KR20190082074A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising: (A) 30 to 45 wt% of a rubber modified vinyl copolymer; (B) 40 to 65 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer; (C) 4 to 15 wt% of a phenyl maleimide copolymer; and 0.5 to 3 wt% of a styrene-acrylonitrile copolymer having the weight-average molecular weight of 5,000,000 g/mol, and to a molded article using the same. The thermoplastic resin composition of the present invention has excellent chemical resistance and moldability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition and a molded article using the thermoplastic resin composition.

A thermoplastic resin composition and a molded article using the same.

BACKGROUND ART Styrenic resins typified by ABS resins are widely used in automobiles, home appliances, OA machines, etc. due to their excellent moldability, mechanical properties, chemical resistance and secondary processability.

The styrenic resin can be blow molded through a hollow mold, and then subjected to a sanding and painting process to be processed into a molded product. However, when a molded product is produced by blow molding a styrene resin, there is a possibility that a defect may occur depending on external environmental variables when the subsequent coating step is carried out. For example, in a facility where the temperature control can not be precisely controlled according to seasonal changes such as summer and winter, the proportion of the thinner and the coating liquid in the coating process becomes uneven in the coating process, .

Therefore, there is a need to develop a styrene resin having improved chemical resistance to a chemical agent such as a coating diluent or the like, and at the same time having a good moldability.

A thermoplastic resin composition excellent in chemical resistance and moldability, and a molded article using the same.

According to one embodiment, there is provided a rubber composition comprising (A) 30 to 45% by weight of a rubber-modified vinyl-based copolymer; (B) 40 to 65% by weight of an aromatic vinyl compound-cyanide vinyl compound copolymer; (C) 4 to 15% by weight of a phenylmaleimide-based copolymer; And (D) 0.5 to 3% by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more.

The (C) phenylmaleimide-based copolymer may be an N-phenylmaleimide-styrene-maleic anhydride copolymer.

The (C) phenylmaleimide-based copolymer contains 21 to 55% by weight of the component derived from N-phenylmaleimide, 43 to 72% by weight of the component derived from styrene, based on 100% by weight of the phenylmaleimide- From 2 to 7% by weight of components derived from acid anhydrides.

The glass transition temperature (Tg) of the phenylmaleimide-based copolymer (C) may be 150 to 200 ° C.

The aromatic vinyl compound-cyanide vinyl compound copolymer (B) may have a weight average molecular weight of 100,000 g / mol to 200,000 g / mol.

The aromatic vinyl compound-cyanide vinyl compound copolymer (B) may contain 30 to 40% by weight of the component derived from the vinyl cyanide compound based on 100% by weight of the aromatic vinyl compound-cyanide vinyl compound copolymer.

In the aromatic vinyl compound-cyanide vinyl compound copolymer (B), the aromatic vinyl compound may be selected from the group consisting of styrene substituted with a halogen or a C1-C10 alkyl group, unsubstituted α-methylstyrene, and combinations thereof.

In the aromatic vinyl compound-cyanide vinyl compound copolymer (B), the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

The aromatic vinyl compound-cyanide vinyl compound copolymer (B) may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000 g / mol to 200,000 g / mol.

The rubber-modified vinyl copolymer (A) may be an acrylonitrile-butadiene-styrene graft copolymer.

The rubber-modified vinyl copolymer (A) may include a core formed of a butadiene rubber-like polymer, and a shell formed by graft-polymerizing a copolymer of an acrylonitrile monomer and a styrene monomer onto the core.

Meanwhile, a molded article using the thermoplastic resin composition according to one embodiment can be provided.

The thermoplastic resin composition according to one embodiment and the molded article using the thermoplastic resin composition have excellent chemical resistance and blow moldability, and thus can be widely applied to various products used for painting and unpainting.

1 is a Scanning Electron Microscope (SEM) image obtained by photographing a cross section of a specimen after evaluating the chemical resistance of the specimen according to Example 2, FIG. 2 is a graph showing the SEM image of the specimen according to Comparative Example 2, Is an image taken by scanning electron microscope.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the appended claims.

In the present invention, unless otherwise stated, the average particle diameter means a volume average diameter, which means a Z-average particle diameter measured using a dynamic light scattering analyzer.

According to one embodiment, there is provided a rubber composition comprising (A) 30 to 45% by weight of a rubber-modified vinyl-based copolymer; (B) 40 to 65% by weight of an aromatic vinyl compound-cyanide vinyl compound copolymer; (C) 4 to 15% by weight of a phenylmaleimide-based copolymer; And (D) 0.5 to 3% by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more.

