KR20130075466A - Fabrication of electrospun nanocomposite fibers containing germanium and silica - Google Patents

Abstract

PURPOSE: An electrospinning complex nanofiber containing germanium and silicon dioxide, and a manufacturing method thereof are provided to be used as healthy and comfort textile by having infrared radiation spinning ability and anti-bacterial ability in complex nano fiber web. CONSTITUTION: An electrospinning complex nano fiber containing germanium and silicon dioxide, and a manufacturing method thereof comprises: electrospinning a PVA aqueous solution of germanium and silicon dioxide manufactured by adding PVA in a mixture of germanium colloid and silicon dioxide colloid; The mixture of germanium colloid and silicon dioxide colloid comprises: 1-20wt% of polyvinylalcohol, 0.1-5wt% of Ge colloid, and 0.1-5wt% of SiO_2 colloid.

Description

Technical Field [0001] The present invention relates to an electrospinning composite nanofiber containing germanium and silicon dioxide, and to a method of manufacturing the same. [0002] Fabrication of electrospun nanocomposite fibers containing germanium and silica [

In the present invention, germanium and silicon oxide nanoparticles are added to poly vinyl alcohol (PVA) through an electrospinning process to produce Ge / SiO ₂ composite nanofibers produced under specific spinning conditions and optimal heat treatment conditions and their manufacture ≪ / RTI >

Health and comfort materials in clothing can be classified into thermal insulation materials, absorbing and absorbing materials, moisture permeable and waterproof materials, deodorizing materials, and antimicrobial materials. Recently, ceramic materials have been applied to fibers to develop materials that emit far-infrared rays Try is active.

Far infrared rays penetrate deeply into the skin in the wavelength range of 4 ~ 1000μm and turn into heat. This absorption effect is concentrated in the wavelength range of 5 ~ 30μm. When the wavelength of the vibration is absorbed into the human body, atoms and molecules in the living body resonate and change into heat energy, activating each cell to promote metabolism, and it is known that far-infrared rays are emitted from germanium, silicon oxide, and elvan.

Conventional commercialized far-infrared material was developed to warm the body from the inside to smoothly flow blood and promote metabolism. It is applied to underwear, bedding, socks, etc. by coating or laminating ceramic on the fabric. It is becoming. However, these products are deteriorated due to damage to the coating after washing, and they are somewhat lacking in terms of durability and feel.

Germanium (Ge) has excellent heat resistance and low thermal expansion properties, and is known to emit far infrared rays higher than other oxides. Therefore, it has been used in many studies as a far-infrared radiation material. When germanium contacts skin, germanium ions , Resonance, and resonance exercise. When ingested, it is released into the body within 20 ~ 30 hours with various harmful substances, so there is no poisoning or side effects. In addition, germanium is a building material, deodorizing, anti-fungal, dehumidification, air purification, heat and more.

Silicon dioxide (SiO ₂ ) is an oxide of silicon, also called silica, and is used as a major component of mullite, cordierite and loess, well known for emitting far infrared rays. It has the effect of releasing a large amount of far-infrared rays in a small amount and is also inexpensive. Amorphous silica is estimated to have no human carcinogenicity and is used as a main raw material for cosmetics.

The electrospun nanofiber web has very small pores and a large surface area, and it is very thin, flexible, and ultra-light as well as maximizing its performance when added with functional particles inside the fiber. Electrospun nanofiber webs can be applied to garments, filters, sensors, etc., and can be applied to clothing as light, thin and flexible functional materials.

In general, electrospinning is a phenomenon in which fibers are formed when a polymer solution or melt having a sufficient viscosity is given an electrostatic force. Nanofibers have a very small diameter, are flexible, and have many fine pores between fibers. , And does not inhibit water discharge. Therefore, the electrospinning can be produced in an easy and relatively simple process for the ultrafine fibers are used to produce a functional composite material by mixing a polymer and a ceramic, a polymer and a functional particle.

If the germanium and silicon oxide nanoparticles are enclosed in the nanofiber to give the far-infrared ray performance, it can be applied to clothes for the elderly, patient's clothes, etc. for the health, and can be applied to the medical supplies such as the protector wrapping the knee and the joint, There will be. Especially, if it is applied to the inner skin, the skin and the material will adhere to each other, thereby helping to maximize the far infrared ray performance by the skin temperature. In addition, underwear can be used as a new functional garment that satisfies both health and comfort if antimicrobiality is given to the far-infrared radiation performance as an apparel which needs antimicrobial properties because a lot of sweat is emitted.

Accordingly, the present invention proposes a Ge / SiO ₂ composite nanofiber by encapsulating germanium and silicon oxide nanoparticles in PVA through an electrospinning process and a manufacturing method thereof.

The present invention provides a Ge / SiO ₂ composite nanofiber containing germanium and silicon oxide nanoparticles encapsulated in PVA through an electrospinning process and a method for producing the same.

Another problem to be solved by the present invention is to provide a Ge / SiO ₂ composite nanofiber produced under optimal electrospinning conditions capable of producing composite nanofibers in which functional particles are uniformly dispersed through electrospinning, .

