KR101967351B1 - Antimicrobial fiber and method of prepating the same - Google Patents

Abstract

The present invention relates to a fiber comprising at least one of a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) and a metal halide in a molecular structure; Glycidyltrimethylammonium chloride (GTAC) combined with the fibers; Wherein the silver nanoparticles are bound to the fiber by ring opening of an epoxy group and the silver nanoparticles are combined with a quaternary ammonium salt present in the GTAC, And a manufacturing method thereof.

Description

FIELD OF THE INVENTION [0001] The present invention relates to an antimicrobial fiber,

The present invention relates to an antibacterial fiber and a method for producing the same, and more specifically, to an antibacterial fiber surface-treated with silver nanoparticles and a method for producing the same.

Silver has been widely used as a material to control poisons, both east and west. For example, in the case of the Orient, the king checked the poison with the chopsticks before eating, or the clergyman used the needle made with silver. In the United States, silver was put in the milk bowl to store the milk for a long time. In Egypt, I wrapped a plate made of silver and treated it. In addition, Dongbok can be used for the prevention and treatment of women's diseases such as epilepsy and sports such as epilepsy and cold weather, and when the body has silver in the main river gangmok, it is comfortable for the five people and the mind and body are stabilized. It is said that it helps to extension.

Furthermore, as the technology has been developed, it has become clear through various experiments that silver can kill most single cell bacteria and bacteria that exist around us, so that the well-being product that grafts silver particles can be more easily seen around us . In addition, as the economy becomes more abundant and the quality of life gradually improves, the demand for antimicrobial products is increasing day by day as consumers' desire for a healthy and comfortable life grows, and the demand for antibacterial products is increasing day by day. And textile products. It has been used in various fields such as wallpaper, table top, tableware, washing machine, etc. Especially, development of technology to make fine nano particles of silver is becoming more widespread.

Although the exact mechanism of silver nanoparticles (AgNPs) has not been elucidated yet, the silver cation (Ag +) strongly binds to the -SH, -COOH, and -OH groups of bacteria to destroy the cell membranes of bacteria, The theory that the function is disturbed is that the theory that oxygen is converted to active oxygen (O ²⁺ , O ^2- , O) by the catalytic action of silver cations (Ag +), And that the microorganisms consuming the silver particles of the size cause respiratory or metabolic disorders and die.

However, when silver nanoparticles alone are used, there is a limit to apply directly to polymers or other materials since there is no reactor. Conventional literatures 1 and 2 disclose a method of using a crosslinking agent such as 3-mercaptopropyltrimethoxysilane (3-MPTMS) and cysteamine 12, a physical method in Conventional Document 3, and a method of reducing silver And thus the antimicrobial activity was imparted.

On the other hand, Japanese Patent Laid-Open No. 2002-293705 discloses a silver antimicrobial agent composed of an inorganic adsorbent carrying silver colloid particles and a cationic surfactant, and JP-A-5-195438 discloses an acrylic fiber Discloses an antibacterial deodorant fiber obtained by kneading a silver compound as an antibacterial agent in a fiber material rich in adsorbability such as water, and then impregnating the resulting fiber into a quaternary ammonium salt solution.

However, the method of physically fixing silver particles in the process of silver particles still has a limitation in that silver particles can not be bonded firmly. Particularly, when applied to fibers, it is used in repetitive chemical processes such as finishing and washing, The antimicrobial material is often separated from the fibers by the frequent friction of the fibers. If an adhesive or a resin is used in order to compensate for this, the effect obtained by silver may be lowered and the product stability may be lowered.

- Conventional Document 1: Guo, H .; Tao, S. Sensor. Actuat. B-Chem. 2007, 123, 578-582. - Conventional Document 2: Yin, J .; Yang, Y .; Hu, Z .; Deng, B. J. Membrane. Sci. 2013, 441, 73-82. - Conventional Document 3: Stejskal, J .; Trchova, M .; Kovarova, J .; Prokes, J .; Omastova, M. Chem. Pap. 2008, 62, 181-186. - Conventional Document 4: Xue, C .; Chen, J .; Yin, W .; Jia, S .; Ma, J. Appl. Surf. Sci. 2012, 258, 2468-2472.

