KR100430625B1 - Fiber product having excellent antibacterial properties and production thereof - Google Patents

Abstract

PURPOSE: A method of making a fiber product using acrylamido methyl chitosan as an antibacterial agent is provided. The product has excellent antibacterial properties and washing durability while maintaining the original texture of fiber. CONSTITUTION: The fiber product is prepared by padding a fiber product in an acid aqueous solution in which acrylamido methyl chitosan is dissolved, subsequently in an aqueous alkaline solution and then subjecting to a heat treatment. It is characterized in that the acrylamido methyl chitosan is grafted to the interior and surface thereof. The acrylamido methyl chitosan is obtained by reacting low molecular weight chitosan having a molecular weight of 500 to 2,000 and N-methylol acrylamide or ester compounds thereof under acidic conditions.

Description

Textile products with excellent antimicrobial properties and preparation method thereof

The present invention relates to a textile product excellent in antimicrobial properties and a method for producing the same. Microorganisms, such as bacteria and fungi, are widely distributed and reproduced in human living environments, some of which multiply in textile products and cause odors, or discolor, fade, or embrittle textile products. Microorganisms can also invade the body through fiber products and cause disease. Therefore, many studies have been conducted to give antimicrobial properties to textile products.

As prior arts for providing antimicrobial properties to textile products, Japanese Patent Laid-Open Nos. 57-51874 and 59-133235 disclose antimicrobial agents such as organosilicon quaternary ammonium salts, aromatic halogen compounds, or metal-containing inorganic antibiotics. The method of mixing or impregnating fiber cloth is disclosed.

However, this method has poor laundry durability because organosilicon quaternary ammonium salts, aromatic halogen compounds or metal-containing inorganic antibiotics are low molecular weight and do not directly bond with fibers. And some of these antimicrobial agents may be toxic to the human body and thus not suitable for use in clothing.

In addition, Japanese Patent Application Laid-Open No. 3-51369 discloses a method of using an animal polysaccharide kitting or chitosan as an antimicrobial agent by placing emphasis on the affinity between the antimicrobial agent and the human body. Specifically, high molecular weight chitosan may be mixed with synthetic resins such as polyurethane, polyacrylic acid, polymethacrylic acid, polyester or polyamino acid urethane copolymer having a film forming ability, and then imparted to a fiber product or directly reacted with a fiber. It is mixed with an isocyanate-containing polyurethane or epoxy modified polyester having a functional group to impart it to the textile product.

However, this method does not penetrate the inside of the fiber due to the use of high molecular weight chitosan, adheres only to the surface, so it is not excellent in washing durability, and also uses a synthetic resin to fix chitosan to the fiber. There is a problem that hurts.

The present invention uses acrylamido methyl chitosan, which is made of low molecular weight chitosan and can easily penetrate into the fiber, as an antimicrobial agent, and has excellent antibacterial and durable laundry properties, and maintains the natural texture of textile products. It is intended to provide a method of preparation thereof.

The present invention relates to an antimicrobial fiber product excellent in antimicrobial and laundry durability and maintaining a natural feel of the fiber, and a method of manufacturing the same.

Specifically, the present invention relates to a method for producing an antimicrobial fiber product using acrylamido methyl chitosan produced by reacting low molecular weight chitosan with N-methylol acrylamide or an ester compound thereof.

Textile products having excellent antimicrobial properties of the present invention is characterized in that acrylamido methyl chitosan is ion-grafted to the textile product. In addition, the production method of the present invention is a solution of acrylamido methyl chitosan prepared by reacting low molecular weight chitosan and N-methyl with acrylamide or an ester compound thereof under acidic conditions, and then dissolving at least 0.5% by weight in an acid aqueous solution. The textile products are padded, and these textile products are padded again with an aqueous alkali solution, followed by heat treatment.

The present invention will be described in more detail.

First, in order to produce low molecular weight chitosan, high molecular weight chitosan having a deacetalization degree of 30 to 100% is treated with sodium nitrite and low molecular weight. The low molecular weight chitosan used in the present invention has a molecular weight of 500 to 2,000.

