KR20100077896A - Preparation method for functional fabric having antibiotic and moisture absorption properties using sliver nanopaticles incorporated mesoporous sillica - Google Patents

Abstract

PURPOSE: A manufacturing method of antibacterial and moisture-absorptive functional fabric using mesoporous silica containing silver nanoparticles is provided to improve moisture-absorptive property of fabric by silica, and to secure antibacterial property through desorption reduction of nanosilver particles. CONSTITUTION: A composition for inner skin coating of fiber textile includes mesoporous silica in which nanosilver particle is sealed. The average pore size of mesoporous silica is 5-25nm. The average particle size is 0.5-2 μm. A manufacturing method of the composition for the inner skin coating of fiber textile includes the following steps: manufacturing mesoporous silica by reacting poly(alkylene oxide) block copolymer and tetraethyl orthosilicate; sealing the nanosilver particles of the average particle size 2-3nm in the mesoporus silica; and mixing mesoporous silica 1 parts by weight and polymer resin 100-1000 parts by weight.

Description

Preparation method for functional fabric having antibiotic and moisture absorption properties using sliver nanopaticles incorporated mesoporous sillica

The present invention relates to a fabric coating technology having a maximizing antibacterial effect and hygroscopic function of a fabric product including an industrial fabric fabric. In particular, by coating a nanoporous silica (mesoporous silica) coating solution in which silver nanoparticles are encapsulated, the present invention relates to a process technology having a continuous antimicrobial effect through the reduced desorption of silver nanoparticles and a hygroscopic function using silica.

The textile fabrics can be divided into two categories, industrial and general textile fabrics.

In the case of industrial textile fabrics, for example, cut protective gloves or clothing used in industrial sites. And with the development of small and medium-sized enterprises in the automotive industry and manufacturing sectors, the use of presses, which are the culprit of cutting accidents, is expected to increase gradually, but protective gloves and clothing for cutting protection are used to improve the work efficiency of users in fine work such as cutting. In most cases, even if you wear it, even if you wear it for a long time does not ventilate sweating caused by the phenomenon of unpleasant to feel uncomfortable use for a long time to stop wearing. However, for industrial fabrics, they focus only on the outside of the fabric, that is, cutting strength, slippage, and waterproofing, and there is no research or production plan on the fabric's inner skin.

In addition, not only industrial textiles but also general textile fabrics are neglected for washing, or if the skin is injured, the hygienic condition of the textile fabric becomes an important factor. In order to overcome this problem, a technique of coating silver nanoparticles as an antimicrobial expression material on a fiber or a textile fabric has been studied, but there is a problem in that the coating is peeled off by washing or the like and the antimicrobial properties are deteriorated. There is a possibility of harm. In particular, the coating technology of textile fabrics that express antimicrobial effect by replacing ion with porous ceramic material such as zeolite by using ion exchange method, shows that antimicrobial effect expressed by silver ions falls on silver nanoparticles, and in zeolites with fine pores of 2 nm or less There was a problem in that the encapsulation efficiency and encapsulation stability of the silver nanoparticles are lowered. Therefore, there is an urgent need for a stable encapsulation technique of silver nanoparticles suitable for use in coating of textile fabrics.

Porous silicas, on the other hand, include silica zero gels with disordered pores in the structure and mesoporous silicas with very uniform pore sizes and arrangements. Among them, mesoporous silica nanoparticles were used in the early 90's using mesoporous silica called MCM-41 (Mobile Composition of Matter-41) having an array of uniform pores in the structure using a liquid crystal template. Since the first synthesis, due to the uniform pore size, high specific surface area, and large pore volume, much research has been conducted on catalyst, electrical and optical applications, and the applicability of new nanomaterials in the fields of medicinal materials is noted. have.

An object of the present invention is to impart functionalities such as hygroscopicity, antimicrobial activity and deodorization to the textile fabrics for industrial and general clothing to complement the unsanitary part of the conventional textile fabrics, while increasing the preference for wearing, while conventional silver nanoparticles It is to provide a coating technology of the textile fabric that solves the problem of peeling the coating by.

