KR19980085574A - Antibacterial Fabric - Google Patents

Abstract

The present invention relates to an antibacterial fabric, in which cotton-containing fabrics, that is, cotton fabrics, cotton blended fabrics, or cotton fabrics are treated with a water-soluble quaternary ammonium chitosan derivative.

The quaternary ammonium salt chitosan derivative is made water-soluble by introducing an ammonium base group into an amine group of chitosan.

The antimicrobial fabric of the present invention can improve the washing resistance by treating the chitosan derivative with a non-ion binder or a crosslinking agent.

Description

Antibacterial Fabric

The present invention relates to an antimicrobial cotton-containing fabric treated with a quaternary ammonium salt chitosan derivative.

As our lives become more advanced and attention to hygiene increases, various textile products that provide functionality have been released, including antimicrobial fabrics.

There are two methods for imparting antimicrobial performance to fabrics: the method of mixing and spinning antimicrobial agents directly in the manufacture of yarns, and attaching the antimicrobial agents during post-processing after fabrics are manufactured. Antimicrobial agents used in yarn manufacturing should be stable even at high temperatures and should be well dispersed in fine powders. The most widely used antimicrobial agents are silver ion zirconium compounds and silver ion zeolites. 63-5403)

However, in the case of natural fiber cotton products, antimicrobial agent cannot be added during the manufacturing of yarn like synthetic fiber, so the method of attaching the antimicrobial agent during the post-fabrication process must be used. In addition, many products such as underwear, panties, socks, and duvets that require antimicrobial performance are mostly used in cotton products, which are natural fibers. Hospital clothes, sheets, or textile products used in areas where the elderly live are likely to be contaminated with pathogens.

As an antimicrobial agent to be processed into a cotton product, an antimicrobial fabric is prepared by post-processing a silicon having a quaternary ammonium group on a fabric. However, these silicone antimicrobial agents have a disadvantage of being post-processed using a suspending agent. On the other hand, there is a technique of manufacturing antimicrobial fabric by fixing chitosan in a synthetic resin binder liquid by fixing treatment in the processing of textile products, but these products have a disadvantage of low antimicrobial properties. -51369)

The present invention is to manufacture a water-soluble chitosan derivative from chitosan, a natural polymer, to improve the inconvenience of post-fabric processing and to improve the antimicrobial, and applied to the fabric, antimicrobial performance is significantly improved compared to natural chitosan, The suspension does not need to be used. The present invention further provides an antimicrobial fabric having excellent washing resistance by post-processing a water-soluble chitosan derivative antimicrobial agent having a quaternary ammonium base with a binder or a crosslinking agent.

Since chitin and chitosan are natural polymers, because they are biodegradable and biocompatible, recent researches and interests on them are increasing along with environmental issues, and these fields of use are expanding to health foods, wastewater treatment, and medical fields. Among them, chitosan is obtained by deacetylating chitin, which forms upper shells of crabs, shrimps, insects, etc., and is the second most abundant natural resource on earth, which is harmless to humans and has antimicrobial properties.

In addition, chitosan has a primary amine group, which is more reactive than chitin, and easily dissolves in organic acids having functional groups such as dilute hydrochloric acid and carboxyl groups.

It is easy to synthesize functional polymers having new properties by reacting chitosan primary amine groups with other drugs. Among the various applications of chitosan, the application to the textile field is the hygienic processing field which imparts antimicrobial and deodorizing properties to the fibers. The amine groups of chitosan form ammonium fever with acetic acid and the like, wherein NH ₃ ⁺ imparts antimicrobial properties. These cations are known to exhibit antimicrobial properties by electrically attracting (-) charges, such as phospholipids, which make up the cell wall of microorganisms, thus constraining their freedom and causing growth inhibition. In order to impart such antimicrobial, researchers have been studying how to lower the molecular weight of chitosan, dissolve it in acid and treat it with fiber, or spin the low molecular weight chitosan with cellulose. Chitosan having a specific range of molecular weight should be prepared, and its useful value is low in view of the treatment cost for chitosan outside this range. In addition, chitosan swells due to protonization of some amine groups in water, but is insoluble in water due to hydrogen bonding between molecular chains, and in dilute acid aqueous solution, salts are formed between amine groups and acids of chitosan to dissolve in water. However, it is insoluble in alkaline liquid. Therefore, it is difficult to use chitosan by direct aqueous solution in general fiber process.

