WO2019124855A1 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention is characterized by comprising: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 0.1 to about 4 parts by weight of a silver (Ag)-based compound; and about 0.7 to about 4 parts by weight of zinc oxide, wherein the zinc oxide has an average particle size (D50) of about 0.8 to about 3 ㎛, which is measured by a particle size analyzer, and wherein at the time of measurement of photo luminescence, the intensity ratio (B/A) of peak A at a region of 370 to 390 nm and peak B at a region of 450 to 600 nm is about 0.01 to about 0.1. The thermoplastic resin composition is excellent in weather resistance, antibacterial properties, mechanical properties, and the like.

Description

Thermoplastic resin composition and molded article produced therefrom

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 excellent in weatherability, antibacterial properties, mechanical properties, and the like and a molded article produced therefrom.

Recently, there has been an increasing demand for thermoplastic resin products containing antibacterial and hygienic functions, as the interest in personal health and hygiene and income levels have improved. As a result, thermoplastic resin products that have been subjected to antimicrobial treatment that can remove or inhibit bacteria on the surfaces of household products and electronic products are increasing, and development of functional antibacterial material (antibacterial thermoplastic resin composition) having stable and reliable is very important It is an assignment.

In order to prepare such an antibacterial thermoplastic resin composition, it is necessary to add an antibacterial agent, and the antibacterial agent can be divided into an organic antibacterial agent and an inorganic antibacterial agent.

Organic antimicrobial agents are relatively inexpensive and have good antimicrobial activity in a small amount. However, they sometimes have human toxicity and may be effective only for certain bacteria. have. In addition, there is a disadvantage in that discoloration after processing may cause discoloration and that the antibacterial persistence is short due to the elution problem, and thus the range of the organic antibacterial agent applicable to the antibacterial thermoplastic resin composition is extremely limited.

The inorganic antimicrobial agent is an antimicrobial agent containing a metal component such as silver (Ag) and copper (Cu) and is excellent in thermal stability and is widely used for producing an antimicrobial thermoplastic resin composition (antibacterial resin). However, Excessive use is required and there are disadvantages such as relatively high price, uniform dispersion problem during processing, discoloration due to metal components, and there are many restrictions in use.

Accordingly, there is a need to develop a thermoplastic resin composition which is excellent in weather resistance (discoloration resistance), antimicrobial property and antimicrobial persistence, and which is capable of realizing antifungal property and the like.

The background art of the present invention is disclosed in Korean Patent No. 10-0696385.

An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance, antibacterial properties, mechanical properties, and the like.

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

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

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; About 0.1 to about 4 parts by weight of a silver (Ag) based compound; And about 0.7 to about 4 parts by weight of zinc oxide, wherein the zinc oxide has an average particle size (D50) as measured by a particle size analyzer of about 0.8 to about 3 mu m, a photoluminescence measurement of 370 to 390 nm (B / A) of the peak A of the region and the peak B of the region of 450 to 600 nm is about 0.01 to about 1.0.

2. In one embodiment, the weight ratio of the silver compound and the zinc oxide (silver compound: zinc oxide) may be about 1: about 2: about 1: about 8.

3. The rubber-modified aromatic vinyl-based copolymer resin according to one or two embodiments above, may comprise a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

4. In the above-mentioned first to third embodiments, the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubbery polymer.

5. In the above-mentioned first to fourth embodiments, the aromatic vinyl-based copolymer resin may be an aromatic vinyl-based monomer and a polymer of a monomer copolymerizable with the aromatic vinyl-based monomer.

6. In the above-mentioned Embodiments 1 to 5, the silver compound may include at least one of a metal, silver oxide, silver halide and a silver-containing support.

7. The zinc oxide according to any one of the above 1 to 6, wherein the zinc oxide has a peak position 2? Value in the range of 35 to 37 ° in X-ray diffraction (XRD) analysis, The crystallite size value of the crystallite size may be from about 1,000 to about 2,000 A:

[Formula 1]

Microcrystalline size (D) =

In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).

8. In the above-mentioned Embodiments 1 to 7, the zinc oxide has a size ratio (B / A) of the peak A in the region of 370 to 390 nm and the peak B in the region of 450 to 600 nm 0.1 to about 1.0.

9. In the above-mentioned embodiments 1 to 8, the zinc oxide may have an average particle size (D50) measured by a particle size analyzer of about 1 to about 5 mu m.