Hereinafter, each component contained in the thermoplastic resin composition will be described in detail.

(A) a rubber-modified vinyl copolymer

The rubber-modified vinyl-based copolymer according to one embodiment may include a rubber-like polymer and a vinyl-based copolymer. In the rubber-modified vinyl copolymer, the vinyl copolymer may be partially or entirely graft-polymerized to a rubbery polymer.

The rubbery polymer may be at least one selected from the group consisting of a butadiene rubber, an acrylate rubber, an ethylene / propylene rubber, a styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an isoprene rubber, a terpolymer of ethylene- Alkyl (meth) acrylate rubber composites, or combinations thereof.

The vinyl-based copolymer may be an aromatic vinyl monomer, an acrylic monomer, or a combination thereof. Monomers capable of copolymerizing with the aromatic vinyl monomer may further be used.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

The monomer copolymerizable with the aromatic vinyl monomer may be a vinyl cyanide monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof.

As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile, fumaronitrile, or a combination thereof may be used.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate.

A specific example of the rubber-modified vinyl copolymer may be a graft copolymer of a mixture of styrene, acrylonitrile and optionally methyl (meth) acrylate on a butadiene rubber, an acrylate rubber or a styrene / butadiene rubber.

Another specific example of the rubber-modified vinyl-based copolymer includes graft-copolymerized methyl (meth) acrylate with butadiene rubber, acrylate rubber or styrene / butadiene rubber.

In one embodiment, the rubber-modified vinyl-based copolymer is obtained by graft-polymerizing a core comprising a rubbery polymer component and a graft copolymerizable vinyl monomer to the rubbery polymer around the core to form a shell, - core-shell structure.

For example, in the case of an acrylonitrile-butadiene-styrene graft copolymer, a core composed of a butadiene rubber component, a shell composed of an acrylonitrile monomer and a styrene monomer graft- ).

The average particle diameter of the rubber-like polymer particles in the rubber-modified vinyl copolymer may be 0.1 to 4 탆 in order to improve the impact resistance and the surface characteristics of the molded article, and in this case, excellent impact resistance can be secured.

The rubber-modified vinyl-based copolymer may be used singly or in the form of a mixture of two or more thereof.

The rubber-modified vinyl copolymer according to one embodiment may be contained in an amount of 30 to 45% by weight, specifically 30 to 43% by weight based on 100% by weight of the total of the components (A) to (D) To 41% by weight.

The rubber-modified vinyl-based copolymer may include 40 to 60% by weight of the rubbery polymer based on 100% by weight of the rubber-modified vinyl-based copolymer.

The vinyl-based copolymer contained in the rubber-modified vinyl copolymer may have a weight average molecular weight of 90,000 to 230,000 g / mol, for example, 120,000 to 200,000 g / mol.

According to one embodiment of the present invention, the rubber-modified vinyl copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).

On the other hand, the content of the acrylonitrile-derived component of the styrene-acrylonitrile copolymer contained in the acrylonitrile-butadiene-styrene graft copolymer (g-ABS) was 100% by weight of the styrene-acrylonitrile copolymer, By weight based on the total weight of the composition, and may be, for example, 25 to 35% by weight.

(B) an aromatic vinyl compound-vinylidene cyanide copolymer

The aromatic vinyl compound-cyanide vinyl compound copolymer according to one embodiment is formed by copolymerization of a vinyl cyanide compound and an aromatic vinyl compound.

The vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

The aromatic vinyl compound may be selected from the group consisting of styrene substituted with halogen or a C1 to C10 alkyl group, unsubstituted α-methylstyrene, and combinations thereof.

Wherein the aromatic vinyl compound-cyanide vinyl compound copolymer is a copolymer of aromatic vinyl compound and aromatic vinyl compound in an amount of 60 to 70% by weight and 30 to 40% by weight of an aromatic vinyl compound and 30 to 40% by weight, based on 100% by weight of an aromatic vinyl compound- Lt; / RTI >

The aromatic vinyl compound-cyanide vinyl compound copolymer has a weight average molecular weight of 100,000 g / mol to 300,000 g / mol, such as 100,000 g / mol to 280,000 g / mol, such as 100,000 g / mol to 260,000 g / mol For example from 100,000 g / mol to 200,000 g / mol, for example from 100,000 g / mol to 240,000 g / mol, for example from 100,000 g / mol to 220,000 g / / mol. < / RTI >

The aromatic vinyl-cyanide vinyl compound copolymer may be a styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 100,000 g / mol to 200,000 g / mol.