Another problem to be solved by the present invention is to provide an optimal electrospinning process condition capable of producing PVA composite nanofibers in which Ge and SiO ₂ functional particles are uniformly dispersed, a needle gauge 30 gauge, a solution pump speed of 0.2 ml / hr, A Ge / SiO ₂ composite nanofiber manufactured by electrospinning at a voltage of 15 to 17 kV and a radiation distance of 13 cm, and a method for manufacturing the same.

Another object to be solved by the present invention is to provide a Ge / SiO ₂ composite nanofiber manufactured by heat treatment in order to enhance the stability of water-soluble PVA composite nanofibers with respect to moisture, will be.

Another problem to be solved by the present invention is to provide a water-soluble PVA composite nanofiber which is an optimum heat treatment condition for enhancing water stability, and a Ge / SiO ₂ composite nanofiber prepared by heat treatment in a vacuum state at 210 ° C for 30 minutes And a method for producing the same.

Another object to be solved by the present invention is to provide a Ge / SiO ₂ composite nanofiber produced at an optimal condition in which an excellent far-infrared ray emissivity is exhibited at a far-infrared ray emissivity according to the concentration of Ge / SiO ₂ composite nanofiber, .

Another object of the present invention is to provide a Ge / SiO ₂ composite nanofiber having superior far-infrared radiation performance and antibacterial performance and a method for producing the same.

The present invention relates to a method for producing a composite nanofiber containing germanium and silicon dioxide, comprising the steps of: mixing germanium and silicon dioxide colloid with a mixture of germanium and silicon dioxide colloid; And the PVA aqueous solution is electrospun.

The mixture of germanium colloid and silicon dioxide colloid is prepared by mixing 1 to 20 parts by weight of polyvinyl alcohol, 0.1 to 5 parts by weight of Ge colloid and 0.1 to 5 parts by weight of SiO ₂ colloid per 100 parts by weight of the polymer / .

The PVA aqueous solution of germanium and silicon dioxide is stirred for 6 hours at a temperature of 80 ° C.

The germanium and silicon dioxide aqueous solution of PVA was subjected to electrospinning by electrospinning with a needle gauge of 23 to 30 gauge, a solution pump speed of 0.2 ml / hr and a radiation distance of 13 cm, and then spun on a 100% polypropylene non- do.

PVA aqueous solution of germanium and silicon dioxide is electrospun at the time of electrospinning, needle gauge 30 gauge, solution pump speed 0.2 ml / hr, spinning distance 13 cm.

The composite nanofiber containing germanium and silicon dioxide is heat-treated in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour.

In addition, the method for producing a composite nanofiber containing germanium and silicon dioxide of the present invention is mixed with 0.1 to 5 parts by weight of Ge colloid and 0.1 to 5 parts by weight of SiO 2 colloid with respect to 100 parts by weight of the mixed solution for 2 hours at a temperature of 80 ° C. Stirring during the first step; After the first step, 1 to 20 parts by weight of polyvinyl alcohol was added to 100 parts by weight of the nanoparticle mixed solution to prepare a polymer / nanoparticle mixed solution (PVA aqueous solution), and the polymer / nanoparticle mixed solution was prepared at 80 °. Stirring for 6 hours at a temperature of C, followed by cooling to room temperature; After the second step, the needlegauge 23 to 30 gauge, the solution pump speed 0.2 ml / hr, the voltage 15 to 18 kV, spinning distance 13 cm, the electrospinning to be laminated by spinning on a 100% polypropylene nonwoven fabric Steps; characterized in that consisting of.

And a fourth step of performing a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour after the third step.

In the third step, electrospinning is carried out with a needle gauge 30 gauge, solution pump speed 0.2 ml / hr, voltage 15-17 kV, scattering distance 13 cm.

In the fourth step, heat treatment is performed for 30 minutes under a vacuum of 210 캜.

The inner diameter of the needle gauge is 0.15 to 0.33 mm.

The present invention also relates to the composite nanofibers containing germanium and silicon dioxide produced by the method for producing a composite nanofiber containing germanium and silicon dioxide according to any one of claims 1 to 13.

The present invention also provides a PVA aqueous solution obtained by mixing 0.1 to 5 parts by weight of Ge colloid and 1 to 20 parts by weight of polyvinyl alcohol with respect to 100 parts by weight of a polymer / nano-particle mixed solution, A first step of dissolving and cooling at room temperature; After the first step, electrospinning was carried out with a needle gauge of 23 to 27 gauge, a solution pump speed of 0.2 to 0.4 ml / hr, a voltage of 12 to 18 kV and a radiating distance of 13 cm, and spun onto a 100% And a second step of preparing a composite nanofiber containing germanium.

In addition, the present invention, by mixing 0.1 to 5 parts by weight of SiO2 colloid and 1 to 20 parts by weight of polyvinyl alcohol with respect to 100 parts by weight of the polymer / nanoparticles mixed solution to make a PVA aqueous solution, the PVA aqueous solution at a temperature of 80 ° C A first step of completely dissolving for 6 hours and then cooling at room temperature; After the first step, the needle gauge 23-30 gauge, the solution pump speed 0.2 ml / hr, the voltage 12-18 kV, the electrospinning at a spinning distance of 13 cm, the second step of electrospinning so as to be laminated on the fabric; Characterized in that the method for producing a composite nanofiber containing silicon dioxide, including.

And a third step of performing a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour after the second step in the method for producing a composite nanofiber containing germanium and the method for producing a composite nanofiber containing silicon dioxide do.

