JP2005132987A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which excels in both impact resistance and weatherability and has low gas generating properties. <P>SOLUTION: The thermoplastic resin composition comprises 1-99 pts. mass graft copolymer (A) obtained by grafting a vinyl polymer on to a composite rubbery polymer (R) comprising a polyorganosiloxane (S) and a poly(meth)acrylic ester (M) comprising a (meth)acrylic ester monomer unit and 99-1 pt. mass thermoplastic resin (B) other than the graft copolymer (A) (provided that the sum of the graft copolymer (A) and the thermoplastic resin (B) is taken as 100 pts. mass), and 0.1-10 pts. mass sum of a hindered amine light stabilizer (X) and an ultraviolet absorber (Y) having a molecular weight of ≥300. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition that is excellent in impact resistance and weather resistance and has a small amount of gas generation during molding, and a molded product thereof.

Improving the impact resistance and weather resistance of resin materials is extremely useful industrially because it enables applications to be expanded and the thickness and size of molded products to be reduced. I came.
For example, ABS resin, high-impact polystyrene resin, modified PPE resin, MBS resin, reinforced polyvinyl chloride resin, etc. have been put to practical use as materials with improved impact resistance by blending hard resin with rubbery polymer. Has been. Among them, as a material having good weather resistance in addition to impact resistance, a resin using a saturated rubber such as a (meth) acrylic acid alkyl ester rubber as a rubbery polymer, specifically, ASA which is a weather resistant ABS resin Resins and the like have been proposed, and have been used in outdoor electrical equipment such as exterior parts for vehicles, vending machines, casing parts for radio relay stations, and the like.
Further, as means for improving impact resistance at low temperatures, it has been proposed to use a composite rubber of polyorganosiloxane and alkyl (meth) acrylate as a rubbery polymer (see, for example, Patent Documents 1 to 3). ). Furthermore, as a means to improve weather resistance and pigment colorability, it has also been proposed to blend a graft polymer containing a composite rubber of polyorganosiloxane and alkyl (meth) acrylate and a (meth) acrylic ester polymer. (For example, see Patent Documents 4 to 6).
Japanese Patent Laid-Open No. 01-190746 Japanese Patent Laid-Open No. 01-282239 Japanese Patent Laid-Open No. 06-025492 Japanese Patent Laid-Open No. 08-283524 JP 2000-186182 A JP 2001-316559 A

However, in recent years, properties required for materials have become increasingly severe, and it has become impossible to cope with the prior thermoplastic resin compositions. Specifically, the requirement for weather resistance is particularly strict, and in order to meet this demand, light stabilizers are widely blended. However, bleed-out and gas generation are caused at the time of molding, and these may adhere to the molded product and impair the design.
Then, this invention is made | formed in view of this situation, and it aims at providing the thermoplastic resin composition which is excellent in impact resistance and a weather resistance, and has low gas generation property, and its molded article. .

The thermoplastic resin composition of the present invention is a composite rubber-like polymer (R) containing polyorganosiloxane (S) and poly (meth) acrylate ester (M) containing a (meth) acrylate monomer unit. 1) to 99 parts by mass of a graft copolymer (A) grafted with a vinyl polymer,
99 to 1 part by mass of other thermoplastic resins (B) other than the graft copolymer (A) (provided that the total of the graft copolymer (A) and the thermoplastic resin (B) is 100 parts by mass). ,
It contains a hindered amine light stabilizer (X) and a UV absorber (Y) having a molecular weight of 300 or more in total of 0.1 to 10 parts by mass.

  In the present invention, the thermoplastic resin (B) includes polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N. -Substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene- At least one selected from the group consisting of methyl methacrylate terpolymer, modified polyphenylene ether (modified PPE resin), and polyamide is preferred.

As the hindered amine light stabilizer (X), a hindered amine light stabilizer in which nitrogen of the piperidine skeleton is substituted with an alkyl group is preferable.
The thermoplastic resin composition of the present invention contains a light stabilizer (X1) having a molecular weight of less than 1000 and a light stabilizer (X2) having a molecular weight of 1000 or more as the hindered amine light stabilizer (X). The mass ratio ((X1) / (X2)) is particularly preferably 1/5 to 5/1.
As the ultraviolet absorber (Y), a benzotriazole-based compound is preferable, and a compound having two or more benzotriazole skeletons in the molecule is particularly preferable.

  The molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention into a sheet or the like.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which improved the weather resistance can be provided, providing favorable impact resistance and low gas generating property. The balance of impact resistance, weather resistance, and low gas generation in the thermoplastic resin composition of the present invention is at a very high level that could not be achieved by a conventionally known thermoplastic resin composition, and the thermoplasticity of the present invention. The utility value of the resin composition and its molded product as various industrial materials is extremely high.

Hereinafter, the present invention will be described in detail.
"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention comprises a specific graft copolymer (A), another thermoplastic resin (B), a specific light stabilizer (X), and an ultraviolet absorber (Y). Is.

