JP2873893B2 - 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 composition having permanent antistatic properties and, in particular, improved dynamic fatigue properties of a resin.

[0002]

2. Description of the Related Art ABS resins and high-impact polystyrene (HIP) are currently used as thermoplastic resins having excellent impact resistance.
Rubber-modified thermoplastic resins represented by S) are widely used in electric appliances, automobiles, and the like. These resins are widely used because of their advantages such as good processability such as molding, excellent impact resistance, good molded appearance, good molding stability, excellent plating properties, and low cost as products. Used for However, since these resins are electrical insulators, they generate static electricity, which not only impairs the appearance by adhering dust but also causes malfunctions due to static electricity when used in cases of electric or electronic equipment and parts. It has disadvantages such as.

Hitherto, as a means for solving the above-mentioned disadvantages of thermoplastic resins, a method of kneading an antistatic agent into these resins has been widely used. Conventional antistatic agents mainly use anionic, cationic and nonionic surfactants, and thermoplastic resins containing these surfactants can be used to improve mechanical strength and molding appearance, such as impact resistance.
Although the thermal stability is good, the problem that the surfactant kneaded due to external stimuli such as friction and cleaning of the molding resin surface is lost from the resin surface, and the antistatic property is significantly lost. is there.

[0004] As a method for developing a permanent antistatic property which is not changed by an external stimulus, JP-A-64-26674 discloses a method in which an alkylene oxide polymer which is a water-soluble polymer is blended as an antistatic agent. It has been proposed to prevent the generation of static electricity on the surface. However, it is possible to improve the antistatic property by blending the alkylene oxide polymer with the rubber-modified thermoplastic resin as described above, but polyalkylene oxide is used for the rubber-modified thermoplastic resin. The compatibility was poor, and the resin after molding caused delamination, which was not sufficient for practical use.

Further, Japanese Patent Application Laid-Open No. Sho 60-137955 discloses a method of copolymerizing a polyalkylene glycol methacrylate in a resin, but this method is disadvantageous in terms of the production cost of the resin and the production cost. there were. A thermoplastic resin composition having a permanent antistatic property, a soft polymer such as a highly conductive elastomer or polyethylene glycol is blended in the resin, and these polymers are completely mixed with the matrix resin. However, the resin required a certain degree of compatibilization, so that the dynamic fatigue property of the resin was much lower than that of the matrix resin.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have developed an antistatic thermoplastic resin composition which has little delamination, good mechanical properties such as impact resistance, good molded appearance, and excellent dynamic fatigue properties. As a result of intensive studies for the purpose of providing the above, the above problems can be solved by blending a specific alkylene oxide polymer and a specific vinyl polymer, a specific modified vinyl polymer, and an organic alkali metal salt. And arrived at the present invention.

[0007]

According to the present invention, a reduced viscosity ηsp / c (containing 0.2 g of a polymer in 100 ml of dimethylformamide, 25 ° C.) containing ethylene oxide as an essential component is 1.0 to 1.0. 3.0 to 30% by weight of an alkylene oxide polymer (A) of 3.0,
In the presence of 80% by weight, at least one or more monomers selected from the group consisting of an aromatic vinyl monomer, a (meth) acrylate monomer and a vinyl cyanide monomer, Polymer (B) 5 obtained by polymerizing a monomer mixture
~ 95% by weight, obtained by polymerizing a monomer mixture selected from aromatic vinyl monomers, (meth) acrylate monomers, vinyl cyanide monomers, and maleimide monomers. Reduced viscosity ηsp / c (dimethylformamide 100m
(0.2 ° C. containing 0.2 gram of a polymer at 25 ° C.)
1.5 vinyl polymer (C) 0 to 80 wt%, main
Tacrylic acid ester, acrylic acid ester, maleimide
Reduced viscosity ηsp / c containing a vinyl monomer having a carbonyl group selected from the following as an essential component (0.2 g of polymer in 100 ml of dimethylformamide, 25 ° C.)
Is a modified vinyl polymer (D)
50% by weight of (A) to (D) were blended so as to be 100% by weight, and 0.2% of the organic alkali metal salt (E) was added thereto.
To 5 parts by weight of a thermoplastic resin composition.

