KR100331123B1 - Skin-core short fiber comprising chitosan and cellulose - Google Patents

Abstract

The present invention relates to a skin-core short fiber of chitosan and cellulose formed by uniformly coating chitosan on cellulose fibers so that the inner cellulose core layer and the outer chitosan skin layer are in close contact with each other. In the present invention, a skin-core short fiber composed of a conjugate of an outer chitosan skin layer and an inner cellulose core layer is prepared by applying chitosan to a cellulose fiber using a chitosan solution in which chitosan is dissolved in a solvent. The skin-core short fibers which maximize the function of the chitosan which exist in the surface of the are provided. Two-stage fiber can be applied as a raw material for medical coatings with antimicrobial, hemostatic, and biological tissue culture, and can be used as a raw material for clothing, sheet, and paper materials with biocompatibility, antibacterial, and anti-odor properties. It can be.

Description

Skin-core short fiber comprising chitosan and cellulose

The present invention provides a skin-core short fiber having two polymer components of cellulose and chitosan, which are formed by coating the cellulose fiber with chitosan on the whole surface and closely contacting the core layer. It is about.

Chitosan and cellulose are materials that can be obtained abundantly from nature and can be widely supplied as commodities. Chitosan is obtained by deacetylating chitin present in nature. Chitin is a natural substance present in the shells of crabs, shrimps, crayfish, cuttlefish, insects, etc., and is obtained from poly (N-acetyl-D-glucosamine), a natural polymer. Chitin is poorly soluble in water and most solvents, and it is difficult to obtain a solution for preparing fibers, films, and the like.

According to US Pat. No. 3,533,940, chitosan may be prepared from chitin, and chitosan may be dissolved in an organic acid aqueous solution such as acetic acid to form a solution capable of forming fibers, films, and the like.

Chitosan is known to be biotoxic because it is non-toxic and biodegradable, and has biological properties such as cell binding and biotissue culture, antimicrobial activity, hemostatic action, and biocompatibility.

Cellulose is a natural substance that can be widely obtained from natural plants and is obtained in the form of fibers such as cotton, hemp, and pulp. Cellulose is closely related to the daily life of human beings, and is indispensable for living a convenient human life such as clothes, paper, and wood, and is a representative textile material that can be used in various ways from the past to the present as well as the future.

Recently, as the unique properties of chitin and chitosan are known, efforts are being made to utilize them in human life. One way is to develop fibers and apply them to areas that come into contact with the skin and use them to show antibacterial and biocompatible functions.

U.S. Patent No. 4,029,727 explains that chitin can be dissolved in anhydrous organic solvent to produce relatively high strength fibers or films. Here, trichloroacetic acid or the like is used as an organic solvent, so that chitin is easily dissolved, but it is difficult to be widely used in consideration of environmental problems.

U.S. Patent No. 4,699,135 discloses chitin fibers by dissolving chitin in dimethylacetamide-like polar organic solvents containing lithium chloride, and also provides chitosan fibers obtained from chitosan solutions dissolved in an acetic acid solution.

U.S. Patent No. 5,897,821 discloses manufacturing a fiber by wet spinning a chitosan solution in which chitosan is dissolved in an aqueous sodium thiocyanate solution.

On the other hand, US Patent No. 5,900,479 discloses a method for producing an insoluble chitin film, filament and fibers using a chitosan solution in which chitosan is dissolved in an aqueous organic acid solution.

As described above, a lot of techniques related to chitin fiber or chitosan fiber manufactured by using chitin or chitosan as raw materials have been disclosed, and it is possible to make products having biological and hygienic properties using chitin fiber or chitosan fiber. It is open to the public.

Cellulose and chitosan are known to be structurally very similar as polysaccharide-based polymers and have been reported to have a significant affinity between these two polymers.

Noguchi et al. (Kobunshi Kagaku, 30, 320-326, 1973) prepared a composite fiber of cellulose and chitin in cellulose xanthate and chitin xanthate alkaline solution, and Hasegawa et al. (J. Appl. Polym. Sci., Vol. 45, 1837-1879, 1992) shows that cellulose and chitosan can be dissolved in trifluoroacetic acid to obtain a solution from which a brand film of cellulose and chitosan can be prepared.

