JPH06107894A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having permanent antistatic properties and, in particular, improved resistance to dynamic fatigue by incorporating an alkali metal salt into a composition comprising a specific alkylene oxide polymer, a specific graft polymer, a specific vinyl polymer, and a specific modified vinyl polymer. CONSTITUTION:The composition comprises 100wt.% polymer blend and incorporated therein 0.2-5wt.% organic alkali metal salt, the blend comprising 3-30wt.% alkylene oxide polymer containing ethylene oxide units and having a reduced viscosity etasp/c of 1.0-3.0, 5-95wt.% graft copolymer obtained by polymerizing a monomer, e.g. an aromatic vinyl monomer, in the presence of 5-80wt.% rubbery polymer, 0-80wt.% vinyl polymer obtained by polymerizing a monomer mixture including an aromatic vinyl and having a reduced viscosity etasp/c of 0.6-1.5, and 2-50wt.% modified vinyl polymer containing units derived from a carbonylated vinyl monomer and having a reduced viscosity etasp/C of 0.4-1.0.

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 a permanent antistatic property, in particular, a resin having improved dynamic fatigue resistance.

[0002]

2. Description of the Related Art ABS resin, high impact polystyrene (HIP) is currently used as a thermoplastic resin having excellent impact resistance.
The rubber-modified thermoplastic resin represented by S) is widely used in electric devices, automobiles and the like. These resins have a wide range of advantages such as good workability in molding, excellent impact resistance, good molding appearance, good molding stability, excellent plating properties, and low cost as a product. Has been used throughout. However, because these resins are electrical insulators, they generate static electricity, which not only adheres to the dust and impairs the appearance, but also causes malfunctions of the equipment when used in cases or parts of electrical and electronic equipment due to static electricity failure. It has drawbacks such as

Conventionally, as a means for solving the above-mentioned drawbacks of thermoplastic resins, a method of kneading an antistatic agent into these resins has been widely used. Anionic, cationic, and nonionic surfactants are mainly used as conventional antistatic agents, and thermoplastic resins containing these surfactants have mechanical strength such as impact resistance and molding appearance,
Although it has good thermal stability, there is a problem that the surfactant kneaded by external stimuli such as friction and cleaning of the surface of the molding resin is lost from the resin surface, and the antistatic property is significantly lost. is there.

As a method of exhibiting a permanent antistatic property which is not changed by an external stimulus, a resin is prepared by blending an alkylene oxide polymer which is a water-soluble polymer as an antistatic agent in JP-A No. 64-26674. It is proposed to prevent the generation of static electricity on the surface. However, although it is possible to improve the antistatic property by blending this alkylene oxide polymer with a rubber-modified thermoplastic resin as described above, polyalkylene oxide is The compatibility was poor, and the resin after molding caused delamination, which was not sufficient for practical use.

Further, Japanese Unexamined Patent Publication (Kokai) No. 60-137955 discloses a method of copolymerizing polyalkylene glycol methacrylate in a resin, but this method is disadvantageous in terms of manufacturing cost because the method of manufacturing the resin is complicated. there were. A thermoplastic resin composition having a permanent antistatic property is obtained by blending a soft polymer such as a highly conductive elastomer or polyethylene glycol in the resin, and completely adding the polymer to the matrix resin. However, the dynamic fatigue resistance of the resin was significantly inferior to that of the matrix resin, because some degree of compatibilization was required.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have found that the antistatic thermoplastic resin composition has little delamination, good mechanical properties such as impact resistance and good molding appearance, and excellent dynamic fatigue resistance. As a result of extensive studies aimed at providing a specific alkylene oxide polymer and a specific vinyl-based polymer, a specific modified vinyl-based polymer, the above problems can be solved by blending an organic alkali metal salt. And has reached the present invention.

