JPH0241473A - Antimicrobial yarn using chitosan compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain a safe antimicrobial yarn free from evolution of toxic substance resulting from bleaching, heating, etc., by crosslinking the surface of yarn with chitin, chitosan or a derivative compound thereof and bonding. CONSTITUTION:Chitin, chitosan and a derivative compound thereof (e.g., chitosan acetate) are dissolved in an aqueous solution, yarn containing at least one functional group of hydroxyl group, amino group and carboxyl group and the yarn is dried. The yarn after drying is immersed in an organic solvent and reacted with a polyisocyanate compound such as compound shown by formula I or formula II to give antimicrobial yarn having surface of yarn crosslinked with chitin, chitosan and the derivative compound thereof and bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to fibers that exhibit antibacterial and deodorizing effects by crosslinking chitin, chitosan, and their derivative compounds on the fiber surface.

(Conventional technology) Antibacterial and
The use of fibers that exhibit deodorizing properties (antibacterial fibers) has attracted attention, and the manufacturing method involves using aromatic halogen-based, silicone-based quaternary ammonium salts, or organic nitrogen compounds as antibacterial compounds, and physically adsorbing these onto the fiber surface. Or, by a method of mixing it into a polymer and spinning it.

However, with these antibacterial compounds and manufacturing methods, since the bond between the antibacterial compound and the fiber is unstable, the compound tends to denature when subjected to bleaching, heating, UV irradiation, etc., and may even be harmful to the human body or the natural environment. There is a risk of generating substances. For example, it has been pointed out that products using the aromatic halogen triclosan generate a trace amount of dioxin, a toxic substance, when heated to 400 degrees or irradiated with ultraviolet light for 20 hours.

(Problems to be solved by the invention) Therefore, as a result of extensive research in an attempt to eliminate the above-mentioned drawbacks, the present inventors focused on the antibacterial effects of chitin and chitosan, which are collected from nature. By bonding through a strong cross-linking reaction to prevent denaturation over time,
We have succeeded in obtaining stable fibers that are free from toxicity.

(Means for solving the problem) The antibacterial fiber of the present invention uses chitin, chitosan, and its derivative compounds as an antibacterial compound, and uses fibers having at least one functional group among hydroxyl group, amino group, and carboxyl group, It is characterized by crosslinking both with a polyurethane compound.

In addition, the manufacturing method involves dissolving chitin, chitosan, and their derivative compounds in an aqueous solution, and then immersing a fiber having at least one functional group among a hydroxyl group, an amino group, and a carboxyl group in the aqueous VA liquid. Next, the fibers after soaking are dried.

Furthermore, the method is characterized in that the dried fibers are soaked in an organic solvent and then a polyisocyanate compound is administered to cause a crosslinking reaction under certain conditions.

(Actions and Effects) Chitin, chitosan, and their derivative compounds (hereinafter simply referred to as chitosan compounds) are made into powder and dissolved in an aqueous solution, and when cloth, hemp, rayon, nylon, wool, silk, etc. are immersed in this, chitosan compounds are produced. is physically adsorbed on the surface of the fiber.

Next, when the fibers are strongly dried by vacuum drying or the like, the adhering water evaporates, and this serves to prevent the water and the polyisocyanate compound from causing a violent reaction and interfering with the subsequent crosslinking reaction.

Then, when the dried fibers are placed in a container and a polyisocyanate compound is administered, chitosan compounds have hydroxyl groups and amino groups in their six-membered rings, while natural fibers such as cotton, linen, and rayon have hydroxyl groups. Nylon fibers have amino groups, and wool and silk have carboxyl and amino groups, so the strong activity of both functional groups induces a crosslinking reaction with the polyisocyanate compound described below, which strongly bonds the antibacterial compound to the fibers. Work like you do.

Ce1l-OH+C0R-NCO→ C0R-NHCO
-CelChitosan-OH+C0R-NCO→C
OR-Former IC0-ChitosanChitosan-
NH2+ C0R-NCO→Chitosan-Nl
(CONH-Cot? (cell: cellulose, COR-: isocyanate compound, Chitosan-: chitosan derivative) At this time,
When the N H2 group in the chitosan compound is used as chitosan acetate, the CHC00 group increases the reactivity of the other OH groups and CHOH groups bonded to the six-membered ring in glucosamine, and as it is, it does not interact with the NCO group. Although the reaction tends to be concentrated and deflected only on the N 2 H group, it works to disperse the reaction also on the functional groups of the pond and make the bonding uniform. Furthermore, chitin and chitosan normally have weak antibacterial effects, but when oligomers are used to make chitosan oligosaccharides, they can exhibit strong antibacterial effects.