According to Hirano (Biotechnol. Ann. Rev., Vol. 2, 237-258, 1996), chitosan-coated synthetic fiber as well as wetting, antimicrobial and anti-odor, as well as chitin and cellulose and chitin composite fibers It is known that the function appears.

U.S. Patent No. 5,114,788 suggests that cotton fabrics can be immersed in a synthetic resin solution containing chitosan to prepare absorbent fabrics.

In addition, US Pat. No. 5,306,550 shows that a biodegradable composite can be made by mixing an aqueous solution of cellulose fiber, chitosan, and a thermoplastic resin.

It can be seen that cellulose and chitosan have considerable affinity chemically and physically, for example, to produce blend fibers of cellulose and chitosan, to produce a composite of cellulose fiber and chitosan, or to coat a cotton fabric containing chitosan-containing resin. It is known to make one functional fabric.

As described above, it is known that clothes, fabrics, sheets, and fibers containing chitosan may exhibit biological and hygiene functions similar to those of chitosan. To this end, it has been suggested to manufacture and use materials such as chitosan fibers, cellulose-chitosan blend fibers, cellulose fiber-chitosan composites, and fabrics coated with resin containing chitosan.

However, all of them suggest a product coated with chitosan partially on the surface of the fiber and a method of manufacturing the same, but fail to provide a conjugate fiber in which the entire surface of the fiber is completely covered with chitosan.

The present invention provides a skin-core short fiber composed of two high molecular materials of cellulose and chitosan by utilizing sufficient affinity between cellulose and chitosan, the inside of which consists of a cellulose core layer and the outside of a chitosan skin layer. This is because skin-core short fibers, in which cellulose and chitosan form a conjugate, can be obtained by imparting full coverage to the cellulose surface by using cellulose fibers and sufficient adhesion by condition selection.

The present invention relates to a skin-core short fiber composed of chitosan and cellulose, which is composed of two polymer materials, cellulose and chitosan, an cellulose core layer is formed inside, and a chitosan skin layer is formed outside. According to the present invention, a cellulose fiber constituting the inner core layer is subjected to an affinity treatment, and the chitosan solution is immersed and uniformly applied, followed by solidification and drying, to which the cellulose of the inner core layer and the chitosan of the outer skin layer are closely adhered to each other. It is to provide a short fiber.

The present invention provides a skin-core short fiber composed of two polymer materials, cellulose and chitosan, wherein the inner core layer is composed of cellulose and the outer skin layer is composed of chitosan. The skin-core short fibers of the present invention form a skin-core structure consisting purely of these two materials without intervening a third material between cellulose and chitosan, which could not be achieved in the prior art, and the inner cellulose core layer and the outer Full coverage resulting from satisfactory affinity between the chitosan skin layers and sufficient adhesion by selection of optimum conditions are shown.

In the present invention, by applying a pure chitosan solution to the pure cellulose fibers to give sufficient adhesion between the cellulose and chitosan and to maintain the form of the cellulose fibers, the inner core layer of the fiber is occupied by cellulose and the outer skin layer is a chitosan to a certain thickness By presenting skin-core short fibers, which contain relatively very small amounts of chitosan, can exhibit the same function as pure chitosan fibers and have the same physical properties as cellulose fibers.

As such, the present invention proposes an advanced technology for providing a functional skin-core short fiber made by a new type of material composition which has never been produced and composed of two components, chitosan and cellulose.

Figure 1 is a simplified schematic cross-sectional view of the skin-core short fibers of the present invention, in which one part shows an inner core layer made of cellulose and two parts shows an outer skin layer made of chitosan.

FIG. 2 is an electron microscope photograph of the surface of the skin-core short fibers of the present invention composed of 17 wt% chitosan and 83 wt% cellulose by weight, showing that the cellulose fiber is completely covered with chitosan.

Figure 3 is an electron microscope photograph of the cross-section of the present invention skin-core short fibers composed of 17 wt% chitosan and 83 wt% cellulose by weight ratio. The cellulose core layer inside and the chitosan skin layer outside are firmly adhered to the skin- It shows that it forms a core structure.

