KR20010067991A - Functional fiber containing chitosan powder - Google Patents

Abstract

PURPOSE: A process for preparing the titled fiber excellent in antibacterial property and deodorizing property by mixing chitosan with polymer chips and spinning is provided, thereby producing a functional fiber exhibiting a function similar to that of a pure chitosan fiber while containing a relatively low amount of chitosan and permanently maintaining functionality of chitosan. CONSTITUTION: This functional fiber comprises 0.1 to 10% by weight of chitosan powder and 0 to 10% by weight of a dispersing agent, an emulsifier, a heat stabilizer, a dulling agent and residues based on the total weight of the fiber composition. The main material of the fiber is a homopolymer selected from the group consisting of ester, amide, acryl, vinylalcohol, propylene, saccharide, protein and caprolacton, copolymers thereof, mixtures thereof or a blended composition. The fiber takes a shape of a staple fiber having a filament thickness of 0.75 to 5 denier and a length of 1 to 100mm.

Description

Functional fiber containing chitosan powder

Chitosan is a substance that can be obtained abundantly from nature and can be widely supplied as a commodity. Chitosan is obtained by deacetylating chitin that exists in nature, and chitin is a natural substance and natural polymer poly (N-acetyl-D-glucosamine) that is present in the shells of crabs, shrimps, crayfish, cuttlefish and insects. Obtained. 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 can be prepared from chitin, and chitosan can 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.

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

U.S. Patent No. 4,029,727 explains that chitin can be dissolved in an organic solvent to produce a relatively high strength fiber or film. 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 polar organic solvents such as dimethylacetamide containing lithium chloride, and also provides chitosan fibers obtained from chitosan solutions dissolved in acetic acid aqueous 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.

However, most of them are wet using chitosan, which has high manufacturing cost and low physical properties, and thus cannot be widely used for chitosan functionality. Chitosan obtained by adding chitosan powder to the fiber manufacturing process using polymers The fiber containing is absent.

The present invention provides a fiber containing chitosan in which the antimicrobial, biocompatibility, and functionality of chitosan is continuously imposed. The fiber containing chitosan of the present invention has a small amount of chitosan because the fine chitosan powder, which could not be achieved by the conventional technique, is uniformly dispersed in the inside and the outside of the fiber to show satisfactory affinity with the polymer. Its physical properties are similar to pure chitosan fibers, while providing physical fibers that maintain the physical properties of the polymers forming the fibers.

As such, the present invention provides an advanced technique for providing fibers containing novel functional chitosan made by a new type of material composition that has never been produced.

Figure 1 is a photograph of the cross section of the functional fiber containing chitosan of the present invention by electron microscopy shows that chitosan particles having a particle diameter of 2㎛ are in close contact with nylon 6 and present inside the fiber.

Figure 2 shows the side surface of the functional fiber containing chitosan of the present invention at a magnification of 3000 times using an electron microscope, showing that the chitosan particles are sufficiently present on the surface of the fiber.

3 is a cross-sectional view of the functional fiber containing chitosan of the present invention at an magnification of 6000 times using an electron microscope, showing that chitosan particles are evenly present inside and outside the fiber.

The present invention is an antimicrobial, human-friendly, bio-material containing chitosan obtained by spinning after mixing the chitosan between 0.1wt% and 10wt% with respect to the weight of the entire fiber composition in the spinning step and the polymer chip in the spinning step It is to provide a functional fiber having a tissue culture, hemostatic characteristics.

The functional fiber containing chitosan of the present invention has a thickness of between 1 μm and 1 mm, a particle diameter of between 15 μm and 0.15 μm, a degree of polymerization (DP) of 1,000 to 1,000,000, and a degree of deacetylation (DD) of 40% to 99. Chitosan powder, which is between%, is uniformly dispersed inside and outside, present in a weight ratio of 0.1 wt% to 10 wt% with respect to the weight of the entire fiber composition, and 0 wt% to 10 wt% of dispersant, emulsifier, heat stabilizer, quencher and residue. It exists between%.

