WO2023128306A1 - Antiviral molded product - Google Patents

Abstract

An antiviral molded article of the present invention is formed from a thermoplastic resin composition comprising: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 5 to about 35 parts by weight of a polyetheresteramide block copolymer; about 0.05 to about 1.5 parts by weight of a silver (Ag) compound; and about 0.5 to about 15 parts by weight of zinc oxide, and comprises a corrosion surface in which the surface roughness of a specimen with a 0.51 mm × 0.76 mm size measured by using a 20 magnification lens with a shape measuring laser microscope on at least one surface is about 1 to about 10 μm, and of which a surface area is about 0.5 to about 1.5 mm². The antiviral molded article has excellent antiviral properties, impact resistance, appearance characteristics, and the like.

Description

antiviral molded product

The present invention relates to antiviral molded articles. More specifically, the present invention relates to an antiviral molded article having excellent antiviral properties, impact resistance, appearance characteristics, and the like.

After the coronavirus pandemic, demand for thermoplastic resin products (molded products) with antiviral properties is increasing. In particular, cases of applying it to exterior materials such as home appliances used indoors are increasing. Specifically, refrigerator handles, exteriors of small home appliances (air purifiers, humidifiers, etc.), remote controls, and the like correspond to the above uses.

Copper (Cu) compounds are widely known as materials capable of exhibiting antiviral performance. When such a copper compound is applied to a thermoplastic resin composition, it is difficult to process and there are problems such as discoloration due to oxidation, and thus applicable products are very limited. In addition, the molded article to which the existing inorganic antibacterial agent or the like is applied has excellent antibacterial performance, but it has not been confirmed whether antiviral performance is expressed.

Therefore, there is a need to develop an antiviral molded product having excellent antiviral properties, impact resistance, appearance characteristics, and the like.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2020-0065139 and the like.

An object of the present invention is to provide an antiviral molded article having excellent antiviral properties, impact resistance, appearance characteristics, and the like.

The above and other objects of the present invention can all be achieved by the present invention described below.

1. One aspect of the present invention relates to an antiviral molded article. The antiviral molded article contains about 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin, about 5 to about 35 parts by weight of a polyether esteramide block copolymer, about 0.05 to about 1.5 parts by weight of a silver (Ag) compound, and zinc oxide It is formed from a thermoplastic resin composition containing about 0.5 to about 15 parts by weight, and the surface roughness of a 0.51 mm × 0.76 mm size specimen measured using a 20 magnification lens with a shape measuring laser microscope (Keyence VK-X100) on at least one side is from about 1 to about 10 μm and having a surface area of from about 0.5 to about 1.5 mm ² .

2. In the first embodiment, the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

3. In the embodiment 1 or 2, the rubber-modified vinyl-based graft copolymer may be obtained by graft-polymerizing a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

4. In the above 1 to 3 embodiments, the polyetheresteramide block copolymer is an amino carboxylic acid having 6 or more carbon atoms, a lactam or a diamine-dicarboxylic acid salt; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms; it may be a block copolymer of a reaction mixture containing.

5. In the embodiments 1 to 4, the silver-based compound may include at least one of metal silver, silver oxide, silver halide, and a carrier containing silver ions.

6. In the above embodiments 1 to 5, the weight ratio of the polyether esteramide block copolymer and the sum of the silver-based compound and the zinc oxide (polyether esteramide block copolymer: silver-based compound + zinc oxide) is about 1: 0.1 to It may be about 1:2.

7. In the embodiments 1 to 6, the weight ratio (silver-based compound:zinc oxide) of the silver-based compound and the zinc oxide may be about 1:3 to about 1:90.

8. In the above embodiments 1 to 7, the antiviral molded article is prepared by adding porcine epidemic diarrhea virus or influenza A virus solution dropwise to a 5 cm × 5 cm specimen according to the ISO 21702 evaluation method, 25 ° C, RH 50% Under the condition, the virus killing time measured by time period may be about 20 hours or less.

9. In the embodiments 1 to 8, the antiviral molded article may have a notched Izod impact strength of about 14 to about 30 kgf cm/cm of a 1/4" thick specimen measured according to ASTM D256.

10. In the embodiments 1 to 9, the antiviral molded article may have a surface gloss of about 4% or more as measured at an angle of 85 ° according to ASTM D523.

The present invention has the effect of providing an antiviral molded article having excellent antiviral properties, impact resistance, appearance characteristics, and the like.

