JPH051202A - Antistatic thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a rubber-modified thermoplastic resin composition having permanent antistatic properties. CONSTITUTION:The objective composition comprises a blend of 100 pts.wt. resin composition consisting of 1-39wt.% alkylene oxide polymer, 10-99wt.% rubber-grafted copolymer, 0-60wt.% vinyl compound copolymer, and 0.1-20wt.% modified vinyl compound copolymer with 0.1-5 pts.wt. at least one antistatic agent selected from those represented by the formulae R-N(R1R2) and R-SO3Na (wherein R is a 1-18C alkyl group and R1 and R2 each is an alkyl group substituted by a hydroxyl, carboxyl, or sulfo group).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a rubber-modified thermoplastic resin composition having a permanent antistatic property.

[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 the fields of electric devices and automobiles. These resins are
It is used in a wide range of fields because it has 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. ing. However, since these resins are electrically insulative, they generate static electricity during use, which not only adheres to dust and impairs the appearance, but also when used in cases and parts of electrical and electronic equipment, There are drawbacks such as equipment malfunction due to electrostatic damage.

As a means for solving these drawbacks of thermoplastic resins, a method of kneading an antistatic agent into these resins has been widely adopted so far. As the antistatic agent, conventionally, anionic, cationic or nonionic surface active agents have been mainly used. However, the thermoplastic resins containing these surfactants have good mechanical strength such as impact resistance, molding appearance, and thermal stability, but the surfactants present on the surface of the molding resin cannot be rubbed or washed. There is a problem that it is easily lost due to external stimuli such as, and thus the antistatic property is significantly reduced.

As a method of exhibiting a permanent antistatic property which does not change by an external stimulus, JP-A-60-137955 discloses a method of copolymerizing polyalkylene glycol methacrylate in a resin. However, in order to obtain good antistatic property by this method, the amount of polyalkylene glycol methacrylate added must be increased, and the resin production method is complicated, which is disadvantageous in terms of production cost.
JP-A 64-26674 proposes that an alkylene oxide polymer, which is a water-soluble polymer, is blended as an antistatic agent to prevent static electricity generation on the resin surface. However, when the alkylene oxide polymer is blended with the rubber-modified thermoplastic resin as described above, an antistatic property improving effect is produced, but the polyalkylene oxide has poor compatibility with the rubber-modified thermoplastic resin, and therefore, is molded. The product had a problem that the resin caused delamination and was not sufficient as a practical product. Polyalkylene glycol has a low production cost and is very advantageous, but as described above, its compatibility with styrene-based thermoplastic resins is poor,
It is difficult to use as an antistatic agent because the resin is delaminated when added in an amount capable of obtaining good antistatic property, and addition of polyalkylene glycol to the resin makes it difficult to stabilize the heat of the resin. Since it tends to deteriorate the properties, it is necessary to keep the amount of polyalkylene glycol added low.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an antistatic material having good compatibility between a polyalkylene oxide and a rubber-modified thermoplastic resin, little delamination, excellent mechanical properties such as impact resistance, and excellent molding appearance. The purpose of the present invention is to provide a thermoplastic resin.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above-mentioned circumstances, the present inventors have found that a rubber-like graft copolymer obtained by graft-polymerizing a specific vinyl monomer onto a rubber-like polymer. By adding the modified vinyl copolymer and the antistatic agent to the composition of the alkylene oxide polymer and the vinyl copolymer, a rubber-modified thermoplastic resin having less layered peeling and permanent antistatic property can be obtained. They have found that they can be obtained and have reached the present invention.