According to the present invention, germanium and silicon oxide nanoparticles are encapsulated in PVA through an electrospinning process to provide a Ge / SiO ₂ composite nanofiber and a method for producing the same, wherein the composite nanofiber web has far infrared ray emission performance and antibacterial performance It can be used as health and comfort textile.

In particular, the Ge / SiO ₂ composite nanofiber of the present invention can be used not only as a protective garment, a filter, a sensor, but also as a garment for the elderly, patient's, sportswear, and military uniforms. Of the present invention. In particular, when applied to undergarments, undergarments, the skin and the material come into close contact with each other, which helps maximize the performance of the far-infrared rays due to the skin temperature. In addition, So that both health and comfort are satisfied at the same time.

It is another object of the present invention to provide a process for preparing an optically anisotropic layer of an optically anisotropic layer of a water-soluble PVA composite nanofiber, which is capable of producing an optically transparent composite nanofiber by uniformly dispersing the functional particles through electrospinning, Conditions to provide PVA composite nanofibers in which Ge and SiO ₂ functional particles are uniformly dispersed, but thinner and more uniform nanofibers can be obtained and the shape of the fibers can be maintained even after the washing environment.

In particular, the optimum electrospinning conditions for producing the PVA composite nanofibers in which the Ge and SiO ₂ functional particles are uniformly dispersed in the present invention are needle gauge 30 gauge, solution pump speed 0.2 ml / hr, voltage 15 to 17 kV, and radiation distance of 13 cm. As a result, nanofibers of Ge / SiO ₂ composite nanofibers having a diameter of about 250 nm were obtained.

Further, in order to increase the stability of the water-soluble PVA composite nanofiber in the Ge / SiO ₂ composite nanofiber of the present invention to moisture, a composite nanofiber thermally treated at 210 ° C for 30 minutes was prepared. It was confirmed that the fiber shape was maintained even after the environment.

In addition, the present invention has been made to produce at an optimum condition that the far-infrared ray emissivity is excellent in the far-infrared ray emissivity according to the concentration of the Ge / SiO ₂ composite nanofiber, and the Ge / SiO ₂ complex Nanofibers and methods of making the same.

In the Ge / SiO ₂ composite nanofiber of the present invention, the composite nanofiber containing 0.5 wt% of Ge and 1 wt% of SiO ₂ has a far infrared ray emissivity of 0.891 and an excellent far-infrared radiation performance of 3.44 × 10 ² W / m ² , And the Ge / SiO ₂ composite nanofiber of the present invention has antimicrobial activity against Staphylococcus aureus, Pneumoniae bacterium, and Escherichia coli.

In order to verify the Ge / SiO ₂ composite nanofiber prepared by the present invention, a scanning electron microscope and a transmission electron microscope were used to observe the morphology, diameter and dispersion of nanoparticles of the electrospun Ge / SiO ₂ composite nanofiber Respectively. To determine the far-infrared radiation performance of the Ge / SiO ₂ composite nanofibers, far-infrared emissivity and radiant energy were determined using a Fourier transform infrared spectrometer (FT-IR). In order to evaluate the antibacterial activity of composite nanofibers, antibacterial activity was measured against three strains of Staphylococcus aureus, pneumococcus and E. coli.

As a result, optimum electrospinning conditions for producing PVA composite nanofibers in which Ge and SiO ₂ functional particles were uniformly dispersed were needle gauge 30 gauge, solution pump speed 0.2 ml / hr, voltage 15-17 kV, 13 cm. The Ge / SiO ₂ composite nanofiber was about 250 nm in diameter, and nanofibers could be obtained.

In order to improve the water stability of water-soluble PVA composite nanofiber, the heat-treated sample was immersed in water for 1 hour and dried. The surface of the fiber was observed with a scanning electron microscope. As a result, the pure PVA nanofiber web was vacuum- And the Ge / SiO ₂ / PVA nanofiber web showed no change in the morphology of the nanofibers when annealed at 210 ° C under vacuum for 30 min. The composite nanofibers heat - treated at 210 ℃ for 30 min maintained the fiber shape even after the washing environment accompanied by agitation.

To examine the far - infrared radiation performance of composite nanofibers containing germanium and silicon oxide nanoparticles, far - infrared emissivity and radiant energy were measured according to the concentration of Ge and SiO ₂ . The composite nanofibers containing 0.5 wt% of Ge and 1 wt% of SiO ₂ exhibited excellent far infrared ray emission performance with a far infrared ray emissivity of 0.891 and 3.44 × 10 ² W / m ² .

It was found that 99.9% of bacteria were reduced to Staphylococcus aureus and Escherichia coli when 0.5 wt% Ge and 1 wt% SiO ₂ , which are the optimal conditions of composite nanofibers that emit excellent far infrared rays, and 5.55 g / m ² web density, respectively. On the other hand, the rate of microbial reduction was 34.8% for pneumococcal bacteria under the same conditions.

