Thermoplastic resin composition and molded article produced therefrom

Abstract

The thermoplastic resin composition of the present invention comprises about 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin, about 5 to about 50 parts by weight of a polyester resin, about 20 to about 50 parts by weight of a polyetheresteramide block copolymer, about 0.05 to about 2.5 parts by weight of a silver (Ag)-based compound, and about 1 to about 20 parts by weight of zinc oxide, and is characterized in that the weight ratio of the polyetheresteramide block copolymer and the sum of the silver-based compound and the zinc oxide (polyetheresteramide block copolymer:silver-based compound+zinc oxide) is about 1:0.1 to about 1:1. The thermoplastic resin composition is excellent in antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc., and a molded article produced therefrom. [Background technology]

[0002] Since the coronavirus pandemic, there has been an increasing demand for thermoplastic resin products with antiviral properties. In particular, there are an increasing number of cases where these products are used as exterior materials for home appliances used indoors. Specifically, these applications include refrigerator handles, exteriors for small appliances (air purifiers, humidifiers, etc.), remote controls, etc.

[0003] Copper (Cu) compounds are widely known as materials capable of exhibiting antiviral properties. When attempting to apply such copper compounds to a thermoplastic resin composition, the applicable products are very limited due to problems such as difficulty in processing, discoloration due to reduced thermal stability, and limited colorability. In addition, thermoplastic resin compositions to which existing inorganic antibacterial agents are applied have excellent antibacterial properties, but it has not been confirmed whether they clearly exhibit antiviral properties.

[0004] Therefore, there is a need to develop a thermoplastic resin composition that is excellent in antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, and the like.

[0005] The background art of the present invention is disclosed in Korean Patent Publication No. 10-2020-0065139 and the like. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a thermoplastic resin composition which is excellent in antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, and the like.

[0007] Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0008] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0009] 1. One aspect of the present invention relates to a thermoplastic resin composition, which comprises about 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin, about 5 to about 50 parts by weight of a polyester resin, about 20 to about 50 parts by weight of a polyetheresteramide block copolymer, about 0.05 to about 2.5 parts by weight of a silver (Ag)-based compound, and about 1 to about 20 parts by weight of zinc oxide, and is characterized in that the weight ratio of the polyetheresteramide block copolymer and the sum of the silver-based compound and zinc oxide (polyetheresteramide block copolymer:silver-based compound+zinc oxide) is about 1:0.1 to about 1:1.

[0010] 2. In the above embodiment 1, the rubber-modified aromatic vinyl copolymer resin may include a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin.

[0011] 3. In the embodiment of 1 or 2 above, the rubber-modified vinyl-based graft copolymer may be a rubber-like polymer to which a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer is graft polymerized.

[0012] 4. In the specific examples 1 to 3 above, the polyester resin may include one or more of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene dimethylene terephthalate.

[0013] 5. In the specific examples of 1 to 4 above, the polyetheresteramide block copolymer can be a block copolymer of a reaction mixture containing an aminocarboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms; a polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.

[0014] 6. In the specific examples of 1 to 5 above, the silver-based compound can include one or more of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.

[0015] 7. In the specific examples of 1 to 6, the weight ratio of the polyester resin and the polyetheresteramide block copolymer may be about 1:0.5 to about 1:5.

[0016] 8. In the specific examples of 1 to 7, the weight ratio of the silver-based compound to the zinc oxide may be about 1:3 to about 1:90.

[0017] 9. In the specific examples of 1 to 8, the thermoplastic resin composition may have a time period of about 1 to about 15 hours for the virus concentration reduction rate to reach 99%, as measured by dropping a coronavirus S-type (BetaCoV / KCDC03) virus solution onto a test piece measuring 5 cm x 5 cm based on the ISO 21702 evaluation method under conditions of 25°C and 50% RH and measuring each time period.

[0018] 10. In the specific examples of 1 to 9, the thermoplastic resin composition has a flexural modulus of about 14,000 kgf / cm for a 1 / 4" thick specimen measured at 2.8 mm / min according to ASTM D790. 2 ~Approx. 25,000kgf / cm 2 It could be.

