WO2018124657A1 - Thermoplastic resin composition and molded article manufactured therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention is characterized by comprising: about 100 parts by weight of a thermoplastic resin containing a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin; about 10 to about 30 parts by weight of an antistatic agent; and about 0.01 to about 2 parts by weight of zinc oxide, wherein the antistatic agent comprises at least one of a polyether ester amide block copolymer, a polyalkylene glycol, and a polyamide. The thermoplastic resin composition is excellent in antibacterial properties, antistatic properties, impact resistance, and the like.

Description

Thermoplastic Resin Composition and Molded Article Prepared 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 antimicrobial activity, antistatic property, impact resistance and the like and a molded article produced therefrom.

As the thermoplastic resin, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) are excellent in mechanical properties, processability, appearance characteristics, etc. It is widely used as interior / exterior materials for automobiles and exterior materials for construction.

When such resins are used in applications where physical contact with medical devices, toys, food containers, etc. occurs, the material itself requires antimicrobial properties that can remove or suppress bacteria, antistatic properties, shock resistance, etc. Mechanical properties and the like are required. In order to obtain an antimicrobial thermoplastic resin composition, an inorganic or organic antimicrobial agent may be used. However, in the case of the inorganic antimicrobial agent, there is a problem such as discoloration of the thermoplastic resin and a decrease in transparency. It is not easy to apply.

Therefore, there is a need for the development of a thermoplastic resin composition having excellent antimicrobial properties as well as antistatic properties and impact resistance.

Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2005-239904 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in antibacterial, antistatic, impact resistance 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. The thermoplastic resin composition may include about 100 parts by weight of a thermoplastic resin including a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin; About 10 to about 30 parts by weight of an antistatic agent; And from about 0.01 to about 2 parts by weight of zinc oxide, wherein the antistatic agent comprises at least one of polyetheresteramide block copolymers, polyalkylene glycols, and polyamides.

In one embodiment, the rubber-modified vinyl graft copolymer may be a graft polymerized monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.

In an embodiment, the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

In embodiments, the rubber-modified vinyl graft copolymer is included in about 20 to about 50% by weight of 100% by weight of the thermoplastic resin, the aromatic vinyl copolymer resin is from about 50 to 100% by weight of the thermoplastic resin About 80% by weight.

In embodiments, the zinc oxide may have an average particle size of about 0.2 to about 3 μm and a specific surface area BET of about 1 to about 10 m ² / g.

In embodiments, the zinc oxide may have a size ratio (B / A) of peak A in the 370 to 390 nm region and peak B in the 450 to 600 nm region when measured by photo luminescence. have.

In embodiments, the zinc oxide has a peak position 2θ of 35 to 37 ° when analyzed by X-ray diffraction (XRD), and crystallite size according to Equation 1 below. ) Value can be from about 1,000 to about 2,000 mm 3:

[Equation 1]

Microcrystal size (D) =

In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).

In an embodiment, the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm size specimen, based on JIS Z 2801 antimicrobial evaluation method, and measured after incubation at 35 ° C. and RH 90% for 24 hours. The antimicrobial activity may be about 2 to about 7 and about 2 to about 6.5, respectively.

In an embodiment, the thermoplastic resin composition may have a surface resistance value of about 1 × 10 ⁶ to about 1 × 10 ¹⁰ Ω · cm measured according to ASTM D257.

In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of about 1/4 "thick specimen, measured in accordance with ASTM D256, from about 15 to about 25 kgfcm / cm.

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

The present invention has the effect of the invention to provide a thermoplastic resin composition excellent in antimicrobial properties, antistatic properties, impact resistance 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 includes (A) a thermoplastic resin comprising (A1) a rubber-modified vinyl graft copolymer and (A2) an aromatic vinyl copolymer resin; (B) antistatic agents; And (C) zinc oxide.

(A) thermoplastic resin

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

(A1) rubber modified aromatic vinyl graft copolymer

Rubber-modified vinyl graft copolymer according to an embodiment of the present invention may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer. For example, the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer, and, if necessary, processability and The monomer which gives heat resistance can be further included and graft-polymerized. The polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization. In addition, the rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.

In an embodiment, the rubbery polymer may be a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or a saturated rubber hydrogenated to the diene rubber, isoprene rubber, C 2 to C 10 alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymers (EPDM), and the like. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber, (meth) acrylate rubber, etc. can be used, Specifically, butadiene rubber, butyl acrylate rubber, etc. can be used. The average particle size (Z-average) of the rubbery polymer (rubber particles) may be 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. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.

