KR20240062332A - Eco-friendly antibacterial fiber fabric manufacturing method and eco-friendly antibacterial fiber fabric by the method - Google Patents

Abstract

The present invention relates to a method for manufacturing eco-friendly antibacterial fabric, and more specifically, to a method of attaching and crosslinking an organic antibacterial agent instead of an inorganic antibacterial agent to the surface of the fabric. The eco-friendly antibacterial fabric according to the present invention provides the advantages of being harmless to the human body, having an environmentally friendly processing process, and having excellent antibacterial properties.

Description

Eco-friendly antibacterial fiber manufacturing method and eco-friendly antibacterial fiber fabric by the method}

The present invention relates to a method of manufacturing an eco-friendly antibacterial fabric, and specifically, to a method of manufacturing an antibacterial fabric that can be subjected to environmentally friendly antibacterial processing in an inexpensive and simple manner using water as a solvent.

Fabric is a fabric that is used as a raw material for clothes, mats, sofas, etc., and textile products are made using the fabric. Since these textile products are not provided with functionality, they may create favorable conditions for the growth of harmful bacteria or mold. When harmful bacteria or mold grow on textile products, not only can a bad odor be generated, causing discomfort, but bacteria or mold can grow on the skin and cause disease.

In order to prevent the growth of such bacteria or mold, technologies for imparting antibacterial properties to fibers have been developed. Antibacterial fibers are fibers treated with antibacterial and/or antifungal substances and are widely used in the medical field, such as surgical gowns, patient gowns, masks, and bandages.

Commonly known methods of antibacterial and deodorizing processing of fibers include applying inorganic compounds such as silver, copper, zinc, silver oxide, and zinc oxide, or applying organic compounds such as benzyl chloride. However, these methods do not apply the antibacterial substances to the fiber. Because they do not adhere properly, they often lose their antibacterial function within a short period of time.

In other known technologies, zirconium phosphate, quaternary ammonium salts, activated alumina, activated carbon, etc. have been used until recently to impart antibacterial properties, but they have poor dispersibility and poor washing durability. Furthermore, cationic surfactants in the form of quaternary ammonium temporarily exert a softening effect on clothing, but as the amount of use accumulates, yellowing occurs, causing white clothing or fibers to turn yellow.

Recently, the use of metal oxides and inorganic metal antibacterial agents has been restricted worldwide due to controversy over their harmfulness to the human body, so there is a need to develop technology to manufacture antibacterial fabrics that are harmless to the human body, eco-friendly in the processing process, and cost-competitive using materials with excellent antibacterial properties. This is increasing.

The purpose of the present invention is to provide an antibacterial fabric that is harmless to the human body, has an environmentally friendly processing process, and has excellent antibacterial properties and is price competitive.

The present invention relates to a method for manufacturing an eco-friendly antibacterial fabric, which includes a first step of preparing a mixed solution of water, a crosslinking agent, and an N-halamine precursor, a second step of immersing the fabric in the mixed solution, and tenderizing the immersed fabric. A third step of forming N-halamine on the surface of the fabric by heat setting, a fourth step of immersing the fabric after the heat setting step in a chlorine solution, and a fifth step of tender-heat setting the fabric immersed in the chlorine solution. It is done in stages.

The cross-linking agent may be one or more selected from BTCA and Ethylene urea.

The content of the halamine precursor may be mixed at a molar ratio of 30% by weight to 300% by weight based on 100% by weight of the crosslinking agent.

The N-halamine precursor is imidazolidine-2,4-dione (hydantoin), 5,5-dimethylhydantoin, 4,4-dimethyl-2oxazalidione, tetramethyl-2-imidazolidione, 2,2,5,5-tetramethylimidazo -It may be 2,2,5,5-tetramethylimidazo-lidin-4-on, uracil derivative, piperidine, or a combination thereof.

The chlorine solution may be a sodium hypochlorite solution.

In both the third and fifth steps, tendering may be performed at 90 to 120°C for 5 to 10 minutes, and heat setting may be performed at 150 to 200°C for 1 to 5 minutes.

The present invention provides an eco-friendly antibacterial fabric manufactured by any one or more of the above methods.

The present invention uses water, which is not harmful to the human body, as a solvent on the surface of the fabric, and fixes the organic antibacterial agent with a cross-linking agent, thereby enabling antibacterial processing in a cheap and simple way. It also does not require complicated equipment, so it is possible to process the organic antibacterial agent in an eco-friendly way. It provides the effect of imparting antibacterial properties to the fabric.

In addition, the organic antibacterial agent is fixed to the surface of the fabric with a crosslinking agent, providing a fabric that can maintain antibacterial properties even when used for a long time.