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

The alkylene oxide polymer (A) used in the present invention preferably contains an ethylene oxide unit as an essential component and contains at least 50% by weight of the ethylene oxide unit in the polymer (A). 70% by weight or more. If the amount of ethylene oxide units in the polymer (A) is less than 50% by weight, the resin has insufficient antistatic properties, which is not preferable. As a component other than the ethylene oxide unit in the polymer (A), for example, propylene oxide, butylene oxide, epichlorohydrin, tetrahydrofuran and 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 preferable. The degree of polymerization of the polymer (A) is determined by measuring the reduced viscosity ηsp at 25 ° C. of a solution obtained by dissolving 0.2 g of the polymer in 100 ml of dimethylformamide.
/ C is preferably from 1.0 to 3.0, and more preferably from 1.2 to 2.8. When the resin has a reduced viscosity of less than 1.0, the dynamic fatigue resistance of the resin is inferior, and when it exceeds 3.0, the dependency of the antistatic properties of the resin on the molding conditions, especially the molding temperature, becomes high. This is not preferred because the appearance becomes poor, such as deterioration of the gloss. The method for polymerizing the polymer (A) is not particularly limited, but solution polymerization with an alkali catalyst or the like is preferably used.

The rubbery polymer used in the graft polymer (B) includes a diene rubber or an acrylic rubber,
Elastomers such as EPDM rubber, chlorinated polyethylene rubber, and silicone rubber can be used, and are 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. An aromatic vinyl-based monomer, a vinyl cyanide-based monomer, a monomer or a monomer mixture selected from (meth) acrylate-based monomers are graft-polymerized to the rubbery polymer, A graft polymer (B) is obtained.

The aromatic vinyl monomer used in the present invention may be styrene, α-methylstyrene, halogenated styrene such as chlorostyrene or bromostyrene, alkylstyrene such as vinyltoluene, or the like. It is a polymerizable vinyl aromatic compound using at least one kind. Preferably, styrene or α-methylstyrene can be used alone or as a mixture of two.

The vinyl cyanide monomers used in the present invention are acrylonitrile, halogenated acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and these may be used alone or in combination of two or more. Acrylonitrile can be used, preferably acrylonitrile.

Examples of the (meth) acrylate include methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and 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 rubbery polymer and the monomer or the monomer mixture in the graft polymer (B) is such that the rubbery polymer is 5 to 80% in 100% by weight of the graft polymer (B).
%, Preferably 10 to 60% by weight. When the amount of the rubbery polymer in the graft polymer (B) is less than 5% by weight, the impact resistance is insufficient. When the amount exceeds 80% by weight, the hardness and flexural modulus of the resin become insufficient. Absent. The proportion of the rubbery polymer in the graft polymer (B) is
The choice can be made in view of the rubbery polymer occupying the resin. Specifically, a composition is selected so that the rubbery polymer is 3 to 20% by weight in the resin. If the amount of the rubbery polymer in the resin is less than 3% by weight, the impact resistance of the resin is insufficient, and
If the content exceeds% by weight, the flexural modulus of the resin is insufficient, and the dynamic fatigue property is inferior.

The composition ratio of each of the aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylate monomer used in the graft polymer (B) is not particularly limited. It can be selected according to the impact resistance and chemical resistance of the resin. In particular, the effects of the present invention are not impeded by any composition. The method for polymerizing the graft polymer (B) is not particularly limited,
Conventional 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 an aromatic vinyl monomer, a (meth) acrylate monomer, a vinyl cyanide monomer, and a maleimide monomer. . As the aromatic vinyl monomer, (meth) acrylate monomer, and vinyl cyanide monomer that can be used here, the same ones as described above can be used. Vinyl monomers such as maleimide,
Maleimide 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, methyl methacrylate polymer, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, styrene-maleimide copolymer,
There is an acrylonitrile-styrene-maleimide terpolymer.

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

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 from 0.6 to 1.5. Preferably it is 0.9-1.3. When ηsp / c is less than 0.6, the dynamic fatigue property of the resin is insufficient, and when ηsp / c is more than 1.5, the fluidity of the resin deteriorates, which is not preferable.

The modified vinyl polymer (D) used in the present invention includes methacrylic acid ester and acrylic acid ester.
And a polymer having a carbonyl group-containing vinyl monomer selected from maleimide and maleimide as an essential component. In this case, a homopolymer of a vinyl monomer having a carbonyl group or a copolymer with another vinyl monomer may be used. Specific examples of the vinyl monomer having a carbonyl group, methyl acrylate, ethyl acrylate, -n- propyl, isopropyl acrylate, butyl -n- acrylate, isobutyl acrylate, - tert-butyl, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-
Propyl, isopropyl methacrylate, methacrylic acid
n-butyl, isobutyl methacrylate, methacrylic acid-
tert-butyl, phenyl methacrylate , N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide and the like. Preferably, methyl methacrylate and N-phenylmaleimide are used. These vinyl monomers can be copolymerized with other aromatic vinyl monomers as the vinyl monomer, vinyl cyanide monomers can be used. Specifically, styrene and α- methyl styrene, acrylonitrile, methacrylonitrile and the like. Preferably, styrene, α-methylstyrene and acrylonitrile are used.