That is, the thermoplastic resin excellent in permanent antistatic property of the present invention is (A) alkylene oxide polymer 1 to
A group consisting of an aromatic vinyl-based monomer, a (meth) acrylic acid ester-based monomer and a vinyl cyanide-based monomer in the presence of 39% by weight and (B) a rubber-like polymer in an amount of 5 to 80% by weight. 10 to 99% by weight of a rubbery graft polymer obtained by polymerizing at least one vinyl monomer selected from
(C) Aromatic vinyl-based monomer 30 to 95% by weight, (meth) acrylic acid ester-based monomer and / or vinyl cyanide-based monomer 5 to 70% by weight, maleimide-based monomer 0 to
40% by weight of vinyl copolymer 0 to 60% by weight,
And (D), a vinyl monomer having an epoxy group or a vinyl monomer having a carboxyl group at the molecular end, an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and cyanation 100 parts by weight of a resin composition comprising 0.1 to 20% by weight of a modified vinyl copolymer obtained by polymerization with at least one vinyl monomer selected from the group consisting of vinyl monomers, (E) An antistatic agent represented by the general formula RN (R ₁ R ₂ ) (wherein R is a carbon number of 1 to 1)
8 alkyl group, R ₁ and R ₂ are a hydroxyl group, a carboxyl group,
It represents a substituted alkyl group having a sulfonic acid group or the like. ) And an antistatic agent represented by the general formula R—SO ₃ Na (wherein R represents an alkyl group having 1 to 18 carbon atoms).
The antistatic thermoplastic resin composition comprises 0.1 to 5 parts by weight of at least one of the above.

The present invention will be specifically described below. The rubber-modified thermoplastic resin of the present invention comprises (A) an alkylene oxide polymer and (B) a rubber-based graft copolymer, (C) a vinyl-based copolymer, (D) a modified vinyl-based copolymer, and (E) a charge. It consists of an inhibitor. Therefore, these components will be sequentially described.

(1) Alkylene oxide polymer (A) The alkylene oxide polymer (A) in the present invention is
It is shown by the following formula.

[0010]

[Chemical 1]

(Wherein R ₁ , R ₂ and R ₃ represent hydrogen or a group selected from alkyl groups having 1 to 4 carbon atoms, and m, n
Is an integer satisfying 50 <m + n <10000, and p and q are 0
Is an integer of ~ 5. )

In the polymer of the above formula, m and n are 100 <
Those satisfying an integer of m + n <8000 are preferable, and p and q are preferably integers of 1 to 3. More particularly, an ethylene oxide group in which at least one of R ₂ and R ₃ is hydrogen is 3
Those containing 0 to 95% are preferable. And m + n <
When 50, the antistatic property is insufficient, and when m + n> 10000, the compatibility deteriorates and delamination occurs. This alkylene oxide polymer (A) is, for example, ethylene oxide, propylene oxide, n-butylene oxide,
Isobutylene oxide, n-pentylene oxide,
It is a homopolymer or a copolymer of two or more kinds of alkylene oxides such as n-hexylene oxide.

Among the alkylene oxide polymers (A) represented by Chemical formula 1, copolymers of ethylene oxide and other alkylene oxides are particularly preferable.
It is preferable to use ethylene oxide in an amount of 30 to 95% by weight, particularly 50 to 90% by weight, as a constituent unit of the alkylene oxide copolymer. 30 ethylene oxide
If it is less than 10% by weight, it is difficult to obtain good antistatic property.
If it exceeds 5% by weight, the compatibility with the rubber-like graft copolymer tends to be poor, and the mechanical strength of the resin tends to be low, such being undesirable. When an alkylene oxide polymer other than ethylene oxide is used, the mechanical strength of the resin and the compatibility with the rubber-like graft copolymer are improved, but it is inferior to ethylene oxide in terms of antistatic property.

The method for polymerizing the alkylene oxide polymer (A) is not particularly limited, but a method such as ring-opening polymerization of alkylene oxide or cyclic ether under an alkali catalyst can be used. The alkylene oxide polymer (A) is used in an amount of 1 to 39% by weight of the resin composition comprising (A), (B), (C) and (D).

(2) Rubber-based graft polymer (B) The rubber-based graft polymer (B) in the present invention is obtained by graft-polymerizing a vinyl-based monomer on a rubber-like polymer. Examples of this rubber-like polymer include diene rubber, acrylic rubber, EPDM rubber, chlorinated polyethylene rubber,
Elastomers such as silicone rubber can be used, preferably polybutadiene rubber and butadiene copolymer rubber, for example, butadiene copolymer obtained by copolymerizing 30% by weight or less of acrylonitrile, (meth) acrylic acid ester, styrene and other monomers. It is rubber.