1 is a photograph showing the antibacterial test results of an example according to the present invention

The method for producing an eco-friendly antibacterial fabric of the present invention includes a first step of preparing a mixed solution of water, a crosslinking agent, and an N-halamine precursor, a second step of immersing the fabric in the mixed solution, and a tender-heat setting treatment of the immersed fabric. It consists of a third step of forming N-halamine on the surface of the fabric, a fourth step of immersing the fabric after the heat setting step in a chlorine solution, and a fifth step of tender-heat setting the fabric immersed in the chlorine solution. .

The fiber may be a cellulose-based fiber such as cotton fiber, hemp fiber, rayon fiber, acetate fiber, Lycell fiber, and wool.

The N-halamine group is a heterocyclic or monocyclic 4 to 7 membered ring, where at least 3 atoms of the ring are carbon, 1 to 3 atoms of the ring are nitrogen heteroatoms, 0 to 1 atoms of the ring are oxygen heterocycles, and 0 to 2 atoms of the ring are nitrogen heteroatoms. The carbon atom is carbonyl. At least one ring nitrogen has a chlorine or bromine atom attached to it. The precursor N-halamine group is a heterocyclic group that does not have any chlorine or bromine atoms on any of the ring nitrogens. The precursor N-halamine group has a hydrogen or hydroxy alkyl group bonded to all ring nitrogens that are not bonded to a linking group. In one embodiment the linking group is a methylene group. The methylene group bonds the N-halamine or N-halamine precursor group to the benzene ring of polystyrene. Representatives of N-halamine and N-halamine precursor groups are halogenated and non-halogenated hydantoins, imidazolidinones, oxazolidinones and isocyanurates.

The N-halamine precursor is imidazolidine-2,4-dione (hydantoin), 5,5-dimethylhydantoin, 4,4-dimethyl-2oxazalidione, tetramethyl-2-imidazolidione, 2,2,5,5-tetramethylimidazo -It may be 2,2,5,5-tetramethylimidazo-lidin-4-on, uracil derivative, piperidine, or a combination thereof.

Among organic antibacterial substances, a lot of research is being done on the antibacterial properties of polymers made of N-halamine precursor substances, which are similar to those of previously used halogens, ozone, and chlorine dioxide. It was found that it has excellent stability in water and has the advantage of having no byproducts harmful to the body generated through reaction with organic impurities present in water. Positive halogen generated from N-halamine polymer exhibits antimicrobial porperty by killing bacteria by engaging with receptors in bacterial cells.

The crosslinking agent may be one or more selected from BTCA (1,2,3,4-butanetetracarboxylic acid) and ethylene urea. The BTCA and Ethylene urea are both organic antibacterial agents and are harmless to the human body, unlike inorganic antibacterial agents whose harmfulness to the human body is controversial.

BTCA is a cross-linking agent that reacts with cotton to esterify cotton fibers, which occurs in two steps. In the first step, a cyclic acid anhydride intermediate is formed by the acid anhydride of two carboxyl groups in a polycarboxylic acid molecule such as BTCA, and in the second step, a reaction occurs between the acid anhydride intermediate and cellulose to form an ester. .

Ethlyene urea is a substance used in the treatment to inhibit the formation of wrinkles in cellulose-based fabrics. It combines with the hydroxyl groups present in long cellulose chains to prevent the formation of hydrogen bonds in the chains, which is the main cause of wrinkles. Likewise, BTCA also has the effect of preventing wrinkles in fibers.

In the present invention, the fabric is immersed in a mixed solution of the cross-linking agent and the N-halamine precursor and then cured through heat setting, so that the N-halamine precursor is bound to the fiber, and the cross-linking agent is chemically bound to the fiber, The cross-linking agent serves to fix the N-halamine precursor to the fiber.

Meanwhile, since both the cross-linking agent and the antibacterial agent can use water as a solvent, many unnecessary substances harmful to the environment can be reduced during the manufacturing process, making it environmentally friendly.

The N-halamine precursor may be mixed at a molar ratio of 0.5 mole to 2 mole per mole of crosslinking agent.

If the amount of the N-halamine precursor is less than 0.5 mole compared to 1 mole of the crosslinking agent, the effect of chemical bonding between the halamine precursor and the fiber is reduced, and even if it exceeds 2 mole, only crosslinking between the fiber and the crosslinking agent occurs intensively, resulting in halamine The precursor does not chemically bond well with the fiber.

In the third step, tendering may be performed at 90 to 120°C for 5 to 10 minutes, and heat setting may be performed at 150 to 200°C for 1 to 5 minutes. The tender process is a process of drying the coated fabric considering shrinkage and relaxation, and the heat setting treatment is a process of binding N-halamine and a crosslinking agent to the fiber surface.

During heat setting, if the heat setting temperature is less than 150°C, the crosslinking agent may not be able to serve as a crosslink between the N-halamine precursor and the natural fiber, which may lower the adhesion rate of the N-halamine precursor, and if it exceeds 200°C. The color of the fiber may change and attachment of the N-halamine precursor may be difficult. A process of washing the fabric after the third step can be added.