Figure 1 is an example of a nanofiber web electrospun under various conditions to find optimal process conditions for producing Ge / SiO ₂ / PVA composite nanofibers.
FIG. 2 is an example of a result of observation of the surface of a Ge / SiO ₂ / PVA composite nanofiber containing Ge 0.5 wt% and SiO ₂ 1 wt% by a scanning electron microscope.
FIG. 3A is an example of a result of observing the interior of a PVA composite nanofiber containing 0.5 wt% of Ge and 1 wt% of SiO ₂ through a transmission electron microscope (TEM).
3B is an example of a result of analyzing the components of the composite nanofibers through an energy dispersive X-ray analyzer.
FIG. 4 is an example of a result of observing the surface of a nanofiber web dried and immersed in water at 18 ° C for one hour with a scanning electron microscope.
5 is an example of experimental results for examining stability against moisture in a washing environment accompanied by agitation.
6 is a graph showing the far-infrared emissivity of the composite nanofibers.
7 is a graph showing the radiant energy of the composite nanofiber together with the radiant energy of the black body.
Fig. 8 is an example of the results of the antibacterial performance test for samples containing 0.5 wt% of Ge and 1 wt% of SiO ₂ against S. aureus, S. pneumoniae, and E. coli.
9 is an example of a nanofiber web electrospun under various conditions to find the optimum process conditions for producing Ge / PVA composite nanofibers.
10 is an example of a nanofiber web electrospun under various conditions in order to find optimal process conditions for preparing SiO ₂ / PVA composite nanofibers.

Hereinafter, a Ge / SiO ₂ composite nanofiber according to a preferred embodiment of the present invention and a manufacturing method thereof will be described in detail with reference to the accompanying drawings.

In the present invention, germanium composite nanofibers, silicon oxide composite nanofibers, germanium, and silicon oxide composite nanofibers were produced. The germanium colloid was used at a concentration of 0.5 wt% without dilution. In the case of silicon oxide, 20 wt% 0.5 wt% of spinning solution was prepared and the addition concentration was increased according to the far - infrared radiation performance.

In the present invention, poly (vinyl alcohol) (PVA) (> 99% hydrolyzed, Mw = 89,000-98,000, Sigma Aldrich Co., USA) was selected as a polymer for electrospinning. Distilled water was used as a solvent, Germanium (Ge) is a liquid-based water-based Ge (0.5 wt%) manufactured by Nanopoly Co. (Korea), and silicon dioxide (SiO ₂ ) Water-based SiO ₂ (pH 3 to 4, 20 wt%) prepared in the form of liquid phase prepared in Example 1 is used, but it is not intended to limit the present invention, and various commercially available materials such as PVA, Ge and SiO ₂ can be used .

The apparatus for electrospinning according to the present invention uses a vertical electric radiator (NNC-ESP200R2, NanoNC Co., Korea) reciprocating at a distance of 40 cm, but is not intended to limit the present invention, It is noted that a radiator can be used.

<Ge and SiO ₂ composite nanofiber>

The production of Ge and SiO ₂ composite nanofibers according to one embodiment of the present invention will be described.

As a first step, in order to prepare a Ge / SiO ₂ / PVA mixed solution, 0.5 wt% Ge colloid and 1 wt% SiO ₂ The colloid is mixed and stirred at a temperature of 80 ° C for 2 hours.

As a second step, after the first step, an aqueous solution of PVA is prepared by adding 11 wt% of PVA powder to the mixed solution, which is completely dissolved at a temperature of 80 ° C for 6 hours, and then cooled at room temperature.

After the second step, electrospinning is carried out with needle gauge 23 to 30 gauge (inner diameter 0.15 to 0.33 mm), solution pump speed 0.2 ml / hr, voltage 15 to 18 kV, radiation distance 13 cm, To be laminated. This reinforces the strength of the nanofibers. 100% polypropylene nonwoven fabric can be used as the fabric, and other fabrics other than the above can be used.

More preferably, the third step is electrospinning with a needle gauge of 30 gauge, solution pump speed of 0.2 ml / hr, voltage of 15-17 kV, and radiation distance of 13 cm.

In the case of heat treatment after electrospinning, in the fourth step, after the third step, heat treatment is performed to increase the stability of the water-soluble polymer PVA nanofibers, but in a vacuum state at 155 ~ 210 ° C, 10 minutes ~ 1 Heat treatment under vacuum for a time.

More preferably, in the fourth step, heat treatment is performed for 30 minutes in a vacuum state at 210 캜.

In case of no heat treatment after electrospinning, in step 4, after the third step, it is dried at 50 ° C for 24 hours by using a vacuum dryer to remove residual solvent in the fiber. The process of the fourth step is a simple drying process for evaporating the remaining solvent, and it is possible to exclude (delete) the fourth step process in some cases.

Figure 1 is an example of a nanofiber web electrospun under various conditions to find optimal process conditions for producing Ge / SiO ₂ / PVA composite nanofibers.