[0019] 11. In the specific examples of 1 to 10, the thermoplastic resin composition may have a Vicat softening temperature of about 80° C. to about 95° C., measured according to ISO 306 under conditions of a 5 kg load and 50° C. / hr.

[0020] 12. In the specific examples of 1 to 11, the thermoplastic resin composition may have a notch Izod impact strength of about 11 kgf cm / cm to about 25 kgf cm / cm for a ¼” thick specimen measured according to ASTM D256.

[0021] 13. Another aspect of the present invention relates to a molded article. The molded article is formed from the thermoplastic resin composition according to any one of 1 to 12 above.

[0022] 14. In the embodiment of the thirteenth aspect, the molded article may include, on at least one side, a corroded surface having a surface roughness of about 1 μm to about 50 μm as measured with a surface roughness measuring device. Effect of the Invention

[0023] The present invention has an effect of providing a thermoplastic resin composition having excellent antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc., and a molded article formed therefrom. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] [Best Mode for Carrying Out the Invention] The present invention will be described in detail below.

[0025] The thermoplastic resin composition according to the present invention contains (A) a rubber-modified aromatic vinyl copolymer resin; (B) a polyester resin; (C) a polyetheresteramide block copolymer; (D) a silver (Ag)-based compound; and (E) zinc oxide.

[0026] In this specification, the term "a to b" expressing a numerical range is defined as "≧a and ≦b".

[0027] (A) Rubber-modified aromatic vinyl copolymer resin A rubber-modified aromatic vinyl copolymer resin according to one embodiment of the present invention may contain (A1) a rubber-modified vinyl graft copolymer, and (A2) an aromatic vinyl copolymer resin.

[0028] (A1) Rubber-modified vinyl graft copolymer The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention may be a product obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer onto a rubber-based polymer. For example, the rubber-modified vinyl-based graft copolymer may be obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer onto a rubber-based polymer, and may further include a monomer that imparts processability and heat resistance to the monomer mixture, as necessary, and may be graft-polymerized. The polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. In addition, the rubber-modified vinyl-based graft copolymer may form a core (rubber-based polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.

[0029] In specific examples, the rubbery polymer may be diene rubber such as polybutadiene and poly(acrylonitrile-butadiene), hydrogenated saturated rubber obtained by hydrogenating the diene rubber, isoprene rubber, alkyl (meth)acrylate rubber having 2 to 10 carbon atoms, copolymer of alkyl (meth)acrylate having 2 to 10 carbon atoms and styrene, terpolymer of ethylene-propylene-diene monomer (EPDM), etc. These may be used alone or in combination of two or more kinds. For example, diene rubber, (meth)acrylate rubber, etc. may be used, and specifically, butadiene rubber, butyl acrylate rubber, etc. may be used.

[0030] In a specific example, the rubber polymer (rubber particles) may have an average particle size of about 0.05 μm to about 6 μm, for example, about 0.15 μm to about 4 μm, specifically about 0.25 μm to about 3.5 μm. In this range, the impact resistance, appearance properties, etc. of the thermoplastic resin composition may be excellent. Here, the average particle size (z-average) of the rubber polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulation generated during the polymerization of the rubber polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and filled with distilled water to prepare a sample, and then 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubber polymer can be measured using a light scattering particle sizer (Malvern, Nano-ZS).

[0031] In a specific example, the content of the rubber polymer may be about 20% by weight to about 80% by weight, for example, about 25% by weight to about 70% by weight, based on 100% by weight of the total rubber-modified vinyl graft copolymer, and the content of the monomer mixture (including aromatic vinyl monomer and vinyl cyanide monomer) may be about 20% by weight to about 80% by weight, for example, about 30% by weight to about 75% by weight, based on 100% by weight of the total rubber-modified vinyl graft copolymer. Within the above ranges, the thermoplastic resin composition may have excellent impact resistance, appearance properties, etc.

[0032] In a specific example, the aromatic vinyl monomer can be graft-copolymerized with the rubber polymer, and examples thereof include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These can be used alone or in combination of two or more. The content of the aromatic vinyl monomer can be about 10% by weight to about 90% by weight, for example, about 20% by weight to about 80% by weight, based on 100% by weight of the monomer mixture. Within this range, the thermoplastic resin composition can have excellent processability, rigidity, heat resistance, etc.