10. In the above-mentioned embodiments 1 to 9, the zinc oxide may have a specific surface area BET of about 10 m ² / g or less as measured by a BET analysis equipment, using a nitrogen gas adsorption method.

11. In the above-mentioned Embodiments 1 to 10, the zinc oxide may have a specific surface area BET of about 1 to about 7 m ² / g, as measured by a BET analysis equipment, using a nitrogen gas adsorption method.

12. The thermoplastic resin composition according to any one of the above 1 to 11, wherein the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) is measured using a colorimeter for a 50 mm x 90 mm x 3 mm sized injection specimen The injection specimens were tested for weatherability for 3,000 hours in accordance with SAE J 1960 and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter. The resulting color change ([Delta] E) may be from about 4 to about 10:

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

13. The thermoplastic resin composition according to any one of the above 1 to 12, wherein the thermoplastic resin composition is inoculated with a Staphylococcus aureus strain and a Escherichia coli strain in a 5 cm x 5 cm size specimen according to JIS Z 2801 antibacterial evaluation method, After time-culturing, the antimicrobial activity values calculated according to the following formula 3 may be about 2 to about 7, respectively:

[Formula 3]

Antibacterial activity = log (M1 / M2)

In the above formula (3), M1 is the number of bacteria after 24 hours of incubation for the blank specimen, and M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.

14. Another aspect of the present invention relates to a molded article. Wherein the molded article is formed from the thermoplastic resin composition according to any one of 1 to 13 above.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in weather resistance, antibacterial properties, mechanical properties and the like and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) a silver (Ag) based compound; And (C) zinc oxide.

In the present specification, "a to b" representing numerical ranges are defined as "? A and? B".

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

The rubber-modified aromatic vinyl-based copolymer resin of the present invention may comprise (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.

(A1) a rubber-modified vinyl-based graft copolymer

As the rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention, an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer.

In the specific examples, the rubber-modified vinyl-based graft copolymer can be polymerized by adding an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer to the rubbery polymer, and the polymerization can be carried out by emulsion polymerization, Polymerization, and the like.

In the specific examples, the rubbery polymer includes a diene rubber such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubber in which hydrogen is added to the diene rubber, isoprene rubber, polybutylacrylic acid And an ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, a diene rubber can be used, and specifically, a butadiene rubber can be used. The amount of the rubbery polymer is about 5 to about 65 weight percent, such as about 10 to about 60 weight percent, specifically about 20 to about 50 weight percent, of the total weight (100 weight percent) of the rubber modified vinyl based graft copolymer, Lt; / RTI > The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range. In addition, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be from about 0.05 to about 6 microns, for example from about 0.15 to about 4 microns, specifically from about 0.25 to about 3.5 microns. Within the above range, the thermoplastic resin composition may have excellent impact resistance, appearance, and flame retardancy.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery copolymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- But are not limited to, styrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer is about 15 to about 94 wt%, for example, about 20 to about 80 wt%, specifically about 30 to about 60 wt%, based on the total weight (100 wt%) of the rubber-modified vinyl-based graft copolymer % ≪ / RTI > Within the above range, the thermoplastic resin composition may have excellent fatigue resistance, impact resistance, and mechanical properties.

Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. (Meth) acrylic acid and alkyl esters thereof, maleic anhydride, N-substituted maleimide, and the like, which may be used alone or in admixture of two or more. Specifically, acrylonitrile, methyl (meth) acrylate, a combination of these, and the like can be used. The content of the monomer copolymerizable with the aromatic vinyl monomer is about 1 to about 50% by weight, for example about 5 to about 45% by weight, specifically about 10 to about 50% by weight based on 100% by weight of the entire rubber modified vinyl-based graft copolymer 30% by weight. In the above range, the impact resistance, fluidity, appearance and the like of the thermoplastic resin composition can be excellent.

In the specific examples, as the rubber-modified vinyl-based graft copolymer, a copolymer (g-ABS) in which an aromatic vinyl compound and an acrylonitrile monomer, which are aromatic vinyl compounds and a vinyl cyanide compound, are grafted to a butadiene rubber- (G-MBS) in which methyl methacrylate is grafted with a styrene monomer which is an aromatic vinyl compound and a monomer copolymerizable with the aromatic vinyl compound, and the like, but the present invention is not limited thereto.

In an embodiment, the rubber-modified vinyl-based graft copolymer is a copolymer of about 10 to about 40% by weight, for example about 15 to about 35% by weight, of the total rubber-modified aromatic vinyl copolymer resin (A) . The impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.