Next, acrylamido methyl chitosan is produced by reacting the prepared low molecular weight chitosan with N-methylol acrylamide or its ester compound having a vinyl group and an N-methylol group under acidic conditions. In this case, the hydroxyl group of chitosan and the N-methylol group of N-methylol acrylamide or the hydroxyl group of chitosan and N-methoxy group of the ester compound of N-methylol acrylamide are bonded. The detailed reaction mechanism is as follows.

CH₂=CHCONHCH₂ ⁺+H₂O[Stage 1 Reaction] CH ₂ = CHCONHCH ₂ OH + H ⁺

CH ₂ = CHCONHCH ₂ ⁺ + H ₂ O

CH₂=CHCONHCH₂-O-키토산+H⁺ [2-Step Reaction] CH ₂ = CHCONHCH ₂ ⁺ + HO-chitosan

CH ₂ = CHCONHCH ₂ -O-chitosan + H ⁺

The ester compound of N-methylol acrylamide is N-methoxy methyl acrylamide or N-methoxy methyl methacrylamide.

Next, acrylamido methyl chitosan prepared by the method described above is dissolved in a dilute acid solution to prepare an antimicrobial solution. At this time, the content of acrylamido methyl chitosan in the antimicrobial solution is preferably 0.5% by weight or more. If the acrylamido methyl chitosan content is too low, the antimicrobial activity of the textile product is reduced.

Next, the fiber product is padded with the antimicrobial solution, and the padded fiber product is padded again with an aqueous alkali solution and subjected to heat treatment to ion graf the double bond of acrylamido methyl chitosan and the fiber product.

The fiber products used in the present invention are made of polyamide fibers such as nylon 6 and nylon 66, cellulose fibers such as cotton and rayon, or fibers in which these fibers and other fibers are mixed.

When the fiber product is padded in an acid solution containing acrylamido methyl chitosan, the coupling mechanism of the fiber and acrylamido methyl chitosan is as follows.

[For Cellulose Fiber Products]

[Step reaction] cellulose -OH + OH ^- → cellulose -O ^- + H ₂ O

[Step reaction] cellulose _{^{-O - + CH 2 = CHCONH CH}} 2 -O- chitosan

[For polyamide fiber products]

[First step ^{reaction] Nylon-COOH + OH - →} Nylon-COO - + H 2 O

[Step _{^{reaction] Nylon-COO - + CH 2}} = CHCONH CH 2 -O- chitosan

The antimicrobial fiber products of the present invention described above are excellent in antimicrobial and wash durability and maintain the natural feel of the fiber. Chitosan, an antimicrobial agent, is ion-grafted with the fibers on the surface and the inside of the fiber, so the durability of washing is excellent.

The reason why chitosan exhibits antimicrobial activity is not clear, but it is presumed that the free amino group of chitosan takes the form of quaternary ammonium salt in aqueous acid solution and its positive charge destroys the cells of negatively charged microorganisms. Therefore, the higher the degree of deacetylation of chitosan, the better the antimicrobial activity.

In addition, the antimicrobial fiber products of the present invention has excellent washing durability and the reason for maintaining the touch of the present application is that the acrylamido methyl chitosan used as an antimicrobial agent has a low molecular weight, which is advantageous for them to penetrate into the fiber, and they This is because the chemical bond can be directly with the fiber through.

The present invention is described in more detail through Examples and Comparative Examples.

However, the present invention is not limited only to the examples.

Example 1

A high molecular weight chitosan having a deacetalization degree of 70% is treated with sodium nitrite to produce a low molecular weight chitosan having a molecular weight of 600.

The prepared chitosan is reacted with N-methylol acrylamide under acidic conditions to prepare acrylamido methyl chitosan.

The prepared acrylamido methyl chitosan was dissolved in dilute acetic acid aqueous solution to prepare an antibacterial solution. At this time, the content of acrylamido methyl chitosan is 1% by weight.

Nylon taffeta fabric was padded in the prepared antibacterial solution under the condition that the pick-up ratio was 70%, and then dried at 100 ° C. for 2 minutes. These fabrics were padded again with an aqueous 12% sodium carbonate solution and then heat treated at 150 ° C. for 2 minutes, washed and dried to produce antimicrobial fiber products. The results of evaluating the antimicrobial, laundry durability and tactile change of the manufactured product are shown in Table 1.