[0033] In a specific example, the vinyl cyanide monomer can be copolymerized with the aromatic vinyl monomer, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. These can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer can be about 5% by weight to about 60% by weight, for example, about 10% by weight to about 50% by weight, based on 100% by weight of the monomer mixture. Within this range, the thermoplastic resin composition can have excellent chemical resistance, rigidity, heat resistance, etc.

[0034] In specific examples, the monomer for imparting processability and heat resistance may be, but is not limited to, (meth)acrylic acid, alkyl (meth)acrylate having 1 to 10 carbon atoms, maleic anhydride, N-substituted maleimide, etc. When the monomer for imparting processability and heat resistance is used, its content may be about 60% by weight or less, for example, about 1% by weight to about 50% by weight, of the monomer mixture (100% by weight). Within this range, other physical properties are not deteriorated, and the thermoplastic resin composition may be imparted with processability and heat resistance.

[0035] Specific examples of the rubber-modified vinyl graft copolymer include a copolymer (g-ABS) in which a butadiene-based rubber polymer is grafted with a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound; a copolymer (g-MBS) in which a butadiene-based rubber polymer is grafted with a styrene monomer, which is an aromatic vinyl compound, and a monomer for imparting processability and heat resistance, methyl methacrylate; a copolymer (g-MABS) in which a butadiene-based rubber polymer is grafted with a styrene monomer, an acrylonitrile monomer, and methyl methacrylate; and an acrylate-styrene-acrylonitrile graft copolymer (g-ASA) in which a butyl acrylate-based rubber polymer is grafted with a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound.

[0036] In a specific example, the rubber-modified vinyl graft copolymer may be contained in an amount of about 10% by weight to about 50% by weight, for example, about 20% by weight to about 45% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl copolymer resin. In this range, the thermoplastic resin composition may have excellent impact resistance, flowability (moldability), appearance characteristics, and balance of these physical properties.

[0037] (A2) Aromatic vinyl copolymer resin The aromatic vinyl copolymer resin according to an embodiment of the present invention may be an aromatic vinyl copolymer resin used in conventional rubber-modified aromatic vinyl copolymer resins. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

[0038] In a specific example, the aromatic vinyl copolymer resin can be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, and then polymerizing the mixture. The polymerization can be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization.

[0039] In specific examples, the aromatic vinyl monomer may be styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be about 10% by weight to about 95% by weight, for example, about 20% by weight to about 90% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin. In this range, the thermoplastic resin composition may have excellent impact resistance, flowability, etc.

[0040] In a specific example, the monomer copolymerizable with the aromatic vinyl monomer may include at least one of a vinyl cyanide monomer and an alkyl (meth)acrylic monomer, for example, a vinyl cyanide monomer or a vinyl cyanide monomer and an alkyl (meth)acrylic monomer.

[0041] In specific examples, the vinyl cyanide monomer may be, but is not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. may be used.

[0042] In a specific example, the alkyl (meth)acrylic monomer may be (meth)acrylic acid and / or alkyl (meth)acrylate having 1 to 10 carbon atoms. These may be used alone or in combination of two or more. For example, methyl methacrylate, methyl acrylate, etc. may be used.

[0043] In a specific example, the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 5% by weight to about 90% by weight, for example, about 10% by weight to about 80% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin. In this range, the thermoplastic resin composition may have excellent impact resistance, flowability, etc.

[0044] In a specific example, the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 g / mol to about 300,000 g / mol, for example, about 15,000 g / mol to about 150,000 g / mol. In this range, the thermoplastic resin composition may have excellent mechanical strength, moldability, etc.

[0045] In a specific example, the aromatic vinyl copolymer resin may be contained in an amount of about 50% by weight to about 90% by weight, for example, about 55% by weight to about 80% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl copolymer resin. In this range, the thermoplastic resin composition may have excellent impact resistance, fluidity (moldability), etc.