Figure 4 is a photograph of observing the remaining chitosan skin layer by electron microscopy by removing the inner cellulose core layer from the skin-core short fibers of the present invention composed of 17 wt% chitosan and 83 wt% cellulose by weight ratio. It is shown.

The present invention is affinity treatment of the cellulose fibers constituting the inner core layer, it is constantly immersed and applied to the chitosan solution between 0 ℃ to 60 ℃ for 1 minute to 1 day, and then solidified and dried To form an outer skin layer and provide a skin-core fiber in which the inner core layer is made of cellulose and the outer skin layer is made of chitosan.

The skin-core short fibers of the present invention have a thickness of between 5 μm and 100 μm, between 1 mm and 100 mm in length, between 4 μm and 80 μm in thickness of the inner cellulose core layer, and between 0.1 μm and in thickness of the outer chitosan skin layer. 1, wherein a skin-core structure is formed between 20 μm, cellulose is present in a weight ratio of 40 wt% to 99 wt%, chitosan is present in an amount of 1 wt% to 60 wt%, and moisture and residues are present in an amount of 0.1 wt% to 12 wt%. Likewise, it has a skin-core conjugate structure.

Cellulose fibers used in the present invention has a water content of 10wt% or less, containing at least 90% or more of cellulose, having a thickness of between 4 μm and 80 μm and a length of between 1 mm and 100 mm, and seed fiber, stem fiber, and leaf which are natural products. Fibers and root fibers such as cotton fibers, hemp fibers, pulp, sisal, abaca, kapok, flex, jute, ramie, hamp, kenab, coil, sacchaton and other regenerated fibers viscose rayon, dongammonium rayon, polynosic rayon , Lyocells, tencels, cellulose acetates, cellulose triacetates and the like are useful.

The chitosan solution used in the present invention is prepared by dissolving chitosan in a solvent at a concentration of 0.1wt% to 15wt% by weight. As chitosan, it is useful that the polymerization degree is between 20 and 10,000 and the deacetylation degree is between 60% and 99%, and more preferably, the polymerization degree is between 100 and 5,000 and the deacetylation degree is between 70% and 95%. . As the solvent, one selected from an acid aqueous solution, an inorganic salt aqueous solution and an organic solvent is used.

As the acid aqueous solution, an aqueous solution in which acid is dissolved in water at a concentration ratio of 0.1wt% to 20wt% is used, and as acid, acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propinic acid, succinic acid, fish acid, succinic acid, as One or more selected from organic acids such as colic acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid, toluenesulfonic acid, and one or more selected from inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid may be used.

As the inorganic salt aqueous solution, an aqueous solution in which inorganic metal salts are dissolved in water at a concentration ratio of 10wt% to 70wt% is used.Inorganic metal salts include inorganic metal salts such as sodium thiocyanate, zinc chloride, calcium chloride, sodium chloride, potassium chloride and lithium chloride. Any one or more of these may be used.

As the organic solvent, one or more selected from polar organic solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylformamide, diethylacetamide, trifluoroacetic acid, trichloroacetic acid, methylene chloride, and ethane tetrachloride are used. One or more of the above inorganic metal salts may be optionally added to the above organic solvent in a concentration ratio of 1 wt% to 10 wt% to increase the polarity.

