Patent Grant
11505674
This application claims priority to and the benefit of International Application No. PCT/KR2018/010015, filed Aug. 30, 2018, which published as WO 2019/093636 on May 16, 2019, Korean Patent Application No. 10-2017-0147949, filed in the Korean Intellectual Property Office on Nov. 8, 2017, and Korean Patent Application No. 10-2018-0064628, filed in the Korean Intellectual Property Office on Jun. 5, 2018, the entire disclosure of each of which is incorporated herein by reference.
The present invention relates to a thermoplastic resin composition and a molded article manufactured using the same. More particularly, the present invention relates to a thermoplastic resin composition for cross-flow fans of air conditioners, which has good rigidity, antibacterial properties, weather resistance, and appearance characteristics, and a molded article manufactured using the same.
Recently, with increasing interest in personal health and hygiene and increasing income level, there is increasing demand for thermoplastic resin products having antibacterial and hygienic functions. Accordingly, there is an increasing number of thermoplastic resin products subjected to antibacterial treatment to remove or inhibit bacterial growth on surfaces of household goods and electronic products. Therefore, development of a functional antibacterial material having stability and reliability (an antibacterial thermoplastic resin composition) is a very important challenge.
An interior of an air conditioner consists of a heat exchanger generating cold water vapor, a filter filtering out dust, a cross-flow fan creating a current of air to blow out cold air, a ventilation path, and the like. The interior of the air conditioner, which is at high humidity and is partially blocked from the outside environment, is susceptible to mold or bacterial growth.
Among the internal components of the air conditioner, the filter and the ventilation path can secure antibacterial properties using stainless steel materials or plasma sterilization. In contrast, since the cross-flow fan requires both antibacterial properties and mechanical properties such as high rigidity, it is difficult to find a material suitable for the cross-flow fan.
Inorganic antibacterial agents containing metals, such as silver (Ag) and copper (Cu), are sometimes used in manufacture of the cross-flow fan. However, since such inorganic antibacterial agents need to be used in large amounts due to low antibacterial activity and have disadvantages of relatively high price, difficulty in uniform dispersion upon processing, and discoloration due to the metal components, the inorganic antibacterial agents are used in a limited range of applications.
Therefore, there is a need for a thermoplastic resin composition which can provide good rigidity, antibacterial properties, weather resistance (discoloration resistance), and appearance characteristics.
The background technique of the present invention is disclosed in Japanese Patent Publication No. 2002-21774 and the like.
It is one aspect of the present invention is to provide a thermoplastic resin composition which has good rigidity, antibacterial properties, weather resistance, and appearance characteristics.
It is another aspect of the present invention to provide a molded article formed of the thermoplastic resin composition set forth above.
The above and other aspects of the present invention will become apparent from the detailed description of the following embodiments.
One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes: an aromatic vinyl copolymer resin; glass fibers; and zinc oxide, wherein the zinc oxide has an average particle diameter (D50) of about 0.5 μm to about 3 μm, as measured using a particle size analyzer, and a peak intensity ratio (B/A) of about 0.01 to about 1.0, where A indicates a peak in the wavelength range of 370 nm to 390 nm and B indicates a peak in the wavelength range of 450 nm to 600 nm in photoluminescence measurement.
In one embodiment, the thermoplastic resin composition may include: about 100 parts by weight of the aromatic vinyl copolymer resin; about 5 parts by weight to about 40 parts by weight of the glass fibers; and about 0.1 parts by weight to about 20 parts by weight of the zinc oxide.
In one 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 one embodiment, the zinc oxide may have a peak position degree (2θ) in the range of about 35° to about 37° and a crystallite size of about 1,000 Å to about 2,000 Å in X-ray diffraction (XRD) analysis, as calculated by Equation 1:
where K is a shape factor, λ is an X-ray wavelength, β is an FWHM value (degree) of an X-ray diffraction peak, and θ is a peak position degree.
In one embodiment, the zinc oxide may be prepared by melting zinc in a reactor, heating the molten zinc to about 850° C. to about 1,000° C. to vaporize the molten zinc, injecting oxygen gas into the reactor, cooling the reactor to about 20° C. to about 30° C., and heating the reactor to about 400° C. to about 900° C. for about 30 minutes to about 150 minutes.
In one embodiment, the zinc oxide may have a BET specific surface area of about 10 m2/g or less, as measured by a nitrogen gas adsorption method using a BET analyzer.
In one embodiment, the thermoplastic resin composition may have a color variation (ΔE) of about 0.1 to about 2.0, as calculated according to Equation 2 based on initial color values (L0*, a0*, b0*) measured on an injection-molded specimen having a size of 50 mm×90 mm×3 mm using a colorimeter and color values (L1*, a1*, b1*) of the specimen measured in the same manner as above after testing for 3,000 hours in accordance with ASTM D4459:
Color variation (ΔE)=√{square root over ((ΔL*)2+(Δa*)2+(Δb*)2)} [Equation 2]
where ΔL* is a difference (L1*−L0*) between L* values before and after testing, Δa* is a difference (a1*−a0*) between a* values before and after testing, and Δb* is a difference (b1*−b0*) between b* values before and after testing.