Hereinafter, the present invention will be described in detail as follows.

An antiviral molded article according to the present invention includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) a polyetheresteramide block copolymer; (C) a silver (Ag)-based compound; and (D) a thermoplastic resin composition comprising zinc oxide.

In this specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin according to one embodiment of the present invention may include (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.

(A1) Rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention may be obtained by graft polymerization of a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a cyanide-based vinyl monomer on a rubbery polymer, and, if necessary, processability and Graft polymerization may be performed by further including a monomer imparting heat resistance. The polymerization may be performed 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 polymer)-shell (copolymer of monomer mixture) structure, but is not limited thereto.

In embodiments, the rubbery polymer includes diene-based rubber such as polybutadiene and poly(acrylonitrile-butadiene), saturated rubber obtained by adding hydrogen to the diene-based rubber, isoprene rubber, and alkyl (meth)acrylic having 2 to 10 carbon atoms. Late rubber, a copolymer of an alkyl (meth)acrylate having 2 to 10 carbon atoms and styrene, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in combination of two or more. For example, diene-based rubber, (meth)acrylate rubber, and the like can be used, and specifically, butadiene-based rubber, butyl acrylate rubber, and the like can be used.

In embodiments, the rubbery polymer (rubber particle) may have an average particle size of about 0.05 to about 6 μm, for example about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm. Within the above range, the antiviral molded article may have excellent impact resistance and appearance characteristics. Here, the average particle size (z-average) of the rubbery polymer (rubber particle) can be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove the coagulum generated during polymerization of the rubbery polymer, and a solution obtained by mixing 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. , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size meter (Malvern, nano-zs).

In embodiments, the content of the rubbery polymer may be about 20 to about 80% by weight, for example about 25 to about 70% by weight, based on 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic (including vinyl monomers and cyanide-based monomers) may be about 20 to about 80% by weight, for example, about 30 to about 75% by weight, based on 100% by weight of the total weight of the rubber-modified vinyl-based graft copolymer. Within the above range, the antiviral molded article may have excellent impact resistance and appearance characteristics.

In embodiments, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, Monochloro styrene, dichloro styrene, dibromo styrene, vinyl naphthalene, etc. can be illustrated. These may be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 10 to about 90% by weight, for example, about 20 to about 80% by weight, based on 100% by weight of the monomer mixture. Within the above range, processability and impact resistance of antiviral molded articles may be excellent.

In specific embodiments, the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, such as acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. can be exemplified. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be about 5 to about 60 wt%, for example about 10 to about 50 wt%, based on 100 wt% of the monomer mixture. Within the above range, the antiviral molded article may have excellent chemical resistance and mechanical properties.

In specific examples, the monomers for imparting processability and heat resistance may include (meth)acrylic acid, alkyl (meth)acrylates having 1 to 10 carbon atoms, maleic anhydride, and N-substituted maleimides, but are not limited thereto. don't When using a monomer for imparting processability and heat resistance, the content thereof may be about 60% by weight or less, for example about 1 to about 50% by weight, based on 100% by weight of the monomer mixture. Within the above range, processability and heat resistance can be imparted to antiviral molded articles without deterioration of other physical properties.

In a specific embodiment, the rubber-modified vinyl-based graft copolymer is a copolymer (g-ABS) in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted onto a butadiene-based rubbery polymer (g-ABS), butadiene-based A copolymer (g-MBS) grafted with styrene monomer, which is an aromatic vinyl compound, and methyl methacrylate as a monomer for imparting processability and heat resistance to a rubbery polymer, styrene monomer, acrylonitrile monomer, and methyl to a butadiene-based rubbery polymer A copolymer grafted with methacrylate (g-MABS), a copolymer grafted with styrene monomer, an aromatic vinyl compound, and acrylonitrile monomer, a vinyl cyanide compound, on a butyl acrylate-based rubbery polymer, Acrylate-Styrene- Acrylonitrile graft copolymer (g-ASA) etc. can be illustrated.

In embodiments, the rubber-modified vinyl-based graft copolymer may be included in about 10 to about 50% by weight, for example, about 20 to about 45% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the antiviral molded article may have excellent impact resistance, fluidity (molding processability), appearance characteristics, balance of physical properties thereof, and the like.

(A2) Aromatic vinyl copolymer resin

An aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in conventional rubber-modified aromatic vinyl-based copolymer resins. For example, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.