Skin-core short fibers of the present invention is prepared by affinity treatment of cellulose fibers and then uniformly applying it with chitosan solution, followed by solidification and drying. The cellulose fiber is preferably affinity treated with an aqueous solution to improve the affinity so that chitosan can be applied to the cellulose fiber entirely, and to increase the adhesion between the cellulose and the chitosan to be firmly adhered to each other. As the aqueous solution, a basic aqueous solution, an acidic aqueous solution and a saline solution may be used. As the base aqueous solution, a base obtained by dissolving at least one selected from alkali metal oxides such as sodium hydroxide, potassium hydroxide, potassium hydroxide, lithium hydroxide, calcium oxide, barium hydroxide and barium oxide in a weight ratio of 1wt% to 40wt% in water An aqueous solution is used, and as the acid aqueous solution, one or more randomly selected among organic acids such as acetic acid, lactic acid, formic acid, glycolic acid, acetic acid, succinic acid, propinic acid, acrylic acid, succinic acid, glutic acid, tartaric acid, maleic acid, citric acid, glutamic acid, and acrylic acid Acid aqueous solution dissolved in water at a concentration between 0.1wt% and 20wt% is used.As a saline solution, an organic metal salt such as sodium acetate, sodium lactate, potassium acetate, potassium lactate, sodium glycolate, potassium glycolate or sodium ethoxylate Alcohol metal salts such as side, or sodium chloride, lithium chloride, calcium chloride, calcium chloride, zinc chloride, sodium thiocyanate A saline solution in which at least one arbitrarily selected inorganic mineral salt such as hydrate is dissolved in water at a concentration between 1 wt% and 50 wt% is used.

The affinity treatment is immersed in the aqueous solution of cellulose fibers and treated for 1 minute to 10 days at a temperature between 0 ℃ and 90 ℃, then dehydrated and conditioned at room temperature.

As a method of applying the chitosan solution to the cellulose fiber, the cellulose fiber is immersed in the chitosan solution for a certain time, and when completely wet, the excess chitosan solution is removed or the chitosan solution is uniformly sprayed on the surface of the cellulose fiber to cover the entire surface with the chitosan solution. It is useful to have As a method of fixing the chitosan applied to the cellulose fibers on which the chitosan solution has been applied to the fiber surface, heat treatment is performed at a temperature between 60 ° C. and 160 ° C. for 1 minute to 1000 minutes or between 0 ° C. and 80 ° C. with alkaline aqueous solution. It is useful to solidify for a time between 1 minute and 1 day at temperature, which can be treated in parallel. At this time, the alkaline solution is an alkaline aqueous solution in which at least one selected from alkali metal oxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, lithium hydroxide, calcium oxide, barium oxide, barium hydroxide, and the like is dissolved in water at a weight ratio of 1wt% to 20wt%. It is used, it is preferable to add alcohols at a concentration between 0.1wt% and 10wt% in weight ratio in order to enhance the effect more. As alcohols, one or more randomly selected from methanol, ethanol, propanol, butanol, phenol and the like is used. In addition, when solidifying with alkaline aqueous solution, it is necessary to dry after washing with water.

The skin-core short fibers of the present invention form a structure as shown in Fig. 1, which is composed of an inner core layer and an outer skin layer, and the core layer is filled with cellulose and the skin layer is filled with chitosan. It is a revolutionary new textile material that shows the harmony of functionality and the human-friendly properties and the human compatibility of natural materials at the same time.

Skin-core short fibers composed of chitosan and cellulose of the present invention is between 5 μm and 100 μm in thickness and between 1 mm and 100 mm in length, and the inner core layer consists of cellulose having a degree of polymerization between 100 and 20000 and has a thickness of 4 The outer skin layer is composed of chitosan having a polymerization degree of 20 to 10,000 and a deacetylation degree of 50% to 99%, and a thickness of 0.1 μm to 20 μm, and a weight ratio of 40 wt% to cellulose. A skin-core is formed by forming an external chitosan skin layer and an internal cellulose core layer having a composition between 99 wt% and a composition between 1 wt% and 60 wt% of chitosan, and remaining between 0.1 wt% and 12 wt% of moisture and residues. It is a new short fiber having a structure.

In the present invention, it is required to make a pure chitosan solution and to mature it for 1 hour to 10 days between 0 ° C and 50 ° C so that the chitosan can be evenly applied to the cellulose fiber, and also water the chitosan forming the skin layer. Heat treatment for a time between 1 minute and 1,000 minutes at a temperature between 90 ° C. and 160 ° C. to stabilize it insoluble in water, or 1 minute at a temperature between 0 ° C. and 80 ° C. with an alkaline aqueous solution at a concentration between 1 wt% and 20 wt%. It is necessary to chemically process for a time between 1 day and 1 day.