In FIG. 1, 0.5 wt% of Ge and 1 wt% of SiO ₂ were added to 11 wt% PVA aqueous solution to be electrospun, and needle gauge 23 to 30 gauge, solution pump speed 0.2 ml / hr, voltage 15 to 18 kV , And scattering distance of 13 cm. The Ge / SiO ₂ / PVA nanofiber webs irradiated under various conditions were observed with a scanning electron microscope. Fig. 1 (a) shows bead observed by spinning with a needle gauge of 23 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 18 kV, and a radiation distance of 13 cm. Fig. 1 (b) shows the result of electrospinning with a needle gauge of 25 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 16 to 18 kV, and a radiation distance of 13 cm. have. 1 (a) and (b), the diameter of the spinnerette was reduced by the difficulty of this process, and needle gauge 27, 30 gauge, solution pump speed 0.2 ml / hr, voltage 15 ~ 18 kV, and radiation distance of 13 cm. Fig. 1 (c) shows the result of electrospinning with a needle gauge of 27 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 15 to 18 kV, a radiation distance of 13 cm, and a thinner and more uniform nano- We could observe the fibers, but we can see that some fibers have formed beads or spindles. FIG. 1 (d) shows the results of the electrospinning at a needle gauge of 30 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 15 to 17 kV and a radiation distance of 13 cm, One nanofiber could be obtained. Comparing FIGS. 1 (a) to 1 (d) of the same magnification, it can be seen that the diameter of the fiber decreases as the needle gauge increases, that is, as the spinneret size decreases. Therefore, optimum spinning conditions for Ge / SiO ₂ / PVA composite nanofibers were needle gauge 30 gauge, solution pump speed 0.2 ml / hr, voltage 15 ~ 17 kV, radiation distance 13 cm.

Next, the surface of the Ge / SiO ₂ / PVA composite nanofiber obtained from the optimum spinning conditions of FIG. 1 (d) was observed to observe the Ge and SiO ₂ particles uniformly dispersed through a scanning electron microscope (SEM) , And a transmission electron microscope (TEM) was used to observe whether the particles were uniformly distributed within the fibers. An energy dispersive X-ray analyzer (EDX) was used to identify the constituents of the particles inside the fiber.

2 is a result of observing at magnification of 20,000 times the surface of the Ge 0.5 wt% and 1 wt% SiO ₂ is the addition of Ge / SiO ₂ / PVA composite nano-fiber with a scanning electron microscope. The diameter of the composite nanofiber is about 250 nm, and it can be seen that the nanoparticles are dispersed evenly on the surface of the fiber.

3A shows the inside of a PVA composite nanofiber containing 0.5% by weight of Ge and 1% by weight of SiO ₂ through a transmission electron microscope (TEM), and FIG. 3B shows the result of an energy dispersive X-ray analyzer It is the result of analyzing the composition of composite nanofiber. FIG. 3A shows clearly the nanoparticles dispersed on the fiber surface, and Ge and SiO ₂ nanoparticles are dispersed in the fibers. As a result of analysis of the components of the particles inside the fiber, Si and Ge, which are elemental components of SiO ₂ and germanium, can be confirmed as shown in the spectrum of FIG. 3B.

Next, an experiment for stabilizing Ge / SiO ₂ / PVA composite nanofibers through a safe and harmless heat treatment in the present invention was performed.

4 shows the results of observation of the surface of the nanofiber web dried after immersion for one hour at 18 ° C in water with a scanning electron microscope. FIG. 4 (a) shows the PVA nanofiber without heat treatment, FIG. 4 (c) shows the fiber surface of the Ge / SiO ₂ / PVA composite nanofiber after the heat treatment.

4 (a), which is a non-heat-treated sample, was deformed to such an extent that the shape of the fiber could not be determined. The sample of FIG. 4 (b), which is a PVA nanofiber web that was heat-treated, I could see the figure. Thus, the PVA nanofiber web showed a stable fiber shape when it was heat-treated for 10 minutes in a vacuum dryer at 155 ° C. 4 (c) shows the surface of the Ge / SiO ₂ / PVA composite nanofiber after heat treatment for one hour in a vacuum state at 165 ° C. and then immersed in water. Can be seen. Ge / SiO ₂ / PVA composite nanofibers were annealed at a temperature of 170 ° C or higher in order to find the optimal annealing conditions. FIG. 4 (d) is a photograph of the surface after heat treatment at 210.degree. C. for 30 minutes and exposed to the wet environment, and it can be observed that the fiber shape is maintained. Therefore, it can be seen that the optimum condition of heat treatment of Ge / SiO ₂ / PVA composite nanofiber is 210 ° C. for 30 minutes.

FIG. 5 is an example of experimental results for examining stability against moisture in a washing environment accompanied by agitation.

FIG. 5 is a photograph of the surface after washing the Ge / SiO ₂ / PVA composite nanofiber heat treated at 210 ° C. for 30 minutes for 15 minutes in order to examine the stability against moisture in a washing environment accompanied by agitation. As a result, there was no change in the shape of the fibers. Therefore, it can be seen that the fiber shape is maintained even after washing by heat treatment of the Ge / SiO ₂ / PVA composite nanofiber at 210 ° C for 30 minutes.

Next, an experiment on far-infrared ray emission performance of the composite nanofiber of the present invention will be described.

Ge and the ratio of SiO ₂ 1: prescribed by 1 Ge 0.5 wt%, SiO ₂ Experimental results by the addition of 0.5 wt%, showed the radiant energy of the emissivity of ^{0.888, 3.42 × 10 2 W /} m 2, commercially available The emissivity of 0.891 of far infrared radiation functional underwear product was aimed at, and the concentration of SiO ₂ was increased to 1 wt% and the experiment was carried out again. Ge 0.5 wt% and SiO ₂ 1 wt% prior to mixing to produce a composite nano-fiber, SiO ₂ 1 wt%, only one measurement of the far-infrared emissivity of the composite nano-fiber was added resulting in 0.890 emissivity and 3.43 × 10 ² W / m ² , and the far-infrared emissivity and the radiant energy of the composite nanofibers of 0.5 wt% Ge and 1 wt% SiO ₂ were 0.891 and 3.44 × 10 ² W / m ² , respectively. Therefore, optimum conditions of Ge / SiO ₂ / PVA composite nanofiber that exhibits effective far-infrared ray emissivity are 0.5 wt% Ge, 1 wt% SiO _{2 and} 5.55 g / m ² of web density. At this time, far infrared ray emissivity is 0.891, far infrared energy is 3.44 × 10 ² W / m &lt; ^{2 &} gt ;.