In view of the above, the present invention is to prepare a chitosan derivative having a new quaternary ammonium salt group using an amine group, which is a reactive group of chitosan, and to use it as an antimicrobial processing agent for fibers. By properly adjusting the drug used to synthesize chitosan derivatives, a water-soluble derivative can be synthesized with desired properties. The derivative thus synthesized has new performance while maintaining the natural degradability and biocompatibility of chitosan backbone, and thus can be used as a new processing agent for textile products without harming environmental problems. From this point of view, the highly reactive epoxy group drugs were reacted with chitosan while using chitosan as a natural polymer to synthesize a water-soluble chitosan derivative having a new quaternary ammonium salt of the following general formula (1).

next

HO {C ₆ H _{11 -m} NO ₄ (R ¹ ) _m (R ² ) _n } _p H... … (I)

In the above formula,

or,

X = Cℓ, Br, I or CH ₃ SO ₄

R ³ = alkyl group having 1 to 4 carbon atoms

m: 0 to 0.5

n: 0 to 6

p: 10 to 50,000

R ¹ : represents an acetyl group, the lower the value, the higher the degree of deacetylation and the number of primary amine groups increases.

In this case, chitosan having a structure similar to cellulose forms a covalent bond by reacting the amine group at the C2 position with the epoxide moiety, and the quaternary ammonium base is always attached to the chitosan.

In this case, it is the glycidyltrimethylammonium chloride (GTCC) mainly used in the present invention, wherein × of the quaternary ammonium base is C 1, and × may be Br, or I or CH ₃ SO ₄ instead of C ₁ .

In general, most anti-microbial processing agents have a quaternary ammonium salt structure, so attaching quaternary ammonium salts to chitosan increases the effect of some of the antimicrobial properties of chitosan and quaternary ammonium salts present in derivatives. Action is expected to increase antimicrobial activity.

By the way, in general, there are many quaternary ammonium salt compounds among the substances used as antimicrobial, but not all quaternary ammonium salts exhibit antimicrobial properties.

The present inventors treated the cotton fabric and examined the antimicrobial properties of the treated fabric to see if the water soluble chitosan derivative exhibited antimicrobial properties. In particular, when comparing the antimicrobial changes between the two groups using chitosan and water-soluble glycidyltrimethylammonium chitosan chloride (GTCC) obtained through the reaction of glycidyltrimethylammonium chloride (GTMAC) and chitosan, It showed much higher antimicrobial activity than chitosan. GTCC is a water-soluble polymer that is soluble in water and this water soluble property is very advantageous when used as a fibrous processing agent. For example, other polymer processing agents that are insoluble in water must be dissolved in organic solvents or made into emulsions and processed into fibers, but this problem does not occur when water-soluble. In addition, since the processing of general textile products uses almost aqueous solution, this derivative may be added and used together during processing.

The present invention is characterized in that the water-soluble quaternary ammonium salt chitosan derivative is used at a concentration of 0.02% to 5%, preferably treated with a fabric having a concentration of 0.025% to 4%. If the concentration is less than 0.02%, the effect of reducing the bacterium is insignificant, and if it exceeds 5%, it is difficult to use the coating because it becomes high viscosity.

Figure 1 shows the uniformity reduction of fabrics treated by dissolving GTCC in water at several concentrations and then simply padding-drying the cotton fabric. Padding with a GTCC concentration of 0.01% showed little antimicrobial activity, whereas padding with a GTCC concentration of 0.025% or more showed excellent antimicrobial nearly 100%. Such antimicrobial concentrations of about 0.025% to about 100% of antimicrobial agents are antimicrobial agents with a smaller amount of drugs than any of the known processing agents. Since GTCC is a polymer, it dissolves in water and does not enter the fiber, but exists on the surface of the fiber, making it easier to kill bacteria from outside. On the other hand, chitosan itself is known to show antimicrobial activity at a certain molecular weight. Figure 2 shows the reduction rate for the sample which does not neutralize acid-treated samples by dissolving chitosan under acidic conditions and treating them in the same manner.

These results showed that the bactericidal rate was less than 30% even if the chitosan concentration was increased to 1%.

For samples that were not neutralized or washed after dissolving chitosan in acetic acid, even if the concentration of chitosan increased up to 1%, the reduction rate was between 20-25%, and less than 15% when neutralized and washed with water. In the case of samples that are not neutralized or washed with water, the rate of reduction of bacteria is rather high due to the inhibition of bacterial growth by the acid remaining in the sample. In case of using Shake Flask method, it is judged that the microbial reduction rate should be more than 70%. Therefore, if chitosan is treated only, it can be considered that there is no antimicrobial treatment. GTCC, which is a water-soluble chitosan derivative in the present invention, shows superior antimicrobial properties compared to chitosan, and such antimicrobial properties are due to GTCC itself having a substituent of quaternary ammonium base rather than chitosan.