(A2) an aromatic vinyl-based copolymer resin

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

In an embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing aromatic vinyl-based monomers and aromatic vinyl-based monomers with a monomer copolymerizable therewith and the like, and the polymerization may be carried out by emulsion polymerization, suspension polymerization, Of the present invention.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, and the like can be used, but the present invention is not limited thereto. These may be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example about 30 to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. (Meth) acrylic acid and alkyl esters thereof, maleic anhydride, N-substituted maleimide, etc. may be used alone or in admixture of two or more. The content of the monomer copolymerizable with the aromatic vinyl-based monomer may be about 10 to about 80% by weight, for example about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In embodiments, the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 300,000 g / mol, such as from about 15,000 to about 150,000 g / . Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

In an embodiment, the aromatic vinyl-based copolymer resin may include about 60 to about 90% by weight, for example about 65 to about 85% by weight, of 100% by weight of the whole rubber-modified aromatic vinyl-based copolymer resin (A) have. The impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.

(B) is a silver (Ag) based compound

The silver-based compound of the present invention is not particularly limited as long as it is a compound containing a silver component as an antimicrobial agent. Examples of the silver-based compound include metals, silver oxide, silver halide, a silver-containing carrier, have. Among them, a carrier containing silver ions can be used. Examples of the support include zeolite, silica gel, calcium phosphate, zirconium phosphate, phosphoric acid-sodium-zirconium, and phosphoric acid-sodium-hydrogen-zirconium. The carrier is preferably a porous structure. Since the porous structure of the carrier can hold the silver component up to the inside thereof, not only the content of the silver component can be increased but also the sustainability (maintenance performance) of the silver component is improved. Specifically, the silver compound may be silver sodium hydrogen zirconium phosphate or the like.

In an embodiment, the silver based compound has an average particle size (D50) as measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument) of less than about 1.5 microns, such as from about 0.1 to about 1 micron Lt; / RTI >

In an embodiment, the silver compound may be included in an amount of about 0.1 to about 4 parts by weight, for example about 1 to about 1.5 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the silver compound is contained in an amount of less than about 0.1 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the weather resistance, antimicrobial properties and the like of the thermoplastic resin composition may deteriorate. When the silver compound exceeds about 4 parts by weight , The dispersibility and the discoloration resistance of the thermoplastic resin composition may be lowered.

(C) Zinc oxide

The zinc oxide of the present invention is capable of improving the weather resistance and antimicrobial properties of the thermoplastic resin composition and is characterized in that the peak A in the region of 370 to 390 nm and the ratio of the peak B in the region of 450 to 600 nm (B / A) of from about 0.01 to about 1.0, such as from about 0.1 to about 1.0, specifically from about 0.2 to about 0.7. If the size ratio (B / A) of the peak A and the peak B of the zinc oxide is less than about 0.01, antimicrobiality and the like may be deteriorated. When the ratio B / A is more than about 1.0, the problem of initial discoloration of the thermoplastic resin, There is a concern.

In an embodiment, the zinc oxide may have various shapes and may include, for example, spheres, plates, rods, combinations thereof, and the like. The average particle size (D50) of single particles (the particles do not form secondary particles) measured by using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) is about From about 0.8 to about 3 microns, such as from about 1 to about 3 microns. Within the above range, the thermoplastic resin composition may be excellent in discoloration resistance, weather resistance, and the like. If the average particle size (D50) of the zinc oxide is less than about 0.8 mu m, the discoloration resistance and the like may be lowered. If the average particle size is more than about 3 mu m, there is a concern that the Izod impact physical properties may be lowered.

In an embodiment of the present invention, the zinc oxide has a peak position 2θ value in the range of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (Full of diffraction peak the crystallite size value calculated by applying Scherrer's equation (Equation 1) based on the width at half maximum may be about 1,000 to about 2,000 A, for example, about 1,200 to about 1,800 A. Within the above range, the initial color of the thermoplastic resin composition, weather resistance (discoloration resistance), antimicrobial property, mechanical property balance thereof and the like can be excellent.

[Formula 1]

Microcrystalline size (D) =

In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).

In embodiments, the zinc oxide may have a specific surface area BET of less than or equal to about 10 m < ² > / g, as measured by a BET analytical instrument (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 instrument) To about 7 m < ² > / g, and the purity may be greater than about 99%. Within the above range, the thermoplastic resin composition may have excellent mechanical properties, discoloration resistance, and the like.

