KR20200021007A - Method of producing a chemically transformed chitosan fiber - Google Patents

Abstract

Disclosed in the present invention is a manufacturing method for a highly functional chitosan fiber, which is capable of further improving biodegradability, tensile strength, anti-inflammatory properties, and anti-bacterial properties by coagulating emitted chitosan or a copolymer of chitosan and poly-gamma-glutamic acid in a coagulation solution composed of a buffer solution where silicate, a natural medicinal ingredient extract, and an aqueous herb solution are mixed. Therefore, the manufacturing method for a chitosan fiber can raise functionality by using a steam distillation extract made of natural medicinal ingredients, which are collected from the nature, and having pharmaceutical efficacy to promote cell tissue activation and metabolism; and can significantly improve the quality of a fiber by mixing a silicate with sodium hydroxide, instead of a combination of sodium sulfate and sodium hydroxide, that is, a basic composition of a coagulation solution, to increase buffer strength and a stretching ratio and thus, improve strength, fineness, ductility, anti-inflammation, and anti-bacteria. In addition, the manufactured fiber is a highly functional fiber with further reinforced anti-inflammatory properties, anti-bacterial properties, deodorant properties, and vital function adjusting action through effects of mixing and radiating medicinal herb water besides the functions of chitosan.

Description

Method of producing a chemically transformed chitosan fiber

The present invention relates to a method for producing a chemically modified chitosan fiber, and more particularly in a coagulation solution consisting of a buffer solution in which the spun chitosan or chitosan and the polygamma glutamic acid copolymer is mixed with a silicate, a natural medicinal extract and an aqueous herbal solution. The present invention relates to a method for producing a high functional chitosan fiber which is further solidified by further improving biodegradability, tensile strength, anti-inflammatory and antibacterial properties.

Since chitosan fiber is made of high purity natural chitosan as it is, it is harmless to the human body and has no side effects. Due to the unique function of chitosan, such as anti-inflammatory, antibacterial, deodorization and immunity improvement, it can be a very good product as a coating and medical fiber. Chitosan fiber is generally extruded and spun through a spinning nozzle in a chitosan solution in which high-purity natural chitosan is dissolved. It is prepared by coagulation.

However, these chitosan fibers, like other regenerated fibers, have a reduced tensile strength when wet, making them difficult to be used practically as fibers, and in particular, cannot be used as a single filament. .

In order to solve this problem, various chitosan fiber products have been developed to improve tensile strength, but until now, the situation has not been completely solved.

Thus, the present inventors have developed and commercialized a method for producing a chemically modified chitosan fiber as disclosed in Korean Patent Publication No. 10-0912644 (Registration Date: August 11, 2009). The patent has developed a human-friendly and biodegradable chitosan fiber by using a silicate which is a natural product as a coagulation liquid instead of a chemical coagulation liquid conventionally used to coagulate chitosan fibers.

However, the present inventors have recognized that the coagulation process needs to be improved to further double the effects of improving human affinity, antimicrobial activity, deodorization, and immunity of chitosan fibers prepared by the above-mentioned patent.

Republic of Korea Patent Publication No. 10-0912644 (Registration Date: August 11, 2009) Republic of Korea Patent Publication No. 10-1862855 (Registration Date: May 24, 2018)

In order to solve the problems and problems as described above, the inventors of the present invention, when the solidified herbal mixture containing silicate and natural medicine in the process of coagulating the spun chitosan coagulated by coagulation liquid, silicate powder (Si0 ₂ ) in chitosan fiber This makes the surface of the fiber more glossy and smooth, which greatly improves the tensile strength, fineness, and elongation, which are the characteristics of porous chitosan fiber, greatly improves biodegradability, antibacterial and far-infrared radiation function, and does not stick to each other when solidifying Invented.

Therefore, the technical problem to be solved by the present invention is to produce a chitosan fiber that significantly improved the tensile strength and friction (smoothness) of the surface by producing the solidified spinning chitosan in the coagulation liquid containing silicate, natural herbal extracts and herbal extracts To provide.

In order to solve the technical problem as described above, the present invention, in the method for producing chitosan fibers by spinning and solidifying chitosan solution,

It provides a method for producing chitosan fibers characterized in that the produced chitosan is prepared by coagulating in a coagulation solution containing a silicate, natural medicinal extracts and herbal extracts.