Therefore, it is required to develop a technique for enhancing the antimicrobial properties and improving the sustainability of the silver nanoparticles by firmly binding a sufficient amount of the silver nanoparticles to the fibers. To this end, the present invention relates to a silver halide photographic light- Silver nanoparticles and a binding structure thereof, and a process for producing the same.

In order to solve the above problems, a first preferred embodiment of the present invention relates to a method for producing a metal halide, which comprises reacting a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) Fibers comprising at least one; Glycidyltrimethylammonium chloride (GTAC) combined with the fibers; Wherein the silver nanoparticles are combined with the GTAC and the GTAC is bound to the fibers by ring opening of an epoxy group and the silver nanoparticles are combined with a quaternary ammonium salt present in the GTAC.

The fibers according to the first embodiment may include glass fibers, polyamide fibers, PVA (poly vinyl alcohol) fibers, polyester fibers, wool, aramid fibers The silver nanoparticles may be one or more selected from the group consisting of aramid fiber, polyimide fiber, PBI fiber and cellulose fiber. The silver nanoparticles may be 0.1 To 10 parts by weight.

In order to solve the above-described problems, a second preferred embodiment of the present invention is a method for manufacturing a semiconductor device, comprising: (S1) adding a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) Treating the fiber including at least one of metal halide with glycidyltrimethylammonium chloride (GTAC); And (S2) immersing the fiber pretreated with GTAC in a silver (Ag) colloid solution to bind silver nanoparticles.

In the second embodiment, the fiber is selected from the group consisting of glass fiber, polyamide fiber, PVA (poly vinyl alcohol) fiber, polyester fiber, wool, aramid fiber Aramid fibers, polyimide fibers, PBI fibers, and cellulose fibers. [0033] The term " fibers "

In the second embodiment, step (S1) is a step of immersing the fiber in a 10 to 50% diluted solution of GTAC in distilled water, pre-drying at 60 to 90 DEG C and curing at 180 to 200 DEG C , And step (S2) may be performed at 30 to 80 ° C.

In the second embodiment, the silver (Ag) colloidal solution of step (S2) may have a silver (Ag) nanoparticle concentration of 7,500 to 50,000 ppm.

Further, a third preferred embodiment of the present invention for solving the above problems is the antibacterial fiber produced by the second embodiment.

According to the present invention, the silver nanoparticles can be chemically bonded to the fiber surface through a relatively simple method, and the silver nanoparticles having a higher content can be firmly bonded, thereby enhancing the antibacterial property of the fiber and improving the sustainability thereof .

1 is a schematic view showing a bonding structure of silver nanoparticles, GTAC, and fibers (glass fiber) according to the present invention.
2 is a graph showing the atomic (%) value of silver (Ag) present on the fiber (glass fiber) surface according to the concentration condition of GTAC.
3 is a graph showing the atomic (%) value of silver (Ag) present on the surface of the fiber (glass fiber) according to the temperature condition.
4 is a graph showing the atomic (%) value of silver (Ag) present on the surface of the fiber (glass fiber) according to the concentration condition of the silver (Ag) colloid.
5 is an image obtained by scanning electron microscopy (SEM) of the surfaces of Comparative Examples 9-A to 11-A (a to c) and Example 3-A (d).
FIG. 6 is a two-dimensional (left) and three-dimensional (right) image obtained by photographing the surfaces of Comparative Examples 9-A (a) and 3-A (b) using an atomic force microscope (AFM).

The present invention relates to a fiber comprising at least one of a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) and a metal halide in a molecular structure; Glycidyltrimethylammonium chloride (GTAC) combined with the fibers; Wherein the silver nanoparticles are bound to the fiber by ring opening of an epoxy group and the silver nanoparticles are bound to a quaternary ammonium salt present in GTAC do.

The present invention also relates to a method for producing the antimicrobial fiber, which comprises the steps of (S1) adding a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) Halide) with glycidyltrimethylammonium chloride (GTAC); And (S2) immersing the fiber pretreated with GTAC in a silver (Ag) colloid solution to bind silver nanoparticles.