In embodiments, the zinc oxide may be prepared by melting zinc in the form of a metal and then heating to about 850 to about 1000 캜, such as about 900 to about 950 캜, And then heating at about 400 to about 900 DEG C, for example, about 500 to about 800 DEG C for about 30 to about 150 minutes, for example, about 60 to about 120 minutes.

In embodiments, the zinc oxide may be included in an amount of from about 0.7 to about 4 parts by weight, for example, from about 1 to about 1.5 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When zinc oxide is contained in an amount of less than about 0.7 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the weather resistance and antibacterial property of the thermoplastic resin composition may be lowered. When the zinc oxide is more than about 4 parts by weight , The mechanical properties of the thermoplastic resin composition may be deteriorated.

In an embodiment, the weight ratio of the silver compound and the zinc oxide (silver compound: zinc oxide) may be from about 1: about 2 to about 1: about 8. The weatherability, antibacterial properties, mechanical properties, and the like of the thermoplastic resin composition can be further improved in the above range.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, a flame retardant, a filler, an antioxidant, a dripping inhibitor, a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye and mixtures thereof. When the additive is used, 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, per 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl copolymer resin).

The thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above components and melt-extruding at a temperature of about 200 to about 280 캜, for example, about 220 to about 250 캜, using a conventional twin-screw extruder. .

In an embodiment, the thermoplastic resin composition may be prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter on a 50 mm × 90 mm × 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test using a colorimeter, and then the color change calculated according to the following formula (2) ? E) can be from about 4 to about 10, for example from about 4 to about 8.

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

In the specific examples, the thermoplastic resin composition has antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, Pneumococcus and MRSA (Methicillin-Resistant Staphylococcus aureus) After incubation for 24 hours at 35 DEG C and RH 90%, the antimicrobial activity values calculated according to the following formula 3 were independently in the range of about 2 to about 7 , For example from about 2 to about 6.

[Formula 3]

Antibacterial activity = log (M1 / M2)

In the above formula (3), M1 is the number of bacteria after 24 hours of incubation for the blank specimen, and M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.

Here, the "blank specimen" is a control specimen of the test specimen (thermoplastic resin composition specimen). Specifically, in order to confirm whether or not the inoculated bacteria were normally grown, bacteria were inoculated on a petri dish and incubated for 24 hours in the same manner as the test specimens. The antibacterial activity of the test specimens . In addition, the "number of bacteria" can be counted by inoculating each specimen with the bacteria, orienting it for 24 hours, collecting the inoculated bacterial solution, diluting it, and growing it into a colony again on a culture dish. Colony grows too much, and when century is difficult, divide the divisions and count them, then convert them to actual numbers.

In an embodiment, the thermoplastic resin composition may have an IZOD impact strength of about 18 to about 22 kgf / cm / cm, as measured according to ASTM D256, of a 1/8 "thick extruded specimen.

The molded article according to the present invention is formed from the thermoplastic resin composition. The antimicrobial thermoplastic resin composition may be produced in the form of a pellet. The pellet may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is useful as an antimicrobial function product or an exterior material having frequent physical contact because it is excellent in weather resistance, antimicrobial property, impact resistance, flowability (molding processability) and physical properties thereof.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only 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) a rubber-modified aromatic vinyl-based copolymer resin

Modified aromatic vinyl copolymer resin containing 28% by weight of the rubber-modified vinyl-based graft copolymer (A1) and 72% by weight of the (A2) aromatic vinyl-based copolymer resin was used.

(A1) a rubber-modified vinyl-based graft copolymer

G-ABS in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were graft copolymerized with polybutadiene rubber (PBR) having a Z-average of 310 nm and 45 wt% was used.

(A2) an aromatic vinyl-based copolymer resin

SAN resin (weight average molecular weight: 130,000 g / mol) in which 68 wt% of styrene and 32 wt% of acrylonitrile were polymerized was used.

(B) is a silver (Ag) based compound

Silver sodium hydrogen zirconium phosphate (manufactured by Toa Gosei Co., LTD, product name: Novaron AGZ030) was used.

(C) Zinc oxide

(C1) After dissolving zinc in the form of metal, it was heated to 900 DEG C and vaporized. Then, oxygen gas was introduced and cooled to room temperature (25 DEG C) to obtain a primary intermediate. Next, zinc oxide prepared by cooling the primary intermediate at 700 DEG C for 90 minutes and then cooled to room temperature (25 DEG C) was used.