[0007]

The present invention has a reduced viscosity ηsp / c (containing 0.2 g of a polymer in 100 ml of dimethylformamide, 25 ° C.) of 1.0 to 10 with ethylene oxide as an essential component. Alkylene oxide polymer (A) of 3 to 30% by weight, rubbery polymer 5 to
In the presence of 80% by weight, at least one monomer selected from the group of aromatic vinyl-based monomers, (meth) acrylic acid ester-based monomers and vinyl cyanide-based monomers or a monomer or monomer. Graft polymer (B) 5 obtained by polymerizing a mixture of monomers
~ 95% by weight, a monomer mixture selected from aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl cyanide monomers and maleimide monomers is polymerized. Reduced viscosity ηsp / c (Dimethylformamide 100m
0.2 g of polymer in 1 l, 25 ° C) is 0.6-
0 to 80% by weight of a vinyl polymer (C) having a ratio of 1.5, and a reduced viscosity ηsp / c containing vinyl monomer having a carbonyl group as an essential component (0.2 g of the polymer in 100 ml of dimethylformamide). Including, 25 ° C.) is 0.4-1.
The modified vinyl polymer (D) of 0 to (A) to (D) of 2 to 50% by weight is blended so as to be 100% by weight,
The present invention relates to a thermoplastic resin composition containing 0.2 to 5 parts by weight of an organic alkali metal salt (E).

The present invention will be specifically described below. The thermoplastic resin composition of the present invention comprises an alkylene oxide polymer (A), a rubber graft polymer (B), a vinyl polymer (C), a modified vinyl polymer (D), and an organic alkali metal salt ( E).

The alkylene oxide polymer (A) used in the present invention preferably contains ethylene oxide units as an essential component and contains 50% by weight or more of ethylene oxide units in the polymer (A), and more preferably. It is 70% by weight or more. When the ethylene oxide unit content in the polymer (A) is less than 50% by weight, the antistatic property of the resin is insufficient, which is not preferable. As the component other than the ethylene oxide unit in the polymer (A), for example, propylene oxide, butylene oxide, epichlorohydrin, tetrahydrofuran or the like can be used. In particular, a homopolymer of ethylene oxide or a copolymer of ethylene oxide and propylene oxide is preferable, and a copolymer of ethylene oxide and propylene oxide is more preferably used. The degree of polymerization of the polymer (A) is the reduced viscosity ηsp at 25 ° C. of a solution prepared by dissolving 0.2 g of the polymer in 100 ml of dimethylformamide.
/ C is preferably 1.0 to 3.0, and more preferably 1.2 to 2.8. If the one having a reduced viscosity of less than 1.0 is used, the dynamic fatigue resistance of the resin is inferior, and if it exceeds 3.0, the dependency of the antistatic property of the resin on the molding conditions, particularly on the molding temperature, becomes high. It is not preferable because it causes poor appearance such as deterioration of gloss. The method for polymerizing the polymer (A) is not particularly limited, but solution polymerization using an alkali catalyst or the like is preferably used.

The rubbery polymer used in the graft polymer (B) is a diene rubber or an acrylic rubber,
Elastomers such as EPDM rubber, chlorinated polyethylene rubber and silicone rubber can be used, preferably polybutadiene rubber and acrylic rubber, for example 50% by weight.
It is a polymer containing the following monomers such as acrylonitrile, (meth) acrylic acid ester and styrene. A monomer or monomer mixture selected from aromatic vinyl-based monomers, vinyl cyanide-based monomers, and (meth) acrylic acid ester-based monomers is graft-polymerized to the rubber-like polymer, A graft polymer (B) is obtained.

Aromatic vinyl monomers used in the present invention include styrene, α-methylstyrene, halogenated styrene such as chlorostyrene and bromostyrene, alkylstyrene such as vinyltoluene, etc., alone or in combination. It is a polymerizable vinyl aromatic compound using at least one species. Preferably styrene or α-methylstyrene can be used alone or as a mixture of two kinds.

The vinyl cyanide-based monomer used in the present invention is acrylonitrile, halogenated acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof. These may be used alone or in combination of two or more. It can be used and preferably acrylonitrile is used.

Examples of the (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate. And their derivatives are used. Preferably, methyl methacrylate, methyl acrylate and ethyl acrylate are used. If necessary, other vinyl monomers such as maleic anhydride, maleimide, N-methylmaleimide, N
Maleimide monomers such as phenylmaleimide and derivatives thereof, acrylamide and derivatives thereof and the like can be used.

