WO2019093636A1 - Thermoplastic resin composition and molded article produced from same - Google Patents

Abstract

The present invention is characterized by including an aromatic vinyl-based copolymer, glass fiber, and zinc oxide, wherein the zinc oxide has an average particle size (D50) of about 0.5 to 3 µm as measured by a particle size analyzer, and a size ratio (B/A) of peak B, spanning the range of 450 to 600 nm, to peak A, spanning the range of 370 to 390 nm, of about 0.01 to 1.0 when measuring photoluminescence. The thermoplastic resin composition exhibits excellent rigidity, antibacterial properties, weather resistance, external appearance 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 for an air-conditioner cross-fan excellent in rigidity, antibacterial properties, weather resistance, and appearance characteristics, 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.

The inside of the air conditioner is composed of a heat exchanger generating cold water vapor, a filter for filtering dust, a cross fan for blowing out cold air by generating wind, and an air blower. Since the inside of the air conditioner is high in humidity and has a structure that is blocked from the outside partly, it is vulnerable to fungi and bacteria.

Among the internal components of the air conditioner, the filter, the blowing furnace, etc. are secured with antimicrobial effect by using stainless steel and plasma sterilization. However, since the cross fan material requires mechanical properties such as antibacterial property and high rigidity, It is a reality.

Inorganic antimicrobial agents containing metal components such as silver (Ag) and copper (Cu) are used for the cross fan material. However, the antibacterial agent is insufficient in antibacterial power and requires an excessive amount of the antimicrobial agent. There is a disadvantage such as discoloration due to the use of the photoreceptor.

Therefore, it is necessary to develop a thermoplastic resin composition capable of realizing excellent rigidity, antimicrobial property, weather resistance (discoloration resistance), appearance characteristics and the like.

The background art of the present invention is disclosed in Japanese Patent Application Laid-Open No. 2002-21774.

An object of the present invention is to provide a thermoplastic resin composition excellent in rigidity, antimicrobial property, weather resistance, appearance 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 is an aromatic vinyl-based copolymer resin; glass fiber; And zinc oxide. The zinc oxide has an average particle size (D50) measured by a particle size analyzer of about 0.5 to about 3 占 퐉, a peak A in the region of 370 to 390 nm and a peak of 450 And a size ratio (B / A) of the peak B in the region of from 600 nm to about 600 nm is about 0.01 to about 1.0.

In an embodiment, the thermoplastic resin composition comprises about 100 parts by weight of the aromatic vinyl-based copolymer resin; About 5 to about 40 parts by weight of the glass fiber; And about 0.1 to about 20 parts by weight of the zinc oxide.

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 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 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).

In embodiments, the zinc oxide is dissolved in zinc and then heated to about 850 to about 1000 < 0 > C to form a vapor, then oxygen gas is introduced and cooled to about 20 to about 30 & For about 30 to about 150 minutes.

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 analysis instrument, using a nitrogen gas adsorption method.

In the specific example, the thermoplastic resin composition was measured for an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter for a 50 mm × 90 mm × 3 mm size injection specimen, and measured according to ASTM D4459 (L ₁ ^* , a ₁ ^* , b ₁ ^* ) may be measured in the same manner after 3,000 hours of testing, and then the color change (ΔE) calculated according to the following formula 2 may be about 0.1 to about 2.0:

[Formula 2]

Color change (ΔE) =

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

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 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.

In embodiments, the thermoplastic resin composition may have a flexural modulus of greater than about 74,000 kgf / cm ² measured on a 6.4 mm thick specimen at 2.8 mm / min under ASTM D790.

In an embodiment, the thermoplastic resin composition comprises a continuous phase of an aromatic vinyl copolymer resin, wherein the glass fiber and the zinc oxide form a dispersed phase, and the ratio of the average particle size (D50) of the zinc oxide to the diameter of the glass fiber is about 1: About 1.7 to about 1: about 200.

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

In an embodiment, the shaped article may be a cross fan of an air conditioner.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in rigidity, antimicrobial property, weather resistance, appearance 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) an aromatic vinyl-based copolymer resin; (B) glass fibers; And (C) zinc oxide.

(A) 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 thermoplastic resin composition for an air-conditioner cross-fan. 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 an embodiment, 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 20,000 to about 200,000 g / . Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

The aromatic vinyl-based copolymer resin may be a mixture of two or more aromatic vinyl-based copolymer resins having different weight average molecular weights. For example, a first aromatic vinyl copolymer resin having a weight average molecular weight (Mw) of about 10,000 to about 100,000 g / mol and a second aromatic vinyl copolymer resin having a weight average molecular weight (Mw) of about 100,000 g / mol to about 300,000 g / An aromatic vinyl copolymer resin may be mixed and used.

(B) glass fiber

The glass fiber according to one embodiment of the present invention can improve the mechanical properties such as rigidity of the thermoplastic resin composition and can be a glass fiber used in a conventional thermoplastic resin composition for an air conditioner cross fan.