In producing the thermoplastic resin composition, the aromatic vinyl compound-cyanide vinyl compound copolymer is contained in an amount of 40 to 60% by weight, for example, 40 to 58% by weight, for example, 40 to 60% by weight based on 100% by weight of the total of components (A) By weight, for example from 40 to 54% by weight, for example from 42 to 54% by weight, for example from 44 to 54% by weight, for example from 46 to 54% by weight.

When the content of the aromatic vinyl compound-cyanide vinyl compound copolymer is out of the above range, the compatibility between the components constituting the thermoplastic resin composition is lowered, which may lower the blow moldability of the thermoplastic resin composition. There is a possibility that the impact resistance of the molded article is lowered.

(C) a phenylmaleimide-based copolymer

The phenylmaleimide-based copolymer according to one embodiment imparts heat resistance properties to the thermoplastic resin composition. The phenylmaleimide-based copolymer may be an N-phenylmaleimide-styrene-maleic anhydride copolymer and may be prepared through imidation reaction of styrene and maleic anhydride copolymer.

The phenylmaleimide-based copolymer contains 21 to 55% by weight of the component derived from the N-phenylmaleimide based on 100% by weight of the phenylmaleimide-based copolymer, 43 to 72% by weight of the maleimide derived from the styrene, From 2 to 7% by weight of components derived from acid anhydrides.

The glass transition temperature (Tg) of the phenylmaleimide-based copolymer may be, for example, from 150 캜 to 190 캜, for example, from 160 캜 to 190 캜, for example, from 160 캜 to 180 캜.

In preparing the thermoplastic resin composition, the phenylmaleimide-based copolymer is used in an amount of from 0 to 20% by weight, for example, from 2 to 20% by weight, for example, from 4 to 20% by weight based on 100% by weight of the components (A) , For example from 4 to 19% by weight, for example from 4 to 18% by weight, for example from 4 to 17% by weight, for example from 4 to 16% by weight, for example from 4 to 15% by weight, 5 to 15% by weight.

When the content and the glass transition temperature of the phenylmaleimide-based copolymer in the thermoplastic resin composition satisfy the above ranges, the blow moldability and fluidity of the thermoplastic resin composition can be improved, and the heat resistance of the molded article produced using the same can be improved. The impact resistance can be maintained at the same time.

(D) a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more

The styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more according to one embodiment has a weight average molecular weight of at least 5,000,000 g / mol, such as 5,000,000 g / mol to 10,000,000 g / mol, g / mol to 9,000,000 g / mol, such as 5,000,000 g / mol to 8,000,000 g / mol, such as 6,000,000 g / mol to 8,000,000 g / mol.

The styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more has the role of improving the compatibility of components constituting the thermoplastic resin composition like the above-mentioned aromatic vinyl compound-cyanide vinyl compound copolymer, It is possible to improve the chemical resistance and moldability of the thermoplastic resin composition.

If the styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more is not included or is too low in the thermoplastic resin composition according to one embodiment, the chemical resistance improving effect is not exhibited. If the styrene-acrylonitrile copolymer is too high, There is a possibility that the moldability and the productivity are deteriorated.

Accordingly, the styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more according to an embodiment is contained in an amount of, for example, not less than 0% by weight and not more than 4% by weight based on 100% by weight of the total of components (A) For example, from 0.3 to 4% by weight, such as from 0.5 to 4% by weight, such as from 0.5 to 3% by weight, for example from 1 to 3% by weight.

(E) Other additives

The thermoplastic resin composition may further include additives in accordance with the use thereof. The additive may further include a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer or a colorant, and may be used in a mixture of two or more kinds depending on the properties of the final molded product.

The flame retardant is a material that reduces combustibility and may be a phosphate compound, a phosphite compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate compound or a melamine compound But it is not limited thereto.

The lubricant is a material that lubricates a metal surface contacting with the thermoplastic resin composition during processing / molding / extrusion to aid flow or movement of the thermoplastic resin composition, and a commonly used material can be used.

The plasticizer is a material which increases the flexibility, workability or extensibility of the thermoplastic resin composition, and a commonly used material can be used.

The heat stabilizer is a substance which inhibits thermal decomposition of the thermoplastic resin composition when kneaded or molded at a high temperature, and a commonly used material can be used.