{Graft Copolymer (A)}
The graft copolymer (A) is a composite rubber-like polymer (R) containing a polyorganosiloxane (S) and a poly (meth) acrylate ester (M) containing a (meth) acrylate monomer unit. In addition, a vinyl polymer is grafted.

<Polyorganosiloxane (S)>
Although there is no restriction | limiting in particular as polyorganosiloxane (S), The polyorganosiloxane containing a vinyl polymerizable functional group is preferable, and especially dimethylsiloxane unit 97-99.7 mol% and vinyl polymerizable functional group containing siloxane unit 0 A polyorganosiloxane comprising 3 to 3 mol% and having 3 or more siloxane bonds in an amount of 1 mol% or less with respect to all silicon atoms in the polyorganosiloxane is preferred.

  The dimethylsiloxane unit constituting the polyorganosiloxane (S) is preferably a three-membered or higher dimethylsiloxane-based cyclic body, and particularly preferably a 3- to 7-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

  The vinyl polymerizable functional group-containing siloxane unit is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethyl siloxane via a siloxane bond, but the reactivity with dimethyl siloxane is considered. Then, the various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane; And mercaptosiloxanes such as methylsilane and γ-mercaptopropyltrimethoxysilane. . These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

  The polyorganosiloxane (S) may contain a siloxane-based crosslinking agent as a constituent component. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The polyorganosiloxane (S) can be produced, for example, as follows.
First, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and vinyl polymerizable functional group-containing siloxane as necessary, and then emulsified using an emulsifier and water to obtain a siloxane mixture latex.
Next, the siloxane mixture latex is made into fine particles by using a homomixer that makes fine particles by a shearing force generated by high-speed rotation, a homogenizer that makes fine particles by a jet output from a high-pressure generator, or the like. In this step, since the particle size distribution of the polyorganosiloxane (S) latex can be reduced, it is particularly preferable to use a high-pressure emulsifier such as a homogenizer.
Next, the finely divided siloxane mixture latex is put into an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. After the polymerization reaction has sufficiently progressed, the reaction solution is cooled, and further neutralized with an alkaline substance such as caustic soda, caustic potash, sodium carbonate or the like to stop the polymerization, and polyorganosiloxane (S) is obtained.

  Examples of emulsifiers suitable for use in the production of polyorganosiloxane (S) include anionic emulsifiers. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferable. These emulsifiers are used in the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture.

  Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among these, aliphatic substituted benzene sulfonic acid is preferable and n-dodecyl benzene sulfonic acid is particularly preferable because of its excellent stabilizing effect on the polyorganosiloxane (S) latex. Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the effect of the emulsifier used in the polyorganosiloxane (S) latex on the color and the like of the molded product can be minimized. .

The mass average particle diameter of the polyorganosiloxane (S) is not particularly limited, but is preferably less than 100 nm, more preferably less than 90 nm, from the viewpoint of improving pigment colorability of the resulting thermoplastic resin composition. Particularly preferred is less than 80 nm. Further, in the production process, it is possible to prevent an increase in the viscosity of latex and generation of agglomerates (coagulum), so that the mass average particle diameter is preferably 10 nm or more, more preferably 20 nm or more, and 30 nm or more. Is particularly preferred.
In addition, the particle diameter of polyorganosiloxane (S) can be controlled by the method described in Unexamined-Japanese-Patent No. 5-279434, for example.

  The content of the polyorganosiloxane (S) in the composite rubbery polymer (R) is not particularly limited, but is preferably 1 to 99% by mass, more preferably 2 to 80% by mass, It is especially preferable that it is 50 mass%. By setting the polyorganosiloxane (S) content within such a range, a thermoplastic resin composition having more excellent impact resistance and molded appearance can be obtained.

<Poly (meth) acrylic acid ester (M)>
The poly (meth) acrylic acid ester (M) constituting the composite rubber-like polymer (R) contains a (meth) acrylic acid ester monomer unit, a crosslinking agent and / or a graft crossing agent. is there.

  Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, acrylic acid n-propyl, acrylic acid n-butyl, acrylic acid alkyl esters such as 2-ethylhexyl acrylate, and methacrylic acid. And methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Among these, n-butyl acrylate is preferable because the resulting resin composition has excellent impact resistance.

Examples of the graft crossing agent include allyl compounds, and specific examples thereof include allyl methacrylate, triallyl cyanurate and triallyl isocyanurate. Examples of the cross-linking agent include dimethacrylate compounds, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. . By using such a crosslinking agent and / or graft crossing agent, the pigment colorability of the resulting thermoplastic resin composition can be improved.
The lower limit of the total amount of the crosslinking agent and / or the grafting agent is preferably from the viewpoint of pigment colorability of the thermoplastic resin composition with respect to 100% by mass of the (meth) acrylic acid ester monomer unit. 1% by mass, more preferably 0.2% by mass, and particularly preferably 0.5% by mass. In addition, the upper limit is set to 100% by mass of (meth) acrylic acid ester monomer units from the viewpoint of reducing agglomerates (coagulum) during the production of the composite rubber-like polymer (R) and the graft copolymer (A). On the other hand, it is preferably 5% by mass, more preferably 3% by mass, and particularly preferably 2% by mass.