The vinyl monomer is at least one vinyl monomer selected from the group consisting of aromatic vinyl monomers, (meth) acrylic acid ester monomers and vinyl cyanide monomers. It is a quantity. Aromatic vinyl monomers that can be used in the present invention include styrene, α-methylstyrene, halogenated styrene such as chlorostyrene and bromostyrene, and alkylstyrene such as vinyltoluene.
These may be used alone or in combination of two or more. Styrene or α-methylstyrene is preferably used alone or as a mixture of two kinds.

The (meth) acrylic acid ester-based monomer that can be used in the present invention is methyl acrylate,
Methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate and the like and derivatives thereof. These can be used alone or in combination of two or more. Methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate and the like are preferable.

The vinyl cyanide-based monomers that can be used in the present invention are acrylonitrile, halogenated acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. and their derivatives, which may be used alone or in combination of two or more. Can be used together. Acrylonitrile and / or methacrylonitrile are preferred. In the present invention, other vinyl-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide and other maleimide-based monomers and their derivatives, and acrylamide and its derivatives are used, if necessary. You can do it.

The composition ratio of the rubber-like polymer and the vinyl-based monomer in the rubber-like graft polymer is from 1 to 50.
The amount is 80% by weight, preferably 5 to 70% by weight, and the vinyl monomer is 20 to 99% by weight, preferably 30 to 95% by weight.
If the amount of the rubber-like polymer is less than 1% by weight, the impact resistance is insufficient, and if it exceeds 80% by weight, the hardness of the resin is insufficient, which is not preferable.

The composition ratio of the aromatic vinyl-based monomer and / or the (meth) acrylic acid ester-based monomer and the vinyl cyanide-based monomer in the rubber-like graft polymer is the aromatic vinyl-based monomer. Body and / or (meth) acrylic acid ester monomer is 30 to 99% by weight, preferably 50 to 90% by weight, and vinyl cyanide monomer is 1 to 70% by weight, preferably 10 to 50% by weight. 30 aromatic vinyl monomers
If the amount is less than 10% by weight, the impact resistance of the resin will be insufficient, and if the amount of the vinyl cyanide monomer is less than 1% by weight, the chemical resistance of the resin will decrease, which is not preferable.

The method for polymerizing the rubber-like graft copolymer is not particularly limited, but emulsion polymerization or the like is preferably used. The rubbery graft copolymer (B) is
10 to 99% by weight of the resin composition comprising (A), (B), (C) and (D) is used.

(3) Vinyl Copolymer (C) The vinyl copolymer (C) usable in the present invention is an aromatic vinyl monomer, a (meth) acrylic acid ester monomer and / Alternatively, it is a polymer composed of a vinyl cyanide-based monomer. As the aromatic vinyl-based monomer, (meth) acrylic acid ester-based monomer and vinyl cyanide-based monomer that can be used here, the same ones as used in the above (2) can be used. If necessary, other vinyl-based monomers, for example, maleimide-based monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide and derivatives thereof, acrylamide and derivatives thereof, and the like can be used.

Examples of vinyl copolymers are methyl methacrylate polymers, acrylonitrile-styrene copolymers, acrylonitrile-α-methylstyrene copolymers,
Examples thereof include a styrene-maleimide copolymer and an acrylonitrile-styrene-maleimide terpolymer.

The composition ratio of each vinyl monomer is 30 to 95% by weight of the aromatic vinyl monomer, preferably 50 to 85.
% By weight, (meth) acrylic acid ester-based monomer and / or vinyl cyanide-based monomer 5 to 70% by weight, preferably 1
It is 5 to 50% by weight, and the maleimide monomer is 0 to 40% by weight, preferably 0 to 30% by weight. When the amount of the aromatic vinyl-based monomer is less than 30% by weight, the impact resistance of the resin is insufficient, and when the amount of the vinyl cyanide-based monomer is less than 5% by weight, the chemical resistance of the resin is poor, which is not preferable. The amount of the vinyl copolymer (C) used is 0 to 60% by weight of the resin composition comprising (A), (B), (C) and (D).