When the fabric that has gone through the tender heat setting steps in steps 4 to 3 is immersed in a chlorine solution, chlorine causes a substitution reaction with the hydrogen or hydroxyl group of the N-halamine precursor, converting the N-halamine precursor into N-halamine.

The chlorine solution may be a sodium hypochlorite solution, and the concentration of the hypochlorite solution is preferably 4 to 8%. If the concentration of the hypochlorous acid solution is lower than 4%, chlorine substitution may not occur well or the time for the fourth step may be excessively long, and if the concentration of the hypochlorous acid solution exceeds 8%, the structure of the fiber may be destroyed.

In the fifth step, the fabric immersed in the chlorine solution of the fourth step is subjected to a tender-heat setting treatment. It is preferable that the tender temperature and heat setting temperature in the fifth step are the same as the tender heat setting treatment in the third step. As with the third step, if the temperature exceeds the above temperature, it is difficult to expect the crosslinking effect of halamine.

When the tender-heat setting treatment is performed in two steps, the third step before chlorine treatment and the fifth step after chlorine treatment as above, N-halamine is better attached to the fabric surface and the antibacterial effect of chlorine is much greater. Provides lasting effects.

After the fifth step, a process of washing the fabric to which N-halamine is fixed may be additionally included.

The present invention provides an eco-friendly antibacterial fabric manufactured according to the above manufacturing method.

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

[Example]

23.4 parts by weight of BTCA and 18.8 parts by weight of hydantoin (imidazolidine-2,4-dione) were added to 100 parts by weight of water as a solvent, and 3 parts by weight of the mixed solution was added, and the cellulose fabric was mixed with the water containing the mixed solution. Tender-heat setting-water washing was performed, where the tender temperature was 100°C for 5 minutes and heat setting was performed at 180°C for 2 minutes. Afterwards, the tender-heat-set fabric was immersed in a 4% hypochlorous acid solution for 60 minutes to convert the hydantoin into N-halamine, and then the tender-heat-set-washing process was further performed, and padding and Heat setting was performed under the same conditions as tender-heat setting after immersion of the fabric in BTCA-hydantoin solution.

[Comparative example]

The same procedure as in Example 1 was carried out, except that after immersion in the hypochlorous acid solution, only water washing was performed without further tender-heat setting treatment.

[Experimental example]

For each final fabric manufactured in the above examples and comparative examples, Staphylococcus aureus (ATCC 6538, staphylococus aureus) and pneumoniae (ATCC 4352, klebsiella pneumoniae strain 2) 2 according to KS K 0693:2016 of the Korea Apparel Testing & Research Institute. Antibacterial properties against eggplant strains were measured. The test conditions used TWEEN80 (0.05%) as a nonionic surfactant, and machine washing was performed at a temperature of 40°C in accordance with KS K ISO 6330: 2011 and dried on a horizontal net. The measurement results are shown in Table 1.

division Example Comparative example Staphylococcus aureus initial bacterial count 2.3Х10 ⁴ 2.3Х10 ⁴ 18 hours later <20 0.99Х10 ³ Bacteria reduction rate (%) 99.9% 95.7% pneumoniae initial bacterial count 1.9Х10 ⁴ 1.9Х10 ⁴ 18 hours later <20 1.14Х10 ³ Bacteria reduction rate (%) 99.9% 99.4%

Figure 1 is a photograph showing the antibacterial test results of the above example.

As shown in Table 1, the example showed a bacterial reduction rate of 99.9% for both Staphylococcus aureus and pneumoniae, showing excellent antibacterial activity compared to the comparative example.

Claims (5)

A first step of preparing a mixed solution of water, cross-linking agent, and N-halamine precursor;
A second step of immersing the fabric in the mixed solution;
A third step of forming N-halamine on the surface of the fabric by tender-heat setting the immersed fabric;
A fourth step of immersing the fabric after the heat setting step in a chlorine solution;
A fifth step of tender-heat setting the fabric immersed in the chlorine solution;
A method of manufacturing a fabric with antibacterial properties, characterized in that it consists of. According to paragraph 1,
A method of manufacturing a fabric with antibacterial properties, wherein the crosslinking agent is at least one selected from BTCA (1,2,3,4-butanetetracarboxylic acid) and ethylene urea. According to paragraph 1,
A method of producing a fabric with antibacterial properties, characterized in that the N-halamine precursor is mixed in a molar ratio of 0.5 mole to 2 mole per mole of crosslinking agent. According to paragraph 1,
In both the third and fifth steps, the tender is performed at 90 to 120 ° C. for 5 to 10 minutes, and the heat setting is performed at 150 to 200 ° C. for 1 to 5 minutes. An eco-friendly antibacterial fabric manufactured according to any one of claims 1 to 4.