The present invention features a composition for endothelial coating of a textile fabric containing mesoporous silica containing silver nanoparticles.

The mesoporous silica in the coating composition of the present invention is characterized in that the average pore size is 5 ~ 25 nm.

The mesoporous silica in the coating composition of the present invention is characterized in that the average particle size of 0.5 ~ 2 μm.

In the coating composition of the present invention, the silver nanoparticles are characterized in that the average particle size is 2 ~ 3 nm.

In the coating composition of the present invention, the silver nanoparticles are characterized by including 100 to 1000 parts by weight of the polymer resin in 1 part by weight of the mesoporous silica encapsulated.

In the coating composition of the present invention, the polymer resin is a coating composition, characterized in that the polyurethane resin.

In another aspect, the present invention comprises the steps of reacting a poly (alkylene oxide) block copolymer and tetraethyl ortho silicate to prepare mesoporous silica having an average pore size of 5 to 25 nm and an average particle size of 0.5 to 2 μm; Encapsulating silver nanoparticles having an average particle size of 2 to 3 nm in mesoporous silica; And mixing 100 to 1000 parts by weight of the polymer resin to 1 part by weight of the mesoporous silica in which the silver nanoparticles are encapsulated.

In another aspect, the present invention is characterized in that the coating composition or the coating composition prepared by the method is applied to the inner skin of the fabric or blend of the fiber selected from polyethylene, polyester, nylon and cotton. .

In the fiber fabric of the present invention, the fiber is characterized in that the polyethylene fiber having a density of 0.9 ~ 1.0 g / cm ³ and a tensile strength of 2 GPa or more, a tensile modulus of 50 GPa or more.

The textile fabric of the present invention is characterized in that it is for cutting protective gloves or clothes production.

Cut protective gloves and clothes of the present invention is characterized in that the fiber fabric is made of raw materials.

This method is applied to most fabrics, such as industrial, clothing, and medical textile fabrics, to supplement conventional unsanitary areas, increase the preference for the use of the fabrics and their wearing, and also in terms of the human harmfulness of silver nanoparticles. Stability can be guaranteed.

1 is a schematic view showing a process of coating a fiber fabric with a coating composition containing mesoporous silica encapsulated silver nanoparticles according to an embodiment of the present invention.

In order to prepare mesoporous silica in the present invention, poly (alkylene oxide) block copolymers such as Pluronic P123 (manufactured by BASF) and tetraethyl ortho silicate (TEOS) are used as precursors. Mesoporous silica is prepared by mixing a poly (alkylene oxide) block copolymer with water, adding an acid to dissolve, and then ageing under warm pressurization with the addition of TEOS. At this time, the mesoporous silica having a more uniform pore size can be obtained by aging the mesoporous silica under a constant pressure and temperature.

Preferably the mesoporous silica of the present invention has a pore size of 5 to 25 nm, more preferably 10 to 20 nm. Mesoporous silica having a pore size of less than 5 nm has a problem that the encapsulation efficiency is very low because it is smaller than or similar to the particle size of silver nanoparticles, and when it exceeds 25 nm, it is repeated when fabricating textile fabrics or gloves or clothing. There is a problem that the amount of silver nanoparticles released by phosphorus friction or washing increases and the antimicrobial activity decreases.

The pore size of mesoporous silica is adjustable by conventional techniques known in the art and is not particularly limited. For example, in order to increase the pore size of mesoporous silica, the pore size may be controlled by adding 1,3,5-trimethylbenzene (TMB) as a pore expanding agent.

Mesoporous silica in the present invention can be prepared by mixing Pluronic P123, HCl and water. The mixed solution becomes an increasingly clear solution with stirring. After stirring at about 40 ° C. for about 24 hours, tetraethyl ortho silicate (TEOS) is added and stirred. While stirring, the solution becomes an opaque solution. The opaque mesoporous silica solution is administered to a steel press and then placed in a hot oven for ageing. The aged mesoporous silica is cooled to room temperature, washed with water, and the mesoporous silica is dried and sintered at room temperature to prepare mesoporous silica with fine pores. The obtained mesoporous silica is used as a support for encapsulation of silver nanoparticles.