The inventors of the present invention have published an academic paper on research for imparting antimicrobial activity by modifying the surface of already-existing silver nanoparticles with 3-MPTMS and then treating the surface with 3-MPTMS (Sam Soo Kim; Jeong Eun Park; Jae Woong Lee. Journal of Applied Polymer Science, Vol.119, 2011, 2261-2267). However, in the above study, it was found that the surface treatment using 3-MPTMS and silver nanoparticles did not have sufficient antimicrobial activity against Staphylococcus aureus when the amount of the microorganism was increased. Further, .

Through repeated research and numerous trial and error, we have found a way to increase the content of silver nanoparticles and form a dense bond by increasing the bonding force on the surface of the fiber. As a result, we have found that the quaternary ammonium ion At the same time, when glycidyltrimethylammonium chloride (GTAC) containing an epoxy group is used as a compound capable of chemical bonding with fibers, silver particles can be firmly bonded to the surface of the fiber at a higher content when 3-MPTMS is used, Effect and its sustainability can be improved.

GTAC has an epoxy ring as a functional group. The epoxy group is ring-opened at a high temperature, that is, a ring opening is performed, and a hydroxyl group (-OH), a thiol group (-SH) and an amine group And can be bound to the fiber surface by causing a dealcohol reaction with a metal halide (see FIG. 1). At this time, the amine group is available for both primary and secondary amines.

When the GTAC is bonded to the fiber as described above, a larger space can be secured than when silver nanoparticles are surface-modified by 3-MPTMS, resulting in binding of silver nanoparticles having a higher content to the surface. As a result, Can contain 0.1 to 10 parts by weight of silver nanoparticles based on 100 parts by weight of the cellulose fiber.

Fibers applicable to the present invention include glass fibers; Polyamide fibers including nylon and the like; Poly vinyl alcohol (PVA) fibers; Polyester fibers including PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), and PPT (Polytrimethylene terephthalate); Wool; aramid fibers including para aramid and meta aramid; Polyimide fibers; Polyvinylidene fluoride (PBI) fiber, and cellulose fiber including cotton, hemp, rayon, viscose rayon, and lyocell, and may further contain at least one selected from the group consisting of hydroxyl group (-OH), thiol A functional group containing a group (-SH) and an amine group (-NH) or a fiber imparted with a metal halide is also possible.

The antibacterial fiber manufacturing method of the present invention will be described in more detail as follows.

First, fibers are immersed in distilled water using a solution diluted with 5-50% of GTAC, pre-dried at a temperature of 60 to 90 ° C, and cured at a temperature of 180 to 200 ° C to perform a pretreatment process. If the concentration of the GTAC is less than 10%, there may be a restriction to bind more silver nanoparticles, and since the number of functional groups present in the fibers may be limited, there is no need to dilute more than 50%. Also, the pre-drying temperature is suitably 60 to 90 ° C., which is relatively high, in order to prevent GTAC from rapidly migrating to the fiber surface due to the drying of the GTAC aqueous solution penetrated into the fiber, It is preferable to perform curing at 180 to 200 占 폚 in order to securely bond the substrate to the substrate at a temperature within a range of not lower than 200 占 폚.

After the fiber is pretreated with GTAC, the GTAC pretreated fiber is immersed in the silver colloid. In this case, the silver colloid means a solution in which silver nanoparticles are dispersed. To bind a sufficient amount of nanoparticles to the fiber surface, the concentration of the dispersed silver nanoparticles, that is, the concentration of the colloid, is preferably 7,500 to 50,000 ppm Do.

In the present invention, when the fibers pretreated with GTAC are immersed in silver colloid, the temperature condition is preferably in the range of 30 to 60 ° C from the viewpoint of the rapid adhesion of silver nanoparticles which can occur at high temperatures, that is, , The immersion time is not limited thereto, but 30 minutes to 2 hours may be suitable for sufficient reaction.

After completion of the pretreatment and after the completion of the final reaction, the reaction product may be sufficiently washed with deionized water or distilled water. .

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.

Preparation Example

GTAC was purchased from Sigma Aldrich (St. Louis, Mo., USA), and four kinds of A: glass fibers (glass fiber microfiber filters: GF / F, UK), B: m-aramid fiber (Yantai, China), C: Nylon (Hyosung, Korea) and D: wool fiber (Testfabrics Korea, Korea).