[0046] (B) Polyester resin The polyester resin according to one embodiment of the present invention is a polyester resin used in ordinary thermoplastic resin compositions, which is applied to the rubber-modified aromatic vinyl copolymer resin together with a polyether ester amide block copolymer, a silver compound, and zinc oxide to improve the antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc. of a thermoplastic resin composition (molded product). For example, the polyester resin may contain, as a dicarboxylic acid component, aromatic dicarboxylic acids such as terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and aromatic dicarboxylates such as dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl-1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate, dimethyl-2,3-naphthalate, dimethyl-2,6-naphthalate, and dimethyl-2,7-naphthalate. dicarboxylate) and the like, and a cyclic alkylene diol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or 1,4-cyclohexanedimethanol as a diol component.

[0047] In specific examples, the polyester resin may include one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polytrimethylene terephthalate (PTT), polycyclohexylene dimethylene terephthalate (PCT).

[0048] In a specific example, the polyester resin of the present invention may have an intrinsic viscosity of about 0.6 dl / g to about 1.5 dl / g, for example, about 0.7 dl / g to about 1.3 dl / g, as measured by dissolving it in an o-chlorophenol solution (concentration: 0.5 g / dl) and using an Ubbelohde viscometer (capillary viscometer) at 25° C. Within this range, the thermoplastic resin composition may have excellent processability, dimensional stability, etc.

[0049] In a specific example, the polyester resin may be included in an amount of about 5 parts by weight to about 50 parts by weight, for example, about 10 parts by weight to about 40 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the polyester resin is less than about 5 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the antiviral, antibacterial, antifungal properties, etc. of the thermoplastic resin composition (molded product) may be reduced, and if it exceeds about 50 parts by weight, the rigidity, heat resistance, impact resistance, dimensional stability, etc. of the thermoplastic resin composition (molded product) may be reduced.

[0050] (C) Polyetheresteramide block copolymer The polyether ester amide block copolymer according to one embodiment of the present invention is applied to the rubber-modified aromatic vinyl copolymer resin together with a polyester resin, a silver compound and zinc oxide, and can improve the antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties and the like of a thermoplastic resin composition (molded product). A block copolymer of a reaction mixture containing an aminocarboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms; a polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms can be used.

[0051] In a specific example, examples of the salt of the aminocarboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms include aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc.; lactams such as caprolactam, enantholactam, capryllactam, laurolactam, etc.; and salts of diamines and dicarboxylic acids such as salts of hexamethylenediamine-adipic acid, salts of hexamethylenediamine-isophthalic acid, etc. For example, salts of 1,2-aminododecanoic acid, caprolactam, and hexamethylenediamine-adipic acid can be used.

[0052] In specific examples, the polyalkylene glycol may include polyethylene glycol, poly(1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, block or random copolymers of ethylene glycol and propylene glycol, copolymers of ethylene glycol and tetrahydrofuran, etc. For example, polyethylene glycol, copolymers of ethylene glycol and propylene glycol, etc. may be used.

[0053] Specific examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecanocarboxylic acid.

[0054] In a specific example, the bond between the aminocarboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond, the bond between the aminocarboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and the bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms may be an ester bond.

[0055] In a specific example, the polyetheresteramide block copolymer can be produced by known synthesis methods, for example, according to the synthesis methods disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424.

[0056] In a specific example, the polyetheresteramide block copolymer may contain about 10% by weight to about 95% by weight of a polyether-ester block. In this range, the thermoplastic resin composition (molded product) may have excellent impact resistance, antiviral properties, etc.

[0057] In a specific example, the polyetheresteramide block copolymer may be contained in an amount of about 20 parts by weight to about 50 parts by weight, for example, about 25 parts by weight to about 45 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the polyetheresteramide block copolymer is less than about 20 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the antiviral, antifungal, antibacterial, etc. of the thermoplastic resin composition (molded article) may be reduced, and if it exceeds about 50 parts by weight, the antiviral, rigidity, heat resistance, thermal stability, etc. of the thermoplastic resin composition (molded article) may be reduced.

[0058] In a specific example, the weight ratio of the polyester resin to the polyetheresteramide block copolymer (polyester resin:polyetheresteramide block copolymer) may be about 1:0.5 to about 1:5, for example, about 1:0.7 to about 1:4. In this range, the thermoplastic resin composition (molded product) may have even better antiviral properties, impact resistance, moldability, etc.