Preferably the mesoporous silica of the present invention has a particle size of 0.5 ~ 2 μm, more preferably 1 ~ 1.5 μm. If the particle size is less than 0.5 μm, the internal pore volume and porosity are significantly reduced, and the efficiency decreases when encapsulating silver nanoparticles. If the particle size exceeds 2 μm, the size of silica becomes too large, which may cause a decrease in adhesion efficiency when coating the fabric. .

The mesoporous silica of the present invention contains silver nanoparticles in many pores of the silica. In this case, the silver nanoparticles may be prepared in the form of a solution (water or alcohol as a solvent) and then included in the pores of mesoporous silica.

Preferably the silver nanoparticles of the present invention has a particle size of 2-3 nm.

The composition for endothelial coating of the textile fabric of the present invention further comprises a polymer resin in mesoporous silica in which silver nanoparticles are encapsulated. The composition of the polymer resin in the coating composition includes 100 to 1000 parts by weight of the polymer resin, preferably 150 to 500 parts by weight, and 100 parts by weight of the polymer resin with respect to 1 part by weight of the mesoporous silica solid content containing the silver nanoparticles. If less than the coating composition is difficult to uniformly apply to the fiber fabric, when the polymer resin exceeds 1000 parts by weight there is a problem that the antimicrobial and hygroscopicity is lowered.

The polymer resin of the present invention is to form a microporous film to allow moisture permeability and waterproofing as the inner skin of the textile fabric, and a polyurethane resin or a special synthetic rubber NBR (Nitrile Butadiene Rubber) latex resin may be used. Polyurethane resin.

In the case of using polyurethane, mesoporous silica and polyurethane resin encapsulated with silver nanoparticles are coated with a textile fabric by adjusting the viscosity with an organic solvent such as dimethylformamide, and then the textile fabric is dipped in water to The dimethylformamide contained in the polyurethane polymer formed on the coating layer is eluted to form a fine porous coating layer. By the wet method as described above, the coating layer formed on the inner layer of the textile fabric has moisture permeability and waterproofness, and is also provided with breathability, volume, and soft touch.

The textile fabric of the present invention is not particularly limited as long as it is a fabric for manufacturing industrial and general clothing and gloves. For example, a woven or blended fabric of fibers selected from polyethylene, polyester, nylon and cotton can be used.

Preferably, the coating composition of the present invention can be used for the coating of gloves, garments for cutting prevention of industrial use, inter alia. As the cut-resistant fiber fabric, a polyethylene fiber fabric (trade name Dyneema or Spectra) having a density of 0.9 to 1.0 g / cm ³ and a tensile strength of 2 GPa or more and a tensile modulus of 50 GPa or more may be used.

Dyneema fabric is one of many materials in the industrial field. It has high specific strength and inelasticity, so it has excellent shock energy absorption and low density, making it a lightweight material. Dyneema fabrics are produced from polyethylene and do not have other chemical groups that are susceptible to any cyclic aromatics, amides, hydroxyls or other aggressive agents. The result is an excellent crystalline fiber with excellent resistance to water, moisture, strong chemicals, UV rays and microorganisms. Dyneema fabric is not used in water, sea water, moisture, or hydrolysis, so it is widely used as a material for protecting industrial sites or body armor.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely to aid the understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Mesoporous Silica with Pore Size of 10 nm

4 g of Pluronic P123 (EO ₂₀ PO ₇₀ EO ₂₀ ) was placed in a polypropylene container, and 120 g of 2 M HCl and 30 g of water were mixed and stirred for 24 hours until completely dissolved at 40 ° C. The mixed solution becomes an increasingly clear solution with stirring, where micelles are formed. It was made to react for 8 hours by adding 8.5 g of tetraethyl ortho silicate (TEOS), maintaining 40 degreeC. The solution became an opaque solution, with the mesoporous silica solution calcined in an oven at 120 ° C. for 8 hours to have a more uniform pore size of the opaque mesoporous silica solution after stirring for 8 hours. The mesoporous silica powder was filtered through filter paper, washed with distilled water and dried. The completely dried powder was calcined at 550 ° C. for 6 hours to produce mesoporous silica powder.

