JPH07216181A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in weather resistance, heat resistance and impact resistance by mixing a composition comprising a polycarbonate, a rubber-modified thermoplastic resin and a styrene resin with titanium oxide, zinc oxide or barium sulfate. CONSTITUTION:This resin composition is prepared by mixing 100 pts.wt., in total, 5-95wt.% aromatic polycarbonate, 95-5wt.% rubber-modified thermoplastic resin obtained by grafting an aromatic vinyl compound or an aromatic vinyl compound and a copolymerizable vinyl monomer with an aromatic vinyl compound in the presence of a rubbery polymer, and 0-90wt.% styrenic resin obtained by (co)polymerizing an aromatic vinyl compound or an aromatic vinyl compound and a copolymerizable vinyl monomer with an aromatic vinyl compound with 0.5-20 pts.wt. titanium oxide, and 0.5-10 pts.wt. zinc oxide and/or barium sulfate.

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 excellent weather resistance, heat resistance and impact resistance.

2. Description of the Related Art Rubber-reinforced styrene resins such as ABS are excellent in molding processability, impact resistance, surface appearance of molded products, etc. Although it is used, it has the drawback of insufficient heat resistance depending on the intended use. As an improvement of these drawbacks, there is an alloy material with a polycarbonate resin. Since this alloy material has an excellent balance of heat resistance and impact resistance,
Widely used mainly in the A equipment field. However, such an alloy material has a drawback that the weather resistance is poor when it is colored with titanium oxide as a pigment.

The present invention has been made against the background of the above-mentioned problems of the prior art, and is a thermoplastic resin composition which is excellent in weather resistance, heat resistance and impact resistance and can be used in a wide range of applications. The purpose is to provide.

[0002]

The present invention provides (A) 5 to 95% by weight of an aromatic polycarbonate, (B) an aromatic vinyl compound in the presence of a rubbery polymer, or an aromatic vinyl compound and an aromatic vinyl compound. Copolymerized with 95 to 5% by weight of a rubber-modified thermoplastic resin obtained by graft-polymerizing another vinyl monomer copolymerizable with (C) an aromatic vinyl compound or an aromatic vinyl compound and an aromatic vinyl compound. Styrene-based resin obtained by (co) polymerizing other possible vinyl monomers 0 to 90% by weight, the above (A) + (B) +
0.5 to 20 parts by weight of (D) titanium oxide and 0.5 to 10 parts by weight of (E) zinc oxide and / or barium sulfate are mixed with 100 parts by weight of component (C). A thermoplastic resin composition.

And (A) component (A) of claim 1
95% by weight, (B) component (B) of claim 1 95 to 5% by weight, (C) component (C) of claim 1 0 to 90% by weight, the above (A) + (B) + (C) (D) 0.5 to 20 parts by weight of the component (D) according to claim 1 with respect to 100 parts by weight of the component,
(F) A thermoplastic resin composition comprising 0.01 to 5 parts by weight of an alkali metal halide. Hereinafter, the present invention will be described in detail.

As the polycarbonate (A) used in the present invention, those obtained by the reaction of various dihydroxyaryl compounds with phosgene, or those obtained by the transesterification reaction of the dihydroxyaryl compound with diphenyl carbonate are mentioned. Can be mentioned.
A typical example is a polycarbonate obtained by the reaction of 2,2'-bis (4-hydroxyphenyl) propane and phosgene. Examples of the dihydroxyaryl compound used as a raw material for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-)
Methylphenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2 '
-Bis (4-hydroxy-3-bromophenyl) propane, 2,2'-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1, 1'-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4 '
-Dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4 '
-Dihydroxy-3,3'-dimethylphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfone, 4,
There are 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, hydroquinone, resorcin, and the like, and these are used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane {bisphenol A}.

The viscosity average molecular weight of the polycarbonate is preferably 15,000 to 40,000, more preferably 17,000 to 35,000. (A) of the present invention
The amount of component (A) used in component + (B) + (C) is 5
˜95% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight. If it is less than 5% by weight, the heat resistance is poor, and if it exceeds 95% by weight, the impact resistance is poor.