The coagulant solution containing the silicate, natural medicinal extracts and herbal extracts is characterized in that consisting of a buffer solution of 10 to 80% by weight of sodium hydroxide aqueous solution and 10 to 80% by weight aqueous solution of natural medicinal mixture mixture .

In addition, in order to solve the technical problem as described above, the present invention, in the method for producing chitosan fibers by spinning and solidifying the solution copolymerized chitosan solution and poly-gamma glutamic acid solution,

Preparation of chitosan fiber characterized in that the spun chitosan copolymer is prepared by coagulation in a coagulation solution consisting of a buffer solution of 10 to 80% by weight of a sodium hydroxide aqueous solution of 10 to 80% by weight of an aqueous solution of silicate and natural medicine mixture Provide a method.

Moreover, in order to solve the technical subject mentioned above, this invention is a manufacturing method of a chitosan fiber,

Pretreatment of chitosan to remove and deacetylate inorganic salts and proteins from the material containing chitin (S1);

Preparing a chitosan spinning stock solution by dissolving the chitosan obtained in the step (S1) in a solvent (S2);

Adding a plasticizer to the chitosan spinning stock solution prepared in step (S2), stirring well and filtering to remove bubbles (S3);

After passing through the step (S3) and the filtered spinning raw solution to a spinning dope tank (dope tank), the step of spinning the spinning raw solution through a spinning nozzle by controlling the discharge amount by a pump (gear pump) (S4) );

Coagulating the chitosan spun in the step (S4) in a coagulant solution consisting of a buffer solution of 10 to 80% by weight of a sodium hydroxide aqueous solution of 10 to 80% by weight in a sodium hydroxide aqueous solution and a natural herbal extract and an aqueous solution of herbs (S5) );

After the step (S5), washing the solidified fibers with water and ethanol (S6);

Stretching the washed water in the step (S6) in boiling water to obtain a stretched fiber (S7); And

It provides a method for producing chitosan fibers comprising a; (S8) to obtain a stretchable chitosan fiber by post-treatment, drying the stretched fiber obtained in the step (S7).

In the step (S2), the chitosan solution is characterized in that the chitosan spinning stock solution is prepared by copolymerizing polygamma glutamic acid solution (PGA), nicotinic acid amide or salicylic acid.

In the step (S2), the chitosan solution, natural herbal extracts and polygamma glutamic acid solution of the copolymerization of 3: 1: 1 is characterized in that the chitosan spinning stock solution.

As mentioned above, according to the present invention, a silicate powder (Si0 ₂ ) adheres to chitosan fiber by coagulating by mixing the herbal extract containing silicate and natural medicine in the coagulating solution in the process of solidifying the spun chitosan. This makes the surface of the fiber more glossy and smooth, which greatly improves tensile strength, fineness, and elongation, which are characteristic of porous chitosan fibers. In addition, the chitosan fiber of the present invention is excellent in biodegradability, anti-inflammatory, antibacterial, deodorant, far-infrared radiation, and the like, and is easy to apply in commercial aspects, such as medical, food, cosmetics, chemicals. In particular, it can be used as a single filament, which is difficult to use practically because of its strength, and thus can be used for surgical sutures made of a single filament.

Chitosan fiber manufacturing method according to the present invention is a very simple process can be produced in a good yield economically fibers without the need for a new device. In addition, in the method of the present invention, the mixture of silicate and natural medicinal extract during solidification coagulates chitosan fibers and at the same time, silicic acid (Si0 ₂ ) is attached and the fibers do not stick together. In addition, the chitosan fiber of the present invention is a human-friendly, excellent biodegradation and does not cause pollution by using a natural silicate, herbal extract, herbal solution as a coagulant instead of the conventional chemical coagulant.

Chitosan fiber produced by the method of the present invention is a new biofunctional material that can be used for medical, animal medicine, and plant wound healing, and is prepared in the form of fiber, cotton, film, artificial skin, nonwoven fabric, sponge, powder, and gel. These fibers may be used alone or mixed and mixed with natural fibers such as cotton, dog, hemp and wool, and also synthetic fibers such as recycled fibers, artificial fibers, polyester, nylon and acrylic.

In addition, chitosan fibers copolymerized with polygamma glutamic acid (PGA), nicotinic acid amide, and salicylic acid have excellent physical properties such as tensile strength, fineness, and elongation, and low solubility in water.