<Composite rubbery polymer (R)>
The production method of the composite rubber polymer (R) is not particularly limited. For example, the polyorganosiloxane (S) latex and the poly (meth) acrylate (M) latex produced individually are hetero-aggregated or co- enlarged. And a method in which the other polymer is produced and combined in the presence of either one of a polyorganosiloxane (S) latex and a poly (meth) acrylate (M) latex.
Among them, since the resulting thermoplastic resin composition is more excellent in impact resistance and pigment colorability, in the presence of the polyorganosiloxane (S) latex, a (meth) acrylate monomer and a crosslinking agent and / or Or the method of carrying out emulsion polymerization of the monomer mixture containing a graft crossing agent is preferable.

Suitable emulsifiers used in the above production method include, for example, sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, palmitic acid, or sodium lauryl sulfate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate. And sodium alkyldiphenyl ether disulfonate. Among these, an acid emulsifier having two or more functional groups in one molecule or a salt thereof is preferable because it can further suppress gas generation during molding of the thermoplastic resin composition.
Furthermore, among the acid type emulsifiers having two functional groups in one molecule, dipotassium alkenyl succinate or sodium alkyldiphenyl ether disulfonate is preferable. Particularly, sulfuric acid is added to coagulate the composite rubber polymer (R) from the latex. From the viewpoint of easy recovery, dipotassium alkenyl succinate is more preferable. Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate. These can be used alone or in combination of two or more.

<Graft part>
The vinyl polymer that forms the graft portion of the graft copolymer (A) is not particularly limited as long as it is a hard polymer at room temperature, but the resulting resin composition has impact resistance, rigidity, heat resistance, and weather resistance. And at least one selected from a vinyl cyanide monomer, an aromatic vinyl monomer, and a (meth) acrylate monomer because it is excellent in one or more items of molding processability and dimensional stability. Those composed of one kind of monomer are preferred.
Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene and the like. Specific examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and the like. Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like. Among these monomers, those composed of monomers containing styrene and acrylonitrile are particularly preferred because the resulting graft copolymer (A) has excellent thermal stability.

  In the graft copolymer (A), the content ratio of the composite rubber-like polymer (R) and the vinyl polymer forming the graft portion is not particularly limited, but is excellent in impact resistance and pigment colorability. Since the composition is obtained, the former content is preferably 20 to 80% by mass, and the latter content is preferably 80 to 20% by mass, and the former content is 25 to 75% by mass and the latter content. Is more preferably 75 to 25% by mass, particularly preferably the former content is 30 to 70% by mass and the latter content is 70 to 30% by mass.

<Production of graft copolymer (A)>
The graft copolymer (A) can be produced, for example, by emulsion graft polymerization. Specifically, it can be produced by a known radical polymerization technique in the presence of an emulsifier in the presence of an emulsifier by adding a monomer constituting the graft portion to the composite rubber-like polymer (R) latex. At this time, various chain transfer agents may be added to the monomer solution to be added in order to control the graft ratio and the molecular weight of the graft component.

Suitable radical polymerization initiators for use in the polymerization include peroxides, azo initiators, redox initiators in which these are further combined with an oxidizing agent / reducing agent, and the like. Among these, redox initiators are preferable, and redox initiators that combine ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, hydroperoxide are particularly preferred. Agents are preferred.
There is no restriction | limiting in particular as an emulsifier, The emulsifier illustrated for manufacture of a composite rubber-like polymer (R) can be utilized. In addition, it is also possible to use the emulsifier used for manufacture of composite rubber-like polymer (R) as it is, without adding an emulsifier before a graft polymerization process.

  As a method for recovering the graft copolymer (A) from the graft copolymer (A) latex obtained by emulsion graft polymerization, the latex is put into hot water in which a coagulant is dissolved, and then in a slurry state. A method of coagulating and recovering (wet method), a method of spraying the latex in a heated atmosphere to recover the graft copolymer (A) semi-directly (spray drying method), and the like.

Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. The coagulant is selected in consideration of the emulsifier used in the polymerization. That is, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as the emulsifier, the graft copolymer (A) can be recovered using any coagulant, but sodium alkylbenzene sulfonate, etc. In the case where an emulsifier exhibiting a stable emulsifying power is contained even in the acidic region, it is necessary to use a metal salt as a coagulant because the inorganic acid cannot be sufficiently recovered.
In the wet method, in order to obtain a dry graft copolymer (A) from the slurry of the graft copolymer (A), for example, the emulsifier residue remaining in the graft copolymer (A) is eluted in water and washed. Then, the slurry may be dehydrated with a centrifugal or press dehydrator, and then dried with an air dryer or the like. By such a method, a powder or particulate dry graft copolymer (A) is obtained. In addition, dehydration and drying can be simultaneously performed using a press dehydrator or an extruder. Moreover, without recovering the graft copolymer (A) discharged from the press dehydrator or the extruder, the graft copolymer (A) is directly supplied to an extruder or a molding machine for producing the thermoplastic resin composition to produce a molded product. Is also possible.