In order to confirm the internal structure and pore size of the prepared mesoporous silica, TEM analysis was performed, and the results are shown in FIG. 2. The instrument used for analysis was JEOL JEM-4010 400kV (TEM) (TEM Accelerating Voltage: 100-400 kV; Magnification: × 60-2,000,000; Minimum spot size: 0.7 nm). The prepared mesoporous silica formed a channel with a constant pore wall, the pore size was about 10 nm, and the specific surface area affecting the encapsulation efficiency was found to be 778.6 m ² / g (FIG. 3A). Reference).

Preparation Example 2 Preparation of Porous Silica with Pore Size of 17 nm

12 g of Pluronic P123 (EO ₂₀ PO ₇₀ EO ₂₀ ), 360 g of 2 M HCl, 90 g of water, followed by 4.5 g of 1,3,5-trimethylbenzene with 25.5 g of tetraethyl ortho silicate (TEOS) A mesoporous silica having a pore size of 17 nm was prepared under the same conditions as in Preparation Example 1, except that.

Preparation Example 3 Preparation of Mesoporous Silica with Pore Size of 30 nm

10 g of Pluronic P123 (EO ₂₀ PO ₇₀ EO ₂₀ ), 375 g of 2 M HCl and mixing 0.115 g of NH4F instead of water, together with 22.0 g of tetraethyl ortho silicate (TEOS) 1,3,5-trimethylbenzene A mesoporous silica having a pore size of 30 nm was prepared under the same conditions as in Preparation Example 1, except that 10.0 g was used.

Preparation Example 4 Preparation of Silver Nanoparticles

To prepare silver nanoparticles, silver nitrate was dissolved in isopropyl alcohol added with 5% by weight of poly (N-vinyl-2-pyrrolldone), stirred for about 20 minutes, and exposed to Ar gas for about 30 minutes. After the radiation treatment, a solution containing silver nanoparticles having an average particle size of 2 to 3 nm was prepared.

SEM (Scamning Electron Microscope) analysis was performed with the solution containing the silver nanoparticles. For this, a SM-300 / Topcon model (surface coating with Au particles; Resolution 3.5 nm; Magnification: 20X to 300,000X; surface analysis) was used, and the results are shown in FIG. 4. The silver nanoparticles had the characteristics of small particles (see FIG. 4), and these 2 to 3 nm particles could be encapsulated in 10 nm pores of the mesoporous silica.

Preparation Example 5 Preparation of Mesoporous Silica Enclosed with Silver Nanoparticles

Silver nanoparticles prepared by the reduced-reductant process of Preparation Example 4 were encapsulated in the mesoporous silica having a pore size of 5 to 10 nm of Preparation Example 1.

5 ml of the solution containing silver nanoparticles was mixed with 1 g of mesoporous silica having a pore size of 10 nm and 50 ml of ethanol, followed by stirring for 24 hours to prepare a mesoporous silica dispersion solution containing silver nanoparticles. .

The qualitative characteristics of the silver nanoparticles were confirmed through FT-IR analysis of the silver nanoparticles of Preparation Example 4 and the mesoporous silica containing the silver nanoparticles of Preparation Example 5. The apparatus used was a JASCO V-460 FT / IR Spectrometer (Wavelength Range: 650-4000 nm; using Miracle Single reflectance ATR; Resolution: 4 cm ^-1; Scantimes: 30times), and the results are shown in FIG. In Figure 5 of Preparation Example 4 are shown in a group of silver nano-OH In a liquid nanoparticles (Ag group) (3250 ~ 3300cm ^-1) and is available at 1700cm ^-1 in Fig nanoparticles unique peak. In addition, in the mesoporous silica (Ag + Si group) in which the silver nanoparticles of Preparation Example 5 are encapsulated, it can be seen that the Si-O peak appearing at 1100 cm ⁻¹ is a silica having the properties of silver nanoparticles.