Examples of the rubbery polymer used as the component (B) of the present invention include polybutadiene, polyisoprene, butyl rubber, styrene-butadiene copolymer (styrene content of 5 to 60% by weight is preferable), styrene-isoprene. Copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α
-Olefin-polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer,
Examples thereof include hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene-based polymers, ethylene-based ionomers and the like. Further, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer include AB
Type, ABA type, taper type, and radial teleblock type structures are included. Further, the hydrogenated butadiene-based polymer is a hydride of the block copolymer of the styrene block and the styrene-butadiene random copolymer in addition to the hydride of the block copolymer, and the content of 1,2-vinyl bond in polybutadiene. Of 20% by weight or less and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight.

As the aromatic vinyl compound, styrene,
t-butylstyrene, α-methylstyrene, p-methylstyrene, civinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-P-aminoethylstyrene,
Examples include N, N-diethyl-P-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and the like, particularly styrene and α-methyl. Styrene is preferred. These aromatic vinyls may be used alone or in combination of two or more.

Other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, Octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, ethyl acrylate and other acrylates, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
Cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate, maleic anhydride, itaconic anhydride, acid anhydride group-containing unsaturated compounds such as citraconic anhydride, maleimide,
N-methylmaleimide, N-butylmaleimide, N-
Maleimide compounds of unsaturated dicarboxylic acids such as (P-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, unsaturated carboxylic acids such as acrylamide and methacrylamide. Amino group-containing unsaturated compounds such as acid amide, acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, hydroxystyrene, 3-hydroxy-
1-propene, 4-hydroxy-1-butene, cis-4
-Hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and other hydroxyl group-containing unsaturated compounds, acrylic acid , Unsaturated acids such as methacrylic acid, itaconic acid, maleic acid and the like, and oxazoline group-containing unsaturated compounds such as vinyl oxazoli, etc., and these may be used alone or in combination of two or more.

The preferred combinations of the monomer components polymerized in the presence of the rubbery polymer are listed below. 1) Aromatic vinyl compound / vinyl cyanide compound 2) Aromatic vinyl compound / (meth) acrylic acid ester 3) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester 4) Aromatic vinyl compound / maleimide Monomer 5) Aromatic vinyl compound / vinyl cyanide compound / maleimide monomer 6) Aromatic vinyl compound / (meth) acrylic acid ester / maleimide monomer 7) Aromatic vinyl compound / vinyl cyanide Compound / acid anhydride monomer 8) Aromatic vinyl compound / (meth) acrylic acid ester / acid anhydride monomer 9) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester / acid Anhydride monomer 10) Aromatic vinyl compound / maleimide monomer / acid anhydride monomer

The amount of the rubbery polymer in the component (B) of the present invention is preferably 5 to 80% by weight, more preferably 10 to 70% by weight from the viewpoint of impact resistance. The component (B) of the present invention can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization. The graft ratio in the graft copolymer is preferably 5 to 200% by weight, more preferably 10 to 150% by weight. Further, the intrinsic viscosity [η] (methyl ethyl ketone, measured at 30 ° C.) of the methyl ethyl ketone soluble component is preferably 0.2 to
1.2 dl / g, more preferably 0.3-0.8 dl
/ G.

The above-mentioned component (B) of the present invention is one kind or two kinds.
They can be used in combination of one or more species. In order to obtain a thermoplastic resin having excellent weather resistance, which is the object of the present invention, (B)
The preferred rubbery polymer of the component is a hydrogen compound of ethylene-α-olefin- (polyene) copolymer, silicone rubber, acrylic rubber, butadiene-based polymer. (B)
The amount of the component used is 95 to 5% by weight, preferably 90 to 10% by weight, more preferably 80 to 20% by weight in the component (A) + (B) + (C) of the present invention, and 95% by weight. If it exceeds 5, the heat resistance and impact resistance are inferior, and if it is less than 5% by weight, the impact resistance is inferior.