In embodiments, the content of the rubbery polymer may be about 20 to about 70% by weight, for example about 25 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, the monomer mixture (aromatic The vinyl monomer and the vinyl cyanide monomer) may be about 30 to about 80 wt%, for example about 40 to about 75 wt%, of 100 wt% of the total rubber-modified vinyl graft copolymer. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof. The aromatic vinyl monomer may be included in an amount of about 10 wt% to about 90 wt%, for example, about 40 wt% to about 90 wt% in 100 wt% of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.

In one embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be about 10 wt% to about 90 wt%, for example about 10 wt% to about 60 wt%, in 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.

In a specific example, monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like. When using the monomer to impart the processability and heat resistance, the content may be about 15% by weight or less, for example about 0.1 to about 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.

In one embodiment, the rubber-modified vinyl graft copolymer is a copolymer in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted to a butadiene rubber polymer, and butyl acryl. An acrylate-styrene-acrylonitrile graft copolymer (g-ASA) which is a copolymer in which the styrene monomer which is an aromatic vinyl type compound, and the acrylonitrile monomer which is a vinyl cyanide compound is grafted to a latex rubbery polymer can be illustrated. have.

In an embodiment, the rubber modified vinyl graft copolymer is about 20 to about 50 wt%, for example about 100 wt% of the total thermoplastic resin (rubber modified vinyl graft copolymer and aromatic vinyl copolymer resin) 25 to about 45 weight percent. In the above range, the impact resistance, fluidity (molding processability), appearance properties, balance of physical properties, and the like of the thermoplastic resin composition may be excellent.

(A2) aromatic vinyl copolymer resin

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

In an embodiment, the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. 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, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

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 monomer or a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, specifically, a vinyl cyanide monomer and an alkyl (meth) acrylic monomer.

In an embodiment, examples of the vinyl cyanide monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like, but are not limited thereto. Do not. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used.

In specific embodiments, examples of the alkyl (meth) acrylic monomer may include (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 thereof. For example, methyl methacrylate, methyl acrylate, etc. can be used.

In embodiments, when the monomer copolymerizable with the aromatic vinyl monomer is a mixture of a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, the content of the vinyl cyanide monomer may be 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. About 1 to about 40% by weight, for example about 2 to about 35% by weight, and the content of the alkyl (meth) acrylic monomer is about 60 to about 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. 99 weight percent, for example about 65 to about 98 weight percent. In the above range, the thermoplastic resin composition may have excellent transparency, heat resistance, processability, and the like.

In an embodiment, the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 to about 80 wt%, for example about 20 to about 70 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

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 be. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin may be included in about 50 to about 80% by weight, for example about 55 to about 75% by weight of 100% by weight of the total thermoplastic resin. Impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition in the above range may be excellent.

(B) antistatic agent

An antistatic agent according to an embodiment of the present invention may improve antimicrobial properties, antistatic properties, and the like of a thermoplastic resin composition (sample) with a small amount of zinc oxide, and a polyetheresteramide block copolymer and a polyalkylene glycol And polyamides, combinations thereof, and the like. Preferably, a polyetheresteramide block copolymer may be included, and an antistatic agent made of a commercially available polyetheresteramide copolymer may be used.

In embodiments, the polyetheresteramide block copolymers include amino carboxylic acids, lactams or diamine-dicarboxylates having 6 or more carbon atoms; Polyalkylene glycols; And it may be a block copolymer of the reaction mixture comprising a dicarboxylic acid having 4 to 20 carbon atoms.

As a salt of the said C6 or more amino carboxylic acid, lactam, or diamine dicarboxylic acid, it is omega-aminocapronic acid, omega-aminoenanthate, omega-aminocaprylic acid, omega-aminofelconic acid, omega- Aminocarboxylic acids such as aminocaprinic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid and the like; Lactams such as caprolactam, enanthlactam, capryllactam, lauryl lactam and the like; And salts of diamines and dicarboxylic acids such as salts of hexamethylenediamine-adipic acid, salts of hexamethylenediamine-isophthalic acid, and the like. For example, 1,2-aminododecanoic acid, caprolactam, salts of hexamethylenediamine-adipic acid, and the like can be used.

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

As said C4-C20 dicarboxylic acid, terephthalic acid, 1, 4- cyclohexacarboxylic acid, sebacic acid, adipic acid, dodecanoic acid, etc. can be illustrated.

