KR101112448B1 - Complex fiber and method of manufacturing the same - Google Patents

Abstract

In the present invention, a resin composition containing 0.5 to 20 wt% of titanium dioxide (TiO ₂ ) nanopowder and 80 to 99.5 wt% of a polymer resin forms a sheath, and a polymer resin composition forms a core. It provides a method for producing a composite fiber comprising the step of preparing the spun fiber, and the metal particles on the titanium dioxide particles of the composite spun fiber to immerse the composite spun fiber in a metal precursor solution and then photodeposition do.

Titanium Dioxide, Composite Fiber, Antibacterial

Description

Complex fiber and method of manufacturing the same

The present invention relates to a composite fiber having an antibacterial function and an ultraviolet ray blocking function and a method of manufacturing the same.

Conventionally, a polypropylene resin has a composition in which a mixed proportion of titanium dioxide powder, tourmaline powder, sericite powder, silver powder, silica, calcium oxide, zinc oxide, zirconium, etc. having a mean particle size of 0.3 micrometre is added to a predetermined ratio. Make a master batch by mixing with polypropylene resin at a weight ratio of 3: 2, and mix it again with a polypropylene resin at a weight ratio of 5: 5, heat treatment at 120 ~ 140 ℃ for 1 hour to remove moisture and moisture, and then 220 ~ 240 Polypropylene multifilament yarn having antimicrobial, purifying, antifouling, UV blocking, far infrared rays, electromagnetic wave blocking functions, characterized in that the melt spinning at ℃ ℃ and the technology for producing the same.

However, the conventional technology has a problem in that complex mixed powders such as titanium dioxide powder, tourmaline powder, silver powder, silica, and zirconium must be kneaded in the polymer resin in order to manufacture fibers having antibacterial, purification, antifouling, UV blocking, and electromagnetic wave blocking functions. there was.

In addition, the pre-refined wool is immersed in a solution in which conventional acetic anhydride (10% by weight) is dissolved in DMF (90% by weight), the temperature is raised to 50 ° C, the temperature is maintained for 30 minutes, and then the wool is subjected to anion treatment. Wash in water. On the other hand, at least one titanium compound of titanium alkoxide and titanium fluoride is dissolved at a rate of 2.0% owf. The anionized wool is immersed in this aqueous solution and treated at room temperature for 30 minutes. Subsequently, a mixture of boric acid: citric acid: D and L-malic acid = 0.5: 1: 1 was added to the aqueous solution at a rate of 0.5% owf, and treated at 50 ° C for 30 minutes, and then washed with water. As a result, there has been a technique to provide functionality by producing natural fibers in which the fiber surface is plated with titanium oxide.

This conventional technique is also applicable to natural fibers, such as wool, and in the case of synthetic fibers there was a problem in the application.

The present invention provides a composite fiber having a multifunctionality, such as antibacterial, UV protection, deodorant, and a method for producing the same by selectively supporting the semiconductor metal oxide particles on which nanoparticles are loaded, regardless of the type of polymer.

According to one aspect, the present invention is a resin composition containing 0.5 to 20% by weight of titanium dioxide (TiO ₂ ) nanoparticles and 80 to 99.5% by weight of the polymer resin to form a sheath and the polymer resin composition core (core) Forming a) to produce a composite spun fiber, and the composite fiber comprising the step of supporting the metal particles on the titanium dioxide particles of the composite spun fiber to immerse the composite spun fiber in a metal precursor solution and then photodeposition It provides a method of manufacturing.

According to another aspect of the present invention, a resin composition containing 0.5 to 20 wt% of titanium dioxide (TiO ₂ ) nanopowder and 80 to 99.5 wt% of a polymer resin forms a sheath and the polymer resin composition forms a core. ) To provide a composite fiber supporting the metal particles on the titanium dioxide particles.

In this case, the polymer resin is a thermoplastic resin and the polymer resin composition may be a thermoplastic resin composition, wherein the metal particles are one selected from the group consisting of silver (Ag), platinum (Pt), gold (Au), and copper (Cu). Or one or more metal particles.