GTCC has excellent antimicrobial properties, but its water solubility is both an advantage and a disadvantage. That is, in the case of simply dissolving in water using the property of water solubility, it is possible to simply spit the fiber product to be used by drying or to process the fiber product using a spray method. However, in this case, since it is insoluble in water, it has no washing resistance, so its use should be limited to a disposable product or a product which rarely washes. Of course, even in this case, it is expected that there will be many uses of the antimicrobial properties of GTCC, but in order to use it in cotton fabric or cotton knitted fabric, it must have some washing resistance. In the present invention, a method of using a crosslinking agent and a method of using a binder are used as a method of always washing resistance. In the first method, when GTCC is used together during the dipping of cotton fibers, crosslinking with cellulose molecules by a crosslinking agent can greatly enhance washing resistance. In this case, the crosslinking agent should have a functional group capable of reacting with a hydroxy group, and in particular, a compound containing two functional groups in the form of a mixture of dicarboxyl group, diepoxide, dihalogen, or functional groups of carboxyl group, epoxide and halogen is used as a crosslinking agent. It is available. The second method for improving the washing resistance in the treatment of GTCC is to use a binder.

Generally, various types of binders may be used to bind a polymer or a drug having no reactive group or affinity to directly bond with the fiber. In the case of GTCC, an anionic binder cannot be used because it is a cationic polymer itself.

In general, as a binder of cotton fabrics, the effects of the laundry-resistance on washing resistance using polyurethane binders and nonionic binders are shown in Figs. The results show that the use of polyurethane binder does not have a significant effect on the improvement of washing resistance, but the use of non-ionic binders greatly increases the washing resistance. In particular, when the non-ionic binder is used and the GTCC is 0.5%, the GTCC is hardly removed by washing even after 6 washings, which shows a reduction ratio of 90% or more. Figure 7 shows the uniformity reduction rate according to the number of washing times when the binder used above was used while changing the GTCC concentration from 0.1% to 0.5%. Overall, as the number of washes increases, the rate of decrease decreases slightly, and the decrease is larger as the GTCC concentration decreases. However, when the concentration of GTCC is more than 0.1%, the number of washings is 10 times, which shows a reduction rate of at least 80%. On the other hand, in case of simply padding and drying, even if the GTCC concentration is 0.5%, the washing rate is less than 50% when washing twice, indicating no washing resistance. In general, antimicrobial processing of textile products is said to be wash resistant if antimicrobial is maintained even after 10 washings. The antimicrobial laundering resistance test of cotton blended fabrics and cotton fabrics obtained by processing GTCC using a non-ionic binder showed the results as shown in Figure 8 and Figure 9. Cotton fabrics showed better washing resistance than cotton blended fabrics, and cotton blended fabrics showed better wash resistance than cotton blended fabrics.

Preparation of Water Soluble Chitosan Derivatives (GTCC)

A mixture obtained by adding 10 g of chitosan (84% deacetylation, 370,000 molecular weight, 61 mmol), glycidyltrimethylammonium chloride (GTMAC), 60 g (0.36 mol), and 100 ml of water in a 500 ml three-flask with a condenser was prepared. The reaction was stirred at 24 ° C. for 24 hours. The reaction product was precipitated in a large amount of acetone, the powdered product was stirred for 24 hours, filtered, and dried in vacuo at 50 ° C to obtain 15 g of powdered quaternary glycidyltrimethylammonium chitosan chloride (GTCC).

Substituents of the obtained product were also determined from the following formula by measuring the content of chlorine atoms by a combustion flask method. If chitosan with a deacetylation degree of x reacts with GTMAC to give a GTCC with a degree of substitution of z, the molecular weight of this GTCC is (203.20-42.04x) + 151.64z) g, so that the chlorine atom content of this GTCC is y (%). Then, substitution degree z can be calculated as follows. The most important thing in applying this equation is that there should be no unreacted GMAC in the sample.

z = (203.20-42.04x) / {(3545 / y (%))}-151.64}

The substitution degree calculated from the above equation is 0.92 and is water soluble.

As for the substitution degree of the quaternary ammonium group used for this invention, 0.5-2.0 are preferable. If it is less than 0.5, it is insoluble in water, and if it exceeds 2.0, it is uneconomical and difficult to manufacture.