The antioxidant is a substance that prevents the thermoplastic resin composition from being degraded and loss of its inherent properties by inhibiting or blocking the chemical reaction between the thermoplastic resin composition and oxygen. The antioxidant may be a phenol type, phosphite type, thioether type or amine type antioxidant But it is not limited thereto.

The light stabilizer is a substance that inhibits or blocks the loss of color or mechanical properties of the thermoplastic resin composition from ultraviolet rays. Preferably, the light stabilizer is at least one of hindered phenol type, benzophenone type or benzotriazole type light stabilizer But is not limited thereto.

Conventional pigments or dyes may be used as the colorant.

The additive may be included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the components (A) to (D).

The thermoplastic resin composition according to the present invention can be produced by a known method for producing a thermoplastic resin composition.

For example, the thermoplastic resin composition according to the present invention can be prepared by mixing the components of the present invention and other additives at the same time, and then melt-kneading the mixture in an extruder, followed by injection.

The molded article according to one embodiment of the present invention can be produced from the above-mentioned thermoplastic resin composition.

The tensile strength of the molded product at 150 ℃ can be measured at a pulling rate condition of 254 mm / min, for example 10 to 50 kgf / cm ^2, for example 15 to 50 kgf / cm ^2, for example 15 to 45 kgf / cm < ² >, for example 15 to 40 kgf / cm < ² >.

The melt flow index of the molded article measured under a load of 10 kg at 220 캜 according to ASTM D1238 is, for example, in the range of 0.5 to 1.5 g / 10 min, for example, 0.8 to 1.4 g / 10 min, for example, 0.8 To 1.2 g / 10 min.

The heat deflection temperature (HDT) of the molded article measured under the load condition of 18.56 kgf / cm ² according to ASTM D648 may be 90 ° C or more, for example, 95 ° C or more, for example, 100 ° C or more.

As described above, when a molded article is produced using the thermoplastic resin composition according to one embodiment, the molded article is excellent in heat resistance and moldability. Further, since the above-mentioned thermoplastic resin composition has excellent chemical resistance at the same time, it can be applied to a molded article requiring resistance to chemical agents such as a thinner for coating and the like, and can be used for automobile exterior materials that require painting .

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

Example 1, Example 2 and Comparative Examples 1 to 2

The thermoplastic resin compositions of Examples 1, 2 and Comparative Examples 1 to 2 were prepared in accordance with the component content ratios described in Table 1 below.

In Table 1, the components constituting the thermoplastic resin composition are expressed as% by weight based on the total weight of the thermoplastic resin composition.

The components shown in Table 1 were dry-mixed and melted / kneaded by continuously feeding them to a feeding portion of a twin-screw extruder (L / D = 36, F = 45 mm) in a quantitative manner. The pelletized thermoplastic resin composition was dried at about 80 ° C. for about 4 hours, and then subjected to injection molding using a 6 oz injection molding machine having a cylinder temperature of about 220 ° C. and a mold temperature of about 60 ° C. . Thereafter, the injection-molded specimen was aged at room temperature for about 4 hours and then subjected to physical property evaluation.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 (A) 38 38 38 38 (B) 50.5 49 47 52 (C) 10 10 10 10 (D) 1.5 3 5 0

The configurations shown in Table 1 are as follows.

(A) a rubber-modified vinyl copolymer

Butadiene-styrene graft copolymer having a butadiene rubber content of about 58% by weight and an average particle size of butadiene rubber of about 0.28 占 퐉 (Lotte Hidan Co., Ltd.)

(B) an aromatic vinyl compound-vinylidene cyanide copolymer

Acrylonitrile copolymer having a weight average molecular weight of about 120,000 g / mol as a styrene-acrylonitrile copolymer copolymerized with a monomer mixture comprising about 32% by weight of acrylonitrile and about 68% by weight of styrene Material company)

(C) a phenylmaleimide-based copolymer

N-phenylmaleimide-styrene-maleic anhydride copolymer (Denka, MS-NI) having a glass transition temperature (Tg)

(D) a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more

Styrene-acrylonitrile copolymer (AS-869, manufactured by Weihai Jinhass Chemical Co., Ltd.) having a weight average molecular weight of about 5,000,000 g / mol,

Experimental Example

The experimental results are shown in Table 2 below.

(1) High Temperature Tensile Strength (kgf / cm ² ): Tensile strength test specimens of 64 mm x 3.02 mm x 3 mm in height, width and height were placed in a tensile tester and subjected to a test at a rate of 254 mm / And tensile strength was measured.

(2) Flowability (g / 10 min): The melt flow index (MI) of the thermoplastic resin composition pellets was measured according to ASTM D1238 at 220 캜 under a load of 10 kg.