Example  1 to 4 (16 kinds): Example  1-A to 1-D- Example  4-A to 4-D

GTAC was diluted in distilled water to concentrations of 10%, 20%, 30% and 40%, respectively, and the four kinds of fibers were immersed independently in four GTAC diluted solutions for 20 minutes. Thereafter, the treated sample was taken out, preliminarily dried at 80 ° C for 15 minutes, cured at 180 ° C for 5 minutes, washed twice with distilled water, and completely dried at 30 ° C.

Then, the GTAC-pretreated glass fiber was immersed in silver colloid (30,000 ppm) for 90 minutes in a water bath condition of 45 ° C. Then, the sample was washed twice with 100 ml of isopropanol, twice with 100 ml of distilled water, and finally dried at room temperature in air.

Comparative Example  1 to 5 ( 20 species ): Comparative Example  1-A to 1-D- Comparative Example  5-A to 5-D

Comparative Examples 1 to 5 were prepared in the same manner as in Examples 1 to 4 except that the concentrations of GTAC were changed to 0%, 2%, 4%, 6% and 8%, respectively.

Example  5 to 7 (12 species) and Comparative Example  6 to 8 (12 species)

The antimicrobial fiber was prepared in the same manner as in Examples 1 to 4 except that the concentration of GTAC was fixed to 30% and the temperature condition when immersed in silver colloid (30,000 ppm) was changed as shown in Table 1 below .

Example  8 to 11 (16 species) and Comparative Example  9 to 11 (12 species)

The antimicrobial fiber was prepared in the same manner as in Examples 1 to 4 except that the concentration of GTAC was fixed to 30% and the silver colloid concentration condition was changed as shown in Table 1 below.

< Measurement example  1: Atomic %  Measurement>

For the fabricated examples and comparative examples, silver nanoparticles were coated with a platinum sample for analysis of the surface shape and attached components of the fiber to which the nanoparticles were attached, and then a 15 kV Atomic% was measured under the accelerating voltage.

Antimicrobial fiber surface Ag atomic concentration (%) A: Fiberglass B: m-aramid C: Nylon D: Wool GTAC  density( % ) Colloid concentration: 30,000 ppm, silver nanoparticle treatment temperature (占 폚): 45 占 폚 Comparative Example 1 0 0.00 0.00 0.11 0.00 Comparative Example 2 2 1.53 0.25 0.25 1.39 Comparative Example 3 4 1.89 0.26 0.18 1.50 Comparative Example 4 6 3.37 0.35 0.34 1.63 Comparative Example 5 8 4.17 0.65 0.67 2.13 Example 1 10 5.06 1.20 1.01 3.24 Example 2 20 5.21 1.38 1.34 4.80 Example 3 30 6.18 1.49 1.00 5.14 Example 4 40 6.38 1.77 1.88 5.39 Silver nanoparticle treatment temperature (℃) Colloid concentration: 30,000 ppm, GTAC  density( % ): 30% Comparative Example 6 0 2.33 0.17 0.55 1.57 Comparative Example 7 20 2.58 0.37 0.64 1.78 Example 5 30 3.94 0.57 0.78 2.57 Example 6 40 6.07 1.20 1.11 5.22 Example 7 60 8.23 1.29 1.23 6.74 Comparative Example 8 80 9.76 1.66 1.31 7.10 (Ppm) &lt; / RTI &gt; GTAC  density( % ): 30%, silver nanoparticle treatment temperature (占 폚): 45 占 폚 Comparative Example 9 0 0 0 0 0 Comparative Example 10 2,500 2.59 0.36 0.20 1.05 Comparative Example 11 5,000 3.85 0.46 0.23 1.75 Example 8 7,500 4.84 0.66 0.58 2.88 Example 9 10,000 4.72 0.93 0.66 3.24 Example 10 20,000 5.20 1.17 0.91 4.90 Example 11 50,000 6.41 1.20 1.15 5.18