In one embodiment, the thermoplastic resin composition may have an antibacterial activity of about 2 to about 7 against Staphylococcus aureus and an antibacterial activity of about 2 to about 7 against Escherichia coli, as calculated according to Equation 3 after inoculation of 5 cm×5 cm specimens with Staphylococcus aureus and Escherichia coli, respectively, and culturing under conditions of 35° C. and 90% RH for 24 hours in accordance with JIS Z 2801:
Antibacterial activity=log(M1/M2) [Equation 3]
where M1 is the number of bacteria as measured on a blank specimen after culturing for 24 hours and M2 is the number of bacteria as measured on each of the specimens of the thermoplastic resin composition after culturing for 24 hours.
In one embodiment, the thermoplastic resin composition may have a flexural modulus of about 74,000 kgf/cm2 or more, as measured on a 6.4 mm thick specimen at a strain rate of 2.8 mm/min in accordance with ASTM D790.
In one embodiment, the thermoplastic resin composition may have a structure in which the glass fibers and the zinc oxide are present as a dispersed phase in the aromatic vinyl copolymer resin as a continuous phase, and a ratio of average particle diameter (D50) of the zinc oxide to diameter of the glass fibers may range from about 1:1.7 to about 1:200.
Another aspect of the present invention relates to a molded article. The molded article is formed of the thermoplastic resin composition set forth above.
In one embodiment, the molded article may be a cross-flow fan of an air conditioner.
The present invention provides a thermoplastic resin composition which has good rigidity, antibacterial properties, weather resistance, and appearance characteristics, and a molded article formed of the same.
Hereinafter, exemplary embodiments of the present invention will be described in detail.
A thermoplastic resin composition according to the present invention includes: (A) an aromatic vinyl copolymer resin; (B) glass fibers; and (C) zinc oxide.
(A) 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 typical thermoplastic resin composition for cross-flow fans of air conditioners. 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, such as a vinyl cyanide monomer.
In some embodiments, the aromatic vinyl copolymer resin may be obtained by mixing the aromatic vinyl monomer with the monomer copolymerizable with the aromatic vinyl monomer, followed by polymerization of the mixture. Here, the polymerization may be performed by any suitable polymerization method known in the art, such as emulsion polymerization, suspension polymerization, and mass polymerization.
In some embodiments, the aromatic vinyl monomer may include styrene, α-methyl styrene, β-methylstyrene, p-methyl styrene, p-t-butyl styrene, ethyl styrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene, without being limited thereto. These may be used alone or as a mixture thereof. The aromatic vinyl monomer may be present in an amount of about 20 wt % to about 90 wt %, for example, about 30 wt % to about 80 wt %, based on the total weight of the aromatic vinyl copolymer resin. Within this range, the thermoplastic resin composition can have good impact resistance and flowability.
In some embodiments, the monomer copolymerizable with the aromatic vinyl monomer may include, for example, vinyl cyanide monomers, such as acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and fumaronitrile, (meth)acrylic acids and alkyl esters thereof, maleic anhydride, and N-substituted maleimide. These may be used alone or as a mixture thereof. The monomer copolymerizable with the aromatic vinyl monomer may be present in an amount of about 10 wt % to about 80 wt %, for example, about 20 wt % to about 70 wt %, based on the total weight of the aromatic vinyl copolymer resin. Within this range, the thermoplastic resin composition can have good impact resistance and flowability.
In some embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) of about 10,000 g/mol to about 300,000 g/mol, for example, about 20,000 g/mol to about 200,000 g/mol, as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition can have good mechanical strength and moldability.
In addition, the aromatic vinyl copolymer resin may be a mixture of at least two aromatic vinyl copolymer resins having different weight average molecular weights. For example, the aromatic vinyl copolymer resin may be a mixture of a first aromatic vinyl copolymer resin having a weight average molecular weight (Mw) of about 10,000 g/mol to about 100,000 g/mol and a second aromatic vinyl copolymer resin having a weight average molecular weight (Mw) of greater than about 100,000 g/mol and less than or equal to about 300,000 g/mol.
(B) Glass Fibers
The glass fibers according to one embodiment of the present invention serve to improve mechanical properties of the thermoplastic resin composition, such as rigidity, and may be glass fibers used in typical thermoplastic resin compositions for cross-flow fans of air conditioners.
In some embodiments, the glass fibers may have various shapes, such as fibrous, particle, rod-like, needle-like, and flake shapes, and may have various cross-sections, such as circular, elliptical, and rectangular cross-sections. For example, it may be desirable to use fibrous glass fibers having circular and/or rectangular cross-sections in terms of mechanical properties.
In some embodiments, the circular cross-section glass fibers may have a cross-sectional diameter of about 5 μm to about 20 μm and a pre-processing length of about 2 mm to about 20 mm, and the rectangular cross-section glass fibers may have a cross-sectional aspect ratio of about 1.5 to about 10 and a pre-processing length of about 2 mm to about 20 mm. Within this range, the thermoplastic resin composition can have good rigidity and processability.
In some embodiments, the glass fibers may be present in an amount of about 5 parts by weight to about 40 parts by weight, for example, about 10 parts by weight to about 30 parts by weight, specifically about 15 parts by weight to about 25 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. Within this range, the thermoplastic resin composition can have good mechanical properties, appearance characteristics, weather resistance, and antibacterial properties.