In a specific example, the glass fiber may have various shapes such as a fiber shape, a particle shape, a rod shape, an acicular shape, and a flake shape, and may have various shapes such as a circle, an ellipse, and a rectangle. For example, it may be preferable from the viewpoint of mechanical properties to use a fibrous glass fiber having a circular and / or rectangular cross section.

In embodiments, the glass fibers of the circular cross section may have a cross-sectional diameter of from about 5 to about 20 microns and a length before shaping of from about 2 to about 20 mm, the glass fibers of the rectangular cross-section having an aspect ratio of from about 1.5 to about 10, and the length before processing may be from about 2 to about 20 mm. Within the above range, the rigidity, workability and the like of the thermoplastic resin composition can be improved.

In embodiments, the glass fibers may comprise from about 5 to about 40 parts by weight, for example from about 10 to about 30 parts by weight, and especially from about 15 to about 25 parts by weight, based on about 100 parts by weight of the thermoplastic resin. Within the above range, the thermoplastic resin composition may have excellent mechanical properties, appearance characteristics, weatherability, antibacterial properties and the like.

(C) Zinc oxide

The zinc oxide according to one embodiment of the present invention is capable of improving the weather resistance and antibacterial property of the thermoplastic resin composition and is characterized in that it has a peak A of 370 to 390 nm and a peak A of 450 to 600 nm The size ratio (B / A) of the peak B may be about 0.01 to about 1.0, for example about 0.1 to about 1.0, specifically about 0.2 to about 0.7. When the size ratio (B / A) of the peak A and the peak B of 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 and the weather resistance have.

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 0.5 to about 3 microns, such as from about 0.8 to about 3 microns. If it is out of the above range, the discoloration resistance, weather resistance, etc. of the thermoplastic resin composition 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 0.1 to about 20 parts by weight, for example, from about 0.5 to about 10 parts by weight, specifically about 1 to about 5 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. Within the above range, the thermoplastic resin composition may have excellent weather resistance, antibacterial properties, mechanical properties, and appearance characteristics.

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, an antioxidant, a dripping inhibitor, a lubricant, a release agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye and mixtures thereof. When the additive is used, its content may be from about 0.001 to about 40 parts by weight, for example from about 0.1 to about 10 parts by weight, relative to about 100 parts by weight of the thermoplastic 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 comprises a continuous phase of an aromatic vinyl copolymer resin, wherein the glass fiber and the zinc oxide form a dispersed phase, and the ratio of the average particle size (D50) of the zinc oxide to the diameter of the glass fiber is about 1: About 1.7 to about 1: about 200, such as about 1: about 2 to about 1: about 20. Within the above range, the rigidity and creep characteristics of the thermoplastic resin composition can be excellent.

In the specific example, the thermoplastic resin composition was measured for an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter for a 50 mm × 90 mm × 3 mm size injection specimen, and measured according to ASTM D4459 (L ₁ ^* , a ₁ ^* , b ₁ ^* ) is measured in the same manner after 3,000 hours of testing, and the color change (ΔE) calculated according to the following formula 2 is about 0.1 to about 2.0, From about 0.5 to about 1.0.

[Formula 2]

Color change (ΔE) =

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

Here, the? A ^* may be about 1.0 to about 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 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 3 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, culturing it for 24 hours, collecting the inoculated bacterial solution, diluting it, and then growing it into a colony 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 has a flexural modulus of at least about 74,000 kgf / cm ² , such as from about 74,500 to about 80,000 kgf / cm ² , measured on a 6.4 mm thick specimen at 2.8 mm / min, according to ASTM D790. cm < ² >.

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 excellent in stiffness, antimicrobial property, weather resistance, appearance, balance of physical properties, and is useful as an air-conditioner cross fan or the like.

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) an aromatic vinyl-based copolymer resin

(A-1) SAN resin (weight average molecular weight: 80,000 g / mol) polymerized with 68% by weight of styrene and 32% by weight of acrylonitrile was used.

(A-2) SAN resin (weight average molecular weight: 150,000 g / mol) in which 68% by weight of styrene and 32% by weight of acrylonitrile were polymerized was used.

(B) glass fiber

A circular cross section glass fiber having a cross-sectional diameter of 13 탆 and a length of 3 mm before machining 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. (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, and the ratio of the size The crystallite size values were measured and are shown in Table 1 below.

(C2) zinc oxide (manufacturer: Ristec Biz, product name: RZ-950) was used.

(D) Antimicrobial agent

(Ag) -based antimicrobial agent (TOA GOSEI, product name: NOVARON AGZ010) was used.