In the present invention, by aging the chitosan solution to form a skin layer consisting of pure chitosan on the cellulose fiber to improve the adhesion to cellulose and the uniformity of the solution, by securing the uniformity and adhesion of the solution to the chitosan during dipping or coating A breakthrough result is obtained which is evenly coated on the entire surface of this cellulose fiber.

In the prior art, chitosan cannot be entirely coated on the fiber surface, but only the chitosan coating technology partially coated on the fiber surface is proposed. In addition, in order to give durability to the chitosan coated on the fiber surface in the prior art it was merely to increase the adhesion by using a binder, a crosslinking agent and the like.

In the present invention, it is characterized by imparting stability to chitosan itself through heat treatment or chemical treatment.

Skin-core short fibers composed of chitosan and cellulose of the present invention has been found that only the cellulose fibers can be uniformly coated on the entire surface of the fiber in the process of coating the chitosan on the surface of various fibers. It is obtained by applying to.

As shown in Figure 2, the surface of the cellulose fiber is so completely covered with chitosan, and Figure 3 shows that the inner core layer is cellulose and the outer skin layer is a fiber having a skin-core structure consisting of chitosan.

According to the X-ray diffraction diagram of FIG. 4, it can be confirmed that the skin-core short fibers of the present invention show both the diffraction peak and the orientation of the cellulose crystal and the diffraction peak of the chitosan crystal.

Hereinafter, embodiments of the present invention will be described in more detail a part of the present invention, but the content of the present invention is not limited thereto.

Example 1

Affinity Treatment of Cellulose Fibers

1 kg of cotton fiber, distributed between 10 μm and 30 μm in thickness and between 40 mm and 80 mm in length, is first immersed in a 20 wt% aqueous solution of caustic soda and completely wet and compressed to remove the remaining aqueous solution of caustic soda for 1 day at room temperature. After aging, 3 wt% acetic acid solution was treated for 3 hours at a temperature of 20 ° C., and then dehydrated to give an affinity treatment. The treated cellulose fiber improved the coating property and adhesion so that the chitosan could be completely covered.

Chitosan Solution Preparation

A solution of 1 wt% chitosan dissolved in 1 wt% acetic acid solution was dissolved in 100 g of chitosan with a viscosity of 102 cps and a deacetylation degree of 94% in 1.9 L of 5 wt% acetic acid solution, which was then stored for 48 hours at a temperature of 5 ° C. Mature. 3 L of water is added thereto to dissolve completely to prepare a chitosan solution.

Preparation of Skin-Core Short Fibers

5 kg of chitosan solution was immersed in 1 kg of affinity-treated cotton fibers, and the surface was completely coated with chitosan solution and maintained for 1 hour. Then, the excess chitosan solution was compressed and removed and conditioned at room temperature for 3 hours. The conditioned chitosan coated cotton fibers are placed in a dryer and partially dried at a temperature of 60 ° C. for 30 minutes. The partially dried fibers form a skin-core structure that is uniformly coated with chitosan and that consists of cellulose inside. This was placed in a hot air dryer and stabilized by heat treatment at a temperature of 150 ° C. for 2 hours to prepare a skin-core short fiber.

Stabilization chemical treatment

Take 1 kg of the partially dried chitosan-coated cotton fiber, immerse it in 5 l of 5wt% caustic soda solution, chemically treat it at 20 ℃ for 1 hour, and wash it with water until it is neutral with hot water and cold water to wash the chitosan skin layer. Stabilize. In the prepared skin-core short fibers, the inner core layer is composed of cellulose, the outer skin layer is composed of chitosan, the thickness of the chitosan skin layer is evenly distributed between 0.5 μm and 4 μm, and the inner cellulose core layer is completely covered with chitosan. It is covered.