(C2) zinc oxide (manufactured by Liz Tech Biz, product name: RZ-950) was used.

(C3) zinc oxide (manufacturer: Hanil Chemical, product name: TE30) was used.

The ratio of the peak A in the region of 370 to 390 nm and the peak B of the region of 450 to 600 nm in the range of 370 to 390 nm in the measurement of the average particle size, the BET surface area, the purity, and the photo luminescence of the zinc oxide (C1, B / A) and the crystallite size were measured and are shown in Table 1 below.

	(C1)	(C2)	(C3)
Average particle size (占 퐉)	1.2	0.890	3.7
BET surface area (m 2 / g)	4	15	14
Purity (%)	99	97	97
PL size ratio (B / A)	0.28	9.8	9.5
The crystallite size (A)	1417	503	489

How to measure property

(1) Average particle size (unit: 占 퐉): The average particle size (volume average) was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument).

(2) BET surface area (unit: m ² / g): The BET surface area was measured with a BET analyzer (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 instrument) using a nitrogen gas adsorption method.

(3) Purity (unit:%): Purity was measured using TGA thermal analysis at a temperature of 800 ° C.

(4) PL size ratio (B / A): According to the photoluminescence measurement method, the spectrum emitted from a He-Cd laser (KIMMON company, 30 mW) having a wavelength of 325 nm at room temperature is measured by a CCD detector The temperature of the CCD detector was maintained at -70 ℃. (B / A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured. The injection specimen was subjected to PL analysis by injecting a laser into the specimen without any additional treatment. The zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to form a flat specimen. Respectively.

 (5) Crystallite size (unit: Å): A high resolution X-ray diffractometer (manufacturer: X'pert, device name: PRO-MRD) position 2θ value is in the range of 35 to 37 ° and is calculated by applying Scherrer's equation (Equation 1) based on the measured FWHM value (full width at half maximum of the diffraction peak). In this case, both the powder shape and the injection specimen can be measured. For the more accurate analysis, the injection specimen was subjected to heat treatment at 600 ° C. and air for 2 hours to remove the polymer resin, and then XRD analysis was carried out.

[Formula 1]

Microcrystalline size (D) =

In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).

Example  1 to 4 and Comparative Example  1 to 8

The above components were added in the amounts as shown in Table 2, and then extruded at 230 캜 to prepare pellets. The pellets were extruded at a temperature of 230 DEG C and a mold temperature of 60 DEG C for 6 hours at 80 DEG C for 4 hours or more, . The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 2 below.

How to measure property

(L ₀ ^* , a ₀ ^* , and A ₀ ^* ) were measured using a colorimeter (KONICA MINOLTA, CM-3700A) with respect to an injection sample having a size of 50 mm × 90 mm × 3 mm. b ₀ ^* ) was measured. The injection specimen was subjected to weather resistance test for 3,000 hours according to SAE J 1960, and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter Next, the color change (? E) was calculated according to the following formula (2).

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

(2) Antibacterial activity value: Staphylococcus aureus and E. coli were inoculated on a 5 cm x 5 cm specimen according to JIS Z 2801 antibacterial evaluation method, and cultured at 35 ° C and RH 90% for 24 hours. Respectively.

[Formula 3]

Antibacterial activity = log (M1 / M2)

In the above formula (3), M1 is the number of bacteria after 24 hours of incubation for the blank specimen, and M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.

(3) Impact resistance (Notch Izod impact strength (unit: kgf cm / cm)): The notched Izod impact strength of a 1/8 "thick specimen was measured according to ASTM D256.

	Example				Comparative Example
	One	2	3	4	One	2	3	4	5	6	7	8
(A) (parts by weight)	100	100	100	100	100	100	100	100	100	100	100	100
(B) (parts by weight)	0.2	0.2	0.5	0.5	-	0.1	0.1	1.0	2.0	5.0	0.5	0.5
(C1) (parts by weight)	1.0	1.5	1.0	1.5	-	0.3	0.5	0.1	0.3	5.0	-	-
(C2) (parts by weight)	-	-	-	-	-	-	-	-	-	-	1.0	-
(C3) (parts by weight)	-	-	-	-	-	-	-	-	-	-	-	1.0
Color change (ΔE)	6.5	6.3	7.2	6.9	12	11	6.6	14	15	15	11.8	12.5
The antibacterial activity value (E. coli)	2.5	2.8	3.0	3.1	0.1	1.1	1.5	3.3	6.3	6.3	3.2	2.9
Antibacterial activity value (Staphylococcus aureus)	2.2	2.3	2.5	2.5	0.2	1.3	1.5	2.5	4.6	4.6	2.7	2.2
Notch Izod impact strength	20	19.6	19	18.7	21	20.5	20.3	17.8	16	14	18.2	17.5

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in all of weather resistance (color change (? E)), antimicrobial activity (antibacterial activity value) and mechanical properties (notch Izod impact strength (impact resistance)).