{Thermoplastic resin (B)}
In the present invention, the other thermoplastic resin (B) used in combination with the above graft copolymer (A) is not particularly limited, and examples thereof include polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile. -Styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene Styrene elastomers such as terephthalate (PET resin), polyolefins such as polyvinyl chloride, polyethylene, polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS) ,each Olefin-based elastomers, various polyester-based elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate terpolymer, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene -Vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resin, polyamide resin (nylon) and the like. These can be used singly or in combination of two or more according to the purpose.

  Among them, since the obtained resin composition satisfies two or more items among impact resistance, rigidity, heat resistance, weather resistance, molding processability and dimensional stability at the same time, polymethyl methacrylate, acrylonitrile-styrene Copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene Terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate terpolymer, modified polyphenylene ether (modified PPE resin), polyamide resin Preferably, in addition, polymethacrylic acid methyl methacrylate , Acrylonitrile - styrene copolymer (AS resin), acrylonitrile - styrene - methyl methacrylate terpolymer, and the like are particularly preferable.

 In the present invention, as the thermoplastic resin (B), the resin exemplified above and another graft rubber copolymer different from the graft copolymer (A) can be used in combination. Other graft rubber copolymers include ABS resin and MBS resin. Moreover, although the compounding quantity is not specifically limited, It is preferable to set it as 0-50 mass parts with respect to 100 mass parts of total amounts of a thermoplastic resin (B).

{Light stabilizer (X) and UV absorber (Y)}
In the present invention, in order to improve the weather resistance while ensuring good impact resistance, the above-mentioned graft copolymer (A) and other thermoplastic resin (B) are added with a specific light stabilizer (X) and An ultraviolet absorber (Y) is blended.

Specifically, a hindered amine light stabilizer is used as the light stabilizer (X).
The hindered amine light stabilizer (X) is not particularly limited, and examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6, -tetramethyl- 4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) sebacate , Dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3 , 5-Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] n-butyl malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1 2,3,4-butanetetracarbosylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarbosylate, poly [[6- ( 1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [ [2,2,6,6-tetramethyl-4-piperidyl] imino]], 2,2,6,6-tetramethyl-4-piperidinol (N-methyl) and a mixture of tridecyl alcohol and 1,2, Condensates with 3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2, 3,4-bu Tetracarboxylic acid, 2,2-bis (hydroxymethyl-1,3-propanediol), 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl-4-piperidinol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl) A polycondensate of -4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine is preferably used. Or a combination of two or more It can be used.

  Among these, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl) are superior in weather resistance in the high energy accelerated weathering test. -1 (octyloxy) -4-piperidyl) sebacate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis (1,2,2,6 , 6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] n-butyl malonate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarbosylate, 2,2,6,6-tetramethyl-4-piperidinol (N-methyl) and tridecyl alcohol Condensate of the mixture with 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,3,4-butanetetracarboxylic acid and 2 , 2-bis (hydroxymethyl-1,3-propanediol), 3-hydroxy-2,2-dimethylpropanal and 1,2,2,6,6-pentamethyl-4-piperidinol, N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine-2 -Yl) -4,7-diazadecane-1,10-diamine, N, N′-1,2-ethanediyl-bis (1,3-propanediamine) and N-butyl-2,2,6,6-tetra Methyl-4-piperidineamine and 2,4 It is preferable that the nitrogen of the piperidine skeleton such as a condensate with 1,6-trichloro-1,3,5-triazine is sealed with an alkyl group.

 Since the hindered amine light stabilizer (X) is excellent in weather resistance in the high energy accelerated weathering test, the hindered amine light stabilizer (X1) having a molecular weight of less than 1000 and a hindered amine light stabilizer having a molecular weight of 1000 or more ( X2) is preferably used in combination. Furthermore, the mass ratio ((X1) / (X2)) of the hindered amine light stabilizer (X1) having a molecular weight of less than 1000 to the hindered amine light stabilizer (X2) having a molecular weight of 1000 or more should be 1/5 to 5/1. Is preferable, and it is particularly preferable to set to 1/2 to 2/1.