(4) Modified Vinyl Copolymer (D) The modified vinyl copolymer (D) used in the present invention is
Vinyl-based monomer having epoxy group or carboxyl group at molecular end, aromatic vinyl-based monomer, (meth) acrylic acid ester-based monomer and vinyl cyanide-based monomer It is a modified vinyl copolymer obtained by polymerizing at least one vinyl monomer selected from the group consisting of: This copolymer is used for the purpose of improving the compatibility of the rubber-like graft polymer (A) and the vinyl-based copolymer (B) with the polyalkylene oxide, and it is necessary to determine the composition from this viewpoint. There is.

The modified vinyl-based monomer having an epoxy group at the terminal is, for example, an epoxy-modified (meth) acrylic acid ester-based monomer represented by the general formula 2, specifically glycidyl methacrylate.

[0027]

[Chemical 2]

(In the formula, R ₁ is hydrogen or has 1 to 4 carbon atoms.
Up to an alkyl group, preferably hydrogen or a methyl group. n is an integer of 1 to 5, preferably 1 to 3. ) For example, glycidyl methacrylate is used.

The vinyl-based monomer having a carboxyl group is a carboxylic acid copolymerizable with other vinyl-based monomers, and the structure of the carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. Acid, maleic anhydride,
Phthalic acid, phthalic anhydride, etc. are used, preferably acrylic acid, methacrylic acid, maleic anhydride, and more preferably maleic anhydride.

The aromatic vinyl-based monomer, (meth) acrylic acid ester-based monomer and vinyl cyanide-based monomer used here are the same as those used in the rubber-like graft polymer described above. Anything can be used. For the purpose of improving the compatibility between the matrix phase of the rubbery thermoplastic resin used and the polyalkylene oxide, it is necessary to determine the monomer constitution of the modified vinyl copolymer.

The composition ratio of each of the modified vinyl copolymers is
0.5 to 50% by weight, preferably 1 to 40% by weight, of a vinyl monomer having an epoxy group at the end or a vinyl monomer having a carboxyl group, an aromatic vinyl monomer, a (meth) acrylic acid ester 50 to 99.5% by weight, preferably 60 to 99% by weight, of at least one vinyl-based monomer selected from the group consisting of base-based monomers and vinyl cyanide-based monomers. More specifically, the aromatic vinyl monomer 1
0-80% by weight, (meth) acrylic acid ester-based monomer 0-80% by weight, vinyl cyanide-based monomer 0-50% by weight, epoxy group-containing vinyl monomer or carboxyl group-containing vinyl It is composed of 0.5 to 50% by weight of the system monomer.

If the amount of the aromatic vinyl monomer is less than 10% by weight, the compatibility between the modified vinyl copolymer and the resin is insufficient,
When it exceeds 80% by weight, the reactivity between the modified vinyl copolymer and the polyalkylene oxide is deteriorated. (Meta)
If the amount of the acrylic ester exceeds 80% by weight or the amount of the vinyl cyanide-based monomer exceeds 50% by weight, the impact resistance of the resin becomes insufficient, which is not preferable. When the vinyl monomer having an epoxy group or the vinyl monomer having a carboxyl group is less than 0.5% by weight, the compatibility of the polyalkylene oxide with the resin is poor and delamination occurs, and 50% by weight is added. If it exceeds, the molding appearance of the resin deteriorates.

The method for polymerizing the modified vinyl copolymer is not particularly limited, but these monomers or a mixture of monomers may be prepared by a conventional method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method or a bulk polymerization method. Can be polymerized according to. The modified vinyl copolymer (D) includes (A), (B), (C) and (D).
0.1 to 20% by weight of the resin composition is used.