In embodiments, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer, and then polymerizing them, wherein the polymerization is emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be carried out by a known polymerization method of.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 10 to about 95% by weight, for example, about 20 to about 90% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. Within the above range, the antiviral molded article may have excellent impact resistance and fluidity.

In embodiments, 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, it may be a vinyl cyanide-based monomer or a vinyl cyanide-based monomer and an alkyl (meth)acrylic monomer.

In specific embodiments, examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and fumaronitrile, but are not limited thereto. don't These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used.

In a specific embodiment, 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. can be used.

In embodiments, the content of the monomer copolymerizable with the aromatic vinyl-based monomer may be about 5 to about 90% by weight, for example about 10 to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. Within the above range, the antiviral molded article may have excellent impact resistance and fluidity.

In embodiments, the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) of about 10,000 to about 300,000 g/mol, for example, about 15,000 to about 150,000 g/mol, as measured by gel permeation chromatography (GPC). can Within the above range, the antiviral molded article may have excellent mechanical strength and moldability.

In embodiments, the aromatic vinyl-based copolymer resin may be included in about 50 to about 90% by weight, for example, about 55 to about 80% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the antiviral molded article may have excellent impact resistance, fluidity (molding processability), and the like.

(B) polyetheresteramide block copolymer

The polyether esteramide block copolymer according to one embodiment of the present invention is applied together with a silver compound and zinc oxide to the rubber-modified aromatic vinyl copolymer resin to improve antiviral properties and impact resistance of antiviral molded articles. As possible, amino carboxylic acids having 6 or more carbon atoms, lactams or diamine-dicarboxylic acid salts; polyalkylene glycol; and a block copolymer of a reaction mixture comprising; and a dicarboxylic acid having 4 to 20 carbon atoms.

In a specific embodiment, the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms is ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminofelcon acids, aminocarboxylic acids such as ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid and the like; lactams such as caprolactam, enantlactam, capryllactam, and lauryllactam; and salts of diamines and dicarboxylic acids, such as salts of hexamethylenediamine-adipic acid and salts of hexamethylenediamine-isophthalic acid. For example, salts of 1,2-aminododecanoic acid, caprolactam, hexamethylenediamine-adipic acid and the like can be used.

In embodiments, the polyalkylene glycol is polyethylene glycol, poly(1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, block or random copolymer of ethylene glycol and propylene glycol. , copolymers of ethylene glycol and tetrahydrofuran, and the like can be exemplified. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like can be used.

In specific examples, 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.

In embodiments, the bond between the amino carboxylic acid, lactam or diamine-dicarboxylic acid salt having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond, and the amino carboxylic acid, lactam or diamine having 6 or more carbon atoms may form an ester bond. The bond between the diamine-dicarboxylic acid salt; 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 is It may be an ester bond.

In a specific embodiment, the polyether esteramide block copolymer may be prepared by a known synthesis method, for example, prepared according to the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424 It can be.

In embodiments, the polyetheresteramide block copolymer may include about 10 to about 95% by weight of the polyether-ester block. Within the above range, the antiviral molded article may have excellent impact resistance.

In embodiments, the polyether esteramide block copolymer is about 5 to about 35 parts by weight, for example about 8 to about 30 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. It may be included in about 12 to about 30 parts by weight. When the content of the polyether esteramide block copolymer is less than about 5 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, antiviral properties of antiviral molded articles may deteriorate, If it exceeds about 35 parts by weight, there is a concern that the impact resistance, thermal stability, etc. of the antiviral molded article may deteriorate.

(C) silver (Ag) compound

The silver-based compound according to one embodiment of the present invention is applied to the rubber-modified aromatic vinyl-based copolymer resin together with a polyether esteramide block copolymer and zinc oxide to improve antiviral properties and impact resistance of antiviral molded articles. it can be done The silver-based compound is an antibacterial agent and is not particularly limited as long as it is a compound containing a silver component, and may include, for example, metal silver, silver oxide, silver halide, a carrier containing silver ions, a combination thereof, and the like. Among these, a carrier containing silver ions can be used. Examples of the carrier include zeolite, silica gel, calcium phosphate, zirconium phosphate, sodium phosphate-zirconium, phosphate-sodium-hydrogen-zirconium, and the like. It is preferable that the said carrier has a porous structure. Since the carrier having a porous structure can retain the silver component even therein, not only the content of the silver component can be increased, but also the retention performance (retention performance) of the silver component is improved. Specifically, as the silver-based compound, silver sodium hydrogen zirconium phosphate or the like may be used.