As described above, the composite fiber according to the present invention and a method for manufacturing the same have an effect of having multi-functionality such as antibacterial, UV protection, deodorization by selectively supporting the semiconductor metal oxide particles loaded with nanoparticles regardless of the type of polymer There is.

In addition, the composite fiber and the manufacturing method thereof according to the present invention has another effect that can be utilized as UV blocking, magnetic shielding, deodorization and antimicrobial material.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but between components It will be understood that may be "connected", "coupled" or "connected".

According to one embodiment, a resin composition containing 0.5 to 20% by weight of titanium dioxide (TiO ₂ ) nanopowder of 500 nm or less and 80 to 99.5% by weight of a thermoplastic resin forms a sheath of the composite spun fiber and is a thermoplastic resin. After preparing a composite fiber forming a core, the fiber is immersed in a solution consisting of an aqueous solution of a metal ion such as silver (Ag), gold (Pt), gold (Au), copper (Cu), and alcohol Photodeposition is performed to produce functional nano composite fibers in which nanoparticles such as silver (Ag), gold (Pt), gold (Au), and copper (Cu) are supported on titanium dioxide particles containing titanium dioxide particles. Can be.

Referring to the manufacturing method of the composite fiber described above in detail.

First, melt titanium dioxide particles into a thermoplastic resin. Kneaded and dispersed to prepare their master batch. The prepared master batch is applied to the sheath during compound spinning. Resin which forms a core part is applicable to the commercially available general thermoplastic resin.

The titanium dioxide (TiO ₂ ) particles may be commercially available or synthesized at 500 nm (0.5 μm) or less, for example, 2 nm to 500 nm, and the crystalline phase has anatase phase photoactivity or a composite phase of anatase and rutile to increase photoactivity. You can use the form with.

Examples of the thermoplastic resin include polyacrylonitrile, polyvinyl alcohol, polyamide, polyester, polylactic acid, polyethylene oxide, polyethylene vinyl alcohol copolymer, cellulose acetate, polymethacrylate, polyester copolymer, and polyvinyl acetate. Can be used.

In order to melt-knead the titanium dioxide (TiO ₂ ) particles to the polymer resin, 0.1 to 20 parts of titanium dioxide (TiO ₂ ) particles are added to 100 parts of the polymer resin by weight using a melt mixer at a melting temperature of the polymer resin. Each is prepared by mixing until a complete mixed melt is obtained. Here, as a mixer, a sigma mixer, a brabender, a single screw extrusion mixer, a twin screw extrusion mixer, a compounder, etc. may be used, and a compounder and a twin screw extrusion mixer may be used to more effectively perform mechanical mixing.

The resin composition is introduced to form the sheath of the composite spun fiber and the thermoplastic resin composition is injected into the composite spinning device to form a core, the spinning temperature is complex spinning at an appropriate spinning speed near the melting point of the polymer resin After stretching at a suitable temperature near the glass transition temperature of the polymer resin, the fiber is immersed in a solution consisting of an aqueous solution of a metal ion such as silver (Ag), gold (Pt), gold (Au), copper (Cu) and alcohol. Photodeposition is performed to produce a composite fiber in which nanoparticles such as silver (Ag), gold (Pt), gold (Au), and copper (Cu) are supported on the titanium dioxide particles of the composite spun fiber containing titanium dioxide particles.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited only to the following examples.

The yarns produced in the examples consisted of about 75d / 24f and weaving was R.P.M 450 weaving in a 190 type loom equipped with a W.J.Lom (Thudakoma, Japan) apparatus equipped with a Dobby apparatus.

