KR20190011432A - Fiber having deodorant and antimicrobial function and method for producing the same - Google Patents

Abstract

The present invention is to provide a deodorant and antibacterial dispersion including TiO_2 in which anatase and rutile are mixed. Desirably, the present invention is to provide a dispersion in which the ratio of anatase and rutile is between 1 : 1 and 1 : 9. The TiO_2 dispersion can show deodorant and antibacterial effects even without UV since the TiO_2 dispersion is in a mixed phase of anatase and rutile. In addition, titania sol dispersed through surface treatment of the mixed anatase and rutile TiO_2 has an average particle size distribution of 100 nm or less. Thus, when a fiber or clothing is immersed in a titania dispersion and then is dried, titania particles can be fixed to the fiber or clothing even without a binder. Therefore, a manufacturing method for a deodorant and antibacterial dispersion can manufacture a functional fiber and clothing having deodorant and antibacterial functionality because the fiber and clothing with the dispersion fixed thereto can have deodorant and antibacterial functions.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fiber having a deodorizing and antimicrobial function,

The present invention relates to a deodorizing and antimicrobial fiber using a TiO ₂ dispersion of an anatase and a rutile mixture.

Textiles made of natural fibers / synthetic fibers / chemical fibers, or textiles made of the above-mentioned fabrics in various ways, have numerous pores, and therefore, there is a tendency that odors such as sweat odor, cigarette smoke, Such as dust, is easily adsorbed on the pores and becomes easily dirty. Therefore, in order to maintain a clean state, it is necessary to wash frequently, in which case the durability life of the fiber product is reduced in inverse proportion to the number of times of washing.

Recently, photocatalysts have been widely used in various fields, from global environmental purification such as pollution air and purification of polluted water to deodorization, pollution prevention, and purification of living environment such as antibacterial, by positively utilizing the high oxidizing power and reducing power exhibited by photocatalysts Research and development is under way.

As a compound having a photocatalytic action, studies have been conducted on transition metal oxides such as noble metals such as Pt and Rh, NiO and the like, which use a cocatalyst or a carrier in parallel to accelerate the reaction. The most representative oxides having a photocatalytic action include anatase Type titanium oxide is known.

However, titanium oxide has a problem in that it is active only under irradiation of ultraviolet rays of not more than 4% among solar rays shorter than 400 nm, and various improvements have been attempted with the aim of enhancing the capability of titanium oxide in outdoor and the response of visible light .

When a photocatalyst having a visible light response characteristic of 46% of the sunlight is developed, not only a highly efficient photocatalyst can be produced under the sunlight but also the fluorescent lamp in the room where the sunlight can not reach can be sensitized, .

That is, among the methods for removing harmful substances, a photocatalyst using clean and infinite solar energy has been attracting attention. Since TiO ₂ , which has been known to be the most effective so far, absorbs only ultraviolet rays having short wavelengths in the sunlight, It is urgently required to develop a photocatalyst capable of absorbing visible light.

It is an object of the present invention to provide a functional photocatalyst having various functions such as deodorization, antibacterial and decomposition of air pollutants required for health and comfort textile.

It is another object of the present invention to provide a dispersion body which can be coated and fixed to clothing without a binder.

Another object of the present invention is to produce functional fibers and garments having deodorant, antibacterial function.

In order to solve the above problems, an anatase of the present invention and a rutile mixed TiO ₂ Is characterized in that it comprises the following steps.

a) synthesizing Ti (OH) ₄ hydrate using NH ₄ OH (Ammonium hydroxide, 28%) in TiOCl ₂ (Titanium Oxychloride, 40%) solution;

b) In order to remove the NH ₄ Cl ion, the Ti (OH) ₄ Cleaning the hydrate;

c) the Ti (OH) ₄ Drying the hydrate;

d) The dried Ti (OH) ₄ Heat treating the hydrate at 700 to 800 DEG C; and

e) subjecting the TiO ₂ powder of Anatase + Rutile mixed phase to a surface treatment after the heat treatment to obtain a titania water dispersion having an average particle size distribution of 100 nm or less;

The synthesis temperature of the Ti (OH) ₄ is 20 ° C or less.

Among the production methods of the present invention, in the step a), TiOCl ₂ 1 to 50 parts by weight of Zinc acetate, Zinc nitrate and Zinc sulfate salt is mixed with TiO ₂ . The salts exhibit an antibacterial function even in a small amount of 1 part by weight or more, and it is preferable to add up to 50 parts by weight. The titania dispersion thus produced has an antibacterial function.

The surface treatment step comprises the steps of: f) wet milling with a Beads Mill followed by agitation; and g) stirring the mixture after adding N- (2-aminoethyl) 3-aminopropyltrimethoxysilane hydrolyzate and drying at 80 to 100 ° C .

