KR101861482B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

100 parts by weight of the thermoplastic resin of the present invention; (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 is in the range of 0.1 to 1.0. The thermoplastic resin composition is excellent in weather resistance, antibacterial properties, and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article obtained from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More particularly, the present invention relates to a thermoplastic resin composition excellent in weatherability, antibacterial properties, and molded articles 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 antibacterial 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 antibacterial 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 weatherability, antibacterial 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.

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; (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 is in the range of 0.1 to 1.0.

In an embodiment, 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 crystallite size ) Value may be a crystallite size value of 1,000 to 2,000 A:

[Equation 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 an embodiment, the zinc oxide is obtained by melting zinc, heating it to 850 to 1,000 DEG C and vaporizing it, injecting oxygen gas, cooling to 20 to 30 DEG C, heating at 400 to 900 DEG C for 30 to 150 minutes .

In an embodiment, the thermoplastic resin includes at least one of a rubber-modified aromatic vinyl resin, a polyolefin resin, an aromatic vinyl resin, a polycarbonate resin, a polyalkyl (meth) acrylate resin, a polyester resin and a polyamide resin .

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

In an embodiment, the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubber-like polymer.

In an embodiment, 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.

In a specific example, the zinc oxide may have a size ratio (B / A) of 0.2 to 1.0 between the peak A in the region of 370 to 390 nm and the peak B in the region of 450 to 600 nm in the photoluminescence measurement.

In an embodiment, the zinc oxide may have a size ratio (B / A) of 0.2 to 0.7 between peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm in photo luminescence measurement.

In the specific example, the thermoplastic resin composition was measured for initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) according to ASTM D4459 for a 50 mm x 90 mm x 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the constant temperature and humidity test were measured in the same manner after exposure for 200 hours under the condition of 85% humidity and the color change (ΔE) Lt; / RTI > to 12:

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference between L ^* values before and after the constant temperature and humidity test (L ^* ₁ -L ^* ₀₎ and, Δa ^* is the difference between (a ₁ a ^* values before and after the constant temperature and humidity test ^* - a ₀ ^* ) And Δb ^* is the difference (b ₁ ^* - b ₀ ^* ) of the b ^* value before and after the constant temperature and humidity test.

In a specific example, the thermoplastic resin composition is a thermoplastic resin which is a rubber-modified vinyl-based copolymer resin, and the hue change (ΔE) may be 7 to 10.

In an embodiment, the thermoplastic resin composition is a thermoplastic resin is a polyolefin resin, and the hue (? E) may be 2 to 3.3.

In an embodiment, the thermoplastic resin composition is an aromatic vinyl resin, and the color change (ΔE) may be 10 to 12.

In the specific example, the thermoplastic resin composition is prepared by inoculating Staphylococcus aureus and Escherichia coli into a specimen of 5 cm x 5 cm in size according to JIS Z 2801 antibacterial evaluation method, culturing at 35 ° C and RH 90% for 24 hours, 3 may have an antibacterial activity value of 2 to 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.

Another aspect of the present invention relates to a molded article. And the molded article is formed from the thermoplastic resin composition.

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 thermoplastic resin; And (B) zinc oxide.

(A) a thermoplastic resin

The thermoplastic resin of the present invention may be a thermoplastic resin used in a conventional thermoplastic resin composition. For example, a rubber-modified aromatic vinyl resin, a polyolefin resin, an aromatic vinyl resin, a polycarbonate resin, a polyalkyl (meth) acrylate resin, a polyester resin, a polyamide resin, or a combination thereof may be used. Specifically, it may be (A1) a rubber-modified vinyl copolymer resin, (A2) a polyolefin resin, (A3) an aromatic vinyl resin, or a combination thereof.

(A1) a rubber-modified vinyl copolymer resin

The rubber-modified vinyl-based copolymer resin according to one embodiment of the present invention may include (A1-1) a rubber-modified vinyl-based graft copolymer and (A1-2) an aromatic vinyl-based copolymer resin.