Example 1

5 parts by weight of 20 nm titanium dioxide (TiO ₂ ) was added to a twin screw compounder (Wrarner & Pfleiderer, Type ZSK 25) based on polyethylene terephthalate (PET) resin, and the screw speed was 250 rpm, at a temperature of 260 ° C. to 290 ° C. The resin composition was made into chips by mixing at a discharge amount of l5 kg / h. A resin composition containing titanium dioxide (TiO ₂ ) was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, it was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.28 to prepare 74 denier / 24 filament fibers (FIG. 1 and (A) of FIG. 3).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersed in a solution consisting of aqueous solution of aqueous gold chloride (HAuCl ₄ H ₂ O) and methanol at a concentration of 1.5 × 10 ⁻⁴ mol. The composite fiber loaded with gold (Au) on TiO ₂ particles was washed with distilled water and dried at room temperature (see (c) of FIG. 3).

Example 2

7 parts by weight of titanium dioxide (TiO ₂ ) of 20 parts by weight of polyethylene terephthalate (PET) resin was added to a twin screw compounder (Wrarner & Pfleiderer, Type ZSK 25), and the screw speed was 250 rpm at a temperature of 260 ° C. to 290 ° C. The mixture was discharged at l 5 kg / h to make a resin composition into chips. A resin composition containing titanium dioxide (TiO ₂ ) was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, the spinning machine was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.2 to prepare 76 denier / 24 filament fibers (FIG. 2 and (B) of FIG. 3).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersed in a solution consisting of aqueous solution of aqueous gold chloride (HAuCl ₄ H ₂ O) and methanol at a concentration of 1.5 × 10 ⁻⁴ mol. The composite fiber loaded with gold (Au) on TiO ₂ particles was washed with distilled water and dried at room temperature (see FIG. 3 (d)).

As can be seen from the XPS result of FIG. 4A, it can be seen that gold particles are supported. As can be seen in Figure 5 it can be seen that the gold particles are supported on the titanium dioxide particles.

Example 3

5 parts by weight of 20 nm titanium dioxide (TiO ₂ ) was added to a twinscrew compounder (Wrarner & Pfleiderer, Type ZSK 25) with respect to polyethylene terephthalate (PET) resin, and the screw speed was 250 rpm at a temperature of 260 ° C to 290 ° C. The mixture was discharged at l 5 kg / h to make a resin composition into chips. A resin composition containing titanium dioxide (TiO ₂ ) was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, it was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.28 to prepare 74 denier / 24 filament fibers (FIG. 1 and (A) of FIG. 3).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersing in a solution consisting of an aqueous solution of silver nitrate (AgNO ₃ ) and methanol at a concentration of 1.5 × 10 ⁻⁴ mol. The composite fiber loaded with silver (Ag) on TiO ₂ particles was washed with distilled water and then dried at room temperature (see (e) of FIG. 3).

Example 4

7 parts by weight of 20 nm titanium dioxide (TiO ₂ ) was added to a twin screw compounder (Wrarner & Pfleiderer, Type ZSK 25) based on polyethylene terephthalate (PET) resin, and the screw speed was 250 rpm, at a temperature of 260 ° C. to 290 ° C. The resin composition was made into chips by mixing at a discharge amount of l5 kg / h. Titanium dioxide (TiO ₂ ) -containing resin composition was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, the spinning machine was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.2 to prepare 76 denier / 24 filament fibers (FIG. 2 and See FIG. 3 (b)).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersing in a solution consisting of an aqueous solution of silver nitrate (AgNO ₃ ) and methanol at a concentration of 1.5 × 10 ⁻⁴ mol. The composite fiber loaded with silver (Ag) on TiO ₂ particles was washed with distilled water and dried at room temperature ((f) of FIG. 3).

As can be seen from the XPS result of FIG. 4B, it can be seen that silver particles are supported.