(5) Antistatic Agent (E) As the antistatic agent (E) component, an ordinary antistatic agent for kneading can be used, but a surfactant type antistatic agent is preferably used. .. For example, anionic antistatic agents such as alkylsulfonates and alkylphosphates, cationic antistatic agents typified by quaternary ammonium salts, and nonionic antistatic agents such as alkylamines and trialkyl phosphates. Etc. can be used.

Among the above-mentioned antistatic agents, a particularly preferable one is a substituted alkylamine represented by RN (R ₁ R ₂ ) (wherein R is an alkyl group having 1 to 18 carbon atoms, R is
₁ , R ₂ represents a substituted alkyl group having a hydroxyl group, a carboxyl group, a sulfonic acid group, etc.), or R—SO ₃ Na
Is an alkyl sulfonate represented by the formula (wherein R represents an alkyl group having 1 to 18 carbon atoms). Both of the above compounds are not preferable when the number of carbon atoms of the alkyl group exceeds 18, because the antistatic property does not appear.

The amount of antistatic agent added is (A), (B),
It is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the resin composition comprising (C) and (D). When the amount is less than 0.1 parts by weight, the antistatic property of the resin is insufficient, and when the amount is more than 5 parts by weight, the molding appearance of the resin is poor and the antistatic agent bleeds out, which is preferable. Absent.

The polymer thus obtained is composed of 1 to 39% by weight of the polyalkylene oxide (A), 10 to 99% by weight of the rubber-like graft copolymer (B), and 0 to the vinyl type copolymer (C). ~ 60 wt% and (D) modified vinyl copolymer (D) 0.1-20 wt% (A) + (B) + (C)
The antistatic thermoplastic resin composition of the present invention is obtained by adding the antistatic agent (E) in an amount of 0.1 to 5 parts by weight by blending so that the total of + (D) is 100% by weight. If the polyalkylene oxide (A) is less than 1% by weight, good antistatic property is not exhibited, and if it exceeds 39% by weight, the resin becomes flexible and the polyalkylene oxide undergoes phase separation to cause delamination. Not preferable. If the rubber graft copolymer (B) is less than 10% by weight, impact resistance is insufficient, and 9
If it exceeds 9% by weight, the antistatic property is insufficient.

The vinyl copolymer (C) is 60% by weight.
If it is above, the impact resistance of the resin is insufficient, which is not preferable.
When the modified vinyl copolymer (D) is less than 0.1% by weight,
The compatibility of polyalkylene oxide is poor and the resin causes delamination, and when it exceeds 20% by weight, the appearance of the resin after molding is deteriorated. When the amount of the antistatic agent (E) is less than 0.1 part by weight, the amount of polyalkylene oxide added must be increased in order to obtain good antistatic property. If it exceeds 5 parts by weight, the antistatic agent bleeds out from the resin surface, which is not preferable.

The antistatic thermoplastic resin composition of the present invention comprises
Further, an ammonium salt can be added as a catalyst. As this ammonium salt, if the reaction rate between the alkylene oxide and the modified vinyl-based copolymer can be accelerated, and if it does not impair the molding appearance or mechanical strength of the resin, its structure is particularly Not limited. For example, ammonium chloride, ammonium bromide, tetramethylammonium bromide, tetra-n-butylammonium bromide, etc. are used.

The method for producing the rubber-like thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include alkylene oxide (A), rubber-like graft copolymer (B), vinyl-based copolymer (C), The modified vinyl copolymer (D) and the antistatic agent (E) are mixed and kneaded with a vent type extruder or a roll to form pellets or sheets, and then a resin molding material is obtained by injection molding. Obtainable.

At this time, in order to further improve the performance as a molding material, other antistatic agents such as anionic or cationic, nonionic or metallic salts are added to further improve the antistatic property, An antioxidant and a heat stabilizer for further improving the heat stability, and if necessary, a lubricant, a plasticizer, a dye or a pigment, a further compatibilizer, and a flame retardant can be added.