(C) Zinc Oxide
The zinc oxide according to one embodiment of the present invention serves to improve weather resistance and antibacterial properties of the thermoplastic resin composition, and may have a peak intensity ratio (B/A) of about 0.01 to about 1.0, for example, about 0.1 to about 1.0, specifically about 0.2 to about 0.7, where A indicates a peak in the wavelength range of 370 nm to 390 nm and B indicates a peak in the wavelength range of 450 nm to 600 nm in photoluminescence measurement. If the peak intensity ratio (B/A) of the zinc oxide is less than about 0.01, the thermoplastic resin composition can have poor antibacterial properties. If the peak intensity ratio (B/A) of the zinc oxide exceeds about 1.0, there can be a significant difference between initial colors of the thermoplastic resin and the thermoplastic resin composition and the thermoplastic resin can have poor weather resistance.
In some embodiments, the zinc oxide may have various shapes, for example, a spherical shape, a plate-like shape, a rod-like shape, and combinations thereof. In addition, the zinc oxide may have an average particle diameter (D50) of about 0.5 μm to about 3 μm, for example, about 0.8 μm to about 3 μm, as measured in a single particle state (not forming a secondary particle through agglomeration of particles) using a particle size analyzer (Laser Diffraction Particle Size Analyzer LS I3 320, Beckman Coulter Co., Ltd.). If the average particle diameter (D50) of the zinc oxide is outside this range, the thermoplastic resin composition can have poor discoloration resistance and weather resistance.
In some embodiments, the zinc oxide may have a peak position degree (2θ) in the range of about 35° to about 37° and a crystallite size of about 1,000 Å to about 2,000 Å, for example, about 1,200 Å to about 1,800 Å, in X-ray diffraction (XRD) analysis, as calculated by Scherrer's equation (Equation 1) with reference to a measured FWHM value (full width at half maximum of a diffraction peak). Within this range, the thermoplastic resin composition can have good initial color, weather resistance (discoloration resistance), antibacterial properties, and balance between mechanical properties.
where K is a shape factor, λ is an X-ray wavelength, β is an FWHM value (degree) of an X-ray diffraction peak, and θ is a peak position degree.
In some embodiments, the zinc oxide may have a BET specific surface area of about 10 m2/g or less, for example, about 1 m2/g to about 7 m2/g, as measured by a nitrogen gas adsorption method using a BET analyzer (Surface Area and Porosity Analyzer ASAP 2020, Micromeritics Co., Ltd.), and a purity of about 99% or more. Within this range, the thermoplastic resin composition can have good discoloration resistance and mechanical properties.
In some embodiments, the zinc oxide may be prepared by melting metallic zinc in a reactor, heating the molten zinc to about 850° C. to about 1,000° C., for example, about 900° C. to about 950° C., to vaporize the molten zinc, injecting oxygen gas into the reactor, cooling the reactor to about 20° C. to about 30° C., and heating the reactor to about 400° C. to about 900° C., for example, 500° C. to about 800° C., for about 30 minutes to about 150 minutes, for example, about 60 minutes to about 120 minutes.
In some embodiments, the zinc oxide may be present in an amount of about 0.1 parts by weight to about 20 parts by weight, for example, about 0.5 parts by weight to about 10 parts by weight, specifically about 1 part by weight to about 5 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. Within this range, the thermoplastic resin composition can have good weather resistance, antibacterial properties, mechanical properties, and appearance characteristics.
The thermoplastic resin composition according to one embodiment of the present invention may further include additives used in typical thermoplastic resin compositions. Examples of the additives may include flame retardants, fillers, antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, pigments, dyes, and combinations thereof, without being limited thereto. When used in the thermoplastic resin composition, the additives may be present in an amount of about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 10 parts by weight, relative to about 100 parts by weight of the thermoplastic resin.
The thermoplastic resin composition according to the present invention may be prepared in pellet form by mixing the aforementioned components, followed by melt extrusion in a typical twin-screw extruder at about 200° C. to about 280° C., for example, about 220° C. to about 250° C.
In some embodiments, the thermoplastic resin composition may have a structure in which the glass fibers and the zinc oxide are present as a dispersed phase in the aromatic vinyl copolymer resin as a continuous phase, and a ratio of average particle diameter (D50) of the zinc oxide to diameter of the glass fibers may range from about 1:1.7 to about 1:200, for example, about 1:2 to about 1:20. Within this range, the thermoplastic resin composition can have good rigidity and creep properties.
In some embodiments, the thermoplastic resin composition may have a color variation (ΔE) of about 0.1 to about 2.0, for example, about 0.5 to about 1.0, as calculated according to Equation 2 based on initial color values (L0*, a0*, b0*) measured on an injection-molded specimen having a size of 50 mm×90 mm×3 mm using a colorimeter and color values (L1*, a1*, b1*) of the specimen measured in the same manner as above after testing for 3,000 hours in accordance with ASTM D4459.
Color Variation (ΔE)=√{square root over ((ΔL*)2+(Δa*)2+(Δb*)2)} [Equation 2]
where ΔL* is a difference (L1*−L0*) between L* values before and after testing, Δa* is a difference (a1*−a0*) between a* values before and after testing, and Δb* is a difference (b1*−b0*) between b* values before and after testing.