Example 5

5 parts by weight of 20 nm titanium dioxide (TiO ₂ ) was added to a twin screw compounder (Wrarner & Pfleiderer, Type ZSK 25) based on polyethylene terephthalate (PET) resin, and the screw speed was 250 rpm, at a temperature of 260 ° C. to 290 ° C. The resin composition was made into chips by mixing at a discharge amount of l5 kg / h. A resin composition containing titanium dioxide (TiO ₂ ) was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, it was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.28 to prepare 74 denier / 24 filament fibers (FIG. 1 and (A) of FIG. 3).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersed in a solution consisting of an aqueous solution of chloroplatinic acid (H ₂ PtCl ₆ H ₂ O) at 1.5 × 10 ^-4 mol concentration and methanol. The composite fiber loaded with silver (Pt) on TiO ₂ particles was washed with distilled water and dried at room temperature ((g) of FIG. 3).

Example 6

7 parts by weight of 20 nm titanium dioxide (TiO ₂ ) was added to a twin screw compounder (Wrarner & Pfleiderer, Type ZSK 25) based on polyethylene terephthalate (PET) resin, and the screw speed was 250 rpm, at a temperature of 260 ° C. to 290 ° C. The resin composition was made into chips by mixing at a discharge amount of l5 kg / h. A resin composition containing titanium dioxide (TiO ₂ ) was added to the sheath and polyethylene terephthalate (PET) resin was added to the core.

At this time, the ratio of S (second part) / C (deep part) was 5: 5. After inserting a spinneret with a spinneret having a hole number of 24 holes, the spinning machine was spun at a spinning speed of 4200 m / min at a spinning temperature of 280 ° C., followed by stretching at a draw ratio of 3.2 to prepare 76 denier / 24 filament fibers (FIG. 2 and See FIG. 3 (b)).

The fiber was photodeposited by ultraviolet irradiation for 60 seconds while immersed in a solution consisting of an aqueous solution of chloroplatinic acid (H ₂ PtCl ₆ H ₂ O) at 1.5 × 10 ^-4 mol concentration and methanol. The composite fiber loaded with platinum (Pt) on TiO ₂ particles was washed with distilled water and dried at room temperature (FIG. 3 (h)).

As can be seen from the XPS result of FIG. 4C, it can be seen that platinum particles are supported.

Experimental Example

The antimicrobial and ultraviolet ray blocking properties of the woven fabric of the composite fibers obtained in Examples 1 to 6 described above were measured by the following method.

Antimicrobial activity was followed by KS K 0693 method. Staphylococcus aureus and Klebsiella pneumoniae were used as test strains.

UV protection evaluation test was evaluated according to KS K 0850 (UV protection rate and blocking index test method of textile products) and the blocking rate was calculated by the following equation (1).

Ultraviolet-A (UV-A) in Equation 2 is a solar ultraviolet region having a wavelength of 315 to 400 nm, and UV-B in Equation 3 is a solar ultraviolet region having a wavelength of 290 to 315 nm. In the ultraviolet experiment, the sample is fixed to the sample hold of the spectrophotometer, and then the wavelength of 290 to 400 nm is scanned in 5 nm wavelength units to measure the ultraviolet transmittance of the sample.

[Equation 1]

[Equation 2]

&Quot; (3) "

In this case, Tλ in Equations 2 and 3 is the spectral transmittance at the wavelength λ.

Table 1 is a table showing the results of the evaluation of the antimicrobial and UV-protective properties of the composite fibers of Examples 1, 2, 3, 4, 5, 6 of the present invention.

As can be seen from Table 1, it can be seen that the silver, platinum, and gold of the present invention are excellent in the antimicrobial and ultraviolet ray blocking ability of the composite fiber supported by light deposition, respectively.

[Table 1]

division Bacteriostatic rate UV protection rate
(UV-A) UV protection rate
(UV-B) Staphylococcus aureus Klebsiella pneumoniae Example 1 99.9 99.9 91 96 Example 2 99.9 99.9 93 96.3 Example 3 99.9 99.9 90 96 Example 4 99.9 99.9 93.3 96.4 Example 5 99.9 99.9 90 96 Example 6 99.9 99.9 93 96

With reference to the drawings, a method of manufacturing a composite island in which metal particles are supported on titanium dioxide particles has been described. Hereinafter, a composite fiber according to an embodiment will be described with reference to the drawings.