The composition of the rubber-like polymer and the monomer or the monomer mixture in the graft polymer (B) is such that the rubber-like polymer is 5 to 80 at 100% by weight of the graft polymer (B).
%, Preferably 10 to 60% by weight. When the content of the rubbery polymer in the graft polymer (B) is less than 5% by weight, the impact resistance is insufficient, and when it exceeds 80% by weight, the hardness and flexural modulus of the resin are insufficient, which is preferable. Absent. The proportion of the rubbery polymer in the graft polymer (B) is
It can be selected in consideration of the rubbery polymer contained in the resin. Specifically, the composition is selected such that the rubber polymer is contained in the resin in an amount of 3 to 20% by weight. If the rubbery polymer is less than 3% by weight in the resin, the impact resistance of the resin is insufficient,
If it exceeds 5% by weight, the flexural modulus of the resin becomes insufficient and the dynamic fatigue resistance becomes poor, which is not preferable.

There is no particular limitation on the composition ratio of each of the aromatic vinyl type monomer, the vinyl cyanide type monomer and the (meth) acrylic acid ester type monomer used in the graft polymer (B). , The impact resistance and chemical resistance of the resin can be selected as required. In particular, any composition does not prevent the effects of the present invention. There is no particular limitation on the polymerization method of the graft polymer (B),
Usual methods such as emulsion polymerization and bulk polymerization can be used.

The vinyl polymer (C) used in the present invention
Is a polymer obtained by polymerizing a monomer mixture selected from aromatic vinyl-based monomers, (meth) acrylic acid ester-based monomers, vinyl cyanide-based monomers, and maleimide-based monomers. . As the aromatic vinyl-based monomer, (meth) acrylic acid ester-based monomer, and vinyl cyanide-based monomer that can be used here, the same as those described above can be used, and if necessary, other Vinyl monomers such as maleimide,
Maleimide-based monomers such as N-methylmaleimide and N-phenylmaleimide and derivatives thereof, acrylamide and derivatives thereof, and the like can be used. Examples of vinyl monomers include methyl methacrylate polymer, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, styrene-maleimide copolymer,
Examples include acrylonitrile-styrene-maleimide terpolymer.

The composition ratio of each of the monomers used in the vinyl polymer (C) is 20 to 8 aromatic vinyl monomers.
5% by weight, preferably 30-80% by weight, (meth) acrylic acid ester-based monomer 0-60% by weight, vinyl cyanide-based monomer 15-40% by weight, preferably 20-35% by weight, maleimide The amount of the system monomer is 0 to 40% by weight. If the amount of aromatic vinyl monomer is less than 20% by weight, the moldability and dimensional stability of the resin are poor, and if the amount of vinyl cyanide monomer is less than 15% by weight, the chemical resistance of the resin is poor. Not preferable.

The degree of polymerization of the vinyl polymer (C) is limited, and the reduced viscosity ηsp / c at 25 ° C. of a solution containing 0.2 g of the polymer in 100 ml of dimethylformamide.
Is selected to be 0.6 to 1.5. It is preferably 0.9 to 1.3. When ηsp / c is less than 0.6, the dynamic fatigue resistance of the resin is insufficient, and when it exceeds 1.5, the fluidity of the resin deteriorates, which is not preferable.

The modified vinyl polymer (D) used in the present invention is a polymer containing a vinyl monomer having a carbonyl group as an essential component. In this case, it may be a homopolymer of a vinyl monomer having a carbonyl group or a copolymer with another vinyl monomer. Specific examples of the vinyl monomer having a carbonyl group include acrylic acid ester, methacrylic acid ester, maleic acid ester, maleic anhydride, maleimide, and the like, and more specifically, methyl acrylate and acrylic acid. Ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-
Propyl, isopropyl methacrylate, methacrylic acid-
n-butyl, isobutyl methacrylate, methacrylic acid-
tert-butyl, phenyl methacrylate, dimethyl maleate, diethyl maleate, N-methyl maleimide,
Examples thereof include N-ethylmaleimide and N-phenylmaleimide. Preferably methyl methacrylate, maleic anhydride,
N-phenylmaleimide is used. As other vinyl-based monomers copolymerizable with these vinyl-based monomers, aromatic vinyl-based monomers, vinyl cyanide-based monomers, and vinyl-based monomers having the above carbonyl group can be used. Specifically, styrene and α-methylstyrene, acrylonitrile, methacrylonitrile, the above acrylic acid ester,
Methacrylic acid ester, maleic anhydride, N-phenylmaleimide, and derivatives thereof. Preference is given to using styrene, α-methylstyrene, acrylonitrile.