Meanwhile, UV-VIS analysis was performed on mesoporous silica of Preparation Example 1, silver nanoparticles of Preparation Example 4, and mesoporous silica containing silver nanoparticles of Preparation Example 5. The apparatus used was a JASCO V-550 UV-Vis Spectrophotometer (Wavelength Range: 200-900 nm, Bandwidth Selectable: 0.5 nm, Scanning Speed 400 nm / min, Data Pitch 1 nm), and the results are shown in FIG. In the mesoporous silica in which the silver nanoparticles of Preparation Example 5 were encapsulated, the peaks of the silver nanoparticles and the peaks of the mesoporous silica were confirmed.

Example 1-1 Preparation of Coating Composition

A solution obtained by dispersing the mesoporous silica solution containing the silver nanoparticles of Preparation Example 5 in ethanol and a polyurethane resin in a weight ratio of 1: 5 was mixed, and the viscosity was adjusted with dimethylformamide to prepare a fiber cloth endothelial coating composition. It was. As a polyurethane resin, the thing of the viscosity 20,000-30,000 cps which superposed | polymerized the polyol of 4, 4- diphenylmethane diisocyanate, 1, 4- butanediol, and the polymerization copper 150 was used.

Example 1-2 Preparation of Coating Composition

After preparing mesoporous silica having a pore size of 17 nm of Preparation Example 2, mesoporous silica containing silver nanoparticles containing the silver nanoparticles of Preparation Example 4 as in Preparation Example 5 was prepared. The coating composition was prepared by mixing the polyurethane resin with a 1: 5 weight ratio as in Example 1-1.

Comparative Example 1-1

After preparing a porous silica having a pore size of 30 nm of Preparation Example 3, a porous silica containing silver nanoparticles in which silver nanoparticles of Preparation Example 4 were encapsulated as in Preparation Example 5 was prepared. The coating composition was prepared by mixing the polyurethane resin with a 1: 5 weight ratio as in Example 1-1.

Experimental Example 1 Encapsulation Efficiency of Silver Nanoparticles

A standard calibration curve of silver nanoparticles was obtained by using an ultraviolet visible light spectrometer (UV-Vis. Spectroscope), and mesoporous silica containing silver nanoparticles was measured with a spectrometer to measure silver encapsulation efficiency. .

division Particle size (μm) Pore size (nm) Encapsulation Efficiency (%) Example 1-1 1-1.5 10 90.56 Example 1-2 1-1.5 17 85.48 Comparative Example 1-1 1-1.5 30 74.20

Example 2-1 Preparation of Coated Fiber Fabrics

50 ± 1 g / m ² of the coating composition of Example 1-1 was coated on one surface of Dyneema fabric (SK71, Toyobo, Japan) with a pressing roller, eluted dimethylformamide through a solidification and washing process, and then coated. Fabric was dried at 150 ° C. for 45 seconds.

Example 2-2 Preparation of Coated Fiber Fabrics

Except for using the coating composition of Example 1-2 was prepared a fiber fabric coated in the same manner as in Example 2-1.

Comparative Example 2-1: Preparation of Coated Fiber Fabric

Except that the coating composition of Comparative Example 1-1 was used to prepare a fiber fabric coated in the same manner as in Example 2-1.