Referring to Figures 1 and 2, 3, and 5, but mainly referring to Figure 5, the composite fiber according to an embodiment of the titanium dioxide (TiO ₂ ) nano powder 0.5 ~ 20% by weight and polymer resin 80 ~ 99.5 weight A resin composition containing% forms a sheath, a polymer resin composition forms a core, and metal particles are supported on the titanium dioxide particles.

Referring mainly to FIG. 5, it can be seen that metal particles, for example, gold particles are supported on titanium dioxide nanoparticles.

In this case, the polymer resin may be a thermoplastic resin and the polymer resin composition may be a thermoplastic resin composition. In addition, the polymer resin is polyester, polypropylene, polyethylene, polyamide, polypriylene terephthalate, polybutylene terephthalate, polyamide, polyacrylonitrile, polyvinyl alcohol, polylactic acid, polyethylene oxide, polyethylene vinyl alcohol Copolymers, cellulose acetates, polymethacrylates, polyester copolymers, polyvinyl acetates, polyvinylcarbazoles, collagen, polyanilines, polystyrenes, polyurethanes, polycarbonates, nylons, polyethylene-vinylacetate copolymers, synthetic rubbers, and It may be one or more than one selected from the group consisting of natural rubber.

On the other hand, the titanium dioxide nanopowder is 2nm ~ 500nm, the crystal phase may be one of the form having anatase phase photoactivity, a complex form of anatase and rutile.

The titanium dioxide nano powder may be mixed with the polymer resin to be 0.1 to 20 parts by weight based on 100 parts by weight of the polymer resin.

The metal particles may be one or more metal particles selected from the group consisting of silver (Ag), platinum (Pt), gold (Au), and copper (Cu).

Although the present invention has been described above with reference to the drawings, the present invention is not limited thereto.

For example, the particle size or shape of titanium dioxide has been exemplarily described, but the present invention is not limited thereto.

In addition, although the thermoplastic resin was described as an exemplary polymer resin, the present invention is not limited thereto, and any type of polymer resin may be used.

In addition, it was described as irradiating ultraviolet rays for photodeposition, but any type of electromagnetic wave capable of photodeposition besides ultraviolet rays is possible.

In addition, although silver (Ag), platinum (Pt), gold (Au), and copper (Cu) are exemplarily described as metal precursors for photodeposition, any type of metal particles may be used as metal precursors. It is possible.

In addition, although the weight percent of the titanium dioxide powder and the polymer resin has been exemplarily described, the composite spun fiber may be produced by any weight ratio of both.

Figure 1 is a micrograph of the composite fiber consisting of the core and the core used in Examples 1 and 3, 5.

Figure 2 is a micrograph of the composite fiber consisting of the core and the core used in Examples 2 and 4, 6.

3 is a photograph of the composite fiber fabrics of Examples 1 to 6, wherein a is a woven fabric of 5 wt% titanium dioxide-containing composite fibers at the beginning, and b is a woven of 7 wt% titanium dioxide-containing composite fibers at the beginning One fabric, c is a photodeposited gold on a fabric woven with 5 wt% titanium dioxide-containing composite fibers at the beginning, and d is a photodeposit of gold on a fabric woven with 7 wt% titanium dioxide-containing composite fibers at the beginning. It is a good fabric, e is a fabric obtained by photo-depositing silver on a fabric woven with 5 wt% titanium dioxide-containing composite fiber at the beginning, and f is a silver fabric on a fabric woven with 7 wt% titanium dioxide-containing composite fiber at the beginning. It is a good fabric, g is a fabric obtained by depositing platinum on a fabric woven with 5 wt% titanium dioxide-containing composite fiber at the beginning, and h is a platinum on a fabric woven with 7 wt% titanium dioxide-containing composite fiber at the beginning. It is a nice fabric.

Figure 4 is an XPS analysis picture of the composite fiber fabrics of Examples 2 and 4, 6.