1 is a manufacturing process of chitosan fiber according to a preferred embodiment of the present invention.

Hereinafter, a method of manufacturing chitosan fiber according to a preferred embodiment of the present invention with reference to the accompanying drawings in detail.

[Pretreatment of Polymer Resources]

The pretreatment process of the polymer raw material is to improve the dissolving power of the raw material and also to modify the polymer. Substances containing chitin, such as shrimp and crabs, are treated with 5% by weight aqueous hydrochloric acid solution to remove inorganic salts containing calcium carbonate as a main component. Chitin from which the inorganic salt was removed is treated with 5% by weight aqueous sodium hydroxide solution to remove the protein. The protein was removed chitin was treated with 50% by weight aqueous sodium hydroxide solution to remove the acetate group (-COCH3) in the chitin molecule to prepare a high purity chitosan (= step S1).

[Production of Chitosan Spinning Solution]

A chitosan spinning stock solution is prepared by dissolving chitosan obtained in the step (S1) in a solvent (= step S2). The content in the solution of chitosan is preferably 3 to 30% by weight. If the chitosan content is less than 3% by weight, the spinning stock solution is too dilute, and if it is 30% by weight or more, the viscosity is increased and spinning is not performed.

As the solvent, various organic or inorganic acids may be used, but in the case of the inorganic acid, molecular weight may be lowered. Organic acids may be preferably used, but lactic acid is most preferably used.

In addition, a solution obtained by copolymerizing a chitosan solution, a natural herbal extract, and a polygamma glutamic acid solution in a 3: 1: 1 ratio may be used as the chitosan spinning stock solution. The content of the polygamma glutamic acid and the natural herb extract in the solution is preferably 3 to 30% by weight. If the polygamma glutamic acid content is less than 3% by weight, the solution is too dilute, and if it is 30% by weight or more, the viscosity increases and no spinning occurs.

[Filtering of Radioactive Solution]

Glycerol (glycerol, Sigma) or sorbitol (sorbitol, Sigma) is added to the chitosan spinning stock solution as a plasticizer, stirred well, and filtered to remove bubbles (= step S3). This filtrate shows a high viscosity liquid (150,000-400,000 cps) as a spinning stock solution (DOPE).

[Radiation of spinning solution]

The uniform spinning dope is transferred to a spinning dope tank. In order to solidify this spinning stock solution, the discharge amount is controlled by a gear pump to spin through the nozzle (= step S4). In the spinning method, it is preferable to wet-spin the spinning stock solution with excellent spinning stability such as excellent fiber forming ability, affixing fibers, removing solvents, and improving productivity.

The nozzle used is a strong alkali, so avoid the stainless material that can elute heavy metal ions, and platinum / gold alloy material is required.

[coagulation]

As a step of coagulating the spun chitosan, chitosan fibers are produced by coagulation (neutralization) of the spun filament in an alkaline aqueous solution tank, that is, a solidification bath (nozzle spinning bath) (= step S5).

In the present invention, it is coagulated in a coagulant solution containing a silicate and natural herbal extract solution. Preferably, it is preferable to coagulate in a coagulation solution consisting of a buffer solution of 10 to 80% by weight of a sodium hydroxide aqueous solution of 10 to 80% by weight of the aqueous solution of silicate and natural herbal extracts. This buffer solution maintains a constant hydrogen ion concentration in the solution upon coagulation and hardly changes the pH. As such, the buffer solution does not change the pH of the solution very much even if acid or base is added. Good buffers can also cover a wide pH range by varying the composition.

The buffer solution containing silicate and natural herb extract can also act as a plasticizer to increase the draw ratio and improve fineness strength.

During coagulation, silicate and natural herb extracts coagulate chitosan fibers and at the same time, silicic acid (Si0 ₂ ) is attached to them to increase the tensile strength without fibrilation. .

This effect is an effect that cannot be achieved by coagulation in an aqueous solution containing any alkali metal salt other than silicate and natural medicinal extract.

Solidification and solidification are completed in a short time within 30 seconds to 1 minute in the solidification bath, which is the solidification process.

[Washing, extending]

The solidified chitosan fiber is washed with water through a washing process (= step S6), and the washed chitosan fiber is stretched through boiling water and a steam process to obtain a stretched fiber (= step S7).

