JP4063913B2 - Spinning composition comprising chitosan and anionic polysaccharide aqueous solution and its fiber - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a spinning composition , fiber or hollow fiber comprising a chitosan aqueous solution and an anionic polysaccharide aqueous solution.
[0002]
[Prior art]
When the polyelectrolyte solution having the opposite charge is mixed, both of them immediately release a counter ion and form a polyion complex through the Coulomb force. There have been many studies on utilizing this property to form a polyion complex, that is, a water-insoluble gel, from chitosan, which is a cationic polysaccharide, and an anionic polysaccharide, and to examine its physical properties. Therefore, it has not been known that spinning can be performed continuously by pulling up the polyion complex membrane formed at the interface between the two solutions.
[0003]
[Problem to be Solved by the Invention]
An object of the present invention is to obtain a composition for spinning from an aqueous solution of chitosan and an aqueous solution of anionic polysaccharide to obtain fibers, particularly hollow fibers.
[0004]
[Means for Solving the Problems]
That is, the present invention is a spinning composition comprising a chitosan aqueous solution and an anionic polysaccharide aqueous solution, its fiber and hollow fiber. In the present invention, examples of the anionic polysaccharide include gellan gum, sodium alginate, carrageenan, low methoxy pectin, far celerane, Na-carboxymethyl cellulose, heparin, chondroitin sulfate, xanthan gum, gum arabic, guar gum, agarose, and combinations thereof. Among them, gellan gum is preferable.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
Chitosan has a degree of deacetylation of 50 to 100%, preferably 60 to 90%, and an average molecular weight of 100,000 to 1,000,000, preferably 800,000 to 1,000,000. If the degree of deacetylation is less than 50%, the solubility in dilute acid becomes poor. If the average molecular weight is too low, the spinnability at the time of forming the polyion complex is lost. On the other hand, if the average molecular weight is too high, the solubility in the solvent is deteriorated and handling becomes difficult.
Chitosan has a concentration of 0.1 to 2% (w / v), preferably 0.5 to 1.5% (w / v) in a dilute acid such as hydrochloric acid or acetic acid. To dissolve. Preferred as dilute acid is dilute hydrochloric acid. After removing insoluble matters, the pH is adjusted to 5.8 or less, preferably 3.0 to 5.5 using 1N sodium hydroxide. When the concentration is less than 0.1%, the spinnability at the time of forming the polyion complex is deteriorated, and when it exceeds 2%, the viscosity is too high and the handling becomes difficult. On the other hand, when the pH exceeds 5.8, the dissociation degree of the dissociating group becomes small, and it becomes difficult to form a good polyion complex.
Gellan gum has an average molecular weight of 100,000 to 1,000,000, preferably 80 to 1,000,000. If the average molecular weight is too low, the spinnability at the time of forming the polyion complex is lost, and conversely, if the average molecular weight is too high, the solubility in the solvent is deteriorated and the handling becomes difficult.
The gellan gum aqueous solution is suspended in distilled water and dissolved by heating so that its concentration is 0.1-2% (w / v), preferably 0.5-1.5% (w / v). , Kept at 40-50 ° C. When the concentration is less than 0.1%, the spinnability at the time of forming the polyion complex is deteriorated, and when it exceeds 2%, the viscosity is too high and the handling becomes difficult.
While heating two solutions of approximately the same volume to about 50 ° C, add the other solution from the top to the container containing one of the two solutions, and pull up the film formed at the interface. To form a thread.
Depending on how the yarn is pulled out and how the liquid surface is made, chitosan can be on the inside and gellan gum can be on the outside, or vice versa. The thickness of the drawn yarn, the film thickness of the hollow fiber, etc. can be adjusted by the pulling speed, the concentration of both solutions, and the like.
[0006]
【Example】
Next, an Example is given and this invention compound is demonstrated further more concretely.
[0007]
Example
Chitosan (deacetylation degree 73%, average molecular weight 940,000) was dissolved in 0.1N hydrochloric acid so that the concentration became 0.5% (w / v). After the chitosan solution was filtered through a glass filter, the pH of the solution was adjusted to 5.5 using 1N sodium hydroxide. Gellan gum (average molecular weight 900,000) was dissolved in hot water and kept at 50 ° C. to obtain a 0.75% (w / v) aqueous solution. While heating two solutions of approximately the same volume to 50 ° C. together, the chitosan solution was added from above to the container containing the gellan gum solution, and the film formed at the interface was pulled up with tweezers. The spinning of this polyion complex can be carried out continuously and automatically by gravity (self-weight), and as in the interfacial polymerization of nylon 66, yarns are formed one after another at the interface between the two solutions. Was done until all was consumed.
[0008]
【The invention's effect】
The form of the yarn at the time of forming the chitosan solution and the gellan gum solution has a bead chain structure and a straight yarn structure, and both become straight yarns when dried.
When chitosan was on the outside of the yarn, the shape of the yarn was like a chain of beads, resembling a spider yarn. Similarly, spider filamentous material was obtained when gellan gum was outside the yarn.
The yarn of the present invention has an excellent property that can be continuously spun by gravity (self-weight).
When the obtained yarn was dried at room temperature and observed with a microscope (100 times magnification), it was found to be a hollow fiber. Its diameter was about 50-200 microns.
Immediately after spinning, when the yarn was passed through an organic solvent (ethanol, acetone, dioxane, etc.), it was dehydrated and the same yarn as when dried was obtained, and the yarn could be wound.
Since the obtained yarn is hollow and has penetrability, it can be used by a method of weaving a cloth filled with a fragrance, a fungicide, a deodorant and the like.
In addition, by dissolving or dispersing a fragrance, antibacterial agent, deodorant, etc. in one or both of chitosan or an anionic polysaccharide aqueous solution, a fiber incorporating these properties into the hollow part of the hollow fiber or membrane, It can also be a film.
In addition, biofouling protective substances, antifouling paints, medicines, physiologically active substances, agricultural chemicals, etc. are taken into hollow parts or membranes, and processed into shapes suitable for each purpose such as sticks, fiber bundles, nets, and films. It can also be used.
The hollow fiber of the present invention can be used as a sustained release agent by filling the above-mentioned various active ingredients and the like, and the fiber of the present invention has biodegradability.

Claims (10)

A spinning composition comprising a chitosan aqueous solution and an anionic polysaccharide aqueous solution. A fiber spun from a spinning composition comprising a chitosan aqueous solution and an anionic polysaccharide aqueous solution. The fiber according to claim 2, wherein the fiber to be spun is a hollow fiber. The composition, fiber or hollow fiber according to any one of claims 1 to 3, wherein the anionic polysaccharide is gellan gum. The composition, fiber or hollow fiber according to any one of claims 1 to 4, wherein the deacetylation degree of chitosan is 50 to 100% and the average molecular weight is 100,000 to 1,000,000. The average molecular weight of gellan gum is 100,000-1 million, The composition, fiber or hollow fiber according to any one of claims 4 and 5. The composition, fiber or hollow fiber according to any one of claims 4 to 6, wherein the chitosan aqueous solution has a concentration of 0.1 to 2% (w / v) in dilute acid. 8. The composition, fiber or hollow fiber according to claim 7, wherein the dilute acid is dilute hydrochloric acid. The composition, fiber or hollow fiber according to any one of claims 4 to 8, wherein the pH of the aqueous chitosan solution is adjusted to 5.8 or less. The composition, fiber or hollow fiber according to any one of claims 4 to 9, wherein the concentration of the gellan gum aqueous solution is 0.1 to 2% (w / v).