FIG. 5 is a TEM analysis picture of (a) the composite fiber carrying gold nanoparticles of Example 2, and (b) is an enlarged TEM photograph of (a).

Claims (13)

A resin composition containing 0.5 to 20% by weight of titanium dioxide (TiO ₂ ) nanoparticles and 80 to 99.5% by weight of a polymer resin forms a sheath and a polymer resin composition forms a core to form a composite spun fiber. Manufacturing step; A method of producing a composite fiber comprising the step of supporting the metal particles on the titanium dioxide particles of the composite spun fiber to immerse the composite spun fiber in a metal precursor solution and then photodeposition. The method of claim 1, The photodeposition is by ultraviolet irradiation, the polymer resin is a thermoplastic resin and the polymer resin composition is a method for producing a composite fiber, characterized in that the thermoplastic resin composition. The method of claim 1, The polymer resin may be polyester, polypropylene, polyethylene, polyamide, polypriylene terephthalate, polybutylene terephthalate, polyamide, polyacrylonitrile, polyvinyl alcohol, polylactic acid, polyethylene oxide, polyethylene vinyl alcohol copolymer , Cellulose acetate, polymethacrylate, polyester copolymer, polyvinyl acetate, polyvinylcarbazole, collagen, polyaniline, polystyrene, polyurethane, polycarbonate, nylon, polyethylene-vinylacetate copolymer, synthetic rubber and natural rubber Method for producing a composite fiber, characterized in that one or more selected from the group consisting of. The method of claim 1, The titanium dioxide nano powder is 2nm ~ 500nm, the crystal phase is a method of producing a composite fiber, characterized in that one of the forms having anatase phase photoactivity, a composite form of anatase and rutile. The method of claim 1, The titanium dioxide nano powder is mixed with the polymer resin so that 0.1 to 20 parts by weight based on 100 parts by weight of the polymer resin. The method of claim 1, The photodeposition is a method of producing a composite fiber, characterized in that by irradiating ultraviolet light by immersing the composite spun fiber in a solution consisting of a salt (metal) salt solution and alcohol. The method of claim 1, The metal precursor solution is a method of producing a composite fiber, characterized in that the metal salt solution containing at least one metal selected from the group consisting of silver (Ag), platinum (Pt), gold (Au), and copper (Cu). . A resin composition containing 0.5-20 wt% of titanium dioxide (TiO ₂ ) nanoparticles and 80-99.5 wt% of a polymer resin forms a sheath, and a polymer resin composition forms a core, and the titanium dioxide A composite fiber carrying metal particles on the particles. The method of claim 8, Wherein said polymer resin is a thermoplastic resin and said polymer resin composition is a thermoplastic resin composition. 10. The method of claim 9, The polymer resin may be polyester, polypropylene, polyethylene, polyamide, polypriylene terephthalate, polybutylene terephthalate, polyamide, polyacrylonitrile, polyvinyl alcohol, polylactic acid, polyethylene oxide, polyethylene vinyl alcohol copolymer , Cellulose acetate, polymethacrylate, polyester copolymer, polyvinyl acetate, polyvinylcarbazole, collagen, polyaniline, polystyrene, polyurethane, polycarbonate, nylon, polyethylene-vinylacetate copolymer, synthetic rubber and natural rubber Composite fiber, characterized in that one or more than one selected from the group consisting of. 10. The method of claim 9, The titanium dioxide nano powder is 2nm ~ 500nm, the crystalline phase is a composite fiber characterized in that one of the forms having anatase phase photoactivity, a composite form of anatase and rutile. 10. The method of claim 9, The titanium dioxide nano powder is mixed with the polymer resin to be 0.1 to 20 parts by weight based on 100 parts by weight of the polymer resin. 10. The method of claim 9, The metal particles are composite fibers, characterized in that one or more metal particles selected from the group consisting of silver (Ag), platinum (Pt), gold (Au), and copper (Cu).

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