6 is a graph showing the far-infrared emissivity of the composite nanofibers. Figure 6 shows the lowest emissivity of the polypropylene based fabric in the wavelength range of 5-20 mu m with the highest absorption rate in the human body. Ge / SiO ₂ / PVA composite nanofibers showed high emissivity, except that composite nanofibers containing 0.5 wt% of Ge exhibited high emissivity in the wavelength range of 10 to 14 μm.

7 is a graph showing the radiant energy of the composite nanofiber together with the radiant energy of the black body. The polypropylene-based fabrics showed the greatest difference from the black body values, and the radiant energy of the PVA composite nanofibers containing 0.5 wt% Ge and 1 wt% SiO ₂ was the closest to the black body, It can be confirmed that the far-infrared radiation energy is emitted. Therefore, it is shown that the concentration of Ge and SiO ₂ nanoparticles affects the far-infrared radiation performance, suggesting that Ge / SiO ₂ / PVA composite nanofiber can be used as far-infrared radiation functional material.

Next, the antibacterial performance test of the composite nanofiber of the present invention will be described.

The antibacterial performance of the present invention was evaluated by selecting a composite nanofiber containing 0.5 wt% of Ge and 1 wt% of SiO _2, which exhibited sufficient far infrared ray performance. The antibacterial test procedure is as follows.

The sample is pulverized in one step, placed in an Erlenmeyer flask containing buffer solution, and sterilized at high temperature and high pressure.

In step 2, the bacterial culture is added to an Erlenmeyer flask and vibrated at 37 ± 2 ° C for 24 hours.

In step 3, measure the number of bacteria in the culture medium prior to contact with the antimicrobial agent and the number of bacteria in the flask after 24 hours of vibration culture.

The following table summarizes the antibacterial performance of composite nanofibers containing 0.5 wt% of Ge and 1 wt% of SiO _{2 on} Staphylococcus aureus, pneumococcus and E. coli.

At a web density of 5.55 g / m ² , 99.9% of the bacteria were reduced to Staphylococcus aureus, and 99.9% of the bacteria were also reduced to E. coli. The pneumococcal bacteria showed 34.8% reduction rate and showed less antibacterial activity than Staphylococcus aureus and Escherichia coli.

FIG. 8 is a photograph showing the antibacterial activity against Staphylococcus aureus, pneumococcal bacteria and Escherichia coli of a sample containing 0.5 wt% Ge and 1 wt% of SiO ₂ .

(A1) and (a2) of FIG. 8 is a photograph tested for antibacterial activity on Staphylococcus aureus, (a1) of FIG. 8 is a bacterial solution prior to contact with the sample containing Ge 0.5 wt% and SiO ₂ 1 wt% (A2) of FIG. 8 is a photograph of a sample after vibri- cation for 24 hours under the same conditions. Then, the microbial cells are extracted and cultured in a Petri dish for a certain period of time This is a picture after. Unlike (a1) in FIG. 8, in the photograph of (a2) in FIG. 8, almost no colloid is found in the Petri dish.

(B1) and (b2) of FIG. 8 is a test for Klebsiella pneumoniae, (b1) of Figure 8 is to extract the broth prior to contact with the sample containing Ge 0.5 wt% and SiO ₂ 1 wt% in the Petri dish 8 (b2) is a photograph of a sample after vibrifying the sample and the same solution for 24 hours, showing that the number of bacteria was not significantly reduced as compared with that of FIG. 8 (b1) .

(C1) and (c2) in Fig. 8 is a photo test for a sample of the same conditions in E. coli, (c1) of Figure 8 is to extract the broth prior to contact with the sample of Ge 0.5 wt% and SiO ₂ 1 wt% (C2) of FIG. 8 is a photograph of a sample containing 0.5 wt% of Ge and 1 wt% of SiO ₂ after vibrated for 24 hours together with a sample solution. It can be seen that the bacteria in the petri dish of (c1) in Fig. 8 is mostly disappeared in the photograph of Fig. 8 (c2). In addition to the quantitative values, it can be seen from FIG. 8 that the Ge / SiO ₂ composite nanofiber exhibits excellent antibacterial activity against Staphylococcus aureus and E. coli.

<Ge composite nanofibers>

The production of the Ge-composite nanofiber according to another embodiment of the present invention will be described.

In order to prepare the Ge / PVA mixed solution as the first step, PVA powder was added to the colloidal 0.5 wt% Ge solution to prepare the 11 wt% aqueous solution of PVA. After dissolving, cool at room temperature.

In the second step, after the first step, electrospun with needle gauge 23 to 27 gauge (inner diameter 0.20 to 0.33 mm), solution pump speed 0.2 to 0.4 ml / hr, voltage 12 to 18 kV, radiation distance 13 cm, And then electrospun so as to be laminated. The fabric may be a 100% polypropylene nonwoven fabric or other fabric.