In embodiments, the bond of the amino carboxylic acid, lactam or diamine-dicarboxylic acid salt of 6 or more carbon atoms; and the polyalkylene glycol; may be an ester bond, the amino carboxylic acid, lactam or of 6 or more carbon atoms The combination of the diamine-dicarboxylic acid salt and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and the combination of the polyalkylene glycol; and the dicarboxylic acid having 4 to 20 carbon atoms; It may be an ester bond.

In an embodiment, the polyetheresteramide block copolymer may be prepared by a known synthesis method, for example, according to the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424. Can be.

In an embodiment, the polyetheresteramide block copolymer can comprise about 10 to about 95 weight percent of the polyether-ester block. In the above range, the mechanical properties of the thermoplastic resin composition may be excellent in antistatic properties.

In an embodiment, the antistatic agent may be included in an amount of about 10 to about 30 parts by weight, for example about 12 to about 25 parts by weight, specifically about 14 to about 20 parts by weight, based on about 100 parts by weight of the thermoplastic resin. When less than about 10 parts by weight of the antistatic agent is used, there is a fear that the antimicrobial properties and antistatic properties of the thermoplastic resin composition may be lowered. There is.

(C) zinc oxide

The zinc oxide of the present invention can improve the antimicrobial properties of the thermoplastic resin composition and the like together with the heat stabilizer, and zinc oxide used in a conventional antimicrobial composition can be used.

In embodiments, the zinc oxide may have an average particle size of about 0.2 to about 3 μm, such as about 0.3 to about 2 μm, as measured by a particle size analyzer, and a specific surface area BET of about 1 to about 10 m ² / g, For example, it may be about 1 to about 7 m ² / g, purity may be about 99% or more. In the above range, the antimicrobial properties, weather resistance and the like of the thermoplastic resin composition may be excellent.

In embodiments, the zinc oxide has a size ratio (B / A) of peak A in the 370 to 390 nm region and peak B in the 450 to 600 nm region when measured by photo luminescence, eg, For example from about 0.01 to about 0.09 or from about 0.1 to about 1. In the above range, the thermoplastic resin composition may have excellent antibacterial, low odor or weather resistance.

In embodiments, the zinc oxide has a peak position 2θ of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (full of diffraction peaks). The crystallite size value calculated by applying the Scherrer's equation (Equation 1) based on the width at Half Maximum may be about 1,000 to about 2,000 GPa, for example, about 1,200 to about 1,800 GPa. In the above range, the initial color of the thermoplastic resin composition, weather resistance, antibacterial and the like can be excellent.

[Equation 1]

Microcrystal size (D) =

In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value, and θ is a peak position degree.

In an embodiment, the zinc oxide is dissolved in zinc in the form of metal, vaporized by heating to about 850 to about 1,000 ° C., for example, about 900 to about 950 ° C., followed by injection of oxygen gas and about 20 to about 30 After cooling to ℃, if necessary, the heat treatment for about 30 minutes to about 150 minutes at about 700 to about 800 ℃ while injecting nitrogen / hydrogen gas into the reactor, and then cooled to room temperature (20 to 30 ℃) It can manufacture.

In some embodiments, the zinc oxide may be included in an amount of about 0.01 to about 2 parts by weight, for example, about 0.02 to about 0.5 parts by weight, specifically about 0.03 to about 0.2 parts by weight, based on about 100 parts by weight of the thermoplastic resin. When the zinc oxide is less than about 0.01 part by weight, the antimicrobial activity of the thermoplastic resin composition may be lowered. When the zinc oxide is more than about 0.2 part by weight, the appearance characteristics (transparency) of the thermoplastic resin composition may be lowered.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. The additives may include, but are not limited to, flame retardants, fillers, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like. When using the additive, the content 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 thermoplastic resin.

The thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets mixed with the components and melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 250 ° C, using a conventional twin screw extruder. Can be.

In an embodiment, the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm size specimen, based on JIS Z 2801 antimicrobial evaluation method, and measured after incubation at 35 ° C. and RH 90% for 24 hours. The antimicrobial activity may be about 2 to about 7 and about 2 to about 6.5, respectively.

In embodiments, the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁶ to about 1 × 10 ¹⁰ Ω · cm, for example about 1 × 10 ⁸ to about 1 × 10 ¹⁰ Ω, as measured according to ASTM D257. Can be cm.

In embodiments, the thermoplastic resin composition has a notched Izod impact strength of about 1/4 "thick specimen of about 15 to about 25 kgfcm / cm, such as about 18 to about 23 kgfcm, as measured according to ASTM D256. / cm.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. The molded article is excellent in antimicrobial, antistatic, impact resistance, transparency, fluidity (molding processability), the balance of physical properties thereof, and the like, it is useful as a material for frequent medical supplies, interior / exterior materials of electrical / electronic products.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) thermoplastic resin

(A1) rubber modified aromatic vinyl graft copolymer

A g-ABS graft copolymerized with 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) was used in a butadiene rubber having a Z-average of 310 nm by weight of 45 kW%.