	(C1) zinc oxide	(C2) zinc oxide
Average particle size (占 퐉)	1.2	1.1
BET surface area (m 2 / g)	4	15
Purity (%)	99	97
PL size ratio (B / A)	0.28	9.8
The crystallite size (A)	1417	503

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 2 and Comparative Example  1 to 3

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 ° C. and a mold temperature of 60 ° C. in a 6 Oz extruder at 80 ° C. for 2 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 ^* ) for a 50 mm × 90 mm × 3 mm size injection sample using a colorimeter (KONICA MINOLTA CM-3700A) b ₀ ^*) measurement, and color (L ₁ in the same manner after the 3,000-hour test in accordance with ^{_{ASTM D4459 *, a 1 *,}} b 1 *) was measured, and then, to the color change (ΔE) according to the formula 2 Respectively.

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) of the test before and after the L ^* value of, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the test before and after the a ^* value is, 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) Flexural modulus (FM, unit: kgf / cm ² ): Measured according to the evaluation method specified in ASTM D790 for 6.4 mm thick specimen at 2.8 mm / min.

(4) Thermal deformation temperature (HDT, unit: 占 폚): Measured under the conditions of a load of 1.8 MPa and a temperature raising rate of 120 占 폚 / hr in accordance with ASTM D648.

(5) Appearance evaluation: A specimen having a size of 90 mm x 50 mm x 2.5 mm was prepared, and the presence or absence of a flow mark was visually observed. Without the flow mark, it can be estimated that the compatibility of the thermoplastic resin composition is improved.

(6) Creep evaluation: According to ASTM D638, the strain (displacement, mm) at which the tensile strength measurement specimen was deformed was measured under the conditions of 85 ° C, 100N, and 100 hours.

		Example		Comparative Example
		One	2	One	2	3
(A) (% by weight)	(A1)	37.5	37.5	37.5	37.5	37.5
	(A2)	62.5	62.5	62.5	62.5	62.5
(B) (parts by weight)		20	20	20	20	20
(C1) (parts by weight)		2	4	-	-	-
(C2) (parts by weight)		-	-	4	-	-
(D) (parts by weight)		-	-	-	4	-
Color change (ΔE)		1.0	0.5	3.0	3.5	3.5
The antibacterial activity value (E. coli)		4	6	1.5	One	One
Antibacterial activity value (Staphylococcus aureus)		3	4	1.5	One	One
Flexural modulus (kgf / cm 2 )		7,5000	7,600	74,000	75,000	74,000
Heat deformation temperature (캜)		107	107	106	104	105
Appearance evaluation (flow mark)		radish	radish	U	U	radish
Creep Evaluation (mm)		0.16	0.16	0.17	0.17	0.17

Parts by weight based on 100 parts by weight of the aromatic vinyl copolymer resin (A)

From the results of Table 2, it can be seen from the results of Table 2 that the thermoplastic resin composition of the present invention is excellent in rigidity (flexural modulus), antibacterial properties (antibacterial activity value), weather resistance (color change (ΔE)), heat resistance ) And the like are all excellent.

On the other hand, in Comparative Example 1 in which zinc oxide (C2) having a PL size ratio (B / A) of more than 1.0 (9.8) was used instead of zinc oxide of the present invention and Comparative Example 2 in which silver antimicrobial agent was applied, The appearance characteristics and the like were deteriorated. In the case of Comparative Example 3 in which zinc oxide was not used, it was found that the weather resistance, antibacterial property and the like were 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 (12)

1. An aromatic vinyl-based copolymer resin;

   glass fiber; And

   Zinc oxide,

   The zinc oxide has an average particle size (D50) as measured by a particle size analyzer of about 0.5 to about 3 mu m, 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 thermoplastic resin composition comprises about 100 parts by weight of the aromatic vinyl-based copolymer resin; About 5 to about 40 parts by weight of the glass fiber; And about 0.1 to about 20 parts by weight of the zinc oxide.
3. The thermoplastic resin composition according to claim 1, 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.
4. 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).
5. 2. The method of claim 1, wherein the zinc oxide is dissolved in zinc and then heated to a temperature of about 850 to about 1000 < 0 > C to form a vapor, then oxygen gas is introduced and cooled to about 20 to about 30 ≪ 0 > C for about 30 to about 150 minutes to obtain a thermoplastic resin composition.
6. 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.
7. 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 for a 50 mm × 90 mm × 3 mm size injection sample, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) was measured in the same manner after 3,000 hours of testing according to D4459 and the color change (ΔE) calculated according to the following formula 2 was about 0.1 to about 2.0 A thermoplastic resin composition characterized by:

   [Formula 2]

   Color change (ΔE) =

   

   In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) of the test before and after the L ^* value of, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the test before and after the a ^* value is, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.
8. 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.
9. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flexural modulus of about 74,000 kgf / cm ² or more as measured on a 6.4 mm thick specimen under a condition of 2.8 mm / min according to ASTM D790.
10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises a continuous phase of an aromatic vinyl copolymer resin and a glass fiber and a zinc oxide dispersed phase, wherein the ratio of the average particle size (D50) of the zinc oxide to the diameter of the glass fiber is about 1: about 1.7 to about 1: about 200.
11. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 10.
12. 12. The molded article according to claim 11, wherein the molded article is a cross fan of an air conditioner.