. Then 8 in the system
The temperature was raised to 0 ° C., and a mixed solution of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt and 10 parts of distilled water was added, and 20 parts of methyl methacrylate was added. Then, a mixture of 0.1 part of tertiary butyl peroxide was added dropwise over 30 minutes, and after completion of the addition, the internal temperature was maintained at 80 ° C. for 1 hour to complete the radical polymerization. No solid matter was separated through a series of operations, and a uniform particle dispersion was obtained. The solids concentration of the particle dispersion is 2
At 8.6%, the particle size distribution was relatively broad and the weight average particle size was 220 nm.

349.7 parts of this particle dispersion was poured into 600 parts of 75 ° C. hot water containing 5 parts of calcium chloride to separate a solid, which was filtered and dried to obtain a mixed powder containing polytetrafluoroethylene (C). -3) 98 parts were obtained.

The dried C-3 was shaped into strips at 220 ° C. by a press molding machine, and ultrathin sections were observed with a microtome without staining using a transmission electron microscope.
Polytetrafluoroethylene was observed as a dark part, but no aggregate larger than 10 μm was observed.

Reference Example 4 <Production of Master Pellets (M-1) of Polytetrafluoroethylene-containing Mixed Powder> Tetrafluoroethylene-containing mixed powder obtained in Reference Example 1 for 80 parts of polystyrene [G340 manufactured by Nippon Polystyrene] After blending 20 parts of body B-1 and hand blending, a twin screw extruder (ZW manufactured by WERNER & PFLEIDERER)
Using SK30), the mixture was melt-kneaded at a barrel temperature of 240 ° C. and a screw rotation speed of 200 rpm and shaped into pellets to obtain master pellets of a mixed powder containing polytetrafluoroethylene (hereinafter referred to as M-1).

Examples 1 to 6, Comparative Examples 1 to 3 The thermoplastic polyester resin (A-1), the rubber-reinforced styrene resin (B-1), and the tetrafluoroethylene-containing mixed powder obtained in each of the reference examples ( C-1 to 3) or master pellets (M-1) were blended at the ratios shown in Table 1 and a twin screw extruder (ZS manufactured by WERNER & PFLEIDERER) was added.
The pellets were extruded by K30) at a barrel temperature of 250 ° C. and a screw rotation speed of 200 rpm to prepare pellets. Next, cylinder temperature 250 ° C, mold temperature 60 with an injection molding machine
Test pieces for measuring various physical properties were prepared at ℃. Table 1 shows the evaluation results of the melt tension, tensile strength, weld tensile strength, impact strength, flow mark, and appearance. For comparison, polytetrafluoroethylene-containing mixed powder was extruded without addition (Comparative Example 1), and polytetrafluoroethylene fine powder (Asahi ICI CD123) was added (Comparative Examples 2, 3). Was similarly evaluated. Table 1 shows the results.

[0059]

[Table 1]

[0060]

The thermoplastic resin composition of the present invention has a high melt tension and thus is excellent in various processability, and the obtained molded product has an excellent surface property and can be used for applications such as automobiles, electric appliances and sundries. .

Claims (2)

[Claims] Claims: 1. Thermoplastic polyester resin (A) 97-
10 parts by weight and a total amount of 3 to 90 parts by weight of the rubber-reinforced styrene resin (B) are 100 parts by weight, and
A polytetrafluoroethylene-containing mixed powder (C) comprising the following polytetrafluoroethylene particles and an organic polymer has a polytetrafluoroethylene component of 0.00
A thermoplastic resin composition blended in an amount of from 0.01 to 20 parts by weight. 2. A master pellet made of a thermoplastic resin (D) and a polytetrafluoroethylene-containing mixed powder (C) made of polytetrafluoroethylene particles having an average particle size of 10 μm or less and an organic polymer is a thermoplastic polyester. The polytetrafluoroethylene component is contained in an amount of 0.0001 with respect to 100 parts by weight of the total of 97 to 10 parts by weight of the resin (A) and 3 to 90 parts by weight of the rubber-reinforced styrene resin (B).
A thermoplastic resin composition blended to be 20 parts by weight.