(A1-1) Rubber-modified aromatic vinyl-based graft copolymer

As the rubber-modified aromatic 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 a 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 content of the rubbery polymer may be 5 to 65% by weight, for example, 10 to 60% by weight, specifically 20 to 50% by weight in the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer. The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range. The average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 탆, for example, 0.15 to 4 탆, specifically 0.25 to 3.5 탆. 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 may be 15 to 94% by weight, for example, 20 to 80% by weight, specifically 30 to 60% by weight in the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer . 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 may be 1 to 50% by weight, for example, 5 to 45% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the entire rubber modified vinyl-based graft copolymer . 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, an acrylonitrile monomer, which is an aromatic vinyl compound, 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 aromatic vinyl-based graft copolymer may be contained in an amount of 10 to 40% by weight, for example, 15 to 30% by weight, based on 100% by weight of the whole rubber-modified vinyl copolymer resin (A1). The impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.

(A1-2) The 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 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 20 to 90% by weight, for example, 30 to 80% 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.

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 10 to 80% by weight, for example, 20 to 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 an embodiment, the aromatic vinyl-based copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 300,000 g / mol, for example, 15,000 to 150,000 g / mol. 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 60 to 90% by weight, for example 70 to 85% by weight, of 100% by weight of the entire rubber-modified vinyl-based copolymer resin (A1). The impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.

(A2) Polyolefin resin

As the polyolefin resin according to one embodiment of the present invention, a conventional polyolefin resin can be used. (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer, A polyethylene-based resin such as a mixture; Polypropylene resins such as polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer, and mixtures thereof; Polymers crosslinked therewith; A blend comprising polyisobutene; And mixtures thereof. Specifically, a polypropylene resin or the like can be used.

In embodiments, the polyolefin resin may have a weight average molecular weight (Mw) as determined by gel permeation chromatography (GPC) of 10,000 to 400,000 g / mol, such as 15,000 to 350,000 g / mol. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

(A3) An aromatic vinyl resin

As the aromatic vinyl resin according to one embodiment of the present invention, a usual aromatic vinyl resin can be used. For example, polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer resin (SAN), and the like. These may be used alone or in combination of two or more. The method for producing the aromatic vinyl resin is well known to those skilled in the art, and is commercially available.

In an embodiment, the aromatic vinyl resin may have a weight average molecular weight measured by GPC (Gel Permeation Chromatography) of 10,000 to 300,000 g / mol, for example, 15,000 to 250,000 g / mol. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

(B) 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) may be 0.1 to 1.0, for example, 0.2 to 1.0, specifically 0.2 to 0.7. If the size ratio (B / A) of the peak A and the peak B of the zinc oxide is less than 0.1, the antibacterial property may be deteriorated. If the ratio B / A is more than 1.0, there is a fear that the initial discoloration problem and the weather resistance of the thermoplastic resin have.

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 1,000 to 2,000 A, for example, 1,200 to 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.

[Equation 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 an average particle size (D50) of from 0.5 to 3 microns, such as from 1 to 3 microns, and a specific surface area BET of less than 10 m ² / g, such as from 1 to 7 m ² / g, and the purity may be at least 99%. Within the above range, the thermoplastic resin composition may have excellent mechanical properties, discoloration resistance, and the like.

In an embodiment, the zinc oxide is obtained by melting zinc in the form of a metal, heating it to 850 to 1,000 ° C, for example, 900 to 950 ° C to vaporize it, injecting oxygen gas, cooling the mixture to 20 to 30 ° C, For example, at 400 to 900 DEG C, for example, at 500 to 800 DEG C for 30 to 150 minutes, for example, for 60 to 120 minutes.