The specific ratio of these monomers in the modified vinyl polymer (D) is as follows: 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 amount of the vinyl-based monomer having a carbonyl group is less than 30% by weight, the delamination of the resin is not improved, which is not preferable. The polymer composed of the vinyl monomer having a carbonyl group is substantially compatible with the graft polymer (B), and the monomer is also compatible with the alkylene oxide polymer (A). Thus, a homopolymer of a vinyl-based monomer having a carbonyl group or a copolymer of two or more of these may be used. Of course, it may be a copolymer with another vinyl monomer.

With regard to the degree of polymerization of the modified vinyl polymer (D), the compatibility between the alkylene oxide polymer (A), the graft polymer (B) and the vinyl polymer (C) is improved, and Is selected so as to improve the dynamic fatigue resistance of the steel. Specifically, dimethylformamide 100
A solution containing 0.2 g of the polymer per ml and having a reduced viscosity ηsp / c at 25 ° C. of 0.4 to 1.0 is used. Preferably it is 0.5 to 0.9. The reduced viscosity is 0.
When it is less than 4, the dynamic fatigue properties of the resin are poor, which is not preferable. When it exceeds 1.0, the compatibility with the alkylene oxide polymer (A) is deteriorated, and the effect of improving the laminar exfoliation of the resin is reduced. The method for producing the modified vinyl polymer (D) is not particularly limited, but ordinary suspension polymerization, bulk polymerization, solution polymerization and the like can be used.

As the organic alkali metal salt (E), those generally used widely as surfactants can be used. For example, fatty acid salts and alkyl sulfonates,
A sulfonate represented by an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, a polyoxyethylene alkyl ether sulfonate and the like can be used. Preferably, it is a sulfonate. Specifically, sodium octylsulfonate, sodium decylsulfonate, sodium dodecylsulfonate, sodium cetylsulfonate, sodium stearylsulfonate, sodium octylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, stearylbenzenesulfonate Sodium acid, sodium dodecylnaphthalenesulfonate and the like or lithium salts or potassium salts 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 such that it is not lost by washing with water. . In the presence of the alkylene oxide polymer (A), its mechanism is not clear, but a better permanent antistatic property than when each of the alkylene oxide polymer (A) and the organic alkali metal salt (E) is used alone. Expressing 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 5% of the vinyl polymer (C). ~ 80% by weight, modified vinyl polymer (D)
It comprises 100% by weight of a composition consisting of 2 to 50% by weight and 0.2 to 5 parts by weight of an organic alkali metal salt (E).

If the amount of the alkylene oxide polymer (A) is less than 3% by weight, good permanent antistatic properties are not exhibited, and if it exceeds 30% by weight, the mechanical strength of the resin such as flexural modulus is inferior. . When the amount of the graft polymer (B) is less than 5% by weight, the impact resistance of the resin is insufficient, and when it exceeds 95% by weight, the antistatic property is insufficient. Vinyl polymer (C)
Exceeds 80% by weight, the impact resistance of the resin is insufficient, which is not preferred. If the content of 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 exfoliated. Although peeling is eliminated, the antistatic property deteriorates, which is not preferable. Organic alkali metal salt (E)
Is less than 0.2 parts by weight, the antistatic property is poor and 5
If the amount 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 an alkylene oxide polymer (A), a graft polymer (B), a vinyl polymer (C), and a modified vinyl polymer. Combination (D) and organic alkali metal salt (E) are mixed by a mixer, kneaded with a Banbury mixer, a vented extruder, or a roll to form pellets or sheets, and then a method of obtaining a molded product by an injection molding machine is used. Is done. Also, at this time, in order to further improve the performance as a molding material, an antioxidant or a heat stabilizer for further improving the heat stability, a lubricant or a plasticizer, if necessary,
Dyes and pigments, further compatibilizers and flame retardants can also be added.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Note that “%” in Examples and Comparative Examples,
“Parts” represent “% by weight” and “parts 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 pelletized with a vented extruder. This was used to produce a resin test piece 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
06. (4) Surface resistivity: A resin was molded on a flat plate having a size of 40 mm x 50 mm x 4 mm, and prepared and measured at room temperature of 23 ° C and relative humidity of 50% for 24 hours. Toa Denpa Kogyo for measurement
An SM-10E resistance measuring instrument manufactured by Co., Ltd. was used.