In embodiments, the silver-based compound has an average particle size (D50) of about 15 μm or less, for example, about 0.1 to about may be 12 μm.

In embodiments, the silver-based compound may be included in an amount of about 0.05 to about 1.5 parts by weight, for example, about 0.1 to about 1.2 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based 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, antiviral and antibacterial properties of the antiviral molded article may deteriorate, and about 1.5 parts by weight If it exceeds part, there is a possibility that the impact resistance of the antiviral molded article and the like may decrease.

(D) zinc oxide

Zinc oxide of the present invention can be applied to the rubber-modified aromatic vinyl copolymer resin together with a polyether esteramide block copolymer and zinc oxide to improve antiviral properties and impact resistance of antiviral molded articles, Zinc oxide applied to conventional thermoplastic resin compositions can be used.

In embodiments, the zinc oxide has an average particle size (D50) of about 0.1 to about 10 ㎛, for example, about 0.5 to about may be 5 μm. Within the above range, antiviral properties and impact resistance of the antiviral molded article may be excellent.

In embodiments, the zinc oxide may be included in an amount of about 0.5 to about 15 parts by weight, for example, about 2 to about 12 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. If the content of zinc oxide is less than about 0.5 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, antiviral and antibacterial properties of the antiviral molded article may deteriorate, and about 15 parts by weight If it exceeds the part, there is a fear that the antiviral property, impact resistance, colorability, etc. of the antiviral molded article may deteriorate.

In embodiments, 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: 2, eg For example, it may be about 1:0.15 to about 1:1.5. Within the above range, antiviral properties and impact resistance of the antiviral molded article may be more excellent.

In embodiments, the weight ratio (silver-based compound:zinc oxide) of the silver-based compound and the zinc oxide may be about 1:3 to about 1:90, for example, about 1:3.3 to about 1:80. Within the above range, antiviral properties and impact resistance of the antiviral molded article may be more excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additive include flame retardants, fillers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the content thereof may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.

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

An antiviral molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known to those skilled in the art to which the present invention belongs.

In an embodiment, the antiviral molded article has a surface roughness of about 1 to about 10 μm of a 0.51 mm × 0.76 mm size specimen measured using a 20 magnification lens with a shape measuring laser microscope (Keyence VK-X100) on at least one side , such as from about 1.5 to about 6 μm, and having a surface area from about 0.5 to about 1.5 mm ² , such as from about 0.6 to about 1.2 mm ² .

When the surface roughness of the antiviral molded article is less than about 1 μm, antiviral properties, etc. may be deteriorated, and when it exceeds about 10 μm, appearance characteristics, antiviral properties, etc. may be deteriorated. When the surface area of the antiviral molded article is less than about 0.5 mm ² , antiviral properties and the like may deteriorate, and when the surface area exceeds about 1.5 mm ² , appearance characteristics and antiviral properties may deteriorate.

Here, the corrosion surface formation method is well known to those skilled in the art to which the present invention belongs. For example, the surface roughness of the injection mold can be controlled to control the degree of corrosion formation on the surface of the injection specimen.

In a specific embodiment, the antiviral molded article is prepared by dropping porcine epidemic diarrhea virus (PEDV) or influenza A virus solution on a 5 cm × 5 cm specimen according to the ISO 21702 evaluation method, and at 25 ° C., RH 50%. The virus killing time measured per star may be about 20 hours or less, for example about 6 to about 16 hours.

In a specific embodiment, the antiviral molded article has a notched Izod impact strength of about 14 to about 30 kgf cm / cm, for example, about 16 to about 25 kgf cm, measured according to ASTM D256. It can be cm/cm.

In embodiments, the antiviral molded article has a surface gloss of about 4% or more, for example, about 4 to about 60%, specifically about 5 to It may be about 50%. Appearance suitable for the use of the present invention can be obtained within the above range.

In a specific embodiment, the antiviral molded article is useful as an antiviral exterior material for products that are in frequent physical contact because it has excellent antiviral properties, impact resistance, appearance characteristics, and balance of physical properties thereof.

Hereinafter, the present invention will be described in more detail through examples, but these examples are only for the purpose of explanation and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) rubber-modified aromatic vinyl-based copolymer resin

25% by weight of the following (A1) rubber-modified vinyl-based graft copolymer and (A2) 75% by weight of an aromatic vinyl-based copolymer resin were mixed and used.