As the aromatic vinyl compound used in the component (C) of the present invention, all of those mentioned above are used. Further, as the other vinyl monomer copolymerizable with the aromatic vinyl compound, the above-mentioned ones are all used. The preferable combination of the monomers is the one described in the above-mentioned component (B), but the bonding mode includes a random copolymer and a block copolymer, and a preferable one of the block copolymer is styrene- Acrylonitrile copolymer, (meth) acrylic acid ester polymer and block copolymer (styrene-acrylonitrile copolymer has acrylonitrile content of 22 to 28 wt%), acrylonitrile content of 22 to 28 wt% styrene-acrylonitrile copolymer Polymer and acrylonitrile content 12-19
Examples include block copolymers of styrene-acrylonitrile copolymer in weight%. The method for producing the block copolymer includes a method using a polymeric peroxide, and specifically, it is specifically disclosed in JP-B-60-3327 and JP-B-63-3.
There is a method described in No. 40447. When the above block copolymer is blended in the range of 1 to 10% by weight of the present invention, the weather resistance is particularly excellent and the weld strength of the molded product is improved. The amount of component (C) used is (A) + (B) + of the present invention.
It is 0 to 90% by weight, preferably 0 to 80% by weight, more preferably 0 to 60% by weight, and particularly preferably 5 to 60% by weight in the component (C). If it exceeds 90% by weight, impact resistance and heat resistance are poor.

The titanium oxide which is the component (D) of the present invention is used as a white pigment, and the one having an average particle diameter of 0.2 to 3 μm is usually preferably used. Further, it is also possible to use fine particle titanium oxide having an average particle diameter of 0.1 μm or less. There are two types of titanium oxide, rutile type and anatase type, both of which can be used, but the rutile type is preferred for the purpose of obtaining a titanium oxide having more excellent whiteness. Titanium oxide is usually surface-treated. The surface treatment method is not particularly limited, but those treated with one kind or two or more kinds of silica, alumina, a coupling agent (silane type, titanate type, borane type, etc.), silicone oil and the like are used. Silica is a general formula SiO ₂
And alumina is Al ₂ O ₃ .X
H ₂ O, Al (OH) ₃ , Na ₂ O.11Al ₂ O ₃ ,
It is a compound represented by K ₃ O.11Al ₂ O ₃ .
The amount of component (D) used is (A) + (B) + (C) component 10
0.5 to 20 parts by weight, preferably 1 to 0 parts by weight
15 parts by weight, more preferably 1 to 10 parts by weight.
If the amount used is less than 0.5 part by weight, whiteness cannot be obtained, and if it exceeds 20 parts by weight, weather resistance and impact resistance are poor.

The zinc oxide as the component (E) preferably has an average particle diameter of 0.2 to 3 μm. Or zinc oxide whiskers are used. It is preferable to use zinc oxide whiskers in achieving the object of the present invention. As barium sulfate, those having an average particle diameter of 0.2 to 3 μ are preferable. It is also possible to use fine particles of zinc oxide or barium sulfate having an average particle diameter of 0.1 μm or less. Further, the above zinc oxide and barium sulfate can be used in combination. Further, it can be used after being treated with a usual surface treatment agent, and generally a coupling agent (silane type, titanate type, borane type, etc.) is used. The amount of component (E) used is (A)
0.5 to 1 per 100 parts by weight of + (B) + (C) component
It is 0 part by weight, more preferably 1 to 5 parts by weight. If the amount used is less than 0.5 parts by weight, the weather resistance will be poor, and if it exceeds 10 parts by weight, the impact resistance will be poor. For the purpose of improving the weather resistance, which is the object of the present invention, the preferred (D) / (E) ratio is
(D) / (E) = 90 to 10/10 to 90 is preferable.

Examples of the alkali metal halide which is the component (F) of the present invention include sodium chloride, lithium chloride,
Examples thereof include sodium bromide, potassium bromide, potassium iodide, sodium iodide, lithium iodide, and the like, and potassium iodide is particularly preferable. The amount of component (F) used is
It is 0.
The amount is 01 to 5 parts by weight, preferably 0.03 to 2 parts by weight. If it is less than 0.01 part by weight, the weather resistance is poor, and if it exceeds 5 parts by weight, no further improvement effect of the weather resistance is observed. When the component (F) is used in combination with the component (E), the weather resistance is further excellent. The component (F) may be blended in the thermoplastic resin composition of the present invention as it is, or may be blended by dissolving it in a solvent. As the solvent used here, both organic and inorganic solvents can be used, but an aqueous solution is preferable. When compounded in a solution, the effect of improving weather resistance is particularly large.