Here, Δa* may range from about 1.0 to about 1.5. If Δa* is outside of this range in evaluation of weather resistance, weather resistance (discoloration resistance) of the thermoplastic resin composition can be greatly deteriorated to the extent that a change in color of the composition is apparent to the naked eye.
In some embodiments, the thermoplastic resin composition has an antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, Pneumococcus, and methicillin-resistant Staphylococcus Aureus (MRSA), and may have an antibacterial activity of about 2 to about 7, for example, about 3 to about 6, against Staphylococcus aureus and an antibacterial activity of about 2 to about 7, for example, about 3 to about 6, against Escherichia coli, as calculated according to Equation 3 after inoculation of 5 cm×5 cm specimens with Staphylococcus aureus and Escherichia coli, respectively, and culturing under conditions of 35° C. and 90% RH for 24 hours in accordance with JIS Z 2801.
Antibacterial activity=log(M1/M2) [Equation 3]
where M1 is the number of bacteria as measured on a blank specimen after culturing for 24 hours and M2 is the number of bacteria as measured on each of the specimens of the thermoplastic resin composition after culturing for 24 hours.
Here, the “blank specimen” refers to a control specimen for comparison with a test specimen (specimen of the thermoplastic resin composition). Specifically, the blank specimen is prepared by inoculating bacteria on an empty petri dish, which is suitable for checking whether the inoculated bacteria grow normally, followed by culturing for 24 hours under the same conditions as the test specimen. Antibacterial performance of the test specimen is evaluated based on comparison of the number of cultured bacteria between the blank specimen and the test specimen. Here, the “number of cultured bacteria” may be determined through a process in which each specimen is inoculated with the bacteria, followed by culturing for 24 hours, and then an inoculation solution of the bacteria is recovered and diluted, followed by growth of the bacteria to a colony on a culture dish. When population of the colony is too large to count, the number of cultured bacteria may be determined by dividing the colony divided into multiple sectors, measuring the population size of one sector, and converting the measured value into total population.
In some embodiments, the thermoplastic resin composition may have a flexural modulus of about 74,000 kgf/cm2 or more, for example, about 74,500 kgf/cm2 to about 80,000 kgf/cm2, as measured on a 6.4 mm thick specimen at a strain rate of 2.8 mm/min in accordance with ASTM D790.
A molded article according to the present invention is formed of the thermoplastic resin composition set forth above. The thermoplastic resin composition may be prepared in pellet form. The prepared pellets may be produced into various molded articles (products) by various molding methods such as injection molding, extrusion, vacuum molding, and casting. These molding methods are well known to those skilled in the art. The molded article according to the present invention has good rigidity, antibacterial properties, weather resistance, appearance characteristics, and balance therebetween and thus is useful as a material for cross-flow fans of air conditioners.
Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be in any way construed as limiting the present invention.
Details of components used in Examples and Comparative Examples are as follows:
(A) Aromatic Vinyl Copolymer Resin
(A-1) A SAN resin (weight average molecular weight: 80,000 g/mol) obtained by polymerization of 68 wt % of styrene and 32 wt % of acrylonitrile was used.
(A-2) A SAN resin (weight average molecular weight: 150,000 g/mol) obtained by polymerization of 68 wt % of styrene and 32 wt % of acrylonitrile was used.
(B) Glass Fibers
Circular cross-section glass fibers having a cross-sectional diameter of 13 μm and a pre-processing length of 3 mm were used.
(C) Zinc Oxide
(C1) Metallic zinc was melted in a reactor, followed by heating to 900° C. to vaporize the molten zinc, and then oxygen gas was injected into the reactor, followed by cooling to room temperature (25° C.) to obtain an intermediate. Then, the intermediate was subjected to heat treatment at 700° C. for 90 minutes, followed by cooling to room temperature (25° C.), thereby preparing zinc oxide (C1). For the prepared zinc oxide, average particle diameter, BET surface area, purity, peak intensity ratio (B/A) of peak B in the wavelength range of 450 nm to 600 nm to peak A in the wavelength range of 370 nm to 390 nm in photoluminescence measurement, and crystallite size were measured. Results are shown in Table 1.
(C2) Zinc oxide (Manufacturer: Ristecbiz Co., Ltd., product name: RZ-950) was used.
(D) Antibacterial Agent
A silver (Ag) antibacterial agent (manufacturer: TOA GOSEI Co., Ltd., product name: NOVARON AGZ010) was used.
Property Evaluation
(1) Average particle diameter (unit: μm): Average particle diameter (volume average) was measured using a particle size analyzer (Laser Diffraction Particle Size Analyzer LS I3 320, Beckman Coulter Co., Ltd.).
(2) BET surface area (unit: m2/g): BET surface area was measured by a nitrogen gas adsorption method using a BET analyzer (Surface Area and Porosity Analyzer ASAP 2020, Micromeritics Co., Ltd.).
(3) Purity (unit: %): Purity was measured by thermogravimetric analysis (TGA) based on the weight of remaining material at 800° C.
(4) PL peak intensity ratio (B/A): Spectrum emitted upon irradiation of a specimen using a He-Cd laser (KIMMON, 30 mW) at a wavelength of 325 nm at room temperature was detected by a CCD detector in a photoluminescence measurement method, in which the CCD detector was maintained at −70° C. A peak intensity ratio (B/A) of peak B in the wavelength range of 450 nm to 600 nm to peak A in the wavelength range of 370 nm to 390 nm was measured. Here, an injection molded specimen was irradiated with laser beams without separate treatment upon PL analysis, and zinc oxide powder was compressed in a pelletizer having a diameter of 6 mm to prepare a flat specimen.