In the manufacture of the fiber, in order to produce the functional fiber by adding the polymer chip, the pigment and the functional ingredient to the hopper of the spinning machine, the physical properties and the fine particle diameter of the added functional ingredient have a decisive influence on the production of the stable functional fiber.

Chitosan is one of the representative natural polymers, ester, amide, acrylic, modacryl, vinyl alcohol, propylene, saccharide, collagen, protein, glycolide, glycolic acid, lactide, lactic acid, It exhibits physical properties that can have sufficient affinity with homopolymers, copolymers, mixtures or blend compositions thereof selected from the group consisting of caprolactone, dioxanone, trimethylene carbonate, dimethyl trimethylene carbonate and the like.

In addition, a method of preparing chitosan having a suitable particle diameter useful in the present invention is a method of dry grinding after softening solid chitosan, a method of dry grinding after hardening solid chitosan, and a wet grinding method and spray drying of a chitosan solution. The chitosan powder obtained by the method of pulverizing solid chitosan has a disadvantage in that the size distribution of the particles is relatively large and the production of fine particles is limited, but the physical properties of the chitosan particles are excellent and the energy consumption of the manufacturing process is high. Its advantages are relatively small and simple manufacturing process. Chitosan powder obtained by spray-drying chitosan solution is weak in physical properties of chitosan particles, inefficient due to high energy consumption, and complicated manufacturing process. Relatively uniform and fine size There is one advantage. In addition, there is also a method for producing fibers using the polymer chip coated with soft chitosan as it is.

Chitosan solution for the production of chitosan powder through spray drying may be prepared by dissolving chitosan in a solvent at a concentration of 0.1wt% to 10wt% by weight. As chitosan, it is useful to have a degree of polymerization (DP) of 1,000 to 1,000,000 and a degree of deacetylation (DD) of 40% to 99%, more preferably a degree of polymerization of 1,000 to 100,000 and a degree of deacetylation of 85% to 99%. Can be used. As the solvent, one selected from an acid aqueous solution, an inorganic salt aqueous solution and an organic solvent is used.

As the acid solution, a mixture of acid and water in a weight ratio of 0.1wt% to 20wt% is used. As an acid, acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propinic acid, succinic acid, fish acid, succinic acid, ascorbin One or more randomly selected from organic acids such as acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid, toluenesulfonic acid, and one or more randomly selected from inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid are used.

As an aqueous inorganic salt solution, a solution in which inorganic salts are dissolved in water at a concentration ratio of 10 wt% to 70 wt% is used. For inorganic salts, inorganic metal salts such as sodium thiocyanate, zinc chloride, calcium chloride, sodium chloride, potassium chloride and lithium chloride are used. Any one or more of these are 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. In order to increase the polarity, 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% by weight ratio.

The chitosan solution prepared by the above method is dried through a spray dryer to produce a chitosan powder having a particle size of an appropriate size.

The functional fiber containing chitosan of the present invention is mixed with a polymer chip, a pigment and chitosan in an appropriate ratio during spinning of the polymer fiber, and then put into a hopper of the spinning machine to spin under predetermined spinning conditions such as spinning temperature and the like Functional fibers of the desired physical properties are prepared by stretching between 1 to 4 times the stretching ratio at an appropriate temperature.

In the present invention, the functional fiber containing chitosan is spun into a multifilament consisting of several strands of monofilament between 0.75 denier and 5 denier in thickness, or air cooled or spun into monofilament having a thickness of 0.1 mm to 1 mm. It is produced by cooling after stretching by the water cooling method, it is also possible to manufacture in the form of staple fibers, if necessary.