[00042]

EXAMPLES In order to explain the present invention in more detail, examples will be described below. The antistatic thermoplastic resin composition of the present invention is a mixture of an alkylene oxide polymer and a rubber graft polymer, a vinyl copolymer, a modified vinyl copolymer, and pelletized by an extruder, A resin test piece was prepared by an injection molding machine, and various physical properties were measured by the following test methods.

Izod impact strength: ASTM D-2
56 Surface resistivity: A resin was molded on a flat plate of 40 mm × 50 mm × 4 mm, and the measurement was performed under the conditions of room temperature of 23 ° C. and humidity of 50% RH. For measurement, SM- manufactured by Toa Denpa Kogyo Co., Ltd.
A 10E resistance meter was used. Molding appearance: The appearance (gloss, color) of the above-mentioned molded test piece was visually judged. The judgment results are indicated by ⊚ when the appearance of the test piece was extremely good, by ◯ when it was good, and by X when it was bad. Delamination: A molded flat plate is bent at the center and then cut,
The presence or absence of peeling was determined. The results of the judgment are indicated by ⊚ when hardly delamination was observed, ◯ when slightly delamination was observed, and by X when severe delamination was observed.

[00044]

[Reference Example] (1) Alkylene oxide polymer (A) (A-1): 75 parts by weight of ethylene oxide and 25 parts by weight of propylene oxide are subjected to ring-opening polymerization in an autoclave under an alkali metal catalyst. A colorless rubber-like alkylene oxide copolymer (A-1) was prepared. (A-2): 90 parts by weight of ethylene oxide and 10 parts by weight of propylene oxide are polymerized in the same manner as in (A-1) to give a colorless rubber-like alkylene oxide copolymer (A-).
2) was prepared. (A-3): 100 parts by weight of ethylene oxide (A-
Polymerization was carried out in the same manner as in 1) to prepare a colorless resinous alkylene oxide copolymer (A-3).

(2) Rubber-based graft copolymer (B) (B-1): Polybutadiene latex (rubber particle system 0.3 μ, gel content 82%) In the presence of 45 parts by weight, 39 parts by weight of styrene, 16 parts of acrylonitrile By weight emulsion polymerization was carried out. The obtained latex was coagulated with an aqueous sulfuric acid solution, washed well with water and then dried to prepare a powdery rubber-like graft copolymer (B-1). (B-2): 45 parts by weight of polybutyl acrylate latex, 41 parts by weight of styrene, and 14 parts by weight of acrylonitrile, in the same manner as in (B-1), the graft copolymer (B-
2) was prepared.

(3) Vinyl Copolymer (C) (C-1): Styrene 71 parts by weight, acrylonitrile 2
Suspension polymerization of 9 parts by weight of vinyl copolymer (C-1)
Was prepared. (C-2): Suspension polymerization of 65 parts by weight of styrene and 35 parts by weight of methyl methacrylate to give a vinyl-based copolymer (C-
2) was prepared. (C-3): 60 parts by weight of styrene, acrylonitrile 2
Emulsion polymerization of 0 parts by weight and 20 parts by weight of N-phenylmaleimide was performed to prepare a vinyl copolymer (C-3).

(4) Modified vinyl copolymer (D) (D-1): Acid-modified vinyl copolymer by suspension polymerization of 70 parts by weight of methyl methacrylate, 15 parts by weight of styrene, and 15 parts by weight of maleic anhydride. A combined product (D-1) was obtained. (D-2): "Reseda GP-301" manufactured by Toagosei Kagaku Kogyo Co., Ltd. was prepared as an epoxy-modified vinyl-based copolymer. (D-3): As an epoxy-modified vinyl-based copolymer, “Blemma-CP-10SA” manufactured by NOF CORPORATION was prepared.

(5) Antistatic agent (E) (E-1): amine-based surfactant, Miyoshi Yushi Co., Ltd.
"Daspa-701B" was prepared. (E-2): Anionic surfactant, Miyoshi Yushi Co., Ltd.
"Daspa-802D" was prepared.