(A2) aromatic vinyl copolymer resin

(A2-1) SAN resin (weight average molecular weight: 130,000 g / mol) polymerized with 71% by weight of styrene and 29% by weight of acrylonitrile was used.

(A2-2) Methyl methacrylate-styrene-acrylonitrile copolymer (MSAN, weight average molecular weight: 90,000 g / mol polymerized with 74% by weight of methyl methacrylate, 22% by weight of styrene and 4% by weight of acrylonitrile ) Was used.

(B) antistatic agent

(B1) An antistatic agent (manufacturer: Sanyo, product name: PELECTRON AS) containing a polyetheresteramide block copolymer was used.

(B2) Ultramide 8270HS from BASF was used.

(C) zinc oxide

Average particle size 1.2 μm, BET surface area 5.5 m ² / g, purity 99.9%, size ratio of peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm, when measuring photo luminescence (B / A) Zinc oxide having a crystallite size value of 0.28 and a crystallite size of 1,750 mm 3 was used.

(D) Titanium oxide (manufacturer: Kemira Specialty Corp, product name: WH-01) was used.

Property measurement method

(1) Average particle size (unit: μm): Average particle size was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 equipment).

(2) BET surface area (unit: m ² / g): The BET surface area was measured by BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment) using nitrogen gas adsorption.

(3) Purity (Unit:%): Purity was measured using TGA thermal analysis with weight remaining at 800 ° C.

(4) PL size ratio (B / A): According to the photo luminescence measuring method, a spectrum of light emitted by a He-Cd laser (Kimmon, 30mW) 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 ° C. The size ratio (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. Here, the injection specimen was subjected to PL analysis by injecting a laser into the specimen without any treatment, and the zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to produce a flat specimen. It was.

(5) Crystallite size (unit: Å): High Resolution X-Ray Diffractometer (manufacturer: X'pert, device name: PRO-MRD) was used, peak position (peak position) 2θ value is in the range of 35 to 37 °, it was calculated by applying to the Scherrer's equation (Equation 1) based on the measured FWHM value (full width at Half Maximum of the diffraction peak). Here, both the powder form and the injection specimen can be measured. For more accurate analysis, the injection specimen was subjected to heat treatment at 600 ° C. for 2 hours under air (air) to remove the polymer resin, followed by XRD analysis.

[Equation 1]

Microcrystal size (D) =

In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value, and θ is a peak position degree.

Example  1 to 5 and Comparative example  1 to 6

Each of the components was added in an amount as described in Tables 1 and 2, followed by extrusion at 230 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder with a diameter of L / D = 36 and 45 mm, and the pellets were dried at 80 ° C. for at least 2 hours, and then injected into a specimen at a 6 Oz injection machine (molding temperature 230 ° C., mold temperature: 60 ° C.). Was prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

Property measurement method

(1) Antibacterial activity value: In accordance with JIS Z 2801 antimicrobial evaluation method, 5 cm × 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and measured after culturing for 24 hours at 35 ℃, RH 90% conditions.

(2) Surface resistance value (unit: ohm * cm): Based on ASTMD257, it measured with the surface resistance measuring apparatus (manufacturer: Mitsubishi Chemical, apparatus name: Hiresta-UP (MCP-HT450)).

(3) Notched Izod impact strength (unit: kgf · cm / cm): Notched Izod impact strength was measured on a 1/4 "thick specimen in accordance with ASTM D256.

(4) Haze (unit:%): According to ASTM D1003, haze was measured on a 2.5 mm thick specimen using a Haze meter NDH 2000 instrument from Nippon Denshoku.