Specific ratios of these monomers in the modified vinyl polymer (D) include the alkylene oxide polymer (A), the graft polymer (B) and the vinyl polymer (C). For the purpose of improving compatibility, compositions having compatibility with each other are selected. Specifically, a modified vinyl polymer (D) containing 30 to 100% by weight of a vinyl monomer having a carbonyl group is used.
When the vinyl monomer having a carbonyl group is less than 30% by weight, delamination of the resin is not improved, which is not preferable. The polymer composed of the vinyl monomer having a carbonyl group is almost compatible with the graft polymer (B), and the monomer is also compatible with the alkylene oxide polymer (A). Therefore, it may be a homopolymer of a vinyl monomer having a carbonyl group, or a copolymer of two or more of these. Of course, it may be a copolymer with other vinyl monomers.

Regarding the degree of polymerization of the modified vinyl polymer (D), the compatibility of the alkylene oxide polymer (A) with the graft polymer (B) and the vinyl polymer (C) is improved, and the resin The range is selected so as to improve the dynamic fatigue resistance of Specifically, dimethylformamide 100
A solution containing 0.2 g of the polymer in ml and having a reduced viscosity ηsp / c at 25 ° C. of 0.4 to 1.0 is used. It is preferably 0.5 to 0.9. Reduced viscosity is 0.
If it is less than 4, the dynamic fatigue resistance of the resin is inferior, which is not preferable. The method for producing the modified vinyl polymer (D) is not particularly limited, but usual suspension polymerization, bulk polymerization, solution polymerization and the like can be used.

As the organic alkali metal salt (E), those generally widely used as surfactants can be used. For example, fatty acid salts and alkyl sulfonates,
A sulfonate represented by alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl ether sulfonate, etc. can be used. Preferred is a sulfonate. Specifically, sodium octyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium cetyl sulfonate, sodium stearyl sulfonate, sodium octyl benzene sulfonate, sodium decyl benzene sulfonate, sodium dodecyl benzene sulfonate, stearyl benzene sulfonate. Sodium acid salt, sodium dodecylnaphthalene sulfonate and the like, and lithium salt or potassium salt thereof are used.

When the organic alkali metal salt (E) is added in the absence of the alkylene oxide polymer (A), the antistatic property is good, but this is not permanent so as not to be lost by washing with water or the like. . In the presence of the alkylene oxide polymer (A), its mechanism is not clear, but better permanent antistatic property than the case where the alkylene oxide polymer (A) and the organic alkali metal salt (E) are used alone. Develop sex.

The thermoplastic resin composition thus obtained contains 3 to 30% by weight of the alkylene oxide polymer (A), 5 to 95% by weight of the graft polymer (B), and 0 to 50% of the vinyl polymer (C). ~ 80% by weight, modified vinyl polymer (D)
It is composed of 100% by weight of the composition of 2 to 50% by weight and 0.2 to 5 parts by weight of the organic alkali metal salt (E).