(A1) Rubber-modified vinyl-based graft copolymer

A core-shell type graft copolymer prepared by graft copolymerization of 42% by weight of a monomer mixture containing styrene and acrylonitrile (weight ratio: 75/25) to 58% by weight of butadiene rubber having an average particle size of 0.3 μm ( g-ABS) was used.

(A2) Aromatic vinyl copolymer resin

A SAN resin (weight average molecular weight: 120,000 g/mol) prepared by polymerizing 70% by weight of styrene and 30% by weight of acrylonitrile was used.

(B) block copolymer

Polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo chemical, product name: PELECTRON AS) was used.

(C) silver (Ag) compound

Silver phosphate glass (manufacturer: Fuji Chemical Industries, LTD. product name: BM-102SD) was used.

(D) zinc oxide

Zinc oxide (manufacturer: Hanil Chemical, product name: KS1) was used.

Examples 1 to 5 and Comparative Examples 1 to 10

After adding each of the above components in an amount as shown in Tables 1, 2 and 3 below, pellets were prepared by extrusion at 230 ° C. For extrusion, a twin-screw extruder with L/D = 36 and a diameter of 45 mm was used. After drying the pellets at 80 ° C for more than 2 hours, the mold surface was processed into micro-patterns with a laser and the micro-patterned mold had a thickness of about 1 μm. A mold with controlled surface roughness and surface area was fabricated by applying thin film coating and chemical corrosion treatment to the surface of the mold, and injection was performed in a 6 oz injection machine (molding temperature: 230℃, mold temperature: 60℃) to produce a mold with different surface roughness and surface area. A specimen was prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1, 2 and 3 below.

How to measure physical properties

(1) Surface roughness and surface area of corroded surface: Surface roughness (unit: ㎛) and surface area of a 0.51 mm × 0.76 mm size specimen using a shape measurement laser microscope (manufacturer: Keyence, device name: VK-X100) using a 20 magnification lens (Unit: mm ² ) was measured.

(2) Antiviral evaluation: Based on the ISO 21702 evaluation method, porcine epidemic diarrhea virus (PEDV) or influenza A virus solution was added dropwise to a 5 cm × 5 cm specimen, and the virus Kill time (unit: hours) was measured.

(3) Notched Izod impact strength (unit: kgf cm/cm): In accordance with ASTM D256, the notched Izod impact strength of a 1/4" thick specimen was measured.

(4) surface gloss (unit: %): In accordance with ASTM D523, the surface gloss of the injection specimen was measured at an angle of 85 ° with a gloss meter (manufacturer: Nippon Denshoku Industries, device name: VG7000).

	Example
	One	2	3	4	5
(A) (parts by weight)	100	100	100	100	100
(B) (parts by weight)	20	20	20	20	20
(C) (parts by weight)	0.6	0.6	0.6	0.6	0.6
(D) (parts by weight)	8	8	8	8	8
surface roughness	1.2	4.0	9.0	4.0	4.0
surface area	0.89	0.97	0.93	0.50	1.47
PEDV kill time	14	12	12	18	8
Influenza A kill time	14	12	12	18	8
Notched Izod Impact Strength	22	20	18	24	20
surface gloss	45.3	14.6	5.1	17.2	8.4

	comparative example
	One	2	3	4
(A) (parts by weight)	100	100	100	100
(B) (parts by weight)	20	20	20	20
(C) (parts by weight)	0.6	0.6	0.6	0.6
(D) (parts by weight)	8	8	8	8
surface roughness	0.2	11.1	4.0	4.0
surface area	0.39	0.97	0.43	1.6
PEDV kill time	24	12	24	8
Influenza A kill time	24	12	24	8
Notched Izod Impact Strength	24	22	22	20
surface gloss	87	1.8	18.4	2.7

	comparative example
	5	6	7	8	9	10
(A) (parts by weight)	100	100	100	100	100	100
(B) (parts by weight)	4	38	20	20	20	20
(C) (parts by weight)	0.6	0.6	0.01	2	0.6	0.6
(D) (parts by weight)	8	8	8	8	0.4	16
surface roughness	3.6	4.2	4.0	4.4	3.6	4.8
surface area	0.81	1.05	0.97	1.05	0.85	1.12
PEDV kill time	72	12	48	20	72	20
Influenza A kill time	72	12	48	20	72	20
Notched Izod Impact Strength	28	6	24	8	8	6
surface gloss	18.2	7.2	15.4	7.6	19.6	5.6

From the above results, it can be seen that the antiviral molded article of the present invention has excellent antiviral properties (virus killing time), impact resistance (notched Izod impact strength), and appearance characteristics (surface gloss).