(5) Crystallite size (unit: Å): Crystallite size was measured using a high-resolution X-ray diffractometer (PRO-MRD, X'pert Inc.) at a peak position degree (2θ) in the range of 35° to 37° and calculated by Scherrer's equation (Equation 1) with reference to a measured FWHM value (full width at half maximum of a diffraction peak). Here, both a powder form and an injection molded specimen could be measured. For more accurate analysis, the injection molded specimen was subjected to heat treatment in air at 600° C. for 2 hours to remove a polymer resin therefrom before XRD analysis.
where K is a shape factor, λ is an X-ray wavelength, β is an FWHM value (degree) of an X-ray diffraction peak, and θ is a peak position degree.
The aforementioned components were mixed in amounts as listed in Tables 2 and 3, followed by extrusion at 230° C., thereby preparing a thermoplastic resin composition in pellet form. Here, extrusion was performed using a twin-screw extruder (L/D: 36, Φ: 45 mm). The prepared pellets were dried at 80° C. for 2 hours or more and then subjected to injection molding using a 6 oz. injection machine (molding temperature: 230° C., mold temperature: 60° C.), thereby preparing a specimen. The prepared specimen was evaluated as to the following properties. Results are shown in Table 2.
Property Evaluation
(1) Weather resistance (color variation (ΔE)): For determination of color variation, initial color values (L0*, a0*, b0*) were measured on an injection molded specimen having a size of 50 mm×90 mm×3 mm using a colorimeter (KONICA MINOLTA CM-3700A), followed by testing for 3,000 hours in accordance with ASTM D4459, and then color values (L1*, a1*, b1*) of the specimen were measured in the same manner as above. Thereafter, color variation (ΔE) was calculated according to Equation 2:
Color variation (ΔE)=√{square root over ((ΔL*)2+(Δa*)2+(Δb*)2)} [Equation 2]
where ΔL* is a difference (L1*−L0*) between L* values before and after testing, Δa* is a difference (a1*−a0*) between a* values before and after testing, and Δb* is a difference (b1*−b0*) between b* values before and after testing.
(2) Antibacterial activity: In accordance with JIS Z 2801, 5 cm×5 cm specimens were inoculated with Staphylococcus aureus and Escherichia coli, respectively, and then subjected to culturing under conditions of 35° C. and 90% RH for 24 hours, followed by calculation of antibacterial activity according to Equation 3:
Antibacterial activity=log(M1/M2) [Equation 3]
where M1 is the number of bacteria as measured on a blank specimen after culturing for 24 hours and M2 is the number of bacteria as measured on each of the specimens after culturing for 24 hours.
(3) Flexural modulus (FM, unit: kgf/cm2): Flexural modulus was measured on a 6.4 mm thick specimen at a strain rate of 2.8 mm/min in accordance with ASTM D790.
(4) Heat deflection temperature (HDT, unit: ° C.): Heat deflection temperature was measured at a heating rate of 120 ° C./hr under a load of 1.8 MPa in accordance with ASTM D648.
(5) Appearance: A specimen having a size of 90 mm×50 mm×2.5 mm was prepared, and then the presence of flow marks was observed with the naked eye. When there are no flow marks, the corresponding thermoplastic resin composition can be evaluated as having good compatibility.
(6) Creep: In accordance with ASTM D638, displacement length (unit: mm) of a tensile strength test specimen under conditions of 85° C., 100 N, and 100 hours was measured.
From the results shown in Table 2, it can be seen that the thermoplastic resin composition according to the present invention had good properties in terms of rigidity (flexural modulus), antibacterial effects (antibacterial activity), weather resistance (color variation (ΔE)), heat resistance (heat deformation temperature), and appearance (flow mark, creep).
Conversely, the thermoplastic resin composition of Comparative Example 1, using the zinc oxide (C2) having a PL peak intensity ratio (B/A) of 9.8 (exceeding 1.0) instead of the zinc oxide according to the present invention, and the thermoplastic resin composition of Comparative Example 2, using the silver antibacterial agent, exhibited poor properties in terms of weather resistance, appearance, and antibacterial effects. In addition, the thermoplastic resin composition of Comparative Example 3, free from zinc oxide, exhibited poor properties in terms of weather resistance and antibacterial effects.