The thermoplastic resin composition of the present invention can be obtained by kneading the above-mentioned various components. As a kneading method, there is a method using an extruder, a roll, a Banbury mixer, a kneader or the like. A preferable method is a method using an extruder, and examples of the extruder include a single-screw extruder and a twin-screw extruder. When kneading various components using the above kneading method, all the components may be kneaded together, or some of the components may be kneaded first, and the remaining components may be added or kneaded together or separately. Good. When using the thermoplastic resin composition of the present invention, known colorants, pigments, lubricants, weathering agents, antistatic agents, antioxidants, flame retardants, heat aging inhibitors, plasticizers, antibacterial / antifungal agents are blended. can do.
Further, as the inorganic filler, glass fiber, carbon fiber, glass milled fiber, glass flake, glass beads,
There are glass balloons, calcium carbonate, mica, talc, rock filler, potassium titanate whiskers, metal fibers, magnesium sulfate, expanded graphite, graphite, kaolin, metal flakes, hydroxytalcite and the like. Also,
Other known polymers, such as PM, depending on the performance required
MA resin Polyamide, polybutylene terephthalate, polyethylene terephthalate, polypropylene, polyethylene, polysulfone, polyphenylene sulfide, PT
FE (polytetrafluoroethylene), polyvinylidene fluoride, polyamide elastomer, polyester elastomer, polyphenylene ether, polycaprorafton and the like can be appropriately blended and used. From the viewpoint of weather resistance, it is particularly preferable to add PMMA. The blending amount when these are blended is (A) + (B) + (C)
The total amount is 100 parts by weight or less, preferably 100 parts by weight or less, and more preferably 1 to 50 parts by weight. The thermoplastic resin composition of the present invention can be molded into various molded products by injection molding, sheet extrusion, vacuum molding, profile extrusion, injection press, foam molding, blow molding and the like. The molded products obtained by the above-mentioned various molding methods utilize various properties in the automobile field, various parts of home electric appliances, housings, miscellaneous goods, various parts in the field related to OA equipment, and housings and chassis by utilizing their excellent properties. It can be used for etc.

[0017]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various evaluations in the examples,
It is a value measured as follows. Each component was melt-kneaded with a twin-screw extruder at a cylinder set temperature of 210 to 250 ° C. to prepare pellets. After sufficiently drying with a dehumidifying dryer, a test piece for performance evaluation was prepared using an injection molding machine. The evaluation method is as follows. Weather resistance Sunshine weather meter Black panel temperature 6
The color change (ΔE) after 1000 hours at 3 ° C. and a rain cycle of 18 minutes / 120 minutes was measured. Izod impact strength 1/4 "thick according to ASTM D256, notched, measured at 23 ° C. Heat resistance 1/2" thick according to ASTM D648, load 1
The heat distortion temperature was measured at 8.6 kg / cm ² .

The following polymers are used as the component (A) of the present invention.
Using. Obtained by condensation polymerization of bisphenol A and phosgene. A polycarbonate having the following viscosity average molecular weight was used. A-1: Polycarbonate having a molecular weight of 21,000 A-2: Polycarbonate having a molecular weight of 25,000

Rubber material used for producing the component (B) of the present invention
Polymer rubbery polymer b-1: ethylene-propylene copolymer JSR EP84 manufactured by Japan Synthetic Rubber Co., Ltd. Rubbery polymer b-2: composed of polystyrene (5%) block and 80 parts of styrene and 80 parts of butadiene. Hydrogenation of an A-B-C type block copolymer consisting of a random copolymer block (90%) and a tapered block (5%) consisting of 5 parts of styrene and 3 parts of butadiene with gradually increasing styrene, with a hydrogenation rate of 99%. Diene polymer. Rubbery polymer b-3: from polystyrene (20%) block, polybutadiene block having a 1,2-vinyl content of 35% (55%), and polybutadiene block having a 1,2-vinyl content of 13% (25%) Hydrogenated diene polymer having a hydrogenation rate of 99% of the following ABC block copolymer

Rubbery polymer b-4: Dioctyl sulfosuccinate emulsifier was used as an emulsifier, n-butyl acrylate 100 parts, triallyl isocyanate 0.6 part as a cross-linking agent, and potassium persulfate was used as a polymerization initiator. Emulsion polymerization was performed. The particle size of the obtained acrylic rubber emulsion was 3000 angstrom. Rubbery polymer b-5: 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed, and 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved was mixed. The mixture was put in the inside, stirred for 3 minutes with a homomixer, and then emulsified and dispersed for 5 minutes with an ultrasonic disperser. The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 90 ° C. for 6 hours while stirring and mixing, and cooled at 5 ° C. for 48 hours to complete the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained modified polyorganosiloxane was 98.5%.
Met. The modified polyorganosiloxane latex was neutralized to pH 7 with an aqueous sodium carbonate solution to complete the condensation. The particle size of the silicone rubber emulsion obtained by the above method was 3000 Å. Preparation of component (B) of the present invention The results are shown in Table 1 in the presence of the above rubbery polymers b-1 to b-5.