If the alkylene oxide polymer (A) is less than 3% by weight, good permanent antistatic property is not exhibited, and if it exceeds 30% by weight, the mechanical strength of the resin such as flexural modulus is deteriorated, which is not preferable. . If the graft polymer (B) is less than 5% by weight, the impact resistance of the resin will be insufficient, and if it exceeds 95% by weight, the antistatic property will be insufficient. Vinyl polymer (C)
Is more than 80% by weight, the impact resistance of the resin is insufficient, which is not preferable. When the modified vinyl polymer (D) is less than 2% by weight, the compatibility with the alkylene oxide polymer (A) is poor and the resin is delaminated, and when it exceeds 50% by weight, the compatibilization proceeds and the resin layered. Although peeling disappears, it is not preferable because the antistatic property deteriorates. Organic alkali metal salt (E)
Is less than 0.2 parts by weight, the antistatic property is poor and 5
If it exceeds the weight part, the organic alkali metal salt (E) bleeds out from the resin surface, which is not preferable.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include alkylene oxide polymer (A), graft polymer (B), vinyl polymer (C) and modified vinyl polymer. A method is used in which the coalescence (D) and the organic alkali metal salt (E) are mixed with a mixer, kneaded with a Banbury mixer or a vent type extruder, and kneaded with a roll to form pellets or sheets, and then a molded product is obtained with an injection molding machine. To be done. At this time, in order to further improve the performance as a molding material, an antioxidant or a heat stabilizer for further improving the thermal stability, and if necessary, a lubricant or a plasticizer,
Dyes and pigments, further compatibilizers, flame retardants can also be added.

[0027]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. In addition, "%" in Examples and Comparative Examples,
"Part" means "% by weight" and "part by weight", respectively.

The thermoplastic resin composition of the present invention comprises an alkylene oxide polymer (A), a graft polymer (B), a vinyl polymer (C), a modified vinyl polymer (D) and an alkali metal salt (E). ) And were mixed and pelletized by a vented extruder. A resin test piece was prepared from this using an injection molding machine, and various physical properties were measured by the following test methods. (1) Izod impact strength: Measured according to ASTM D-256. (2) Flexural modulus: Measured according to ASTM D-790. (3) Heat resistance (Vicat softening point temperature): ISO R-3
It measured according to 06. (4) Surface resistivity: A resin was molded on a flat plate having a size of 40 mm × 50 mm × 4 mm and prepared for 24 hours under the conditions of room temperature of 23 ° C. and relative humidity of 50% and measured. Toa Denpa Industry for measurement
A SM-10E resistance measuring instrument manufactured by Co., Ltd. was used.

(5) Charge voltage and its half-life: For the same sample as for measuring the surface resistivity, a voltage of 10 kV was applied to the resin for 30 seconds using a static Honest meter manufactured by Shishido Trading Company, and the resin at that time was charged. The measured voltage and the time until the voltage decreased to half were measured. (6) Appearance of resin molding: Appearance (gloss,
The color) was visually determined. As for the judgment result, the good appearance of the test piece was ◯, and the bad appearance was x. (7) Layered releasability: The molded test piece was bent at the center and then cut to determine whether or not there was peeling. The judgment results were evaluated as ◯ when the layered releasability was good, and as x when the layered release was performed. (8) Dynamic fatigue resistance: Izod impact test (ASTM D
-256; with 1/4 "notch), by fixing one of the test pieces to the other and dropping a weight of 300 g from a height of 10 cm at a cycle of 30 times / minute,
The number of breaks of the test piece was measured.

Examples 1 to 10 and Comparative Examples 1 to 13 1) Preparation of alkylene oxide polymer (A) 1-1) Preparation of alkylene oxide polymer (A-1) Polyethylene oxide (molecular weight 500,000; Meisei Kasei Co., Ltd.) (Manufactured by Co., Ltd.) was prepared. 0.2 g of the polyethylene oxide was dissolved in 100 ml of dimethylformamide,
The measured reduced viscosity ηsp / c was 1.8. 1-2) Preparation of alkylene oxide polymer (A-2) Ethylene oxide 85 parts Propylene oxide 15 parts Normal hexane (anhydrous) 40 parts Toluene (anhydrous) 60 parts Potassium hydroxide 0.2 parts Charged into an autoclave, 50 60 ° C for 3 hours
Polymerization was performed at ℃ for 3 hours. After cooling, the solvent was removed under reduced pressure to give a white lump of alkylene oxide polymer (A-2).
Got The yield was 95%, 0.2 g of the polymer was dissolved in 100 ml of dimethylformamide, and the reduced viscosity ηsp / c at 25 ° C. was measured. As a result, it was 2.4.