In an embodiment, the zinc oxide may be contained in an amount of 0.5 to 30 parts by weight, for example, 0.5 to 20 parts by weight, specifically 1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the zinc oxide is contained in an amount of less than 0.5 parts by weight based on 100 parts by weight of the thermoplastic resin, the weather resistance, antimicrobial properties and the like of the thermoplastic resin composition may be lowered. If the zinc oxide content is more than 30 parts by weight, the mechanical properties of the thermoplastic resin composition There is a risk of degradation.

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 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components at a temperature of 200 to 280 DEG C, for example 220 to 250 DEG C, using a conventional twin-screw extruder.

In the specific example, the thermoplastic resin composition was measured for initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) according to ASTM D4459 for a 50 mm x 90 mm x 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the constant temperature and humidity test were measured in the same manner after exposure for 200 hours under the condition of 85% humidity and the color change (ΔE) Lt; / RTI >

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference between L ^* values before and after the constant temperature and humidity test (L ^* ₁ -L ^* ₀₎ and, Δa ^* is the difference between (a ₁ a ^* values before and after the constant temperature and humidity test ^* - a ₀ ^* ) And Δb ^* is the difference (b ₁ ^* - b ₀ ^* ) of the b ^* value before and after the constant temperature and humidity test.

Here, the? A ^* may be 1.0 to 1.5. In the weatherability evaluation, when it is out of the above-mentioned range of? A ^* , there is a possibility that the weatherability (discoloration resistance) is greatly lowered to such an extent that a color change is visually perceived.

In a specific example, the thermoplastic resin composition is a thermoplastic resin which is a rubber-modified vinyl-based copolymer resin, and the hue change (ΔE) may be 7 to 10, for example, 7.5 to 9.

In an embodiment, the thermoplastic resin composition is a thermoplastic resin is a polyolefin resin, and the hue change (ΔE) may be from 2 to 3.3, for example, from 2.1 to 3.

In an embodiment, the thermoplastic resin composition is an aromatic vinyl resin, and the color change (ΔE) may be 10 to 12, for example, 10.5 to 11.5.

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 antibacterial activity values calculated according to the following formula 3 were independently 2 to 7, For example from 2 to 6.5, in particular from 4 to 6.5.

[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.

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 thermoplastic resin

(A1) a rubber-modified vinyl copolymer resin

Modified vinyl copolymer resin comprising 27% by weight of the rubber-modified aromatic vinyl-based graft copolymer (A1-1) and 73% by weight of the (A1-2) aromatic vinyl-based copolymer resin was used.

(A1-1) Rubber-modified aromatic 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.

 (A1-2) The 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.

(A2) Polyolefin resin

A polypropylene resin having a weight average molecular weight of 248,600 g / mol (manufactured by Lotte Chemical Co., Ltd.) was used.

(A3) An aromatic vinyl resin

High-performance HIPS (manufacturer: Dongbu Chemical, product name: H-834) having a weight average molecular weight of 160,000 g / mol was used.

(B) zinc oxide

(B1) 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.

(B2) zinc oxide (manufacturer: PJ Chemtech, product name: KS-1) was used.

(B3) zinc oxide (manufacturer: Ristec Biz, product name: RZ-950) 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 from 370 to 390 nm (in terms of the average particle size, the BET surface area, the purity and the photo luminescence) B / A) and the crystallite size were measured and are shown in Table 1 below.

(B4) After dissolving zinc in the form of metal, it was heated to 900 DEG C to be 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 800 ° C for 90 minutes and cooling to room temperature (25 ° C) was used.

(B5) After dissolving zinc in the form of metal, it was heated to 900 DEG C to be vaporized, then oxygen gas was introduced and cooled to room temperature (25 DEG C) to obtain a primary intermediate. Next, zinc oxide prepared by heat-treating the primary intermediate at 500 ° C for 90 minutes and cooling to room temperature (25 ° C) was used.

(B6) Zinc oxide (manufacturer: Ristec Biz, product name: RZ-950) The product (B3) was further subjected to heat treatment at 700 ° C for 90 minutes and then cooled to room temperature (25 ° C) Respectively.