[0021]

[Table 1]

Graft-polymerization of monomers to give polymers B-1 to B-1
B-7 was obtained. The polymers B-1, B-2, B-3,
B-4 was obtained by solution polymerization. Polymers B-5 and B-6 were obtained by emulsion polymerization.

Preparation of Component (C) of the Invention Polymers C-1 to C-3 are prepared by polymerizing various monomers by solution polymerization.
Got The results are shown in Table 2.

[0024]

[Table 2]

A titanium oxide surface-treated with silica and alumina having an average particle diameter of the component (D) of the present invention of 0.5 μm was used. Component (E) E-1 of the present invention : Barium sulfate having an average particle diameter of 1 μm and surface-treated with a silane coupling agent was used. E-2: Zinc oxide having an average particle diameter of 1 μm and surface-treated with a silane coupling agent was used. E-3: Zinc oxide Wiker Panatetra ^R manufactured by Matsushita Amtec Co., Ltd. was used. The component (F) of the present invention , potassium iodide, was used.

Examples 1 to 13 and Comparative Examples 1 to 5 Preparation of Thermoplastic Resin Composition The above components were mixed according to the formulation shown in Table 3, melt-kneaded using a twin-screw extruder, and pelletized. The obtained pellets were dried to a water content of 0.05% or less, and weather resistance (flat plate), heat resistance, impact resistance, and test specimens for measurement were molded by injection molding, and evaluated by the above evaluation method. The evaluation results are shown in Table 3.
In the formulation of this composition, TINUVIN P manufactured by Ciba-Geigy Co. was added as a weathering agent to all compositions of 1.5 PHR.

[0027]

[Table 3]

Comparative Example 1 is an example in which the amount of the component (E) used in the present invention was small outside the range of the invention, and the weather resistance was poor. Comparative Example 2 is an example in which the amount of the component (D) of the present invention used is large outside the range of the invention, and the weather resistance and impact resistance are poor. Comparative Example 3
Is an example in which the amount of the component (A) used in the present invention is large outside the range of the invention and the amount of the component (B) used is small outside the range of the invention, but the impact resistance is poor. Comparative Example 4 is an example in which the amount of the component (A) used in the present invention is small outside the range of the invention and the amount of the component (B) used is large outside the range of the invention, but the heat resistance and impact resistance are poor. . Comparative Example 5 is an example in which the amount of the component (F) of the present invention used is small outside the range of the invention, and the weather resistance is poor.

[0029]

The thermoplastic resin composition of the present invention is excellent in weather resistance, heat resistance and impact resistance, and has a wide range of applications, for example, interior / exterior parts of the vehicle field, various parts of home electric appliances, It is useful for housings, miscellaneous goods, various parts in OA equipment related fields, housings, chassis, and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C08L 25/02 LDW LEC 69/00 LPP

Claims (2)

[Claims] 1. (A) Aromatic polycarbonate 5 to 95
% Rubber, (B) A rubber-modified thermoplastic obtained by graft-polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer. Resin 95-5% by weight, (C)
Aromatic vinyl compound or 0 to 90% by weight of a styrene-based resin obtained by (co) polymerizing an aromatic vinyl compound and an aromatic vinyl compound and another copolymerizable vinyl monomer, (A) + ( (B) + (C) component 100 parts by weight, (D) titanium oxide 0.5 to 20 parts by weight, (E) zinc oxide and / or barium sulfate 0.5 to 10 parts by weight. A thermoplastic resin composition comprising: 2. (A) 5 to 95% by weight of the (A) component of claim 1, (B) 95 to 5% by weight of the (B) component of claim 1,
(C) 0 to 90% by weight of the (C) component of claim 1, and (D) 0.5 of the (D) component of claim 1 with respect to 100 parts by weight of the (A) + (B) + (C) component. ~ 20 parts by weight,
(F) A thermoplastic resin composition comprising 0.01 to 5 parts by weight of an alkali metal halide.