The N- (2-aminoethyl) 3-aminopropyltrimethoxysilane hydrolyzate is prepared by mixing silane with ethanol at a ratio of 1: 1, stirring the mixture, adding a small amount of water and 0.1 N nitric acid, and stirring.

The surface-treated Anatase + Rutile TiO ₂ The powder further comprises mixing and mixing with ultra pure water and dispersing using a beads mill.

A deodorant and an antibacterial dispersion prepared by the above-mentioned production method are provided. The ratio of anatase to rutile in the dispersion is preferably 1: 1 to 1: 9.

Further, by supporting the fibers in the deodorizing and antibacterial dispersing bodies, it is possible to provide fibers having a deodorizing and antibacterial function.

The TiO ₂ of the present invention Since the dispersoid is a mixed phase of anatase and rutile, it exhibits deodorizing and antibacterial effect even without UV.

In addition, the titania sol dispersed on the surface of the anatase and rutile mixed phase TiO ₂ of the present invention has an average particle size distribution of 100 nm or less. When the fibers or clothes are carried on a titania dispersion and then dried, the titania particles are fixed .

Accordingly, since the fibers and clothes to which the dispersion is adhered have a deodorizing function and an antibacterial function, functional fibers and clothes having deodorizing and antibacterial functions can be produced.

Fig. 1 is a graph showing the results of anatase + rutile mixed TiO ₂ A schematic view showing a manufacturing process,
FIG. 2 shows the results of FE-SEM of anatase + rutile mixed TiO ₂
FIG. 3 is a graph showing XRD
Fig. 4 is a schematic view showing a TiO2 dispersing process of Anatase + Rutile mixed phase
5 is a graph showing an aqueous dispersion and an average particle size distribution,
Figures 6 and 7 are deodorization evaluation reports.
Fig. 8 is a report of the antibacterial evaluation result.

Hereinafter, the present invention will be described in detail.

One. Anatase ( Anatase ) + Ruta day ( Rutile ) Dominant TiO ₂  Produce

The manufacturing method of the present invention includes each step as shown in Fig.

Anatase + Rutile for honsang TiO ₂ was prepared using the _{TiOCl 2 (Titanium Oxychloride, 40%} ) Solution in the starting material. NH (OH) ₄ (NH ₄ OH) (28%) was used as the neutralization solution. After the hydration was synthesized, it was washed, NH ₄ Cl ion was removed, and then dried and heat treated to form anatase + rutile mixed TiO ₂ . Crystalline phase and particle size were determined according to heat treatment temperature and surface treatment was performed to improve dispersibility.

In the present invention, since the temperature at which Ti (OH) ₄ is produced is very important, the synthesis temperature should be maintained at 20 ° C or lower. To remove NH ₄ Cl, cleaning was carried out using a filter press, and the final conductivity was controlled to be 100 μs or less. TiO ₂ of Anatase + Rutile Phase was obtained when heat treatment was performed at 700 ~ 800 ℃.

FIG. 2 is an FE-SEM of anatase + rutile mixed TiO ₂ under heat treatment at 750 ° C. and FIG. 3 is an XRD showing a change in crystal phase with heat treatment temperature.

It was confirmed that TiO ₂ of the Anatase Phase having an average particle size of about 20 to 30 nm was obtained at the heat treatment at 600 ° C. The heat treatment temperature was 700 ~ 800 ℃ to obtain the Anatase + Rutile mixed phase. At 750 ℃, the ratio of anatase and rutile phase was almost 1: 1. The closer to 800 ℃, the larger the content of rutile. On the other hand, the closer to 600 ℃ the larger the content of anatase was. Respectively. Rutile TiO ₂ could be obtained only at 800 ° C or higher, and the particle size of about 100-200 nm was confirmed by FE-SEM measurement.

1) Raw materials

TiOCl ₂ : Millennium Chemicals

H2 _O (ultrapure water) to itty ㈜ seokgyeong

NH ₄ OH: Dongwoo Fine-Chem

_{Zn (OAc) * 2H 2 O} , Zn (NO 3) 2 * 6H 2 O, ZnSO 4 * 7H 2 O: Junsei

2) Results

 - FE-SEM (see FIG. 2)

In addition to the deodorizing function of TiO ₂ , TiO ₂ Zinc acetate, Zinc nitrate and Zinc sulfate salt can be synthesized by increasing the amount of Zinc acetate to 1 ~ 50 parts by weight relative to TiO ₂ . The salts exhibit an antibacterial function even in a small amount of 1 part by weight or more, and it is preferable to add up to 50 parts by weight.

2. Anatase  + Rutile Congestion TiO ₂  Surface treatment

In order to improve the water dispersibility, TiO ₂ with Anatase + Rutile mixed phase obtained by heat treatment at 750 ℃ was surface treated as follows.