[0059] (D) Silver (Ag)-based compounds The silver-based compound according to one embodiment of the present invention is applied to the rubber-modified aromatic vinyl copolymer resin together with a polyester resin, a polyether ester amide block copolymer, and zinc oxide, and can improve the antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc. of the thermoplastic resin composition (molded product). The silver-based compound is not particularly limited as long as it is a compound containing a silver component as an antibacterial agent, and can include, for example, metallic silver, silver oxide, silver halide, a carrier containing silver ions, and combinations thereof. Of these, a carrier containing silver ions can be used. Examples of the carrier include zeolite, silica gel, calcium phosphate, zirconium phosphate, sodium zirconium phosphate, and sodium hydrogen zirconium phosphate. The carrier preferably has a porous structure. A carrier with a porous structure can hold the silver component inside, so that not only can the content of the silver component be increased, but also the sustaining performance (maintenance performance) of the silver component is improved. Specifically, the silver-based compound may be silver sodium hydrogen zirconium phosphate.

[0060] In a specific example, the silver-based compound may have an average particle size (D50) of about 15 μm or less, for example, about 0.1 μm to about 12 μm, as measured using a particle size analyzer (Beckman Coulter, Laser Diffraction Particle Size Analyzer LS 13 320).

[0061] In a specific example, the silver-based compound may be contained in an amount of about 0.05 parts by weight to about 2.5 parts by weight, for example, about 0.1 parts by weight to about 2.3 parts by weight, specifically, about 0.5 parts by weight to about 2.2 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the silver-based compound is less than about 0.05 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the antiviral, antibacterial, antifungal properties, etc. of the thermoplastic resin composition (molded article) may be reduced, and if it exceeds about 2.5 parts by weight, the impact resistance, thermal stability, etc. of the thermoplastic resin composition (molded article) may be reduced.

[0062] (D) Zinc oxide The zinc oxide of the present invention is applied to the rubber-modified aromatic vinyl copolymer resin together with a polyester resin, a polyether ester amide block copolymer, and zinc oxide, thereby making it possible to improve the antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, etc. of a thermoplastic resin composition (molded article), and zinc oxide applied to ordinary thermoplastic resin compositions can be used.

[0063] In a specific example, the zinc oxide is composed of primary particles (single particles) and secondary particles formed by the primary particles bonding together, and the average particle size (D50) of the primary particles measured with a particle size analyzer (Beckman Coulter, Laser Diffraction Particle Size Analyzer, LS 13 320) may be about 1 nm to about 50 nm, for example, about 1 nm to about 30 nm, and the average particle size (D50) of the secondary particles may be about 0.1 μm to about 10 μm, for example, about 0.5 μm to about 5 μm. Within the above ranges, the thermoplastic resin composition (molded product) may have excellent antiviral properties, etc.

[0064] In a specific example, the zinc oxide may be contained in an amount of about 1 part by weight to about 20 parts by weight, for example, about 2 parts by weight to about 18 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the zinc oxide is less than about 1 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the antiviral, antibacterial, antifungal properties, etc. of the thermoplastic resin composition (molded article) may be reduced, and if it exceeds about 20 parts by weight, the impact resistance, thermal stability, processability, etc. of the thermoplastic resin composition (molded article) may be reduced.

[0065] In a specific example, the weight ratio of the polyetheresteramide block copolymer to the sum of the silver-based compound and the zinc oxide (polyetheresteramide block copolymer:silver-based compound+zinc oxide) may be about 1:0.1 to about 1:1, for example, about 1:0.15 to about 1:0.6. If the weight ratio is less than about 1:0.1, the antiviral properties, rigidity, impact resistance, heat resistance, thermal stability, antibacterial properties, antifungal properties, etc. of the thermoplastic resin composition (molded article) may be reduced, and if it exceeds about 1:1, the antiviral properties, impact resistance, thermal stability, etc. of the thermoplastic resin composition (molded article) may be reduced.

[0066] In a specific example, the weight ratio of the silver-based compound to the zinc oxide (silver-based compound:zinc oxide) may be about 1:3 to about 1:90, for example, about 1:3.3 to about 1:30. In this range, the thermoplastic resin composition (molded product) may have even better antiviral, antibacterial, antifungal properties, etc.