Laundry resistance test

Washing (bath ratio 30: 1, detergent concentration 0.2%, normal temperature, one wash cycle; washing 5 minutes-dehydration-rinsing 2 minutes according to JISL 0217 (103) which defined the test method for washing resistance of antimicrobial treated fiber sample) Dehydration-rinse 2 min-dehydration-drying) to analyze the wash resistance. At this time, the washing machine used a commercially available washing machine (Samsung, SEW-50X1), and used a cotton cloth of the same size as the sample for measurement in order to meet the bath ratio.

As in the DP processing of general cotton fabric, GTCC was added in 0.2% and 0.5% concentrations to the solution containing 8% (w / v) of DMDHEU and 2% of magnesium chloride, respectively. The cotton fabric was padded. The sample was dried at 120 ° C. for 3 minutes, cured at 150 ° C. for 4 minutes in a heat treatment machine, and treated to cotton fabric in the same manner as in general DP processing. The results of the reduction rate according to the number of washings for the cotton fabrics prepared in this way are shown in Figure 3 (GTCC 0.2%) and Figure 4 (GTCC 0.5%). The treatment with DMDHEU shows that the reduction rate of bacteria (antimicrobial) decreases with increasing the number of washings, but the washing resistance is better than that treated with GTCC alone.

Example 1

A 100% cotton fabric with a warp density of 40's, a weft yarn of 40's, a warp density of 136ol / 2.54cm, and a weft density of 72ol / 2.54cm was used as a sample for antimicrobial measurement.

The padding of the processing agent was repeated 1dip and 1nip twice using Mathis (Swiss) Lab Padder, so that the wet pickoup was 75 ± 1%, and the drying was performed using a hot air dryer (DK-11M, Daiei Kagakuseiki). Curing was performed using Mathis (Switzerland) Lab Curing machine.

GTCC was dissolved in water at 0.01, 0.025, 0.05, and 0.1% concentrations, and then simply patterned on cotton fabric and dried at 60 ° C. for 30 minutes. Staphylococcus aureus (Staphylococcus aureus, American Type Culture Collection No. 6538) was used as a test strain and tested by the Shake flask method to calculate the reduction rate. Figure 1 shows the reduction rate (antimicrobial result) according to GTCC concentration. Staphylococcus aureus shows a 100% reduction in bacteria from GTCC concentrations above 0.025%.

Example 2

GTCC concentrations of 0.2% and 0.5%, respectively, were used in combination with a binder for general cotton fabrics to form a treatment solution and then treated to cotton fabrics. Two binders were used: Elastron MF-25, a polyurethane resin, with 5% solution (0.5% catalyst), and TK Binder-202F, a nonionic binder, with 5% solution. The cotton fabric was padded in these treatment liquids, dried at 120 ° C. for 2 minutes in a hot air dryer, and cured at 150 ° C. for 3 minutes with a heat treatment machine. As described above, the results of the laundry resistance test show that the results of washing resistance when using polyurethane binder and nonionic binder are shown in Figure 5 (GTCC 0.2%) and Figure 6 (GTCC 0.5%). The use of non-ionic binders is much better than that of polyurethanes, which results in much better wash resistance.

Example 3

GTCC concentrations were 0.1%, 0.2%, 0.3%, 0.4% and 0.5%, respectively, and TK Binder-202F, a nonionic binder for general cotton fabrics, was prepared as a 5% solution, and then treated to cotton fabrics. The cotton fabric was padded in these treatment liquids, dried at 120 ° C. for 2 minutes in a hot air dryer, and cured at 150 ° C. for 3 minutes with a heat treatment machine. As a result of the washing resistance test, Fig. 7 shows that the treatment with the nonionic binder is much better washing resistance than without the binder.

Example 4

The concentration of GTCC was 0.1%, 0.2%, 0.3%, 0.4% and 0.5%, respectively, and TK Binder-202F of a nonionic binder for general cotton fabric was prepared using a 5% solution, and then treated to a cotton blended fabric. . After the cotton blended fabric was padded with these treatments, the mixture was dried at 120 ° C. for 2 minutes in a hot air dryer, and cured at 150 ° C. for 3 minutes with a heat treatment machine. The results of the laundry resistance test show the results as shown in Fig. 8, and the anti-microbial effect of washing resistance is slightly lower than that of cotton fabric.