		Example
		One	2	3	4	5
(A) (% by weight)	(A1)	29	29	29	29	29
	(A2-1)	60	60	60	60	60
	(A2-2)	11	11	11	11	11
(B) (part by weight)	(B1)	10	20	30	20	20
	(B2)	-	-	-	-	-
(C) (parts by weight)		0.05	0.05	0.05	0.01	0.2
(D) (parts by weight)		-	-	-	-	-
Antibacterial activity level (E. coli)		4.1	6.4	6.1	4.1	6.3
Antibacterial activity level (Staphococcus)		3.3	4	4	2.3	4
Surface resistance value (Ωcm)		4.8 × 10 8	2.4 × 10 9	4 × 10 8	2.3 × 10 9	2.6 × 10 9
Notched Izod Impact Strength (kgfcm / cm)		18.1	21.3	15.7	19.9	18.9
Transparency (Haze)		9.8	14.8	23.1	12.1	31.7

* Parts by weight: (A) parts by weight based on 100 parts by weight

		Comparative example
		One	2	3	4	5	6
(A) (% by weight)	(A1)	29	29	29	29	29	29
	(A2-1)	60	60	60	60	60	60
	(A2-2)	11	11	11	11	11	11
(B) (part by weight)	(B1)	5	35	20	20	-	20
	(B2)	-	-	-	-	20	-
(C) (parts by weight)		0.05	0.05	0.005	4	0.05	-
(D) (parts by weight)		-	-	-	-	-	0.05
Antibacterial activity level (E. coli)		2.1	6.1	1.1	6.8	1.1	0.6
Antibacterial activity level (Staphococcus)		0.3	4	0.3	4	0.2	0.2
Surface resistance value (Ωcm)		4.8 × 10 11	4.2 × 10 8	2.1 × 10 9	2.6 × 10 9	4.8 × 10 13 or more	2.4 × 10 9
Notched Izod Impact Strength (kgfcm / cm)		17.1	12.1	20.1	19.5	17.2	19.6
Transparency (Haze)		8.7	28.6	11.9	50.7	30.2	10.2

* Parts by weight: (A) parts by weight based on 100 parts by weight

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in all antibacterial, antistatic, impact resistance and the like.

On the other hand, in Comparative Example 1 using a small amount of an antistatic agent, the antistatic property is lowered, the measurement resistance value is a level beyond the measurement range, it can be seen that the antibacterial (Stacobacterium) also greatly reduced, compared with the use of an antistatic agent in excess In the case of Example 2, it can be seen that the impact resistance is lowered, and in Comparative Example 3 using a small amount of zinc oxide, it was found that the antibacterial property was greatly reduced, and in Comparative Example 4 using an excessive amount of zinc oxide, it was almost opaque in transparency. You can see that it is in one state. In addition, in the case of Comparative Example 5 to which the antistatic agent (B2) was applied, it was found that the antistatic property and the antimicrobial activity were deteriorated. In the case of the Comparative Example 6 to which titanium oxide was applied as the antimicrobial agent, the antimicrobial activity was greatly reduced.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (11)

1. About 100 parts by weight of a thermoplastic resin including a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin;

   About 10 to about 30 parts by weight of an antistatic agent; And

   From about 0.01 to about 2 parts by weight of zinc oxide,

   The antistatic agent is a thermoplastic resin composition, characterized in that it comprises at least one of a polyetheresteramide block copolymer, polyalkylene glycol and polyamide.
2. The thermoplastic resin composition of claim 1, wherein the rubber-modified vinyl graft copolymer is a graft polymerized monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.
3. The thermoplastic resin composition of claim 1, wherein the aromatic vinyl copolymer resin is a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
4. The rubber-modified vinyl graft copolymer of claim 1, wherein the rubber-modified vinyl graft copolymer is included in about 20 wt% to about 50 wt% of 100 wt% of the thermoplastic resin, and the aromatic vinyl copolymer resin is about 100 wt% of the thermoplastic resin. 50 to about 80% by weight of a thermoplastic resin composition.
5. The thermoplastic resin composition of claim 1, wherein the zinc oxide has an average particle size of about 0.2 to about 3 μm and a specific surface area BET of about 1 to about 10 m ² / g.
6. The method of claim 1, wherein the zinc oxide has a size ratio (B / A) of peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm when measuring photo luminescence. It is a thermoplastic resin composition characterized by the above-mentioned.
7. The method of claim 1, wherein the zinc oxide has a peak position 2θ value of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the size of the microcrystals a thermoplastic resin composition having a crystallite size) value of about 1,000 to about 2,000 mm 3:

   [Equation 1]

   Microcrystal size (D) =

   

   In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).
8. According to claim 1, The thermoplastic resin composition is inoculated with Staphylococcus aureus and E. coli in 5 cm × 5 cm size specimens based on the JIS Z 2801 antimicrobial evaluation method, after incubation at 35 ℃, RH 90% conditions for 24 hours, The measured antimicrobial activity is about 2 to about 7 and about 2 to about 6.5, respectively.
9. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁶ to about 1 × 10 ¹⁰ Ω · cm measured according to ASTM D257.
10. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of about 1/4 "thick specimen measured in accordance with ASTM D256.
11. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 10.