Since the stretching temperature increases as the stretching temperature increases as the stretching temperature increases, the stretching ratio is preferably 80 to 100 ° C., and the stretching bath is stretched once again to 130 ° C. which is a steam process. The draw ratio was changed from 1.0 to 3,5.

[Shipment]

The stretched fiber is worked up and dried to obtain chitosan fiber (= step S8).

Results and Discussion

Tensile strength and elongation test results of the chitosan fiber prepared through the manufacturing process as described above are shown in Table 1 below.

Tensile strength (gf / d) Elongation (%) Example 1 2.5 19.5 Example 2 2.0 18.5 Comparative Example 1 1.7 15.9 Comparative Example 2 1.8 16.5

Next, Table 2 below is a test result for the anti-inflammatory effect of chitosan measured by the Department of Biochemistry, College of Pharmacy, Dongguk University.

TABLE 2

As can be seen from the test results, the chitosan fiber prepared according to the present invention is attached with silicic acid powder (Si0 ₂ ), thereby greatly improving the tensile strength and elongation characteristic of the porous chitosan fiber. In addition, it can be seen that excellent anti-inflammatory properties.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains can understand that various modifications and changes can be made without departing from the essential characteristics of the present invention. Could be. Accordingly, the embodiments represented herein are not intended to limit the technical spirit of the present invention, but to describe the present invention, and the scope of the present invention is not limited to the embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas that are equivalent to or equivalent to the scope of the present invention should be construed as being included in the scope of the present invention.

Claims (6)

In the method for producing chitosan fibers by spinning and coagulating chitosan solution,
A method for producing chitosan fibers, characterized in that it is produced by coagulating the spun chitosan in a coagulation solution containing a silicate, natural medicinal extracts and herbal extracts. The coagulant solution of claim 1, wherein the coagulant solution including the silicate, the natural medicinal herb extract, and the herbal extract is a buffer solution in which an aqueous solution of 10 to 80 wt% of the silicate and the natural medicinal mixture mixture is mixed with 1 to 10 wt% of sodium hydroxide solution. Method for producing chitosan fibers, characterized in that the configuration. In the method for producing chitosan fibers by spinning and coagulating a solution obtained by copolymerizing a chitosan solution and a polygammaglutamic acid solution,
Preparation of chitosan fiber characterized in that the spun chitosan copolymer is prepared by coagulation in a coagulation solution consisting of a buffer solution of 10 to 80% by weight of a sodium hydroxide aqueous solution of 10 to 80% by weight of an aqueous solution of silicate and natural medicine mixture Way. As a manufacturing method of chitosan fiber,
Pretreatment of chitosan to remove and deacetylate inorganic salts and proteins from the material containing chitin (S1);
Preparing a chitosan spinning stock solution by dissolving the chitosan obtained in the step (S1) in a solvent (S2);
Adding a plasticizer to the chitosan spinning stock solution prepared in step (S2), stirring well and filtering to remove bubbles (S3);
After passing through the step (S3) and the filtered spinning raw solution to a spinning dope tank (dope tank), the step of spinning the spinning raw solution through a spinning nozzle by controlling the discharge amount by a pump (gear pump) (S4) );
Coagulating the chitosan spun in the step (S4) in a coagulant solution consisting of a buffer solution of 10 to 80% by weight of a sodium hydroxide aqueous solution of 10 to 80% by weight in a sodium hydroxide aqueous solution and a natural herbal extract and an aqueous solution of herbs (S5) );
After the step (S5), washing the solidified fibers with water and ethanol (S6);
Stretching the washed water in the step (S6) in boiling water to obtain a stretched fiber (S7); And
Post-processing and drying the stretched fiber obtained in the step (S7) to obtain an elastic chitosan fiber (S8);
Chitosan fiber production method comprising a. The method of claim 4, wherein in step (S2), the chitosan fiber is prepared by copolymerizing chitosan solution with polygamma glutamic acid solution (PGA), nicotinic acid amide or salicylic acid. The method of claim 4, wherein in the step (S2), the chitosan fiber, characterized in that the chitosan solution, a solution obtained by copolymerizing the chitosan solution, natural herbal extracts and polygamma glutamic acid solution 3: 1: 1 Way.

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