Experimental Example 2: Antimicrobial Activity

The coated fiber fabrics of Examples 2-1 and 2-2 and Comparative Example 2-1 before and after washing (the washing conditions were 10 minutes of washing with 10 g / l of nonionic detergent, followed by 2 minutes of dehydration. Repeated several times, and finally dried naturally) was subjected to the antibacterial test. The test method used was KS K 0693: 2006 (antimicrobial test of fabrics, shake flask test method), and Staphylococcus aureus (ATCC 6538) and pneumococcal bacterium (Klebsiella pneumoniae, ATCC 4352) were used as test strains. After culturing at 37 ± 1 ° C. for 24 hours, the reduction rate of the strains was calculated. The reduction rate is shown in Table 3 calculated by the following equation.

% Reduction = [(Mb -Mc) / Mb] × 100

Here, Ma is the initial number of bacteria (average value) of the control sample, Mb is the number of bacteria (average value) of the control sample after 24 hours culture, Mc is the number of bacteria (average value) of the test sample after 24 hours culture.

division Before washing After washing ATCC 6538 ATCC 4352 ATCC 6538 ATCC 4352 Example 2-1 99.99% 99.99% 99.8% 99.9% Example 2-2 85.49% 80.47% 85.48% 80.47% Comparative Example 2-1 74.21% 72.48% 74.20% 72.47%

1 is a schematic view showing a process of coating a fiber fabric with a coating composition containing mesoporous silica encapsulated silver nanoparticles according to an embodiment of the present invention.

2 is a TEM analysis picture of mesoporous silica of Preparation Example 1.

3A is Preparation Example 1, FIG. 3B is Preparation Example 2, and FIG. 3C is a specific surface area BET graph of mesoporous silica of Preparation Example 3. FIG.

Figure 4 is a FE-SEM analysis photograph of the silver nanoparticles of Preparation Example 4.

5 is an FT-IR spectrum of the silver nanoparticles of Preparation Example 4 and the silica containing the silver nanoparticles of Preparation Example 5;

FIG. 6 is a UV-VIS analysis spectrum of mesoporous silica of Preparation Example 1, silver nanoparticles of Preparation Example 4, and mesoporous silica containing silver nanoparticles of Preparation Example 5. FIG.

Figure 7a is a plate photograph after incubation in the antimicrobial experiment of the fabric of Example 2-1 before washing for Staphylococcus aureus, Figure 7b is a plate after incubation in the antimicrobial experiment of the fabric of Example 2-1 before washing for pneumococcal It is a photograph.

Claims (11)

A composition for endothelial coating of a textile fabric comprising mesoporous silica in which silver nanoparticles are encapsulated. The coating composition of claim 1, wherein the mesoporous silica has an average pore size of 5 to 25 nm. According to claim 1, wherein the mesoporous silica coating composition, characterized in that the average particle size of 0.5 ~ 2 μm. The coating composition according to claim 1, wherein the silver nanoparticles have an average particle size of 2 to 3 nm. The coating composition according to any one of claims 1 to 4, further comprising 2 to 20 parts by weight of the polymer resin in 1 part by weight of the mesoporous silica in which the silver nanoparticles are encapsulated. The coating composition according to claim 5, wherein the polymer resin is a polyurethane resin. Reacting the poly (alkylene oxide) block copolymer with tetraethyl ortho silicate to prepare mesoporous silica having an average pore size of 5 to 35 nm and an average particle size of 0.5 to 2 μm; Encapsulating silver nanoparticles having an average particle size of 2 to 3 nm in mesoporous silica; And Mixing 1 part by weight of mesoporous silica and 100 to 1000 parts by weight of the polymer resin in which the silver nanoparticles are encapsulated. A fibrous fabric, characterized in that the coating composition of claim 5 or the coating composition prepared by the method of claim 7 is applied to the endothelium of a fabric or blend of a fiber selected from polyethylene, polyester, nylon and cotton. 9. The fabric of claim 8, wherein the fiber is a polyethylene fiber having a density of 0.9 to 1.0 g / cm ³ and a tensile strength of 2 GPa or more and a tensile modulus of 50 GPa or more. 10. The textile fabric as claimed in claim 9, which is used for the production of cut protection gloves or clothing. Cut protective gloves and clothes, characterized in that the textile fabric of claim 10 made of a raw material.

Images