In the present invention, chitosan is a polymer having an amino group, which has excellent biocompatibility and can be easily obtained from chitin having abundant resources because it is widely present in nature, and it is intended to use it as a medical material such as artificial skin, surgical suture, and antithrombogenic material. Recently, the results of studies on tumor suppression effect and anticancer activity have been published. Therefore, applying this useful chitosan to general textile products intended for contact with the skin can quickly heal wounds at the inflamed areas of the skin, at the same time strengthen the connective tissue of the cells and maintain proper moisture on the skin, It is possible to utilize the antibacterial activity that is suppressed and representative of chitosan, and it is possible to semipermanently maintain the functionality of such chitosan.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

Preparation of Chitosan Powder

2 kg of chitosan having a molecular weight of 100,000 and a deacetylation degree of 89% was put into a high-speed grinder, and pulverized for 40 minutes and purified by a filter to prepare 1.2 kg of chitosan powder having a particle size of 1 μm or 3 μm.

Preparation of Functional Fibers Containing Chitosan

Chitosan powder prepared in polypropylene having a melt index (M.I.) of 28 at 230 ° C. was spun by mixing 0.5 wt% by weight. At this time, the temperature of the extruder was adjusted to 240 ℃ and the spinning temperature was adjusted to 230 ℃ 2 spine 48 48 holes of spinneret was combined by air cooling after winding at a speed of 3000m / min to prepare a functional polypropylene multifilament fibers.

Preparation of Staple Fibers Using Functional Fibers

Functional polypropylene staple fibers were prepared by stretching the prepared polypropylene functional fibers containing chitosan at a draw ratio of 2.5 through a drawing machine to improve physical properties and then cutting them into a length of 51 mm.

Example 2

Chitosan powder prepared in the same manner as in Example 1 was spun into a mixture of nylon 6 having a relative viscosity of 24 by weight 0.5wt%. At this time, the temperature of the extruder was adjusted to 250 ℃ and the spinning temperature was adjusted to 240 ℃ by combining the spinneret 48 holes in two combinations and air-wound at a condition of the winding speed 3500m / min to produce a functional nylon multifilament fibers.

Example 3

Chitosan powder prepared in the same manner as in Example 1 was spun into a polyester having an intrinsic viscosity of 0.62 in a weight ratio of 0.3wt% and spun. At this time, the temperature of the extruder was adjusted to 290 ° C and the spinning temperature was adjusted to 280 ° C to combine a 48-hole spinneret, and then wound by air cooling conditions of the winding speed 3500m / min to prepare a functional polyester multifilament fiber.

The functional fiber containing chitosan of the present invention can be used as a raw material for clothing, sheet, and paper having functionalities such as antibacterial, human-friendly, biological tissue culture, and hemostatic properties, and the fiber containing chitosan of the present invention. Textile products made of the fiber retain the physical properties of the fiber and exhibit the functionality of chitosan as it is, underwear, socks, bedding, pajamas, t-shirts, sneakers, soles, medical patches, wound dressings, surgical clothing, children's clothing, It can be widely used as a hygiene product, etc., and it is possible to maximize the various properties and usefulness of chitosan, which is beneficial to human health.

Claims (2)

Chitosan powder is uniformly dispersed inside and outside, present in a weight ratio of 0.1 wt% to 10 wt% with respect to the weight of the entire fiber composition, and dispersant, emulsifier, heat stabilizer, quencher and residue present between 0 wt% and 10 wt%. A functional fiber, wherein the main material forming the fiber is a homopolymer, copolymer, mixture or blend composition thereof selected from the group consisting of ester, amide, acrylic, modacryl, vinyl alcohol, propylene, saccharide, protein, and caprolactone. Multifilament consisting of between 2 and 300 strands of monofilament between 0.75 denier and 5 denier or monofilament between 0.1 mm and 1 mm thick and between 0.75 denier and 5 denier in thickness and 1 mm to Functional fiber containing chitosan in the form of staple fiber between 100 mm The chitosan powder according to claim 1, wherein the chitosan powder has a thickness of between 1 μm and 1 mm, a particle diameter of between 15 μm and 0.15 μm, a degree of polymerization (DP) between 1,000 and 1,000,000, and a degree of deacetylation (DD) between 40% and 99%. Functional fiber containing chitosan, characterized in that