It should be understood that various modifications, changes, alterations, and equivalent embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0147949 | Nov 2017 | KR | national |
| 10-2018-0064628 | Jun 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/010015 | 8/30/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/093636 | 5/16/2019 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3041303 | Nelson | Jun 1962 | A |
| 3354108 | Paradis et al. | Nov 1967 | A |
| 4331786 | Foy et al. | May 1982 | A |
| 4356300 | Isler | Oct 1982 | A |
| 4612340 | Ohachi | Sep 1986 | A |
| 5151457 | Ishida et al. | Sep 1992 | A |
| 5714534 | Kojima et al. | Feb 1998 | A |
| 5714545 | Lee | Feb 1998 | A |
| 5906679 | Watanabe et al. | May 1999 | A |
| 5916947 | Morris et al. | Jun 1999 | A |
| 6166116 | Sleeckx | Dec 2000 | A |
| 6297307 | Eichenauer et al. | Oct 2001 | B1 |
| 6475631 | Yamamoto et al. | Nov 2002 | B1 |
| 6663877 | Appleton et al. | Dec 2003 | B1 |
| 7812078 | Glasgow et al. | Oct 2010 | B2 |
| 8128998 | Li et al. | Mar 2012 | B2 |
| 9150701 | Destro et al. | Oct 2015 | B2 |
| 9422426 | Kwon et al. | Aug 2016 | B2 |
| 9595187 | Drovetskaya et al. | Mar 2017 | B2 |
| 10058489 | Drovetskaya et al. | Aug 2018 | B2 |
| 10472490 | Yang et al. | Nov 2019 | B2 |
| 10472510 | Lee et al. | Nov 2019 | B2 |
| 10544278 | Bae et al. | Jan 2020 | B2 |
| 10787532 | Kim et al. | Sep 2020 | B2 |
| 10815368 | Kim et al. | Oct 2020 | B2 |
| 10829628 | Yang et al. | Nov 2020 | B2 |
| 11034620 | Jeong et al. | Jun 2021 | B2 |
| 20020106413 | Herbst et al. | Aug 2002 | A1 |
| 20020109805 | Baba | Aug 2002 | A1 |
| 20030125413 | Herbst et al. | Jul 2003 | A1 |
| 20050043485 | Lee et al. | Feb 2005 | A1 |
| 20050131100 | Herbst et al. | Jun 2005 | A1 |
| 20060167138 | Ishii et al. | Jul 2006 | A1 |
| 20070009691 | Barre et al. | Jan 2007 | A1 |
| 20070049678 | Kim et al. | Mar 2007 | A1 |
| 20070100038 | Glasgow et al. | May 2007 | A1 |
| 20070197372 | Kurihara et al. | Aug 2007 | A1 |
| 20080071024 | Morishita | Mar 2008 | A1 |
| 20090068755 | Steeves et al. | Mar 2009 | A1 |
| 20090166593 | Kim et al. | Jul 2009 | A1 |
| 20100003179 | Katusic et al. | Jan 2010 | A1 |
| 20100264383 | Tooley et al. | Oct 2010 | A1 |
| 20110027386 | Kurihara et al. | Feb 2011 | A1 |
| 20130137810 | Shin | May 2013 | A1 |
| 20140017335 | Dimov | Jan 2014 | A1 |
| 20140296442 | Fiori et al. | Oct 2014 | A1 |
| 20150210835 | Tamura et al. | Jul 2015 | A1 |
| 20150237866 | Goudswaard et al. | Aug 2015 | A1 |
| 20150284559 | Tai | Oct 2015 | A1 |
| 20150360507 | Benito Lopez et al. | Dec 2015 | A1 |
| 20160326670 | Kang et al. | Nov 2016 | A1 |
| 20170190882 | Park et al. | Jul 2017 | A1 |
| 20170198132 | Choi et al. | Jul 2017 | A1 |
| 20180112056 | Yang | Apr 2018 | A1 |
| 20180118914 | Bae et al. | May 2018 | A1 |
| 20180179314 | Kim et al. | Jun 2018 | A1 |
| 20180179373 | Kim et al. | Jun 2018 | A1 |
| 20180186989 | Lee et al. | Jul 2018 | A1 |
| 20180194164 | Benito Lopez et al. | Jul 2018 | A1 |
| 20190299572 | Hirabayashi | Oct 2019 | A1 |
| 20200115279 | Jeong et al. | Apr 2020 | A1 |
| 20200123057 | An et al. | Apr 2020 | A1 |
| 20200216635 | Chu et al. | Jul 2020 | A1 |
| 20210017371 | Yang et al. | Jan 2021 | A1 |
| 20210371654 | Bae et al. | Dec 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 1710153 | Dec 2005 | CN |
| 1858001 | Nov 2006 | CN |
| 1919542 | Feb 2007 | CN |
| 101001805 | Jul 2007 | CN |
| 101466637 | Jun 2009 | CN |
| 101787165 | Jul 2010 | CN |
| 101880426 | Nov 2010 | CN |
| 103068766 | Apr 2013 | CN |
| 104583329 | Apr 2015 | CN |
| 104743602 | Jul 2015 | CN |
| 105189069 | Dec 2015 | CN |
| 105504567 | Apr 2016 | CN |
| 106700461 | May 2017 | CN |
| 106928862 | Jul 2017 | CN |
| 107974030 | May 2018 | CN |
| 1190622 | Mar 2002 | EP |
| 1510549 | Mar 2005 | EP |
| 3026082 | Jun 2016 | EP |
| 3315546 | May 2018 | EP |
| 3326975 | May 2018 | EP |
| 3339367 | Jun 2018 | EP |
| 3339370 | Jun 2018 | EP |
| 3560902 | Oct 2019 | EP |
| 1439417 | May 1966 | FR |
| 1040287 | Aug 1966 | GB |
| 55-133424 | Oct 1980 | JP |
| 56-045419 | Apr 1981 | JP |