Examples 2-4

(Change of affinity treatment conditions)

1 kg of cotton fiber is first immersed in a 20 wt% aqueous solution of caustic soda, completely wet and compressed to remove residual aqueous solution of sodium hydroxide, aged at room temperature for 1 day, and then washed with water to coat chitosan. Or 3wt% acetic acid solution was treated for 3 hours at a temperature of 20 ℃ and then dehydrated to coat the chitosan. Alternatively, the caustic soda solution treatment and the acetic acid solution treatment are sequentially processed, and then chitosan is coated. To coat chitosan, chitosan solution was prepared by dissolving chitosan having a viscosity of 102 cps and a deacetylation degree of 94.8% to 2 wt% in a 2 wt% acetic acid solution to prepare a chitosan solution, and then applying these solutions to the affinity-treated cellulose fibers. The excess chitosan solution present between the cellulose fibers is then removed and treated by alkaline aqueous solution to stabilize it. The chitosan-cellulose short fibers thus obtained are dried at a temperature of 60 ° C. for 3 hours after washing to obtain the final skin-core short fibers. 1 kg of cotton fiber, distributed between 10 μm and 30 μm in thickness and between 40 mm and 80 mm in length, is first immersed in a 20 wt% aqueous solution of caustic soda and completely wet and compressed to remove the remaining aqueous solution of caustic soda for 1 day at room temperature. After aging, 3 wt% acetic acid solution was treated for 3 hours at a temperature of 20 ° C., and then dehydrated to give an affinity treatment. The treated cellulose fiber improved the coating property and adhesion so that the chitosan could be completely covered.

Example 2 3 4 Affinity Treatment Method Caustic Soda Solution Acetic acid aqueous solution treatment Caustic Soda Solution and Acetic Acid Solution Chitosan cover state Full surface cloth Full surface cloth Full surface cloth

Examples 5-11

(Changing concentration of chitosan solution)

A chitosan solution was prepared by dissolving chitosan having a viscosity of 9.9 cps and a deacetylation degree of 94.8% in a 3wt% aqueous acetic acid solution to 0.5wt%, 1wt%, 2wt%, 3wt%, 5wt%, 7wt%, 9wt%, respectively. Each of these solutions is then applied to affinity-treated cotton fibers, and then the excess chitosan solution existing between the cotton fibers is removed and treated by alkaline aqueous solution to stabilize. The chitosan-cellulose short fibers thus obtained are dried at a temperature of 60 ° C. for 3 hours after washing to obtain the final skin-core short fibers. When the chitosan solution having a concentration of 1wt% to 5wt% in the chitosan solution is used, a more uniform thickness and a more firm skin-core structure are formed.

Example 5 6 7 8 9 10 11 Chitosan solution concentration (wt%) 0.5 One 2 3 5 7 9 Chitosan Skin Thickness (㎛) 0.3-2 0.5-3 0.5-3 0.5-5 0.5-5 1-7 1-7

Examples 12-19

(Concentration change of the solidified caustic soda solution)

A chitosan solution was prepared by dissolving chitosan having a viscosity of 102 cps and a deacetylation degree of 94% to 2 wt% in a 2 wt% aqueous acetic acid solution, and then applying the solution to an affinity-treated cotton fiber, and then excess chitosan present between the cotton fibers. The solution was removed and immersed in an aqueous solution of caustic soda at 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 7.5 wt% and 10 wt%, respectively, and treated at 20 ° C. for 1 hour, followed by hot water. Wash with cold water until neutral to stabilize the chitosan skin layer. The chitosan-cellulose short fibers thus obtained are dried for 3 hours at a temperature of 60 ° C. after washing with water to prepare the final skin-core short fibers.

Example 12 13 14 15 16 17 18 19 Caustic Soda Concentration (wt%) 0.5 One 2 3 4 5 7.5 10 Adhesion Excellent Robustness Robustness Robustness Robustness Robustness Excellent Excellent

The short fiber composed of chitosan and cellulose of the present invention and having a skin-core structure can be used as a raw material of yarn and is a novel fiber material showing antibacterial and deodorizing functionality when applied to clothing, and is applied to yarns, nonwoven fabrics, and cotton. This is possible, and can be used as a raw material for various clothes, sheets, and paper materials having functionalities such as antimicrobial activity, hemostatic action, and living tissue culture. Skin-core short fibers of the present invention can be mixed with cotton, wool, polyester staples, nylon staples, acrylic staples and the like, can be produced as a spun yarn, can be used in the production of a functional nonwoven fabric is added to the nonwoven fabric manufacturing process.