1) Coagulated TiO ₂ by heat treatment Powder was wet-milled with Beads Mill and stirred

2) The hydrolyzate of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane was added to 1), stirred for 1 hour, dried at 90 ° C for 24 hours

Preparation of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane hydrolyzate

 - Silane is mixed with ethanol at a ratio of 1: 1. After stirring, a small amount of water and 0.1 N nitric acid are added and stirred for 1 hour.

* N- (2-aminoethyl) 3-aminopropyltrimethoxysilane

- (CH ₃ O) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH ₂

* Application of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane

 - Acrylic, Nylon, Phenol, Epoxy

3. Anatase  + Rutile Congestion TiO ₂  Dispersion

FIG. 4 shows a process of dispersing the surface-treated Anatase + Rutile TiO ₂ .

To disperse the surface treated Anatase + Rutile TiO ₂ with amino silane, the powder was mixed with ultrapure water, stirred and dispersed using a beads mill. The size of the beads was 0.1 mm.

The average particle size was 60 nm in the titania water dispersion (Solid Content 20 wt%) (see Fig. 5)

Example

Example  One: Anatase  + Rutile Congestion TiO ₂ Sol  Adherence to textiles and clothing

In general, the inorganic particles are mixed with a binder such as an acrylic acid-based polymer, a urethane polymer, or a latex, and coated or printed on a yarn, a fiber, a knitted fabric or a nonwoven fabric. However, this method is technically easy, There is a disadvantage that the durability is poor.

However, the titania sol dispersed by surface treatment with Anatase + Rutile TiO ₂ has an average particle size distribution of 100 nm or less. When the fiber or clothing is loaded on the titania dispersion without the binder and then dried, the titania particles can be fixed to the fibers and clothing without binder there was. In this case, the content of TiO ₂ is preferably 1 to 3 parts by weight of the fiber.

A shirt was produced by carrying the dispersed body of the Anatase + Rutile mixed TiO ₂ prepared above and having a deodorizing and antibacterial function. At this time, 1.8 parts by weight of the dispersion was used for the shirt (see Fig. 6).

Example  2: Deodorant  And antibacterial performance evaluation

One. Deodorant  evaluation

As a result of the evaluation of the deodorization, as shown in FIG. 6 and FIG. 7, it was confirmed that ammonia was removed 85% in the UV irradiation and 43% in the natural state when the TiO ₂ was fixed to 1.8% 95%.

2. Antimicrobial evaluation

As a result of the antibacterial evaluation, it was confirmed that the bacteria were reduced as shown in Fig.

Claims (9)

_{a) TiOCl 2 (Titanium Oxychloride,} 40%) in _{NH 4 OH (Ammonium hydroxide, 28} %) using the Ti (OH) ₄ solution Hydrate synthesis;
b) In order to remove the NH ₄ Cl ion, the Ti (OH) ₄ Cleaning the hydrate;
c) the Ti (OH) ₄ Drying the hydrate;
d) The dried Ti (OH) ₄ Heat treating the hydrate at 700 to 800 DEG C; and
e) subjecting the TiO ₂ powder mixed with Anatase + Rutile to a surface treatment to obtain a titania water dispersion having an average particle size distribution of 100 nm or less after the heat treatment; and a step of mixing anatase and rutile mixed TiO ₂ Wherein the deodorizing and antimicrobial agent is dispersed in water. The method according to claim 1, wherein the synthesis temperature of Ti (OH) ₄ is 20 占 폚 or less. The method of claim 1, wherein in step a), TiOCl ₂ Wherein 1 to 50 parts by weight of Zinc acetate, Zinc nitrate and Zinc sulfate salt are mixed with TiO ₂ . The method of claim 1, wherein the surface treatment step comprises:
f) wet milling with a Beads Mill followed by stirring; and
g) stirring the mixture after the addition of the hydrolyzate of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, followed by drying at 80 to 100 ° C. 5. The method according to claim 4, wherein the N- (2-aminoethyl) 3-aminopropyltrimethoxysilane hydrolyzate is prepared by mixing silane with ethanol at a ratio of 1: 1, stirring the mixture, adding a small amount of water and 0.1 N nitric acid, . The method of claim 1, further comprising: h) subjecting the surface treated Anatase + Rutile TiO ₂ Mixing the powder with ultrapure water and stirring and dispersing using a beads mill. A deodorizing and antibacterial dispersant comprising an anatase and a rutile mixed TiO ₂ produced according to any one of claims 1 to 6. The dispersion according to claim 7, wherein the ratio of anatase to rutile is from 1: 1 to 1: 9. A fiber having a deodorizing and antibacterial function produced by supporting on the dispersion of claim 7.

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