| 62-53739 | Mar 1987 | JP |
| 63278951 | Nov 1988 | JP |
| 06-287547 | Oct 1994 | JP |
| 08-217936 | Aug 1996 | JP |
| 08-253640 | Oct 1996 | JP |
| 09-71727 | Mar 1997 | JP |
| 09-157512 | Jun 1997 | JP |
| 10-182927 | Jul 1998 | JP |
| H10195309 | Jul 1998 | JP |
| 10213091 | Aug 1998 | JP |
| 10-251444 | Sep 1998 | JP |
| 11-035787 | Feb 1999 | JP |
| 11-228844 | Aug 1999 | JP |
| 11-263705 | Sep 1999 | JP |
| 2001-010850 | Jan 2001 | JP |
| 2001-220486 | Aug 2001 | JP |
| 2002-21774 | Jan 2002 | JP |
| 2002-068913 | Mar 2002 | JP |
| 2002-087842 | Mar 2002 | JP |
| 2003-212693 | Jul 2003 | JP |
| 2003-280546 | Oct 2003 | JP |
| 2005-239904 | Sep 2005 | JP |
| 2006-182841 | Jul 2006 | JP |
| 2007-191695 | Aug 2007 | JP |
| 2008-230895 | Oct 2008 | JP |
| 2009-513776 | Apr 2009 | JP |
| 2009-161758 | Jul 2009 | JP |
| 2009-173758 | Aug 2009 | JP |
| 2011-506722 | Mar 2011 | JP |
| 2011-137068 | Jul 2011 | JP |
| 2014-172783 | Sep 2014 | JP |
| 2014-221708 | Nov 2014 | JP |
| 2015-189869 | Nov 2015 | JP |
| 2016-121273 | Jul 2016 | JP |
| 2017-132913 | Aug 2017 | JP |
| 10-1999-0028477 | Apr 1999 | KR |
| 10-0281656 | Nov 2001 | KR |
| 10-2002-0008203 | Jan 2002 | KR |
| 10-0683505 | Feb 2007 | KR |
| 10-0696385 | Mar 2007 | KR |
| 10-2007-0047073 | May 2007 | KR |
| 10-815472 | Mar 2008 | KR |
| 10-0890796 | Mar 2009 | KR |
| 10-2010-0076303 | Jul 2010 | KR |
| 10-2010-0087603 | Aug 2010 | KR |
| 10-2011-0052425 | May 2011 | KR |
| 10-2012-0077313 | Jul 2012 | KR |
| 10-1334283 | Nov 2013 | KR |
| 10-2014-0009892 | Jan 2014 | KR |
| 10-2014-0086729 | Jul 2014 | KR |
| 10-1445304 | Sep 2014 | KR |
| 10-1452020 | Oct 2014 | KR |
| 10-2015-0017706 | Feb 2015 | KR |
| 10-2016-0006969 | Jan 2016 | KR |
| 10-2016-0083527 | Jul 2016 | KR |
| 10-2017-0014647 | Feb 2017 | KR |
| 10-2018-0071973 | Jun 2018 | KR |
| 10-2010-0087603 | Aug 2018 | KR |
| 2126775 | Feb 1999 | RU |
| 9701515 | Jan 1997 | WO |
| 2018117603 | Jun 2018 | WO |
| 2018124657 | Jul 2018 | WO |
| 2019021738 | Feb 2019 | WO |
| 2019066193 | Apr 2019 | WO |
| 2019093636 | May 2019 | WO |
| 2019132385 | Jul 2019 | WO |
| Entry |
|---|
| Machine translation of JP 11-035787 (1999, 13 pages). |
| Zeomic (2020, 5 pages). |
| STNext Abstract of JP 11-035787 (1999, 4 pages). |
| Machine translation of CN 101787165 (2010, 6 pages). |
| Machine translation of JP 10-213091 (1998, 10 pages). |
| International Search Report in commonly owned International Application No. PCT/KR2017/015028 dated Mar. 30, 2018, pp. 1-4. |
| Extended Search Report in commonly owned European Application No. 17885334.7 dated Mar. 24, 2020, pp. 1-7. |
| Office Action in commonly owned Japanese Application No. 2019-530736 dated Aug. 4, 2020, pp. 1-4. |
| International Search Report in commonly owned International Application No. PCT/KR2018/006676 dated Oct. 30, 2018, pp. 1-4. |
| Prasanna et al., “Insight into the Mechanism of Antibacterial Activity of ZnO: Surface Defects Mediated Reactive Oxygen Species Even in the Dark”, ACS Publications, Langmuir 2015, vol. 31, No. 33, pp. 9155-9162. |
| Office Action in commonly owned U.S. Appl. No. 16/470,317 dated Oct. 1, 2020, pp. 1-10. |
| International Search Report in counterpart International Application No. PCT/KR2018/010015 dated Feb. 1, 2019, pp. 1-4. |
| Vijayaraghavan, Rajagopala etc., “Insight into the Mechanism of Antibacterial activity of ZnO: surface defects mediated reactive oxygen species even in the dark”, American Chemical Society, 2015, vol. 31, No. 33, p. 9155-9162. |
| Office Action in commonly owned Chinese Application No. 201880048166.7 dated May 10, 2021, pp. 1-7. |
| Office Action in commonly owned Korean Application No. 10-2016-0177857 dated Nov. 20, 2018, pp. 1-8. |
| Extended Search Report in commonly owned European Application No. 17210117.2, dated Apr. 30, 2018, pp. 1-5. |
| Search Report in commonly owned European Application No. 17210669.2 dated Apr. 20, 2018, pp. 1-5. |
| Office Action in commonly owned Korean Application No. 10-2016-0184170 dated Sep. 6, 2018, pp. 1-6. |