Example 2

A high molecular weight chitosan having a deacetalization degree of 70% is treated with sodium nitrite to produce a low molecular weight chitosan having a molecular weight of 600.

The prepared chitosan is reacted with N-methoxy methyl acrylamide under acidic conditions to prepare acrylamido methyl chitosan.

The prepared acrylamido methyl chitosan was dissolved in dilute acetic acid aqueous solution to prepare an antibacterial solution. At this time, the content of acrylamido methyl chitosan is 1% by weight.

The cellulose fabric was padded in the prepared antibacterial solution under the condition that the pick-up ratio was 70%, and then dried at 100 ° C. for 2 minutes. These fabrics were padded again with an aqueous 12% sodium carbonate solution and then heat treated at 150 ° C. for 2 minutes, washed and dried to produce antimicrobial fiber products. The results of evaluating the antimicrobial, laundry durability and tactile change of the manufactured product are shown in Table 1.

Example 3

An antimicrobial fiber product was prepared in the same manner as in Example 1 except that the content of acrylamido methyl chitosan in the acetic acid aqueous solution was changed to 0.5% by weight.

The results of evaluating the antimicrobial, laundry durability and tactile change of the manufactured product are shown in Table 1.

Comparative Example 1

An antimicrobial fiber product is prepared by padding a nylon taffeta fabric in an antimicrobial solution consisting of 1% by weight of high molecular weight chitosan, 1% by weight of acetic acid, 10% by weight of water-soluble polyurethane resin, and 88% by weight of water. . The results of evaluating the antimicrobial, laundry durability and tactile change of the manufactured product are shown in Table 1.

Comparative Example 2

As an antimicrobial agent, Senitase 1977 (manufactured by Nippon Senitase Co., Ltd.) was dissolved in water at 3% by weight, and then padded with nylon taffeta fabric, followed by heat treatment at 150 ° C. for 1 minute to produce an antimicrobial fiber product. The results of evaluating the antimicrobial, laundry durability and tactile change of the manufactured product are shown in Table 1.

TABLE 1

Property evaluation result

Textile products of the present invention is excellent in antimicrobial properties and at the same time excellent washing durability and maintains the feel of the fiber as it is.

Claims (13)

An antimicrobial fiber product, wherein acrylamido methyl chitosan is ion-grafted on the inside and the surface of the fiber product. The antimicrobial fiber product according to claim 1, wherein acrylamido methyl chitosan is prepared by reacting low molecular weight chitosan with N-methylol acrylamide or an ester compound thereof under acidic conditions. The antimicrobial fiber product according to claim 2, wherein the ester compound of N-methylol acrylamide is N-methoxy methyl acrylamide or N-methoxy methyl methacrylamide. The antimicrobial fiber product according to claim 2, wherein the chitosan has a molecular weight of 500 to 2,000. The antimicrobial fiber product according to claim 1, wherein the fiber product is made of polyamide fiber, cellulose fiber or a fiber mixed with these fibers and other fibers. A method for producing an antimicrobial fiber product, characterized in that the acrylic product is padded with an aqueous acid solution in which methyl chitosan is dissolved and then heat-treated after being padded with an aqueous alkali solution. The method for producing an antimicrobial fiber product according to claim 6, wherein acrylamido methyl chitosan is dissolved in an aqueous solution of 0.5% by weight or more. The method for producing an antimicrobial fiber product according to claim 6, wherein the fiber product is made of polyamide fiber, cellulose fiber or a fiber mixed with these fibers and other fibers. The method for producing an antimicrobial fiber product according to claim 6, wherein acrylamido methyl chitosan is prepared by reacting chitosan of low molecular weight with N-methylol acrylamide or an ester compound thereof. The method for producing an antimicrobial fiber product according to claim 9, wherein the chitosan has a molecular weight of 500 to 2,000. The method for producing an antimicrobial fiber product according to claim 9, wherein the ester compound of N-methylol acrylamide is N-methoxy methyl acrylamide or N-methoxy methyl methacrylamide. 10. The method of claim 9, wherein the low molecular weight chitosan is prepared by treating high molecular weight chitosan with sodium nitrite. The method for producing an antimicrobial fiber product according to claim 9, wherein the N-methylol acrylamide or its ester compound has a vinyl group and an N-methylol group.