[0067] The thermoplastic resin composition according to an embodiment of the present invention may further include additives contained in ordinary thermoplastic resin compositions. Examples of the additives include flame retardants, fillers, antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, etc., but are not limited thereto. When the additives are used, the content thereof may be about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 10 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin.

[0068] The thermoplastic resin composition according to one embodiment of the present invention can be in the form of pellets obtained by mixing the above-mentioned components and melt-extruding the mixture at about 200°C to about 280°C, for example, about 220°C to about 250°C, using a conventional twin-screw extruder.

[0069] In a specific example, the thermoplastic resin composition may take about 1 hour to about 15 hours, for example, about 1 hour to about 5 hours, for a virus concentration reduction rate measured by dropping a coronavirus S-type (BetaCoV / KCDC03) virus solution onto a test piece measuring 5 cm x 5 cm according to the ISO 21702 evaluation method, at 25°C and 50% RH, for each time period to reach 99%.

[0070] In a specific example, the flexural modulus of a 1 / 4" thick specimen measured at 2.8 mm / min according to ASTM D790 is about 14,000 kgf / cm 2 ~Approx. 25,000kgf / cm 2 , for example, about 14,000 kgf / cm 2 ~Approx. 20,000kgf / cm 2 It could be.

[0071] In a specific example, the thermoplastic resin composition may have a Vicat softening temperature of about 80°C to about 95°C, for example about 80°C to about 90°C, measured under conditions of a 5 kg load and 50°C / hr according to ISO 306.

[0072] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in the form of pellets, and the prepared pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding, etc. Such molding methods are well known to those skilled in the art to which the present invention pertains.

[0073] In a specific example, the molded article has excellent antiviral properties, rigidity, heat resistance, impact resistance, thermal stability, antibacterial properties, antifungal properties, and a balance of these physical properties, and is therefore useful as an antiviral exterior material for products that come into frequent physical contact.

[0074] In a specific example, the molded article may have a corroded surface on at least one surface, the surface roughness of which is about 1 μm to about 50 μm, for example about 5 μm to about 40 μm, as measured by a surface roughness measuring device. Methods for forming a corroded surface are well known to those skilled in the art to which the present invention pertains. Within the above surface roughness range, the molded article may have better antiviral properties, and a low-light product may be obtained.

[0075] In a specific example, the molded article including the corroded surface may have a gloss of about 0.5% to about 40%, for example, about 1% to about 20%, of the corroded surface of a 3.2 mm thick specimen measured at an angle of 85° based on ASTM D523. Within this range, the molded article may have excellent low light properties, antiviral properties, etc.

[0076] [Mode for carrying out the invention] The present invention will be described in more detail with reference to the following examples. However, these examples are merely for the purpose of illustration and should not be construed as limiting the present invention.

[0077] Working Example The specifications of the components used in the examples and comparative examples are as follows:

[0078] (A) Rubber-modified aromatic vinyl copolymer resin A mixture of 25% by weight of the following (A1) rubber-modified vinyl graft copolymer and 75% by weight of (A2) aromatic vinyl copolymer resin was used.

[0079] (A1) Rubber-modified vinyl graft copolymer A core-shell graft copolymer (g-ABS) was used, which was prepared by graft copolymerizing 58% by weight of butadiene rubber with an average particle size of 0.3 μm with 42% by weight of a monomer mixture containing styrene and acrylonitrile (weight ratio: 75 / 25).

[0080] (A2) Aromatic vinyl copolymer resin SAN resin (weight average molecular weight: 150,000 g / mol) prepared by polymerizing 70% by weight of styrene and 30% by weight of acrylonitrile was used.

[0081] (B) Polyester resin Polyethylene terephthalate (PET, manufacturer: Lotte Chemical, product name: BCN76, intrinsic viscosity: 0.76 dl / g) was used.

[0082] (C) Block copolymer (C1) Polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo Chemical, product name: PELECTRON AS) was used.

[0083] (C2) Polypropylene-polyethylene oxide block copolymer (PP-b-PEO, manufacturer: Sanyo Chemical, product name: PELECTRON PVL, refractive index: 1.50) was used.