As shown in Table 1, the atomic concentration of Ag on the surface of the antimicrobial fiber according to the condition was analyzed. As the fiber pretreated in the high concentration of GTAC solution, the atomic% of Ag tended to increase. For example, the atomic concentration of Ag is less than 5% in the case of less than 10% of the GTAC solution, while the concentration of the GTAC in the case of 10% or more of GTAC It was confirmed that atomic% of Ag exceeded 5% in the solution. However, in the GTAC solution of 10% or more, the atomic% of Ag did not increase with the increase of the concentration of GTAC, because the number of functional groups capable of reacting with GTAC was limited

According to the results of Ag atomic% analysis according to the temperature, as shown in Table 1, the Ag atomic% increases and the standard deviation of the Ag atomic% value increases as the treatment temperature increases. FIG. 3 is a graph showing the results of the Ag atomic% analysis according to the treatment temperature of the silver nanoparticles in a more detailed manner in the case of glass fiber. The standard deviation of the Ag atomic% value rapidly increases from 30 ° C., Was actively performed at 30 DEG C or higher. However, the standard deviation of the Ag atomic% value was the greatest at 60 to 80 ° C, but it was confirmed that the silver nanoparticles were adhered to the GTAC at an excessively high temperature, resulting in unevenness.

Finally, the silver colloid concentration was also found to affect the Ag atomic% value. In particular, Ag atomic% increased steadily (see Table 1 and Fig. 4), especially when the silver colloid concentration increased to 7,500 ppm. From these results, silver colloids of at least 7,500 ppm concentration were required to bind sufficient silver nanoparticles to the fiber surface . However, in this case, as the number of functional groups in the fiber capable of reacting with GTAC was limited and the concentration of the silver particles associated with the GTAC did not increase continuously as well as the concentration of the GTAC particles did not need to be increased excessively, the content exceeded 50,000 ppm No need was found.

< Measurement example  2: SEM  Shooting>

Among Examples and Comparative Examples, Example 3-A and Comparative Examples 9-A to 11-A with different silver colloid concentrations were selected on the basis of glass fibers whose surface Ag atomic concentration was higher than other fibers , And the surface of the selected fiber was observed under a scanning electron microscope (SEM, Hitachi S-400, Tokyo, Japan) under the conditions of an acceleration voltage of 15 KV and a magnification of 3.00K. However, the sample was coated with platinum by sputtering before the test.

As a result of comparing the fiber surface characteristics, as shown in FIG. 5, the surface of the glass fiber treated with only GTAC without the silver nanoparticle treatment (comparative example 9-A, (a)) was found to be very smooth. On the contrary, the glass fibers (Comparative Examples 10-A (b) and 11-A (c)) treated with silver colloid concentrations of 2,500 ppm and 5,000 ppm, respectively, Can be confirmed. However, when compared with glass fibers treated with 30,000 ppm silver colloid (Example 3-A, (d)), it was confirmed that the roughness was significantly lowered.

< Measurement example  3: AFEM  Shooting>

Next, using the atomic force microscope (AFM, XE-100, Park system) for Example 3-A and Comparative Example 9-A, GTAC and silver The surface changes of the glass fiber after the treatment of nanoparticles were observed in three dimensions. As a result, the surface (a) of the sample not treated with the silver nanoparticles (Comparative Example 9-A) was relatively smooth while the surface of the silver nanoparticle-treated sample (Example 3-A) (b) is more curved than (a).

< Measurement example  4: Antibacterial test>

On the other hand, in order to evaluate the antimicrobial activity of silver nanoparticles, an untreated sample based on glass fiber, Comparative Example 9-A treated only with GTAC, and Example 1-A treated with GTAC and silver nano The results are shown in Table 2 below.

- Antibacterial test: E. coli O157: H7 (E. coli O157: H7, ATCC 43895), which is a pathogenic bacterium from -80 ° C glycerol stock to Luria-Bertani (LB) medium (BD Bioscience, Streaks of S. typhimurium (KCCM 11862) and methicillin-resistant Staphylococcus aureus MRSA (S. aureus, BAA-1707 of ATCC), P. aeruginosa (ATCC 15692) and P. aeruginosa , A single colony was inoculated in LB (25 mL) of a 250 mL flask, and then cultured at 37 DEG C with stirring at 250 rpm. After diluting with a phosphate buffered saline solution (PBS) at a ratio of 1: 500 per day, each sample was immersed in 0.3 mL of a diluted bacterial cell solution and incubated at 37 DEG C for 24 hours. All experiments were performed using at least two media each, and after incubation, the surviving cells were counted as a number of colony forming units (CFUs).