After the reaction is completed, washing with water converts the remaining NCO groups into NHCO
It can be made harmless by converting it into a base.

When the chitosan compound crosslinks on the fiber surface and strong bonds are formed, the bonds remain strong even when the fibers are stimulated by bleaching, heating, ultraviolet rays, etc., so there is no risk of generating toxic substances. It disappears.

The chitosan compound thus formed on the fiber surface is thought to exhibit antibacterial and deodorizing effects based on the following theory.

First, the amino group in glucosamine, which is a constituent unit of chitosan, forms an ammonium salt by forming a salt with acetic acid, and the NHL group is exposed. This NH; group is
It exerts a so-called non-eluting antibacterial effect against bacteria, physically destroying the cell wall and stopping the respiratory function without penetrating into the cells. Since bacteria are killed by this mechanism, the antibacterial properties increase as the number of opportunities for the NH group to come into contact with bacteria increases.

(Effects of the Invention) Based on the above configuration, the present invention can firmly bond a chitosan compound to fibers using a polyisocyanate compound, and does not generate toxic substances due to bleaching, heating, ultraviolet irradiation, etc. Safe antibacterial fibers can be obtained. Therefore,
The fibers can be widely used in socks, shoe insoles, tabi socks, pantoate white fabric, underwear, sportswear, working wear, bedding, filters, etc.

Example 1 First, a 1% chitosan acetate solution was prepared in an aqueous solution of 5% acetic acid, and 15 scouring and bleached 30/2s cotton threads were added in the solution.
Soak the g, pull it out, and use a dehydrator to reduce the reduction rate to 200%.
dehydrated to. Thereafter, this yarn was vacuum dried for 2 hours in a vacuum dryer at 60°C.

Next, using a 400cc stainless steel high-pressure container, Kito o w f was added to benzene at a bath ratio of 1:30.
Add 0.2゜wf of triethylenediamine as a catalyst,
It was sealed in a high-pressure container. Thereafter, a crosslinking reaction was carried out in polyethylene glycol at 100° C. for 5 hours while rotating the high-pressure container. After the reaction is complete, take out the cotton thread and
It was thoroughly washed with benzene, acetone, and ethyl alcohol in that order, and finally with water, and then air-dried.

The sample obtained by the crosslinking reaction between chitosan acetate and cotton thread was mixed with 1/300 mol of sodium hydrogen phosphate as a buffer solution.
Antibacterial activity was tested using the shake flask method, and the number of viable bacteria was determined.

The microorganism used at that time was 5taph, a gram-positive bacterium.
yloccus aureus
, Bacillus 5ubtilis,
and the gram-negative bacterium Escherichbia co.
There are three types of lt (E. coli).

The results are shown in FIG. 11, FIG. 2, and FIG. 3.

Fig. 1 Fig. 2 Fig. 3 has flagella and flagella, so it has good contact with chitosan acetate which is not so swollen, whereas Staphylococcus aureus and Bacillus subtilis have flagella and flagella. Although the chitosan acetate is relatively small at 2μ, when treated with a crosslinking agent, the chitosan acetate crosslinks and swells, which makes contact with bacteria advantageous and is thought to enhance the antibacterial effect.

・〉：〜゛Samples that were cross-linked after treatment with chitosan acetate showed almost the same antibacterial properties, whereas samples that were cross-linked after treatment with chitosan acetate showed almost the same antibacterial properties. The antibacterial properties of the sample were greatly increased.

Claims (1)

[Scope of Claims] 1) An antibacterial agent characterized in that chitin, chitosan, and its derivative compounds are crosslinked with a fiber having at least one functional group among hydroxyl, amino, and carboxyl groups using a polyisocyanate compound. fiber. 2) The antibacterial fiber according to claim 1, wherein the polyurethane compound is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or NCO(CH2)6NCO. 3) After dissolving chitin, chitosan, and their derivative compounds in an aqueous solution, a fiber having at least one functional group among a hydroxyl group, an amino group, and a carboxyl group is immersed in the aqueous solution, and then the fiber is dried. , furthermore,
An antibacterial fiber and a method for producing the same, characterized in that the dried fiber is soaked in an organic solvent, and then a polyisocyanate compound is administered to cause a crosslinking reaction under certain conditions. 4) The antibacterial fiber and method for producing the same according to claim 3, wherein the chitosan derivative compound is chitosan acetate.