[0084] (D) Silver (Ag)-based compounds Silver phosphate glass (manufacturer: Fuji Chemical Industries, LTD. Product name: BM-102SD) was used.

[0085] (E) Zinc oxide Zinc oxide (manufacturer: SH energy & chemical, product name: ANYZON) was used.

[0086] Examples 1 to 9 and Comparative Examples 1 to 11 The components were added in the amounts shown in Tables 1, 2, 3 and 4 below, and extruded at 230°C to produce pellets. A twin-screw extruder with L / D=36 and diameter of 45 mm was used for extrusion, and the produced pellets were dried at 80°C for more than 2 hours and then extruded into a 6 oz injector (molding temperature: 230°C, mold temperature: 60°C) to produce test specimens. The physical properties of the produced test specimens were evaluated using the following methods, and the results are shown in Tables 1, 2, 3 and 4 below.

[0087] Measurement methods for physical properties (1) Antiviral evaluation: Based on the ISO 21702 evaluation method, a coronavirus S-type (BetaCoV / KCDC03) virus liquid was dropped onto a test piece measuring 5 cm x 5 cm, and the time (unit: hours) until the virus concentration reduction rate reached 99% was measured at each time point under conditions of 25°C and 50% RH.

[0088] (2) Rigidity evaluation: Based on ASTM D790, the flexural modulus (unit: kgf / cm) of a 1 / 4" thick specimen was measured at 2.8 mm / min. 2 ) was measured.

[0089] (3) Heat resistance evaluation: The Vicat softening temperature (VST, unit: °C) was measured under conditions of a load of 5 kg and a rate of 50 °C / hr in accordance with ISO 306.

[0090] (4) Impact resistance evaluation: The notch Izod impact strength (unit: kgf cm / cm) of 1 / 4" thick specimens was measured based on ASTM D256.

[0091] (5) Thermal stability evaluation: After an injection test piece measuring 50mm wide x 200mm long x 2mm thick was held at 240℃ for 10 minutes (injector model: Woojin Prime TE150-IE4, clamping force 150TON), the number of gas silver streaks that were generated was checked with the naked eye and evaluated. (Evaluation criteria: 5 points: 4 or less gas silver streaks, 4 points: 5 to 7 gas silver streaks, 3 points: 8 to 10 gas silver streaks, 2 points: 11 to 13 gas silver streaks, 1 point: 14 or more gas silver streaks)

[0092] [Table 1]

[0093] [Table 2]

[0094] [Table 3]

[0095] [Table 4]

[0096] From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in all respects, such as antiviral property (virus death time), rigidity (flexural modulus), heat resistance (Vicat softening temperature), impact resistance (notch Izod impact strength), and thermal stability.

[0097] On the other hand, in Comparative Example 1, where the content of polyester resin is below the range of the present invention, antiviral properties, etc. are reduced, and in Comparative Example 2, where the content of polyester resin exceeds the range of the present invention, rigidity, heat resistance, impact resistance, etc. are reduced. In Comparative Example 3, where the content of polyetheresteramide block copolymer is below the range of the present invention, antiviral properties, etc. are reduced. In Comparative Example 4, where the content of polyetheresteramide block copolymer exceeds the range of the present invention, rigidity, heat resistance, thermal stability, etc. are reduced. In Comparative Example 5, where polypropylene-polyethylene oxide block copolymer (C2) is used instead of the polyetheresteramide block copolymer of the present invention, antiviral properties, rigidity, heat resistance, thermal stability, etc. are reduced. In Comparative Example 6, where the content of silver-based compound is below the range of the present invention, antiviral properties, etc. are reduced. In Comparative Example 7, where the content of silver-based compound exceeds the range of the present invention, impact resistance, thermal stability, etc. are reduced. In Comparative Example 8, where the content of zinc oxide is below the range of the present invention, antiviral properties, etc. are reduced. In Comparative Example 9, where the content of zinc oxide exceeds the range of the present invention, impact resistance, thermal stability, etc. are reduced. In addition, even though the contents of the polyetheresteramide block copolymer (C1), the silver-based compound (D), and the zinc oxide (E) are within the range of the present invention, in the case of Comparative Example 10 in which the weight ratio (C1:D+E) of the sum of the polyetheresteramide block copolymer (C1) and the silver-based compound (D) and the zinc oxide (E) exceeds the range of the present invention (1:1.13), it is found that the antiviral properties, impact resistance, thermal stability, etc. are reduced, and in the case of Comparative Example 11 in which the weight ratio is below the range of the present invention (1:0.02), it is found that the antiviral properties, rigidity, impact resistance, heat resistance, thermal stability, etc. are reduced.