1-3) Alkylene oxide polymer (A
Preparation of -3) All were polymerized in the same manner as in (A-2) except that 40 parts of ethylene oxide and 60 parts of butylene oxide were used to prepare an alkylene oxide polymer (A-3). Yield 88
% And ηsp / c were 2.0. 1-4) Preparation of alkylene oxide polymer (A-4) All except that the solvent was changed from a mixture of 60 parts of toluene and 40 parts of hexane to 100 parts of normal hexane (A-
Polymerized in the same manner as in 2) to give an alkylene oxide polymer (A
-4) was prepared. The yield was 93% and ηsp / c was 0.7.

2) Preparation of graft copolymer (B) 2-1) Preparation of graft polymer (B-1) Polybutadiene latex (solid content 50%, average particle diameter 0.28 μm) 100 parts Distilled water 140 parts Acrylonitrile 15 parts Styrene 35 parts Potassium rosinate 0.9 parts Tertiarydodecyl mercaptan 0.5 parts Dextrin 0.35 parts Ferrous sulfate 0.01 parts Sodium pyrophosphate 0.2 parts Sodium hydroxide 0.05 parts Polymerization tank Was heated to 60 ° C. with stirring. To this, 0.5 part of cumene hydroperoxide was added and polymerized. The polymerization rate was 96%. This graft copolymer latex is coagulated with a dilute sulfuric acid aqueous solution, washed with water,
It was dried to obtain a graft polymer (B-1).

2-2) Preparation of Graft Polymer (B-2) n-Butyl acrylate 50 parts Distilled water 180 parts Potassium rosinate 0.6 parts Triallyl cyanurate 0.4 parts Into a reaction tank, nitrogen was charged. The temperature is raised to 70 ° C. under an air stream. Subsequently, sodium formaldehyde sulfoxylate 0.3 part Ferrous sulfate / heptahydrate 0.01 part Tolylenediamine disodium disodium 0.03 part Cumene hydroperoxide 0.2 part was added to initiate polymerization. . After 150 minutes, a mixture of methyl methacrylate 18 parts styrene 32 parts cumene hydroperoxide 0.3 part was added dropwise over 45 minutes to carry out graft polymerization. After completion of dropping, the mixture was stirred for 1 hour as it was to obtain a graft latex. The latex was coagulated with an aqueous sulfuric acid solution, washed with water and dried to obtain a white powder of the graft polymer (B-2). The yield was 93%.

3) Preparation of vinyl-based polymer (C) 3-1) Preparation of vinyl-based polymer (C-1) styrene 70 parts acrylonitrile 30 parts tertiary dodecyl mercaptan 0.10 part azobisisobutyronitrile 0 .12 parts Distilled water 150 parts Calcium phosphate 0.5 parts was charged into an autoclave, polymerized at 70 ° C. for 4 hours, washed with water and dried to give a bead-shaped vinyl polymer (C-
1) was obtained. The yield was 88%. As a result of dissolving 0.2 g of the polymer in 100 ml of dimethylformamide and measuring the reduced viscosity ηsp / c at 25 ° C., it was 1.2.

3-2) Preparation of vinyl polymer (C-2) styrene 50 parts α-methylstyrene 30 parts acrylonitrile 20 parts tertarydodecyl mercaptan 0.12 parts potassium rosinate 2.0 parts dextrose 0.2 Parts Rongalit 0.3 parts ferric sulfate heptahydrate 0.003 parts ethylenediaminetetraacetic acid disodium salt 0.2 parts distilled water 150 parts was charged into an autoclave and polymerized at 60 ° C. for 4 hours to obtain a latex. Coagulate this latex with sulfuric acid, wash with water,
It was dried to obtain a powdery vinyl polymer (C-2). The yield was 93% and ηsp / c was 1.0. 3-3) Preparation of vinyl-based polymer (C-3) In (C-1), the vinyl-based polymer (C-3) was prepared in the same manner except that the amount of tertiarydodecyl mercaptan was changed to 0.48 part. Obtained. The yield was 90% and ηsp / c was 0.51.