The hindered amine light stabilizer (X1) having a molecular weight of less than 1000 is not particularly limited. Among the hindered amine light stabilizers (X) exemplified above, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] n-butylmalonate, tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarbosylate, 1,2,2,6,6-pentamethyl-4-piperidylmethacrylate Doors and the like.
The hindered amine light stabilizer (X2) having a molecular weight of 1000 or more is not particularly limited. Among the hindered amine light stabilizers (X) exemplified above, 2,2,6,6-tetramethyl-4-piperidinol (N -Methyl) and a tridecyl alcohol mixture and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,3, 4-butanetetracarboxylic acid, 2,2-bis (hydroxymethyl-1,3-propanediol), 3-hydroxy-2,2-dimethylpropanal and 1,2,2,6,6-pentamethyl-4- Condensate with piperidinol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4- Il Amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, N, N′-1,2-ethanediyl-bis (1,3-propanediamine) and N-butyl-2,2 , 6,6-tetramethyl-4-piperidineamine and 2,4,6-trichloro-1,3,5-triazine condensate and the like.
The combination of the hindered amine light stabilizer (X1) having a molecular weight of less than 1000 and the hindered amine light stabilizer (X2) having a molecular weight of 1000 or more is not particularly limited. For example, bis (2,2,6,6-tetramethyl-4 -Piperidyl) sebacate, 1,2,3,4-butanetetracarboxylic acid, 2,2-bis (hydroxymethyl-1,3-propanediol), 3-hydroxy-2,2-dimethylpropanal and 1,2 A combination with a condensate with 2,6,6-pentamethyl-4-piperidinol is particularly suitable.

In the present invention, an ultraviolet absorber having a molecular weight of 300 or more is used as the ultraviolet absorber (Y). Thereby, weather resistance can be improved while suppressing bleeding out and gas generation at the time of molding of the thermoplastic resin composition.
Examples of the ultraviolet absorber (Y) having a molecular weight of 300 or more include 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5-di-t-butylphenyl) benzotriazole, 2- (2' -Hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimi Di (methyl) phenol, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2-methylenebi [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid 3 Hydrate, 2-hydroxy-4-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2 ′, 4′-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, 2′-ethylhexyl 2-cyano-3,3-diphenyl acrylate, bis (5-ben Yl-4-hydroxy-2-methoxyphenyl) methane, and the like. These can be used alone or in combination of two or more.

 Among them, benzotriazole-based compounds are preferable because the resulting thermoplastic resin composition has excellent weather resistance, and particularly excellent in bleed-out resistance, so that the molecule has two or more benzotriazole skeletons. Benzotriazole compounds, specifically 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and the like are preferable.

In this invention, since the compounding quantity of a hindered amine light stabilizer (X) and a ultraviolet absorber (Y) is excellent in the weather resistance in a high energy accelerated weathering test, 100 mass parts of resin components (graft copolymer (A ) And other thermoplastic resins (B) in a total of 100 parts by mass). Moreover, it is preferable to make it 0.15 to 6 parts by mass because it suppresses the occurrence of eyes when extruding the thermoplastic resin composition, and it can reduce defects due to die adhesion and gas generation during the injection molding process. 0.2 to 4 parts by mass is particularly preferable.
When at least one of the hindered amine light stabilizer (X) and the ultraviolet absorber (Y) is blended, a certain degree of weather resistance improvement effect can be obtained, but by using these together, it is remarkable in the high energy accelerated weathering test. The effect of improving weather resistance is obtained. In particular, since a high weather resistance improvement effect is obtained, the hindered amine light stabilizer (X) and the ultraviolet absorber (Y) are mixed at a mass ratio ((X) / (Y)) of 1/3 to 10/1. It is particularly preferable to use it in combination.

{Other ingredients}
In addition to the above essential components (graft copolymer (A), thermoplastic resin (B), light stabilizer (X), and ultraviolet absorber (Y)), the thermoplastic resin composition of the present invention contains Various additives may be blended as necessary within the scope not departing from the gist of the invention.
Other additives specifically include dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers, and the like.

{Preparation of thermoplastic resin composition}
The thermoplastic resin composition of the present invention includes, for example, a graft copolymer (A), a thermoplastic resin (B), a light stabilizer (X), an ultraviolet absorber (Y), and various types as necessary. Additives are mixed and dispersed with a V-type blender or Henschel mixer, and the resulting mixture is prepared by melt-kneading using an extruder, a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like. it can.

"Molding"
By molding the thermoplastic resin composition of the present invention, the molded article of the present invention is obtained.
Examples of the molding method include various known molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. Further, the thermoplastic resin composition of the present invention and other materials can be combined to form a molded product by coating the thermoplastic resin composition of the present invention with another resin or metal. Although it does not specifically limit as base resin which coat | covers the thermoplastic resin composition of this invention, For example, resin modified as a thermoplastic resin (B), rubber modified thermoplastic resins, such as ABS resin and high impact polystyrene, vinyl chloride type resin Specific examples include thermosetting resins such as phenol resins and melamine resins. By these molding methods, a molded product subjected to primary processing (a profile extrusion molded product, a sheet-shaped molded product, a multilayer sheet molded product with other resin or metal, etc.) can be obtained. Moreover, it can utilize for various uses by performing thermoforming, vacuum forming, etc. with respect to the molded article which gave the primary process.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following examples, unless the summary is exceeded. In the following examples, “%” and “part” are based on mass unless otherwise specified.