[0098] The present invention has been described above with reference to the embodiments. It is understood that the present invention can be embodied in modified forms without departing from the essential characteristics of the present invention, as understood by those skilled in the art. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is defined by the appended claims, not the above description, and all differences within the scope of the equivalents thereto should be interpreted as being included in the present invention.

Claims

1. About 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin; About 5 parts by weight to about 50 parts by weight of a polyester resin; About 20 parts by weight to about 50 parts by weight of a polyether ester amide block copolymer; About 0.05 parts by weight to about 2.5 parts by weight of a silver (Ag)-based compound; and Containing about 1 part by weight to about 20 parts by weight of zinc oxide, The weight ratio of the polyether ester amide block copolymer and the sum of the silver-based compound and the zinc oxide (polyether ester amide block copolymer: silver-based compound + zinc oxide) is about 1:0.1 to about 1:1, A thermoplastic resin composition characterized by that.

2. The rubber-modified aromatic vinyl copolymer resin contains a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin, The thermoplastic resin composition according to claim 1, characterized by that.

3. The rubber-modified vinyl graft copolymer is characterized in that a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer is graft polymerized onto a rubber polymer, The thermoplastic resin composition according to claim 2, characterized by that.

4. The polyester resin contains one or more of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene dimethylene terephthalate, The thermoplastic resin composition according to claim 1, characterized by that.

5. The polyether ester amide block copolymer is a block copolymer of a reaction mixture containing an aminocarboxylic acid having 6 or more carbon atoms, a lactam or a diamine-dicarboxylic acid salt; a polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms, The thermoplastic resin composition according to claim 1, characterized by that.

6. The silver-based compound contains one or more of metallic silver, silver oxide, silver halide, and a carrier containing silver ions, The thermoplastic resin composition according to claim 1, characterized by that.

7. The weight ratio of the polyester resin and the polyether ester amide block copolymer is about 1:0.5 to about 1:5, The thermoplastic resin composition according to claim 1, characterized by that.

8. The weight ratio of the silver-based compound and the zinc oxide is about 1:3 to about 1:90, The thermoplastic resin composition according to claim 1, characterized by that.

9. The thermoplastic resin composition is characterized in that, based on the ISO 21702 evaluation method, when a virus solution of coronavirus S-type (BetaCoV / KCDC03) is dropped onto a specimen with a size of 5 cm × 5 cm, the time required for the virus concentration reduction rate measured by time zone at 25°C and RH 50% to reach 99% is about 1 hour to about 15 hours. The thermoplastic resin composition according to claim 1.

10. The thermoplastic resin composition has a flexural modulus of about 14,000 kgf / cm to about 25,000 kgf / cm for a 1 / 4" thick specimen measured under the condition of 2.8 mm / min based on ASTM D790. ２ to about 25,000 kgf / cm ２ The thermoplastic resin composition according to claim 1, characterized in that it is as described above.

11. The thermoplastic resin composition is characterized in that, based on ISO 306, the Vicat softening temperature measured under the conditions of a 5 kg load and 50°C / hr is about 80°C to about 95°C. The thermoplastic resin composition according to claim 1.

12. The thermoplastic resin composition is characterized in that the notched Izod impact strength of a specimen with a thickness of 1 / 4" measured based on ASTM D256 is about 11 kgf·cm / cm to about 25 kgf·cm / cm. The thermoplastic resin composition according to claim 1.

13. A molded article, characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 12.

14. The molded article according to claim 13, characterized in that at least one surface thereof includes a corroded surface with a surface roughness of about 1 μm to about 50 μm measured by a surface roughness measuring instrument.