The average particle size, BET surface area, purity and photoluminescence of the zinc oxide (B1, B2, B3, B4, B5 and B6) were measured at a peak A of 370 to 390 nm and a peak A of 450 to 600 nm The ratio (B / A) of the peak B and the crystallite size of the peak B were measured and are shown in Table 1 below.

(B1) (B2) (B3) (B4) (B5) (B6) Average particle size (占 퐉) 1.2 1.0 1.1 1.2 1.2 1.2 BET surface area (m ² / g) 4 6 15 4.2 4.1 14.9 Purity (%) 99 99 97 99 99 99 PL size ratio (B / A) 0.28 0.05 9.8 0.11 0.98 1.61 The crystallite size (A) 1417 1229 503 1420 1451 519

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.

[Equation 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).

Examples 1 to 12 and Comparative Examples 1 to 24

The respective components were added in the amounts as shown in Tables 2 to 6, and then extruded at 230 占 폚 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 Tables 2 to 6 below.

How to measure property

(L ₀ ^* , a ₀ ^* , b ₀ ^* ) was measured according to ASTM D4459 for a 50 mm x 90 mm x 3 mm sized injection specimen, The color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the constant temperature and humidity test was measured by the same method after exposure for 200 hours under the conditions of 85 ° C. and 85% relative humidity, Respectively.

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference between L ^* values before and after the constant temperature and humidity test (L ^* ₁ -L ^* ₀₎ and, Δa ^* is the difference between (a ₁ a ^* values before and after the constant temperature and humidity test ^* - a ₀ ^* ) And Δb ^* is the difference (b ₁ ^* - b ₀ ^* ) of the b ^* value before and after the constant temperature and humidity 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)): Notch Izod impact strength of a 1/8 "thick specimen was measured according to ASTM D256.

Example One 2 3 4 5 6 7 8 9 10 11 12 (A1) (parts by weight) 100 100 - - - - 100 100 - - - - (A2) (parts by weight) - - 100 100 - - - - 100 100 - - (A3) (parts by weight) - - - - 100 100 - - - - 100 100 (B1) (parts by weight) 2 25 2 25 2 25 - - - - - - (B4) (parts by weight) - - - - - - 10 - 10 - 10 - (B5) (parts by weight) - - - - - - - 10 - 10 - 10 Δa ^* 1.16 1.40 0.12 0.07 2.41 2.21 1.21 1.22 0.14 0.18 1.31 1.48 Color change
(ΔE) 8.03 8.41 2.41 2.29 10.98 10.76 8.11 8.12 2.51 2.93 11.10 11.31 Antimicrobial activity value
(E. coli) 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 Antimicrobial activity value
(Staphylococcus aureus) 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4

Comparative Example One 2 3 4 5 6 7 8 (A1) (parts by weight) 100 100 100 100 100 100 100 100 (B1) (parts by weight) - - - - - - 0.1 31 (B2) (parts by weight) 2 25 - - - - - - (B3) (parts by weight) - - 2 25 - - - - (B6) (parts by weight) - - - - 2 25 - - Δa ^* 1.30 1.23 4.60 4.55 4.53 4.61 1.53 1.98 Color change (ΔE) 11.18 11.01 11.91 11.78 12.10 11.98 12.78 10.81 Antimicrobial activity value
(E. coli) 3.6 4.6 3.0 4.5 3.3 4.6 0.8 4.6 Antimicrobial activity value
(Staphylococcus aureus) 3.1 4.1 3.8 4.0 3.3 3.8 0.6 6.3

Comparative Example 9 10 11 12 13 14 15 16 (A2) (parts by weight) 100 100 100 100 100 100 100 100 (B1) (parts by weight) - - - - - - 0.1 31 (B2) (parts by weight) 2 25 - - - - - - (B3) (parts by weight) - - 2 25 - - - - (B6) (parts by weight) - - - - 2 25 - - Δa ^* 0.21 0.17 2.84 2.14 2.71 2.22 0.27 0.41 Color change (ΔE) 4.52 4.30 6.78 6.07 6.54 6.19 10.11 3.41 Antimicrobial activity value
(E. coli) 3.4 4.6 2.8 4.6 2.4 4.4 0.2 4.6 Antimicrobial activity value
(Staphylococcus aureus) 3.1 4.0 3.0 3.9 2.8 4.0 0.5 6.4