(5) Charged voltage and its half-life: A 10 kV voltage was imprinted on the resin for 30 seconds using a static honest meter manufactured by Shishido Shosha Co., Ltd. for the same specimen as that for surface resistivity measurement, and the resin at that time was charged. The measured voltage and the time until the voltage was reduced by half were measured. (6) Molded appearance of resin: appearance (gloss,
Color) was visually determined. As a result of the judgment, 試 験 indicates that the test piece had a good appearance, and X indicates that the test piece had a bad appearance. (7) Layered peeling property: The molded test piece was bent at the center and then cut to determine the presence or absence of peeling. The results of the evaluation were evaluated as ○ when the layered releasability was good, and × when the layer was peeled. (8) Dynamic fatigue: Izod impact test (ASTM D
-256; 1/4 "notched) using a test piece, fixing one of the test pieces and dropping a weight of 300 g from the height of 10 cm to the other at a cycle of 30 times / min.
The number of breaks of the specimen 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) (Produced by Co., Ltd.). Dissolve 0.2 g of the polyethylene oxide 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 part was charged into an autoclave, and 50 3 hours at 60 ° C
Polymerization was carried out at ℃ for 3 hours. After cooling, the solvent was removed under reduced pressure, and a white blocky alkylene oxide polymer (A-2) was obtained.
I got The yield was 95%. 0.2 g of the polymer was dissolved in 100 ml of dimethylformamide, and the measured reduced viscosity ηsp / c at 25 ° C. was 2.4.

1-3) Alkylene oxide polymer (A)
Preparation of -3) An alkylene oxide polymer (A-3) was prepared by polymerizing in the same manner as in (A-2) except that ethylene oxide was 40 parts and butylene oxide was 60 parts. Yield 88
%, Ηsp / c was 2.0. 1-4) Preparation of alkylene oxide polymer (A-4) Except for changing the solvent from a mixture of 60 parts of toluene and 40 parts of hexane to 100 parts of normal hexane, all (A-
Polymerized in the same manner as in 2), and the 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 Copolymer (B-1) Polybutadiene latex (solid content: 50%, average particle size: 0.28 μm) 100 parts Distilled water 140 parts Acrylonitrile 15 parts Styrene 35 parts Potassium rosinate 0.9 parts Tertiary decyl mercaptan 0.5 parts Dextrin 0.35 parts Ferrous sulfate 0.01 parts Sodium pyrophosphate 0.2 parts Sodium hydroxide 0.05 parts And heated to 60 ° C. while stirring. To this, 0.5 part of cumene hydroperoxide was added and polymerized. The conversion was 96%. The graft copolymer latex is coagulated with a dilute sulfuric acid aqueous solution, and washed with water,
After drying, a graft polymer (B-1) was obtained.

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 part The temperature is increased to 70 ° C. in an air current. Subsequently, polymerization was initiated by adding 0.3 parts of sodium formaldehyde sulfoxylate, 0.01 parts of ferrous sulfate and heptahydrate, 0.03 parts of disodium tillylenediaminetetraacetate and 0.2 parts of cumene hydroperoxide. . After 150 minutes, a mixture of 18 parts of methyl methacrylate, 32 parts of styrene, and 0.3 part of cumene hydroperoxide was added dropwise over 45 minutes to perform graft polymerization. After completion of the dropwise addition, the mixture was stirred for 1 hour to obtain a graft latex. The latex was coagulated with an aqueous sulfuric acid solution, washed with water and dried to obtain a white powdered graft polymer (B-2). The yield was 93%.