On the other hand, in the case of Comparative Example 1 in which the silver compound and zinc oxide were not used, it was found that the weatherability and the antibacterial property were lowered. In Comparative Examples 2 to 6 in which at least one of the silver compound and zinc oxide was used outside the scope of the present invention It was found that at least one of weather resistance, antimicrobial property and impact resistance was lowered, and in case of Comparative Example 7 using zinc oxide (C2), it was found that the weather resistance etc. were lowered and in Comparative Example using zinc oxide (C3) 7, it can be seen that the weather resistance and the impact strength and the like are lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (14)

1. About 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;

   About 0.1 to about 4 parts by weight of a silver (Ag) based compound; And

   From about 0.7 to about 4 parts by weight of zinc oxide,

   The zinc oxide has an average particle size (D50) of about 0.8 to about 3 mu m as measured by a particle size analyzer and a peak A of 370 to 390 nm and a peak B of 450 to 600 nm in the photoluminescence measurement (B / A) of the thermoplastic resin composition is about 0.01 to about 1.0.
2. The thermoplastic resin composition according to claim 1, wherein the weight ratio of the silver compound and zinc oxide (silver compound: zinc oxide) is about 1: about 2: about 1: about 8.
3. The thermoplastic resin composition according to claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
4. The thermoplastic resin composition according to claim 3, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft-polymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubber-like polymer.
5. 4. The thermoplastic resin composition according to claim 3, wherein the aromatic vinyl-based copolymer resin is a polymer of an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.
6. The thermoplastic resin composition according to claim 1, wherein the silver compound comprises at least one of a metal, silver oxide, silver halide and a silver-containing support.
7. The zinc oxide according to claim 1, wherein the zinc oxide has a peak position 2θ value in the range of 35 to 37 ° in the X-ray diffraction (XRD) analysis, and the size wherein the crystallite size value of the thermoplastic resin composition is from about 1,000 to about 2,000 ANGSTROM.

   [Formula 1]

   Microcrystalline size (D) =

   

   In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).
8. The method of claim 1, wherein the zinc oxide has a size ratio (B / A) of a peak A in a range of 370 to 390 nm and a peak B in a range of 450 to 600 nm of from about 0.1 to about 1.0 And the thermoplastic resin composition is a thermoplastic resin composition.
9. 2. The thermoplastic resin composition according to claim 1, wherein the zinc oxide has an average particle size (D50) measured by a particle size analyzer of about 1 to about 5 mu m.
10. The thermoplastic resin composition according to claim 1, wherein the zinc oxide has a specific surface area BET of not more than about 10 m ² / g as measured by a BET analyzer using a nitrogen gas adsorption method.
11. The thermoplastic resin composition according to claim 1, wherein the zinc oxide has a specific surface area BET of from about 1 to about 7 m ² / g as measured by a BET analysis equipment using a nitrogen gas adsorption method.
12. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) measured using a colorimeter on a 50 mm × 90 mm × 3 mm size injection mold, The specimens were subjected to weather resistance test for 3,000 hours in accordance with SAE J 1960, and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter and the color Wherein the change (DELTA E) is about 4 to about 10. The thermoplastic resin composition according to claim 1,

    [Formula 2]

    Color change (ΔE) =

    

    In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.
13. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is inoculated with a Staphylococcus aureus strain and a Escherichia coli strain in a 5 cm x 5 cm size specimen according to JIS Z 2801 antibacterial evaluation method and cultured for 24 hours at 35 ° C and RH 90% Wherein the antimicrobial activity value calculated according to the following formula 3 is about 2 to about 7, respectively:

    [Formula 3]

    Antibacterial activity = log (M1 / M2)

    In the above formula (3), M1 is the number of bacteria after 24 hours of incubation for the blank specimen, and M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.
14. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 13.