Comparative Example 17 18 19 20 21 22 23 24 (A3) (parts by weight) 100 100 100 100 100 100 100 100 (B1) (parts by weight) - - - - - - 0.1 31 (B2) (parts by weight) 2 25 - - - - - - (B3) (parts by weight) - - 2 25 - - - - (B6) (parts by weight) - - - - 2 25 - - Δa ^* 2.71 2.33 5.61 4.88 5.81 4.77 1.51 2.01 Color change (ΔE) 13.11 13.41 18.69 17.11 19.01 16.95 7.88 10.80 Antimicrobial activity value
(E. coli) 3.4 4.6 3.0 4.6 2.4 4.4 0.3 4.6 Antimicrobial activity value
(Staphylococcus aureus) 2.8 4.1 3.3 3.6 2.6 3.9 0.7 6.4

Example Comparative Example One 2 3 4 5 6 8 16 24 (A1) (parts by weight) 100 100 - - - - 100 - (A2) (parts by weight) - - 100 100 - - - 100 - (A3) (parts by weight) - - - - 100 100 - - 100 (B1) (parts by weight) 2 25 2 25 2 25 31 31 31 Notch Izod impact strength 24.2 15.8 6.7 4.4 12.1 7.9 13.2 3.6 6.4

From the results of Tables 2 to 6, it can be seen that the thermoplastic resin composition of the present invention is excellent in weather resistance (color change (? E)), antimicrobial activity (antibacterial activity value), and mechanical properties (impact resistance).

On the other hand, in the case of Comparative Examples 1 and 2 using a rubber-modified vinyl copolymer resin as the thermosetting resin and using zinc oxide (B2) having a PL size ratio (B / A) of less than 0.1 (0.05) (Staphylococcus aureus) of 3.1 and 4.1 was lower than that of the examples, and the BET surface area was more than 10 m ² / g (15) and the PL size ratio (B / A) The antibacterial activity (antibacterial activity value) of Comparative Examples 3 and 4 using zinc oxide (B3) of more than 1 (9.83) and having a small crystallite size (503 angstroms) was lower than that of Examples and decreased in weatherability, It can be confirmed that discoloration has occurred to a large extent. In Comparative Example using a zinc oxide (B6) having a BET surface area of more than 10 m ² / g (14.9), a PL size ratio (B / A) of more than 1 (1.61) 5 and 6, the antimicrobial activity (antibacterial activity value) was lowered compared to the examples, the weatherability was lowered, and the discoloration was visually observed to be severe. When a small amount of zinc oxide (B1) 7). As a result, it was found that the weather resistance and the antibacterial property were significantly lowered, and that when the zinc oxide (B1) was used in an excessive amount (Comparative Example 8), the weather resistance and mechanical properties were relatively lower than those of Examples.

It can be seen that the weatherability and the antibacterial activity value (staphylococci) were lowered in Comparative Examples 9 and 10 using a polyolefin resin as a thermosetting resin and zinc oxide (B2) compared with Examples 3 and 4, In Comparative Examples 11 and 12 using zinc oxide (B3), the antibacterial activity (antibacterial activity value) was lowered and the weather resistance was lowered compared with the examples. In Comparative Examples 13 and 14 using zinc oxide (B6) Antibacterial activity value) was lower than that of the examples, and it was confirmed that the weatherability was lower than that of the examples. It was also found that when the zinc oxide (B1) was used in a small amount (Comparative Example 15), the weather resistance (color change) was lowered and the antibacterial property was greatly lowered. It can be seen that the weather resistance and the mechanical properties are relatively lowered as compared with the examples.