Examples 1 to 9 Polyalkylene oxide (A) prepared in Reference Example and rubber graft copolymer (B), vinyl copolymer (C), modified vinyl copolymer (D) antistatic Agent (E)
And 0.05 part of tetra (n-butyl) ammonium bromide as a catalyst in the amounts and components (parts by weight) shown in Table 1, mixed with a mixer, and then using a vented twin-screw extruder. Pelletized, then the pellets were molded into test pieces on a 10Z injection molding machine. The surface resistivity of this test piece was immediately measured using a SM-10E type resistance measuring device manufactured by Toa Denpa Kogyo Co., Ltd. Subsequently, the surface resistivity was measured after thoroughly washing with distilled water to thoroughly remove surface water and then conditioning the humidity at 23 ° C. and 50% humidity for 1 hour. The measurement results are shown in Table 1.

Comparative Examples 1 to 9 Polyalkylene oxide (A) prepared in Reference Example and rubber graft copolymer (B), vinyl copolymer (C), modified vinyl copolymer (D) and charging With the inhibitor (E), test pieces were prepared in the same manner as in the examples, and various physical properties were measured. The results are shown in Table 1.

[00051]

[Table 1]

From the above results, all of the thermoplastic resin compositions of the present invention (Examples 1 to 9) are excellent in impact resistance, appearance of molded articles, and antistatic property evaluated by surface resistivity. The anti-static property was not lost due to washing or the like, and was permanent.

[00053]

INDUSTRIAL APPLICABILITY According to the present invention, when a polyalkylene oxide (A) is blended with a rubber graft copolymer (B) to obtain an antistatic thermoplastic resin, a modified vinyl copolymer (D) is used. Since they are used in combination, it is possible to prevent delamination of the resin after molding. Further, since the antistatic agent (E) is used in combination, the amount of the polyalkylene oxide (A) used can be reduced, the delamination of the resin after molding can be further prevented, and the properties of the thermoplastic resin are impaired. There is no. Therefore, the antistatic thermoplastic resin of the present invention can produce a molded article having good impact strength and good appearance and having a permanent antistatic effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display area C08L 25/00 LED 9166-4J 33/06 LJA 7242-4J 33/18 LJL 7242-4J 55/02 LME 7142-4J LMF 7142-4J 71/02 LQC 9167-4J LQE 9167-4J C09K 3/16 103 6917-4H 108 6917-4H

Claims (1)

Claims: (A) alkylene oxide polymers 1 to 3
A group consisting of an aromatic vinyl-based monomer, a (meth) acrylic acid ester-based monomer and a vinyl cyanide-based monomer in the presence of 9% by weight and (B) a rubber-like polymer in an amount of 5 to 80% by weight. 10 to 99% by weight of a rubber-like graft polymer obtained by polymerizing at least one vinyl-based monomer selected from the group (C)
From 30 to 95% by weight of aromatic vinyl-based monomer, 5 to 70% by weight of (meth) acrylic acid ester-based monomer and / or vinyl cyanide-based monomer, and 0 to 40% by weight of maleimide-based monomer 0 to 60% by weight of the vinyl copolymer, and (D) a vinyl monomer having an epoxy group or a vinyl monomer having a carboxyl group at the molecular end, an aromatic vinyl monomer, ) Modified vinyl copolymer 0.1 to 20 obtained by polymerizing at least one vinyl monomer selected from the group consisting of acrylic acid ester monomers and vinyl cyanide monomers In 100 parts by weight of the resin composition consisting of 10% by weight, (E) an antistatic agent represented by the general formula RN (R ₁ R ₂ ) (wherein R is a carbon number of 1 to 18)
, R ₁ and R ₂ each represent a substituted alkyl group having a hydroxyl group, a carboxyl group, a sulfonic acid group and the like. ) And an antistatic agent represented by the general formula R—SO ₃ Na (wherein R represents an alkyl group having 1 to 18 carbon atoms).
An antistatic thermoplastic resin composition containing 0.1 to 5 parts by weight of at least one of the above.