Production Example 1 Production of Polyorganosiloxane (S-1) Latex 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this, an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of water was added, stirred for 2 minutes at 10,000 rpm with a homomixer, and then passed once through the homogenizer at a pressure of 20 MPa, A stable premixed organosiloxane latex was obtained.
Further, 10 parts of dodecylbenzenesulfonic acid and 90 parts of water were put into another reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, and a 10% aqueous solution of dodecylbenzenesulfonic acid was added. Prepared. While the aqueous solution was heated to 85 ° C., the previously prepared premixed organosiloxane latex was dropped and polymerized over 4 hours, and after the completion of dropping, the temperature was maintained for 1 hour and then cooled. Next, this reaction product was neutralized with an aqueous caustic soda solution to obtain a polyorganosiloxane (S-1) latex.
The obtained latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. The mass average particle diameter of the polyorganosiloxane (S-1) particles in the latex was 50 nm.

(Production Example 2) Production of polyorganosiloxane (S-2) latex 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts of tetraethoxysilane were mixed. As a result, 100 parts of a siloxane mixture was obtained. An aqueous solution consisting of 1 part of dodecylbenzenesulfonic acid, 1 part of sodium dodecylbenzenesulfonate, and 200 parts of water was added thereto, stirred for 2 minutes at 10,000 rpm with a homomixer, and then subjected to a pressure of 20 MPa in the homogenizer. 1 to obtain a stable premixed organosiloxane latex.
The premixed organosiloxane latex was placed in a reactor equipped with a cooling tube, a jacket heater and a stirring device, polymerized by heating at 80 ° C. for 5 hours with stirring and mixing, and then cooled to about 20 ° C. Allowed to stand for 48 hours. Next, this reaction product was neutralized to pH 7.0 with an aqueous caustic soda solution to complete the polymerization, and a polyorganosiloxane (S-2) latex was obtained.
When the solid content of the obtained latex was determined in the same manner as in Production Example 1, it was 36.5%. Moreover, the mass average particle diameter of the polyorganosiloxane (S-2) particles in the latex was 160 nm.

Production Example 3 Production of Composite Rubber Polymer (R-1) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirrer, polyorganosiloxane (S-1 ) 16 parts of latex (based on solid content), 0.4 part of polyoxyethylene alkylphenyl ether sulfate (“Emar NC-35” manufactured by Kao Corporation) and 297 parts of ion-exchanged water were added and mixed. Next, the following monomer mixture was added to the reactor.
<Monomer mixture>
N-butyl acrylate 84 parts allyl methacrylate 0.6 parts 1,3-butylene glycol dimethacrylate 0.2 parts t-butyl hydroperoxide 0.22 parts The internal temperature was raised to 60 ° C., and when the temperature reached 60 ° C., a redox aqueous solution having the following composition was added to initiate radical polymerization.
<Redox aqueous solution>
Ferrous sulfate heptahydrate 0.00015 parts
Ethylenediaminetetraacetic acid disodium salt 0.00045 parts Rongalite 0.4 parts Ion-exchanged water 20 parts Due to polymerization of the acrylate component, the liquid temperature rose to 78 ° C. This state is maintained for 1 hour to complete the polymerization of the acrylate component, and a latex of a composite rubber-like polymer (R-1) of polyorganosiloxane (S-1) having a mass average particle size of 120 nm and butyl acrylate rubber is prepared. Obtained.

(Production Example 4) Production of composite rubber-like polymer (R-2) Polyorganosiloxane (S-1) latex was changed to polyorganosiloxane (S-2) latex, and the final solid content was composite rubber-like heavy A polyorganosiloxane (S-2) having a mass average particle diameter of 190 nm, butyl acrylate rubber, and the like, except that the amount of ion-exchanged water was changed to be the same as that of the union (R-1) latex A latex of composite rubber-like polymer (R-2) was obtained.

(Production Example 5) Production of Graft Copolymer (A-1) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirring device, the following rubber mixture was stirred. After mixing, the internal temperature was raised to 70 ° C.
<Rubber mixture>
50 parts of composite rubber-like polymer (R-1) latex (based on solid content)
Ion-exchanged water (including water in (R-1) latex) 210 parts Dipotassium alkenyl succinate 0.5 part Rongalite 0.15 part Thereafter, the following first monomer mixture was added dropwise over 30 minutes. Polymerization was started and held for 15 minutes.
<First monomer mixture>
Acrylonitrile 3 parts Styrene 9 parts t-Hydroperoxide 0.1 part Furthermore, the redox aqueous solution of the following composition was added.
<Redox aqueous solution>
Rongalite 0.15 parts Ferrous sulfate heptahydrate 0.001 parts Ethylenediaminetetraacetic acid disodium salt 0.003 parts Water 5 parts Subsequently, the following second monomer mixture was added dropwise over 120 minutes to polymerize. And kept at 70 ° C. for 30 minutes.
<Second monomer mixture>
Acrylonitrile 9.5 parts Styrene 28.5 parts t-Hydroperoxide 0.3 parts Thereafter, the content was cooled to obtain a graft copolymer (A-1) latex.
The obtained latex was charged into a 1.4% amount of 1.2% aluminum sulfate aqueous solution at 50 ° C. while stirring the aqueous solution. The temperature was raised to 70 ° C. and held for 5 minutes, and further raised to 90 ° C. and held for 5 minutes. The slurry thus obtained was repeatedly dehydrated and washed, and finally dried overnight under an air stream to obtain a white powdered graft copolymer (A-1).