| Office Action in commonly owned Korean Application No. 10-2017-0075940 dated Aug. 21, 2017, pp. 1-8. |
| Extended Search Report in commonly owned European Application No. 17198304.2 dated Mar. 12, 2018, pp. 1-5. |
| Office Action in commonly owned Taiwanese Application No. 106136641 dated Aug. 17, 2018, pp. 1-6. |
| Office Action in commonly owned U.S. Appl. No. 15/790,334 dated Apr. 16, 2019, pp. 1-18. |
| Office Action in commonly owned Korean Application No. 10-2017-0111807 dated Nov. 27, 2018, pp. 1-9. |
| Chandrakanth et al., “Synthesis and characterization of ZnO nanorods with a narrow size distribution”, Royal Society of Chemistry, 2015, vol. 5, pp. 49861-49870 (17 pages). |
| Tsai, “The Influence on Intensity Ratio of Peak Emission between Recombination of Free-Excitons and Deep-Defect for ZnO Nanostructure Evolution from Nanorods to Nanotubes”, Proceedings of the 16th International Conference on Nanotechnology, Sendai, Japan, Aug. 22-25, 2016, pp. 387-389. |
| Machine translated English language equivalent of CN 101880426 (2010, 5 pages). |
| Machine translated English language equivalent of JP 2014-221708 (2014, 9 pages). |
| Extended Search Report in commonly owned European Application No. 17199720.8 dated Mar. 7, 2018, pp. 1-7. |
| Database WPI, Week 201463, Thomson Scientific, London, GB, Abstract of JP 2014-172783 (UBE Kagaku Kogyo KK), pp. 1-2. |
| Database WPI, Week 201654, Thomson Scientific, London, GB, Abstract of KR 2016-0083527 (Kolon Plastics Inc.), pp. 1-2. |
| Office Action in commonly owned U.S. Appl. No. 15/845,020 dated Aug. 8, 2019, pp. 1-13. |
| Machine translated English language equivalent of JP Application No. H09-212736, which is the same as publication JP 11-035787 (1999,10 pages). |
| Machine translated English language equivalent of CN 191542 (2007, 5 pages). |
| Office Action in commonly owned Chinese Application No. 201711062077.1 dated Jul. 12, 2019, pp. 1-7. |
| Office Action in commonly owned Chinese Application No. 201711007395.8 dated Jul. 31, 2019, pp. 1-6. |
| Extended Search Report in commonly owned European Application No. 17209267.8 dated Mar. 26, 2018, pp. 1-7. |
| Office Action in commonly owned U.S. Appl. No. 15/798,819 dated May 13, 2019, pp. 1-20. |
| Office Action in commonly owned Korean Application No. 10-2016-0176575 dated Nov. 1, 2018, pp. 1-7. |
| Google translation of JP 11035787 (1999, 8 pages). |
| Google translation of JP 06287547 (1994, 5 pages). |
| Office Action in commonly owned Japanese Application No. 2020-517362 dated Feb. 1, 2022, pp. 1-4. |
| Office Action in commonly owned U.S. Appl. No. 16/466,841 dated Jun. 1, 2020, pp. 1-14. |
| Office Action in commonly owned U.S. Appl. No. 15/845,020 dated Jan. 29, 2020, pp. 1-10. |
| Office Action in commonly owned U.S. Appl. No. 16/757,492 dated May 9, 2022, pp. 1-13. |
| Office Action in commonly owned U.S. Appl. No. 15/844,980 dated Sep. 11, 2019, pp. 1-5. |
| Final Office Action in commonly owned U.S. Appl. No. 15/844,980 dated Mar. 10, 2020, pp. 1-10. |
| Lakshmi et al., “Insight into the Mechanism of Antibacterial Activity of ZnO: Surface Defects Mediated Reactive Oxygen Species Even in the Dark”, Langmuir 2015, vol. 31, pp. 9155-9162 (Jul. 29, 2015) and its supplementary materials (p. 6). |
| International Search Report in commonly owned International Application No. PCT/KR2018/006675 dated Sep. 27, 2018, pp. 1-4. |
| International Search Report in commonly owned International Application No. PCT/KR2017/015364 dated Apr. 16, 2018, pp. 1-4. |
| Office Action in commonly owned Chinese Application No. 201880072900.3 dated Dec. 3, 2021, pp. 1-6. |
| Extended Search Report in commonly owned European Application No. 18895611.4 dated Aug. 17, 2021, pp. 1-7. |
| Office Action in commonly owned Korean Application No. 10-2018-0142400 dated Sep. 18, 2020, pp. 1-6. |
| International Search Report in commonly owned International Application No. PCT/KR2018/016158 dated Mar. 20, 2019, pp. 1-6. |
| Office Action in counterpart Chinese Application No. 201880069060.5 dated Jul. 5, 2022, pp. 1-6. |
| Number | Date | Country | |
|---|---|---|---|
| 20200216635 A1 | Jul 2020 | US |