Example 5

The concentrations of GTCC were 0.1%, 0.2%, 0.3%, 0.4% and 0.5%, respectively, and TK Binder-202F of a nonionic binder for general cotton fabric was prepared using a 5% solution, and then treated to the cotton fabric. After the padding fabric was padded with these treatment liquids, the resultant was dried at 120 ° C. for 2 minutes in a hot air dryer, and cured at 150 ° C. for 3 minutes with a heat treatment machine. The results of the laundry resistance test show the results as shown in Fig. 9, and the antimicrobial decrease due to the laundry resistance is greater than that of cotton or cotton blend.

Comparative Example 1

Chitosan was dissolved in a 1% acetic acid aqueous solution at a concentration of 0.1, 0.2, 0.3, 0.4, 0.5, and 1.0%, and then padded with cotton fabric, followed by hot air drying at 60 ° C. for 30 minutes. The sample was neutralized by immersing in 1% aqueous sodium hydroxide solution, washed with water and dried until neutralized after neutralization. The neutralized and washed samples and the samples which were not neutralized simply by padding and drying were used for the antimicrobial test. Staphylococcal reduction was calculated after testing by the Shake flask method using Staphylococcus aureus (Stap [hylococcus aureus, American Type Culture Collection No.6538]) as a test specimen. Figure 2 shows the reduction rate (antimicrobial results) of neutralized and non-neutralized samples. The better rate of reduction in non-neutralized samples is likely due to the effect of acetic acid remaining in the sample.

The present invention can be easily treated by treating a water-soluble chitosan derivative having a degree of substitution of 0.5 to 2.0 and a concentration of 0.025% to 5% to a cotton-containing fabric, and can easily impart antimicrobial properties. Can be significantly enhanced.

Figure 1.Bacterial reduction rate according to the concentration of GTCC coded in cotton fabric

Figure 2. Bacterial reduction rate according to the concentration of chitosan coated on cotton fabric

(a) neutralizing and laundering; (b) only neutralizing and laundering.

Figure 3. Uniformity Reduction of Coated Cotton Fabrics with Washing Count

(a) Treated with GTCC (0.2%)

(b) treated with GTCC (0.2%) and DMDHEU

Figure 4. Uniformity Reduction of Coated Cotton Fabrics with Washing Count

(a) Treated with GTCC (0.5%)

(b) treated with GTCC (0.5%) and DMDHEU

Figure 5. Uniformity Reduction of Coated Cotton Fabrics with Washing Count

(a) Treated with polyurethane binder with GTCC (0.2%)

(b) treated with GTCC (0.2%) and a non-ionic binder

Figure 6. Uniformity Reduction of Coated Cotton Fabrics with Washing Count

(a) Treated with polyurethane binder with GTCC (0.5%)

(b) treated with GTCC (0.5%) and a non-ionic binder

Figure 7.Flue reduction rate according to the number of times of washing of cotton fabric treated with GTCC and nonionic binder

Figure 8.Flue reduction rate according to the number of times of washing of cotton blended fabric treated with GTCC and nonionic binder

Figure 9.Flue reduction rate according to the number of times of washing of cotton fabrics treated with GTCC and nonionic binder

Claims (7)

A nonwoven biological fabric characterized by having a water-soluble quaternary ammonium salt chitosan derivative of formula (1) having a concentration of 0.025% to 5% on the surface of a cotton-containing fabric. next HO {C ₆ H _{11 -m} NO ₄ (R ¹ ) _m (R ² ) _n } _p H... … (I) In the above formula, or, X = Cℓ, Br, I or CH ₃ SO ₄ R ³ = alkyl group having 1 to 4 carbon atoms m: 0 to 0.5 n: 0 to 6 p: 10 to 50,000 R ¹ : represents an acetyl group, the lower the value, the higher the degree of deacetylation and the number of primary amine groups increases. The antimicrobial fabric of claim 1 wherein the quaternary ammonium salt chitosan derivative is glycidyltrimethylammonium chitosan chloride (GTCC). The antimicrobial fabric according to claim 1, wherein the cotton-containing fabric is a cotton fabric, a cotton blend fabric, or a cotton fabric. The antimicrobial fabric according to claim 1, wherein the quaternary ammonium salt chitosan derivative has a substitution degree of 0.5 to 2.0. The antimicrobial fabric of claim 1 wherein the quaternary ammonium chitosan derivative is attached by a binder. 6. The antimicrobial fabric of claim 5 wherein the quaternary ammonium chitosan derivative is attached by a nonionic binder. The antimicrobial fabric of claim 1 wherein the quaternary ammonium chitosan derivative is crosslinked with cellulose by a crosslinking agent.