More preferably, the second step is electrospinning with a needle gauge of 25 gauge, solution pump speed of 0.2 ml / hr, voltage of 16 kV, and radiation distance of 13 cm.

In the case of heat treatment after electrospinning, in the third step, after the second step, heat treatment is performed to increase the water stability of the water-soluble polymer PVA nanofibers, but in a vacuum state at 155-210 ° C, 10 minutes ~ 1 Heat treatment under vacuum for a time.

After the electrospinning, if the heat treatment is not carried out, in the third step, after the second step, it is dried at 50 ° C for 24 hours by using a vacuum drier to remove residual solvent in the fiber. The third step process is a simple drying process for evaporating the remaining solvent, and in some cases, the third step process can be excluded (deleted).

9 is an example of a nanofiber web electrospun under various conditions to find the optimum process conditions for producing Ge / PVA composite nanofibers.

9, a Ge / PVA composite nanofiber was prepared by adding 0.5% of Ge in the form of liquid to an aqueous 11 wt% PVA solution, and the needle gauge 23 to 27 gauge, the solution pump speed 0.2 to 0.4 ml / hr, the voltage 14 to 18 kV , And a spinning distance of 13 cm. The nanofiber webs were observed with a scanning electron microscope. 9 (a) shows a uniform gauge fiber obtained by electrospinning with a needle gauge 23 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 14 kV, and a radiation distance of 13 cm. However, It fell and fell on the base fabric, and this phenomenon persisted and clogging of the spinning ball appeared. 9 (b) and 9 (c), in order to prevent the clogging of the spinneret, it was possible to obtain a thin and uniform nanofiber by radiating the image by raising the needle gauge to 27 gauge and increasing the solution pump speed to 0.4 ml / hr Beads and spindles were formed. FIG. 9 (d) shows the results of the electrospinning of the needle gauge 25 gauge, solution pump speed 0.2 ml / hr, voltage 16 kV, and radiation distance 13 cm in order to solve the above problem. Uniform nanofibers could be obtained and compared to other conditions, the radiation was relatively well produced without clogging of the spinneret. Therefore, optimum spinning conditions for the Ge / PVA composite nanofibers were needle gauge 25 gauge, solution pump speed 0.2 ml / hr, voltage 16 kV, scattering distance 13 cm.

<SiO ₂ Composite Nanofiber>

The production of the SiO ₂ composite nanofiber according to another embodiment of the present invention will be described.

In order to prepare a SiO ₂ / PVA mixed solution, first, 0.5 wt% of colloidal SiO ₂ was mixed with distilled water and sufficiently stirred. Then, 11 wt% of PVA powder was added thereto, C for 6 hours and then cooled at room temperature.

In the second step, after the first step, electrospinning is carried out with needle gauge 23 to 30 gauge (inner diameter 0.15 to 0.33 mm), solution pump speed 0.2 ml / hr, voltage 12 to 20 kV, radiation distance 13 cm, To be laminated. The fabric may be a 100% polypropylene nonwoven fabric or other fabric.

The PVA nanofibers, which are water-soluble polymers, are subjected to heat treatment in order to increase the stability of the PVA nanofibers to moisture, and they are subjected to heat treatment at 150 to 210 ° C for 5 minutes to 1 Heat treatment in vacuum for a period of time.

After the electrospinning, if the heat treatment is not carried out, in the third step, after the second step, it is dried at 50 ° C for 24 hours by using a vacuum drier to remove residual solvent in the fiber. The third step process is a simple drying process for evaporating the remaining solvent, and in some cases, the third step process can be excluded (deleted).

10 is an example of a nanofiber web electrospun under various conditions in order to find optimal process conditions for preparing SiO ₂ / PVA composite nanofibers.

In FIG. 10, SiO ₂ / PVA composite nanofiber was prepared by adding 1 wt% of liquid phase SiO ₂ to 11 wt% PVA aqueous solution, and needle gauge 23 ~ 30 gauge, solution pump speed 0.2 ml / hr, 20 kV, and a radiation distance of 13 cm. The SiO ₂ / PVA composite nanofiber nanofiber web irradiated under various conditions was observed with a scanning electron microscope. 10 (a) shows a relatively uniform nanofiber obtained by electrospinning with a needle gauge 23 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 17 to 20 kV and a radiation distance of 13 cm, At the end, the spinning solution became dripped and dropped onto the base fabric, and this phenomenon persisted and clogging of the spinning ball occurred. FIG. 10 (b) shows a state in which uneven fibers are stuck to each other as shown in FIG. 10 (a) by increasing the needle gauge to 25 gauge and electrospinning. Fig. 10 (c) shows the result of electrospinning a needle gauge at 27 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 12 to 16 kV, and a spinning distance of 13 cm to obtain a thinner nanofiber of about 300 nm diameter there was. However, in the case of electrospinning, the drops of the spinning solution occurred and some of the fibers were observed to be plugged. In order to prevent clogging of the spinneret, the needle gauge was elevated to perform electrospinning. FIG. 10 (d) shows that the nanofibers uniformly nanofibers having a diameter of about 300 nm could be obtained without being clogged with the spinneret. Therefore, optimum process conditions for SiO ₂ / PVA composite nanofibers were needle gauge 30 gauge, solution pump speed 0.2 ml / hr, voltage 14 ~ 16 kV, scattering distance 13 cm.