Skin-core short fibers of the present invention has a small amount of chitosan because the outer skin layer is composed of chitosan and the inner core layer is formed of cellulose skin-core structure so that the functional polymer chitosan appears on the entire surface of the short fiber. It can be used as a new material that can maximize its function. In addition, the short fiber of the present invention is a conjugate of the cellulose of the core layer and the chitosan of the skin layer can be used as a versatile fiber material in which the physical properties of the cellulose and the chemical functionality of the chitosan are mutually harmonized and have sufficient fiber structure and functionality. It can be used as a material of various properties having workability, flexibility, toughness and durability.

Claims (7)

The inside of the fiber forms a core layer composed of cellulose fibers, and the outside of the fiber forms a skin layer composed of chitosan, which is in close contact with each other, and the cellulose of the inner core layer is uniformly covered by the chitosan of the outer skin layer. Skin-core structured short fibers in which chitosan and cellulose are composed of a skin layer and a core layer, respectively, having a thickness of between 5 μm and 100 μm and a length of short fiber between 1 mm and 100 mm, and a thickness of the cellulose core layer Is between 4 μm and 80 μm, the thickness of the chitosan skin layer is between 0.1 μm and 20 μm, the composition of the short fibers is between 40 wt% and 99 wt% of cellulose in weight ratio, and between 1 wt% and 60 wt% of chitosan, and moisture. And skin-core short fibers of chitosan and cellulose containing residues between 0.1 wt% and 12 wt%. The method according to claim 1, wherein the cellulose fiber is composed of a cellulose polymer having a degree of polymerization of 100 to 20,000, containing at least 90 wt% or more of cellulose, 10 wt% or less of water content, and having a thickness of 4 μm to 80 μm and a length of 1 mm to 100 mm. Cotton fiber, hemp fiber, wood pulp, sisal, abaca, kapok, flex, jute, ramie, hamp, kenab, coil, sacchaton, etc. And skin-core short fibers characterized in that at least one selected from among fibers such as viscose rayon, copper ammonium rayon, polynosic rayon, cellulose acetate, cellulose triacetate, etc. The method according to claim 1, wherein the chitosan has a degree of polymerization of 20 to 10,000, a deacetylation degree of 50% to 99%, more preferably between 100 to 5000 degree of polymerization and a degree of deacetylation of 70% to 95%. Skin-core short fibers After the affinity treatment of the cellulose fibers, the chitosan solution was immersed and applied uniformly for 1 minute to 1 day at a temperature between 0 ° C. and 60 ° C., and then solidified to form a skin layer and dried. Method for producing a skin-core short fiber composed of a skin and the outer skin layer is composed of chitosan The method according to claim 4, wherein the affinity treatment is obtained by dissolving a base aqueous solution, an organic acid or an inorganic acid in which alkali metal hydroxide is dissolved in water at a concentration between 1 wt% and 40 wt% in water at a concentration between 0.1 wt% and 20 wt% by weight. At least one of an acid aqueous solution and a salt solution in which an organometallic salt or an inorganic metal salt is dissolved in water at a weight ratio of 1 wt% to 50 wt% is optionally selected for a time period of 1 minute to 10 days at a temperature of 0 ° C. to 90 ° C. Method for producing a skin-core short fibers, characterized in that the treatment The acid solution of claim 4 wherein the chitosan solution is dissolved in an organic acid or an inorganic acid at a concentration ratio of 0.1 wt% to 20 wt%, an inorganic salt solution in which an inorganic metal salt is dissolved at a concentration of 10 wt% to 70 wt%, and an organic solvent. Skin-core short fibers, characterized in that dogs are randomly selected and dissolved chitosan at a concentration between 0.1 wt% and 15 wt%, more preferably at a concentration between 1 wt% and 10 wt% by weight. Manufacturing Method The method of claim 4, wherein the solidification treatment is performed by chemically treating the alkali metal hydroxide in water at a concentration ratio of 1 wt% to 20 wt% in water at a temperature between 0 ° C. and 80 ° C. for 1 minute to 1 day. Or heat-treating for a time between 1 minute and 1,000 minutes at a temperature between 60 ° C. and 160 ° C. or treating them in parallel.