On the other hand, in the case of Comparative Example 1 in which the surface roughness and surface area of the corroded surface are less than the range of the present invention, it can be seen that the antiviral property is lowered, and in the case of Comparative Example 2 in which the surface roughness of the corroded surface exceeds the range of the present invention , It can be seen that the appearance characteristics are deteriorated, and in the case of Comparative Example 3, in which the surface area of the corroded surface is less than the scope of the present invention, it can be seen that the antiviral property, etc. is reduced, and the surface area of the corroded surface exceeds the scope of the present invention In the case of Comparative Example 4, it can be seen that the appearance characteristics and the like are deteriorated. In addition, in the case of Comparative Example 5 in which the content of the polyetheresteramide block copolymer is less than the scope of the present invention, it can be seen that antiviral properties, etc. are reduced, and the content of the polyetheresteramide block copolymer exceeds the scope of the present invention In the case of Comparative Example 6, it can be seen that the impact resistance is lowered, and in the case of Comparative Example 7, in which the content of the silver-based compound is less than the range of the present invention, it can be seen that the antiviral property is lowered, and the content of the silver-based compound is reduced. In the case of Comparative Example 8 exceeding the scope of the present invention, it can be seen that impact resistance, etc. are reduced, and in the case of Comparative Example 9, in which the content of zinc oxide is less than the scope of the present invention, antiviral properties, impact resistance, etc. are reduced. And, in the case of Comparative Example 12 in which the content of zinc oxide exceeds the range of the present invention, it can be seen that impact resistance and the like are lowered.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a limiting sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (10)

1. About 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin, about 5 to about 35 parts by weight of a polyether esteramide block copolymer, about 0.05 to about 1.5 parts by weight of a silver (Ag) compound, and about 0.5 to about 15 parts by weight of zinc oxide It is formed from a thermoplastic resin composition comprising a part,

   On at least one side, the surface roughness of a specimen measuring 0.51 mm × 0.76 mm using a 20 magnification lens with a shape measurement laser microscope (Keyence VK-X100) is about 1 to about 10 μm, and the surface area is about 0.5 to about 1.5 Antiviral molded article, characterized in that it comprises a corrosion surface of mm ² .
2. The antiviral molded article according to claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin includes a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
3. The antiviral molded article according to claim 2, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft polymerization of a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
4. The polyetheresteramide block copolymer according to any one of claims 1 to 3, wherein the polyetheresteramide block copolymer is selected from an amino carboxylic acid having 6 or more carbon atoms, a lactam or a diamine-dicarboxylic acid salt; polyalkylene glycol; An antiviral molded article characterized in that it is a block copolymer of a reaction mixture comprising; and a dicarboxylic acid having 4 to 20 carbon atoms.
5. The antiviral molded article according to any one of claims 1 to 4, wherein the silver-based compound includes at least one of metal silver, silver oxide, silver halide, and a carrier containing silver ions.
6. The method according to any one of claims 1 to 5, wherein 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 An antiviral molded article, characterized in that 1: 0.1 to about 1: 2.
7. The antiviral molded article according to any one of claims 1 to 6, wherein the weight ratio (silver-based compound:zinc oxide) of the silver-based compound and the zinc oxide is from about 1:3 to about 1:90.
8. The antiviral molded article according to any one of claims 1 to 7, according to the ISO 21702 evaluation method, porcine epidemic diarrhea virus or influenza A virus liquid is added dropwise to a 5 cm × 5 cm specimen, and 25 ° C. , Antiviral molded article characterized in that the virus killing time measured by time zone under 50% RH is about 20 hours or less.
9. The method according to any one of claims 1 to 8, wherein the antiviral molded article has a notched Izod impact strength of a 1/4 "thickness specimen measured according to ASTM D256 of about 14 to about 30 kgf cm / cm Antiviral molded article, characterized in that.
10. The method according to any one of claims 1 to 9, wherein the antiviral molded article has a surface gloss of about 4% or more measured at an angle of 85 ° according to ASTM D523 Antiviral property, characterized in that molding.