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

3-2) Preparation of vinyl polymer (C-2) Styrene 50 parts α-methylstyrene 30 parts Acrylonitrile 20 parts Tertiary decyl mercaptan 0.12 parts Potassium rosinate 2.0 parts Dextrose 0.2 Part Rongalit 0.3 part Ferric sulfate / heptahydrate 0.003 part Ethylenediaminetetraacetic acid / disodium salt 0.2 part Distilled water 150 parts was charged into an autoclave and polymerized at 60 ° C. for 4 hours to obtain a latex. This latex is coagulated with sulfuric acid, washed with water,
After drying, a powdery vinyl polymer (C-2) was obtained. The yield was 93% and ηsp / c was 1.0. 3-3) Preparation of vinyl polymer (C-3) In (C-1), except that the amount of tertiary decyl mercaptan was changed to 0.48 parts, the same procedure was carried out to obtain the vinyl polymer (C-3). 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 parts Azobis Isobutyronitrile 0.15 part Sodium sulfoethyl methacrylate 0.3 part was charged into an autoclave, and after purging with nitrogen, suspension polymerization was carried out at 75 ° C. The resulting polymer was washed with water and dried to obtain a white granular modified vinyl polymer. (D-1) was prepared. The yield is 89
%Met. 0.2 g of the polymer is dissolved in 100 ml of dimethylformamide and the reduced viscosity at 25 ° C. ηsp / c
Was 0.75. 4-2) Preparation of Modified Vinyl Polymer (D-2) Acrylonitrile 20 parts Styrene 45 parts N-Phenylmaleimide 35 parts Tertiary decyl mercaptan 0.10 parts Azobisisobutyronitrile 0.08 parts Continuous bulk polymerization The resulting dope was charged into an apparatus and subjected to bulk polymerization. The resulting dope was sent to an extruder to obtain a colorless pellet-shaped modified vinyl polymer (D-2). The yield is 98%, and ηsp / c is 0.1%.
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 Azobisisobuty Ronitrile 0.15 part Tertiary decyl mercaptan 0.2 part Sodium sulfoethyl methacrylate 0.3 part was charged into an autoclave, and subjected to suspension polymerization at 80 ° C. after purging with nitrogen. The same treatment as (D-1) was carried out to obtain a white granular modified vinyl polymer (D-3). The yield is 92%, ηsp
/ C was 0.72. 4-4) Preparation of modified vinyl polymer (D-4) Except that the amount of tertiary decyl mercaptan was changed to 0.65 parts, polymerization was performed in the same manner as in (D-1), and modified vinyl polymer (D-4) 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) The components were mixed as shown in Tables 1 and 2 and formed into pellets using a vented twin-screw extruder. Then, the pellets were molded into test pieces using a 1-oz injection molding machine.

[0039]

[Table 1]

[0040]

[Table 2]

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

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

From the above results, it was found that the addition of an organic alkali metal salt to a blend of an alkylene oxide polymer, a graft polymer, a vinyl polymer and a modified vinyl polymer provides impact resistance and molded product. To obtain a thermoplastic resin composition having excellent appearance and antistatic properties, and also having antistatic properties that are durable so as not to be lost by washing with water, and have excellent dynamic fatigue properties, which are useful in the electric and electronic fields. be able to.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33/18 C08L 33/18 35/00 35/00 55/02 55/02 71/02 71/02 // (C08L 51 / 04 33:08 71:02 25:04) (C08L 51/04 33:10 71:02 25:04) (C08L 55/02 33:08 71:02 25:04) (C08L 55/02 33:10 71) : 02 25:04) (56) References JP-A-4-198250 (JP, A) JP-A-4-175355 (JP, A) JP-A-3-45641 (JP, A) JP-A-2-272205 (JP, A) JP-A-2-233743 (JP, A) JP-A-4-275356 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 51 / 04,55 / 02 C08L 33/00-35/00 C08L 71/02 C08K 5/42

Claims (1)

(57) [Claims] 1. An ethylene oxide as an essential component,
Reduced viscosity ηsp / c (dimethylformamide 100ml
Containing 0.2 grams of polymer therein at 25 ° C)
3.0 alkylene oxide polymer (A) 3 to 3
0% by weight, in the presence of 5 to 80% by weight of the rubbery polymer, selected from the group consisting of an aromatic vinyl monomer, a (meth) acrylate ester monomer and a vinyl cyanide monomer. 5 to 95% by weight of a graft polymer (B) obtained by polymerizing at least one kind of monomer or monomer mixture, aromatic vinyl monomer, (meth) acrylate monomer, cyanide A reduced viscosity ηsp / c (containing 0.2 g of polymer in 100 ml of dimethylformamide, 25 ° C.) obtained by polymerizing a monomer mixture selected from a vinylated monomer and a maleimide monomer is 0. 0.6 to 1.5% by weight of a vinyl polymer (C), methacrylic acid ester,
Reduced viscosity ηsp containing a vinyl-based monomer having a carbonyl group selected from oxalate and maleimide as an essential component
/ C (0.2 g of the polymer in 100 ml of dimethylformamide, 25 ° C.) is from 0.4 to 1.0, from 2 to 50% by weight of the modified vinyl polymer (D) (A) to
A thermoplastic resin composition comprising (D) in an amount of 100% by weight, and 0.2 to 5 parts by weight of an organic alkali metal salt (E).