Samples Bacterial no. (cfu / sample) E. coli ^a S. aureus ^b P. aeruginosa ^c S. typhimurium ^d Example 1-A 0 0 0 0 Untreated sample 8.9 x 10 ⁴ 4.3 x 10 ⁴ 4.1 x 10 ⁴ 4.3 x 10 ⁴ Comparative Example 9-A 5.6 x 10 ² 0 5.6 x 10 ⁵ 0

^a Total bacteria: 9.4 x 10 ⁴ cfu / sample.

^b Total bacteria: 6.1 x 10 ⁴ cfu / sample.

^c Total bacteria: 5.2 x 10 ⁴ cfu / sample.

^d Total bacteria: 6.6 x 10 ⁴ cfu / sample.

According to the results of the antibacterial test, as shown in Table 2, the antibacterial activity was not exhibited for all of the untreated glass fiber (untreated sample), and for the glass fiber treated only with GTAC (Comparative Example 9-A) The antimicrobial activity against S. aureus and S. typhimurium was found to be insufficient, while the antimicrobial activity against E. coli and P. aeruginosa was found to be insufficient. On the other hand, Example 1-A in which silver nanoparticles were bound after pretreatment of fibers with GTAC showed excellent antibacterial activity against all four bacteria tested.

< Measurement example  5: Washing Fastness  Test>

(Ag atomic concentration) according to the number of times of washing for four kinds of fibers based on Example 3 which was tested under conditions of a colloid concentration of 30,000 ppm, a GTAC concentration (%) of 30%, and a silver nanoparticle treatment temperature (%) Were measured. The washing method was as follows. The results are shown in Table 3.

- Washing method: Washing method was applied according to ISO 105-C01: 1989. Specifically, 5 g of detergent was mixed with 1 L of distilled water and the temperature was maintained at 40 ± 2 ° C. The washing time was 30 minutes, and 5 washing cycles were applied.

Ag atomic concentration (%) according to the number of times of washing 1 time Episode 2 3rd time 4 times 5 times Example 3-A 5.69 4.79 4.62 4.61 3.85 Example 3-B 1.137 1.07 0.997 0.916 0.908 Example 3-C 0.29 0.26 0.25 0.26 0.24 Example 3-D 5.02 3.75 3.11 2.98 2.68

As a result of washing fastness test, it was evaluated that the antimicrobial fibers of Examples 3-A to 3-D showed a decrease in Ag atomic concentration of less than 35% even after washing five times, regardless of the type of fibers.

Claims (9)

delete delete delete (S1) A fiber comprising at least one of a functional group containing a hydroxyl group (-OH), a thiol group (-SH) and an amine group (-NH) and a metal halide in a molecular structure is reacted with glycidyltrimethylammonium chloride (GTAC) Lt; / RTI &gt; And
(S2) immersing the GTAC pre-treated fiber in a silver (Ag) colloid solution to bind silver nanoparticles;
The step (S1) is performed by immersing the fiber in distilled water in which 10 to 40 mass% of GTAC is diluted, for 20 minutes, pre-drying at 80 ° C for 15 minutes and curing at 180 ° C for 5 minutes However,
The step (S2) is to immerse the GTAC pretreated fiber in a silver (Ag) colloid solution containing silver nanoparticles at a concentration of 7,500 to 50,000 ppm at a temperature of 30 to 80 ° C,
The fibers may be selected from the group consisting of glass fiber, polyamide fiber, PVA (poly vinyl alcohol) fiber, polyester fiber, wool, aramid fiber, A polyimide fiber, a polyimide fiber, a PBI fiber, and a cellulose fiber.
A method for producing an antimicrobial fiber having antimicrobial activity against all of S. aureus, S. typhimurium, E. coli and P. aeruginosa.
delete delete delete delete An antimicrobial fiber having antibacterial activity against all of S. aureus, S. typhimurium, E. coli and P. aeruginosa produced by the method of claim 4.

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