Further, in the case of Comparative Examples 17 and 18 in which an aromatic vinyl resin was used as the thermosetting resin and zinc oxide (B2) was used, the weather resistance was greatly lowered and the antibacterial activity value (Staphylococcus aureus) (Antimicrobial activity value) of the comparative examples 19 and 20 in which zinc oxide (B3) was used was lower than that of the examples and the weather resistance was significantly lowered. In comparison example 21 using zinc oxide (B6) (22) and (22), the antibacterial activity (antibacterial activity value) was lowered compared to the examples, and the weatherability was significantly lowered. It was also found that antimicrobial activity was significantly lowered when zinc oxide (B1) was used in a small amount (Comparative Example 23), and mechanical properties were lowered in Comparative Example 24 when zinc oxide (B1) Able to know.

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 (15)

100 parts by weight of a thermoplastic resin; And
0.5 to 30 parts by weight of zinc oxide,
The zinc oxide has a size ratio (B / A) of a peak A in the region of 370 to 390 nm and a peak B in the region of 450 to 600 nm of 0.1 to 1.0 at the time of measurement of photoluminescence, ray diffraction (XRD) analysis, the peak position 2θ value is in the range of 35 to 37 °, and the crystallite size according to the following formula 1 is 1,000 to 2,000 Å. Composition:
[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).
delete The method of claim 1, wherein the zinc oxide is dissolved in zinc, heated to 850 to 1,000 ° C to be vaporized, then injected with oxygen gas, cooled to 20 to 30 ° C, and then heated at 400 to 900 ° C for 30 to 150 minutes Lt; / RTI > by weight of the thermoplastic resin composition.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one of a rubber-modified aromatic vinyl resin, an aromatic vinyl resin, a polyolefin resin, a polycarbonate resin, a polyalkyl (meth) acrylate resin, a polyester resin, and a polyamide resin By weight based on the total weight of the thermoplastic resin composition.
The thermoplastic resin composition according to claim 4, wherein the rubber-modified aromatic vinyl resin comprises a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
The thermoplastic resin composition according to claim 5, 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 rubbery polymer.
The thermoplastic resin composition according to claim 5, 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.
The zinc oxide according to claim 1, wherein the zinc oxide has a size ratio (B / A) of 0.2 to 1.0 in peak A of 370 to 390 nm region and peak B of 450 to 600 nm region in photoluminescence measurement Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The zinc oxide according to claim 1, wherein the zinc oxide has a size ratio (B / A) of 0.2 to 0.7 in peak A of 370 to 390 nm and peak B of 450 to 600 nm in photo luminescence measurement Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The thermoplastic resin composition according to claim 1, wherein the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) is measured according to ASTM D4459 for a 50 mm x 90 mm x 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after a constant temperature and humidity test in the same manner after exposure for 200 hours under the condition of a relative humidity of 85% and a color change (ΔE) Is from 2 to 12:
[Formula 2]
Color change (ΔE) =

In the formula 2, ΔL ^* is a difference between L ^* values before and after the constant temperature and humidity test (L ^* ₁ -L ^* ₀₎ and, Δa ^* is the difference between (a ₁ a ^* values before and after the constant temperature and humidity test ^* - a ₀ ^* ) And Δb ^* is the difference (b ₁ ^* - b ₀ ^* ) of the b ^* value before and after the constant temperature and humidity test.
The thermoplastic resin composition according to claim 10, wherein the thermoplastic resin composition is a rubber-modified vinyl-based copolymer resin, wherein the thermoplastic resin has a color change (ΔE) of 7 to 10.
The thermoplastic resin composition according to claim 10, wherein the thermoplastic resin composition is a polyolefin resin and the hue (? E) is 2 to 3.3.
The thermoplastic resin composition according to claim 10, wherein the thermoplastic resin composition is an aromatic vinyl resin, and the color change (ΔE) is 10 to 12.
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 antibacterial activity values calculated according to the following formula 3 are respectively 2 to 7:
[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.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 14.