Production Example 6 Production of Graft Copolymer (A-2) Production Example 5 except that the composite rubber-like polymer (R-1) latex was changed to the composite rubber-like polymer (R-2) in Production Example 5. In the same manner as in No. 5, a graft copolymer (A-2) was obtained.

(Production Example 7) Production of vinyl-based copolymer (B-1) Composed of 99 parts of methyl methacrylate and 1 part of methyl acrylate, N, N-dimethylformamide solution (100ml solution of polymer 0.2g) An acrylic resin (B-1) having a reduced viscosity (measured temperature: 25 ° C.) of 0.25 dl / g was produced by a known suspension polymerization.
(Production Example 8) Production of vinyl copolymer (B-2) Composed of 7 parts of acrylonitrile, 23 parts of styrene and 70 parts of methyl methacrylate, N, N-dimethylformamide solution (concentration is the same as in Production Example 7) An acrylonitrile-styrene-methyl methacrylate terpolymer (B-2) having a reduced viscosity (measurement temperature of 25 ° C.) of 0.38 dl / g was produced by a known suspension polymerization.
(Production Example 9) Production of vinyl copolymer (B-3) Reduced viscosity (measurement temperature: 25) consisting of 29 parts of acrylonitrile and 71 parts of styrene and having an N, N-dimethylformamide solution (the concentration is the same as in Production Example 7). An acrylonitrile-styrene copolymer (B-3) having a (° C.) of 0.60 dl / g was produced by a known suspension polymerization.

(Examples 1-9, Comparative Examples 1-4) Manufacture of a thermoplastic resin composition The graft copolymers (A-1) and (A-2) manufactured as described above, and a vinyl copolymer (B -1) to (B-3), a hindered amine light stabilizer (X), and an ultraviolet absorber (Y) were blended in the composition shown in Table 1, and mixed by a Henschel mixer. At that time, 0.3 part of barium stearate and 0.4 part of ethylenebisstearylamide were also blended. Subsequently, the obtained mixture was supplied to a deaeration type extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) heated to 260 ° C. and kneaded to obtain pellets of a thermoplastic resin composition.

The following compounds were used as the hindered amine light stabilizer (X) and the ultraviolet absorber (Y).
"Hindered amine light stabilizer (X)"
<Hindered amine light stabilizer (X1) having a molecular weight of less than 1000>
(X1-1):
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate molecular weight 481
(Hydrogen) hindered amine light stabilizer in which nitrogen of piperidine skeleton is not substituted with alkyl group <hindered amine light stabilizer (X2) having a molecular weight of 1000 or more>
(X2-1):
1,2,3,4-butanetetracarboxylic acid, 2,2-bis (hydroxymethyl-1,3-propanediol), 3-hydroxy-2,2-dimethylpropanal and 1,2,2,6 Condensate with 6-pentamethyl-4-piperidinol Molecular weight about 2000
Hindered amine light stabilizer (X2-2) in which the nitrogen of the piperidine skeleton is substituted with a methyl group:
N, N′-1,2-ethanediyl-bis (1,3-propanediamine), N-butyl-2,2,6,6-tetramethyl-4-piperidineamine and 2,4,6-trichloro-1 Condensate with 1,3,5-triazine Molecular weight about 3000
A hindered amine light stabilizer in which the nitrogen of the piperidine skeleton is substituted with a butyl group

"Ultraviolet absorber (Y)"
(Y-1):
2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]
Molecular weight 659
(Y-2):
2- (2′-Hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole Molecular weight 315
(Z-1):
2- (2′-Hydroxy-5′-methylphenyl) benzotriazole molecular weight 225

(Evaluation test)
The following evaluation was performed about the obtained thermoplastic resin composition.
(i) Charpy impact strength In accordance with ISO 179, a test piece with a notch was used, and the test piece was left to stand for 12 hours or more in an atmosphere at 23 ° C., and then measured.
(ii) Weather resistance test 3 parts of titanium oxide added to the composition shown in Table 1 and colored in white was molded into a plate of 100 mm x 100 mm x 3 mm, and a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) ), The black panel temperature was 63 ° C., the cycle condition was 60 minutes (rainfall: 12 minutes), and the treatment was performed for 1,000 hours. Before and after the treatment, each was measured using a color difference meter (spectral colorimeter CM-508d manufactured by Minolta Camera Co., Ltd.), and the degree of color change (ΔE) was calculated.
(iii) Gas generation during molding Occurs when molten resin is flowed down using an injection molding machine “J85-ELII” manufactured by Nippon Steel Works under the conditions of a cylinder set temperature of 280 ° C. and an injection speed of 50%. The gas generating property was evaluated by visually observing the amount of smoke. The criteria for judgment were as follows.
○: Low smoke, △: Medium smoke, ×: High smoke
(iv) 1% mass reduction temperature Using a TG / DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured under a temperature rising condition of 20 ° C./min. The mass reduction is related to gas generation, and the lower the 1% mass reduction temperature, the worse the gas generation.