(3) Chemical resistance: A specimen for tensile strength evaluation according to ASTM D638 was placed on a strainer so as to have a strain of 0.5%, and the surface of the specimen was coated with a thinner for coating (K-DECKE, E-409, Toluene: n-butylacetic acid: xylene = 14 to 24% by volume: 53 to 62% by volume: 14 to 24% by volume).

After 18 hours from the application, it was visually observed whether surface damage such as swelling occurred on the surface of the specimen. The results are shown in Table 2. It is judged to be good when no abnormality is observed on the surface of the specimen, and when it is observed, it is judged to be bad.

1 is a Scanning Electron Microscope (SEM) image obtained by photographing a cross section of a specimen after evaluating the chemical resistance of the specimen according to Example 2, FIG. 2 is a graph showing the SEM image of the specimen according to Comparative Example 2, Is an image taken by scanning electron microscope.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 High temperature tensile strength
(150 DEG C) 20 30 70 10 liquidity
(220 캜, 10 kg) 1.1 1.0 0.5 1.5 Chemical resistance good good good Poor

1 and 2, unlike the specimen prepared using the thermoplastic resin composition according to Comparative Example 2, the specimen manufactured using the thermoplastic resin composition according to Example 2 had a surface with a convexly swollen surface It can be confirmed that it has not occurred.

From the above Tables 1 and 2, it can be confirmed that the thermoplastic resin composition according to the Examples exhibits excellent flowability and chemical resistance and exhibits a moderate high temperature tensile strength. On the other hand, in the case of Comparative Example 1, component (D) was excessively contained and the high temperature tensile strength and chemical resistance were increased, but the fluidity was decreased, which is not preferable from the viewpoint of moldability. In the case of Comparative Example 2, the component (D) was not contained and the chemical resistance was poor and the high temperature tensile strength was low.

Therefore, as described above, the rubber-modified vinyl copolymer, the aromatic vinyl compound-cyanide vinyl compound copolymer, the phenyl maleimide copolymer, and the styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / It can be understood that a thermoplastic resin composition having both moldability and chemical resistance can be realized.

While the present invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the following claims. Those skilled in the art will readily understand.

Claims (12)

(A) 30 to 45% by weight of a rubber-modified vinyl copolymer;
(B) 40 to 65% by weight of an aromatic vinyl compound-cyanide vinyl compound copolymer;
(C) 4 to 15 parts by weight of a phenylmaleimide-based copolymer; And
(D) 0.5 to 3% by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g / mol or more;
And a thermoplastic resin composition. The method of claim 1,
Wherein the (C) phenylmaleimide-based copolymer is an N-phenylmaleimide-styrene-maleic anhydride copolymer. 3. The method of claim 2,
The (C) phenylmaleimide-based copolymer contains 21 to 55% by weight of components derived from N-phenylmaleimide;
43 to 72% by weight of a component derived from styrene; And
And 2 to 7% by weight of a component derived from maleic anhydride. The method of claim 1,
Wherein the glass transition temperature (Tg) of the phenylmaleimide-based copolymer (C) is 150 to 200 占 폚. The method of claim 1,
The aromatic vinyl compound-cyanide vinyl compound copolymer (B) has a weight average molecular weight of 100,000 g / mol to 200,000 g / mol. The method of claim 1,
The aromatic vinyl compound-cyanide vinyl compound copolymer (B) comprises 30 to 40% by weight of a component derived from a vinyl cyanide compound. The method of claim 1,
In the aromatic vinyl compound-cyanide vinyl compound copolymer (B), the aromatic vinyl compound is a thermoplastic resin composition selected from the group consisting of styrene substituted with halogen or a C1 to C10 alkyl group, . The method of claim 1,
In the aromatic vinyl compound-cyanide vinyl compound copolymer (B), the vinyl cyanide compound is selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof. The method of claim 1,
The aromatic vinyl compound-cyanide vinyl compound copolymer (B) is a styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000 g / mol to 200,000 g / mol. The method of claim 1,
The rubber-modified vinyl copolymer (A) is an acrylonitrile-butadiene-styrene graft copolymer. 11. The method of claim 10,
The rubber-modified vinyl copolymer (A) comprises a core composed of a butadiene rubber-like polymer, and a shell formed by graft-polymerizing a copolymer of an acrylonitrile monomer and a styrene monomer onto the core. A molded article using the thermoplastic resin composition according to any one of claims 1 to 11.

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