4) Preparation of modified vinyl polymer (D) 4-1) Preparation of modified vinyl polymer (D-1) Methyl methacrylate 100 parts Distilled water 120 parts Tertiary decyl mercaptan 0.25 part Azobis Isobutyronitrile 0.15 part Sodium sulfoethyl methacrylate 0.3 part was charged into an autoclave, and after nitrogen substitution, suspension polymerization was carried out at 75 ° C. The resulting polymer was washed with water and dried to give a white granular modified vinyl polymer. (D-1) was prepared. Yield 89
%Met. 0.2 g of the polymer was dissolved in 100 ml of dimethylformamide to obtain a reduced viscosity ηsp / c at 25 ° C.
Was 0.75. 4-2) Preparation of modified vinyl polymer (D-2) acrylonitrile 20 parts styrene 45 parts N-phenylmaleimide 35 parts tertarydodecyl mercaptan 0.10 parts azobisisobutyronitrile 0.08 parts continuous bulk polymerization The dope thus formed was fed into an extruder, and a modified vinyl polymer (D-2) in the form of colorless pellets was obtained. The yield is 98%, and ηsp / c is 0.
It was 62.

4-3) Preparation of Modified Vinyl Polymer (D-3) Methyl Methacrylate 70 parts α-Methylstyrene 5 parts Styrene 12.5 parts Maleic anhydride 12.5 parts Distilled water 120 parts Azobisisobutyl Ronitrile 0.15 parts Tertiary decyl mercaptan 0.2 parts Sodium sulfoethyl methacrylate 0.3 parts were charged into an autoclave, and after nitrogen substitution, suspension polymerization was carried out at 80 ° C. The same treatment as in (D-1) was performed to obtain a white granular modified vinyl polymer (D-3). Yield 92%, ηsp
/ C was 0.72. 4-4) Preparation of modified vinyl-based polymer (D-4) Polymerization was performed in the same manner as in (D-1) except that the amount of tertiary dodecyl mercaptan was changed to 0.65 part, and modified vinyl-based polymer ( D-4) was obtained. Yield 91%, ηsp /
c was 0.35.

The alkylene oxide polymer (A) prepared as described above, the graft polymer (B), the vinyl polymer (C), the modified vinyl copolymer (D) and the organic alkali metal salt (E) were added. The composition shown in Tables 1 and 2 was blended, and pelletized by using a vent type twin-screw extruder, and then the pellets were molded by a 1oz injection molding machine.

[0039]

[Table 1]

[0040]

[Table 2]

The results of measuring these physical properties are shown in Tables 3 and 4.

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

From the above results, in the blend of the alkylene oxide polymer, the graft polymer, the vinyl polymer and the modified vinyl polymer, by adding the organic alkali metal salt, the impact resistance and the molded article can be improved. A thermoplastic resin composition that is useful in the electric and electronic fields and has excellent appearance and further antistatic properties, and that its antistatic properties also have durability that is not lost by washing, etc. and that has excellent dynamic fatigue properties. be able to.

Claims (1)

[Claims] 1. An ethylene oxide as an essential component,
Reduced viscosity ηsp / c (dimethylformamide 100 ml
Containing 0.2 g of polymer, 25 ° C) is 1.0-
Alkylene oxide polymer (A) 3 to 3 having 3.0
It is selected from the group of aromatic vinyl-based monomers, (meth) acrylic acid ester-based monomers and vinyl cyanide-based monomers in the presence of 0% by weight and 5 to 80% by weight of rubbery polymer. Graft polymer (B) 5 to 95% by weight obtained by polymerizing at least one monomer or a mixture of monomers, an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and cyan. The reduced viscosity ηsp / c (0.2 g of the polymer in 100 ml of dimethylformamide, 25 ° C.) obtained by polymerizing a monomer mixture selected from vinyl chloride-based monomers and maleimide-based monomers is 0. 0 to 80% by weight of a vinyl polymer (C) having a viscosity of 6 to 1.5, and a reduced viscosity ηsp / c (a polymer is 0 in 100 ml of dimethylformamide) containing a vinyl monomer having a carbonyl group as an essential component. Including 2 grams, 25 ° C) is 0.4 The modified vinyl polymer (D), which is 1.0 to 1.0, has 2 to 50% by weight of 100 to 100% (A) to (D).
A thermoplastic resin composition, which is blended in an amount of 0.2% by weight, and 0.2 to 5 parts by weight of an organic alkali metal salt (E).