As described above, in the present invention, germanium and silicon oxide nanoparticles are added to an aqueous solution of PVA through an electrospinning process to produce composite nanofibers. The composite nanofiber web of the present invention has a far- It is new health, pleasant textile.

Claims (18)

A method for producing a composite nanofiber containing germanium and silicon dioxide,
A composite nanofiber comprising germanium and silicon dioxide, characterized in that an aqueous solution of PVA of germanium and silicon dioxide produced by adding polyvinyl alcohol (PVA) to a mixture of germanium colloid and silicon dioxide colloid is electrospun. Gt; The method of claim 1,
The mixed solution of germanium colloid and silicon dioxide colloid is mixed with 1 to 20 parts by weight of polyvinyl alcohol, 0.1 to 5 parts by weight of Ge colloid and 0.1 to 5 parts by weight of SiO2 colloid with respect to 100 parts by weight of the mixed solution. Method for producing a composite nanofiber containing germanium and silicon dioxide. The method of claim 1,
Germanium and silicon dioxide are stirred for 6 hours at a temperature of 80 ° C. The method of claim 1,
Upon electrospinning the PVA aqueous solution of germanium and silicon dioxide,
Gauge needle gauge, a solution pump speed of 0.2 ml / hr, a voltage of 15 to 17 kV, a radiation distance of 13 cm, and is electrospun to be deposited on the fabric and laminated. (METHOD FOR MANUFACTURING COMPOSITE NANOFIBER) 5. The method of claim 4,
Upon electrospinning the PVA aqueous solution of germanium and silicon dioxide,
A needle gauge of 30 gauge, a solution pump speed of 0.2 ml / hr, a spinning distance of 13 cm, and a voltage of 15 to 17 kV. The method of claim 1,
Wherein the composite nanofibers containing germanium and silicon dioxide are subjected to a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour to produce composite nanofibers containing germanium and silicon dioxide. 0.5 wt% Ge colloid and 1 wt% SiO ₂ Mixing the colloid and stirring the mixture at a temperature of 80 ° C. for 2 hours;
After the first step, to prepare a PVA aqueous solution by adding 11% by weight of PVA powder to the mixed solution, and dissolving the PVA aqueous solution at a temperature of 80 ° C for 6 hours, and then cooled to room temperature;
A third step of electrospinning a needle gauge at 23 to 30 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 15 to 18 kV and a radiating distance of 13 cm after the second step;
Wherein the composite nanofiber comprises germanium and silicon dioxide. The method of claim 7, wherein
A fourth step of performing a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour after the third step;
Wherein the composite nanofiber comprises germanium and silicon dioxide. 9. The method of claim 8,
In the third step, electrospinning is carried out at a needle gauge of 30 gauge, at a solution pump speed of 0.2 ml / hr, at a voltage of 15 to 17 kV, and at a radiation distance of 13 cm. 10. The method of claim 9,
And the fourth step is heat treatment at 210 DEG C for 30 minutes in a vacuum state. The method of claim 7, wherein
Wherein the needle gauge has an inner diameter of 0.15 to 0.33 mm. A composite nanofiber containing germanium and silicon dioxide produced by the method for producing a composite nanofiber containing germanium and silicon dioxide of claim 1. A first step of adding a PVA powder to a 0.5 wt% Ge solution in a colloidal state to make an aqueous 11 wt% PVA solution, completely dissolving at a temperature of 80 ° C for 6 hours, and then cooling at room temperature;
After the first step, a second step of electrospinning with a needle gauge of 23 to 27 gauge, a solution pump speed of 0.2 to 0.4 ml / hr and a radiation distance of 13 cm, spun onto a fabric and electrospun so as to be laminated;
Wherein the germanium-containing composite nanofibers are prepared by mixing the germanium-containing composite nanofibers. The method of claim 13,
A third step of performing a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour after the second step;
Wherein the germanium-containing composite nanofibers have a specific surface area of at least 10 nm. The method of claim 13,
And the second step is electrospinning with a needle gauge of 25 gauge, a solution pump speed of 0.2 ml / hr, a voltage of 16 kV, and a radiation distance of 13 cm. After adding 0.5% by weight of colloidal SiO ₂ to the distilled water and stirring the mixture, 11% by weight of PVA powder was added to prepare a PVA aqueous solution. The PVA aqueous solution was completely dissolved at 80 ° C for 6 hours A first step of cooling at room temperature;
After the first step, a second step of electrospinning with a needle gauge of 23 to 30 gauge, a solution pump speed of 0.2 ml / hr and a spinning distance of 13 cm, spun onto a fabric and electrospun so as to be laminated;
Wherein the composite nanofibers comprise silicon dioxide. 17. The method of claim 16,
A third step of performing a heat treatment in a vacuum state at 150 to 210 ° C for 5 minutes to 1 hour after the second step;
Wherein the composite nanofibers comprise at least one of silicon carbide and silicon carbide. 17. The method of claim 16,
In the second step, electrospinning is carried out at a needle gauge of 30 gauge, at a solution pump speed of 0.2 ml / hr, at a voltage of 14 to 16 kV, and at a radiation distance of 13 cm.

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