(result)
The evaluation results are shown in Table 1.
A graft copolymer in which a vinyl polymer is grafted to a composite rubber-like polymer (R) containing polyorganosiloxane and a poly (meth) acrylate ester containing a (meth) acrylate monomer unit ( In Examples 1 to 9 in which A), other thermoplastic resin (B), a hindered amine light stabilizer (X), and an ultraviolet absorber (Y) were blended, the obtained thermoplastic resin composition was any In addition, it exhibited high Charpy impact strength, little discoloration with a sunshine weather meter, good weather resistance, and low gas generation during molding. Since these thermoplastic resin compositions have such excellent properties, they can be suitably used as houses, building materials, vehicle exteriors, and the like.

  In contrast, in Comparative Example 1 in which the ultraviolet absorber (Y) was not blended and in Comparative Example 2 in which the hindered amine light stabilizer (X) was not blended, the weather resistance of the obtained thermoplastic resin composition was high. It was extremely bad. In Comparative Example 3 in which the graft copolymer (A) was not blended, the impact resistance of the obtained thermoplastic resin composition was extremely poor. Further, in Comparative Example 4 in which an ultraviolet absorbent (Z-1) having a molecular weight of less than 300 was blended instead of the ultraviolet absorbent (Y), the amount of gas generated during molding was remarkably large, which was poor.

In addition, this inventor is the total amount of a hindered amine light stabilizer (X) and a ultraviolet absorber (Y) with respect to a total of 100 mass parts of a graft copolymer (A) and a thermoplastic resin (B). In the range of 0.1 to 10 parts by mass, it has been confirmed that the same effect can be obtained and both good weather resistance and low gas generation can be achieved.
In addition, by comparing Example 1 with Example 8, in particular, by using together a hindered amine light stabilizer (X1) having a molecular weight of less than 1000 and a hindered amine light stabilizer (X2) having a molecular weight of 1000 or more, weather resistance Turned out to be better. However, as can be seen from the comparison of the same Examples, when these hindered amine light stabilizers were used in combination, the gas generation during molding tended to deteriorate.
Further, by comparing Example 1, Example 9 and Comparative Example 4, it was found that as the molecular weight of the ultraviolet absorbent used increased, gas generation during molding was suppressed, and in order to obtain good low gas generation It was found that the molecular weight of the ultraviolet absorber used must be 300 or more.

  The thermoplastic resin composition and molded product thereof according to the present invention are used for building materials such as vehicle parts (particularly various exteriors and interior parts around the dashboard used without painting), wall materials, window frames, rain gutters, and various hose covers. It can be suitably used for parts, miscellaneous goods such as tableware and toys, household appliance parts such as vacuum cleaner housings, television housings, and air conditioner housings, OA equipment housings, interior members, ship members, and communication equipment housings.

Claims (8)

A vinyl polymer is grafted to a composite rubber-like polymer (R) containing a polyorganosiloxane (S) and a poly (meth) acrylate ester (M) containing a (meth) acrylate ester monomer unit. 1 to 99 parts by mass of the graft copolymer (A),
99 to 1 part by mass of other thermoplastic resins (B) other than the graft copolymer (A) (provided that the total of the graft copolymer (A) and the thermoplastic resin (B) is 100 parts by mass). ,
A thermoplastic resin composition comprising a hindered amine light stabilizer (X) and a UV absorber (Y) having a molecular weight of 300 or more in total of 0.1 to 10 parts by mass.   The thermoplastic resin (B) is a polymethyl methacrylate, an acrylonitrile-styrene copolymer, an acrylonitrile-styrene-N-substituted maleimide terpolymer, a styrene-maleic anhydride-N-substituted maleimide terpolymer, At least selected from the group consisting of polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer, acrylonitrile-styrene-methyl methacrylate terpolymer, modified polyphenylene ether, and polyamide. It is 1 type, The thermoplastic resin composition of Claim 1 characterized by the above-mentioned.   The thermoplastic resin composition according to claim 1 or 2, wherein the hindered amine light stabilizer (X) is a hindered amine light stabilizer in which nitrogen of the piperidine skeleton is substituted with an alkyl group.   The hindered amine light stabilizer (X) includes a light stabilizer (X1) having a molecular weight of less than 1000 and a light stabilizer (X2) having a molecular weight of 1000 or more, and their mass ratio ((X1) / (X2)) It is 1/5-5/1, The thermoplastic resin composition of any one of Claims 1-3 characterized by the above-mentioned.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the ultraviolet absorber (Y) is a benzotriazole-based compound.   The thermoplastic resin composition according to claim 5, wherein the ultraviolet absorber (Y) has two or more benzotriazole skeletons in the molecule.   A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 6.   The molded article according to claim 7, wherein the molded article is formed into a sheet shape.