JP2736868B2 - Manufacturing method of chitin fiber and film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing chitin biscos using chitin as a raw material, and a regenerated product obtained by spinning the chitin biscos or an undiluted solution obtained by mixing the chitin biscos with cellulose biscos. The present invention relates to chitin-related fibers and films useful for chitin or regenerated chitin and regenerated cellulose with improved dyeability, sanitary materials, fiber materials having an antibacterial effect, daily necessities and the like. .

[0002]

2. Description of the Related Art Chitin has a chemical formula very similar to that of cellulose. That is, chitin is obtained by substituting the hydroxyl group at the C-2 position of the glucose residue of cellulose with an aminoacetyl group, and is considered to be a kind of cellulose derivative. For this reason, various attempts have been made to convert chitin into a fiber in the same manner as cellulose. That is, chitin is dissolved in a trichloroacetic acid solution to produce chitin dope, and acetone,
A method of performing wet spinning at a temperature of 40 to 55 ° C. using a coagulating liquid composed of methanol or ethanol (Japanese Patent Application Laid-Open No.
171712), (JP-A-58-214512),
(JP-A-5-25289). However, although chitin has a chemical structure very similar to cellulose,
Its properties are significantly different from cellulose. Therefore, conventionally, for example, it has not been possible to produce uniform chitin biscose by the same production method as for cellulose.

[0003]

As described above, chitin is considered to be one of the derivatives of cellulose, but due to the presence of an aminoacetyl group in the chitin molecule, the chemical activity of chitin is lower than that of cellulose. And chitin utilization has been significantly lower in the past compared to cellulose. However, chitin has a hydroxyl group in the molecule as in the case of cellulose, and attempts have been made to make bistin into chitin.However, as described above, under the same conditions as those for making cellulose into biscosyl, Chitin viscos failed. That is, the freezing method is used for the biscosification of chitin to destroy the micelle structure of chitin, and to prevent deacetylation of chitin by caustic soda as much as possible, and at the same time xanthogenate alkali chitin to form chitin biscos. The chitin biscos can be produced by improving the reactivity of the chitin, but in that case, the biscosification of chitin requires a long-term alkaline immersion of chitin at low temperature and a long freezing step under reduced pressure. did. Therefore, chitin biscosification was possible only in the laboratory by the above method, but there was a problem that it was extremely difficult industrially. Therefore, the present inventors have conducted intensive studies on the industrial production method of chitin viscos, and as a result, the present invention has found that ordinary cellulosic cellulose is produced.
Without using the above-mentioned freezing process using the sbiscos manufacturing equipment, the conventional biscos manufacturing process was improved and the chitin was successfully biscosylated. Biscosylation of chitin and ordinary cellulose from a stock solution prepared by mixing chitin biscose prepared according to the present invention or chitin biscose with cellulose biscose
It is intended to produce a chitin fiber by spinning by a sviscos spinning method, or to produce a film by a conventional vicos method cellulos film (abbreviated as cellophane).

[0004]

According to the present invention, 10 to 48% by weight, preferably 25 to 40% by weight of caustic soda is dissolved in a solution in an amount equal to or more than the equivalent weight of chitin, preferably 2 to 20 times by weight. At a temperature of 10 to 60 ° C, preferably 15 to 35 ° C.
The mixture is stirred for 0 minutes or more, preferably for 15 to 150 minutes, and then crushed by pressing to 1 to 10 times, preferably 2 to 5 times the weight of the raw chitin. Next, 10 to 80% by weight of the raw chitin,
Preferably, 40 to 50% by weight of carbon disulfide is added under reduced pressure and the mixture is stirred at a temperature of 10 to 40 ° C., preferably at a temperature of 20 to 30 ° C. for at least 10 minutes to carry out the xanthogenation reaction of chitin. Then, 2 to 10 times, preferably 5 to 20 times the amount of crushed ice with respect to the chitin weight of the obtained chitin zante is added, and the mixture is stirred and melted at room temperature of 5 to 30 ° C. for at least 30 minutes. And further mixing the produced chitin viscose alone or the chitin viscos with the cellulose viscos produced by a conventionally known method at an arbitrary weight ratio, and reducing the pressure. A method for producing a fiber of chitin alone or a fiber blended with cellulose, which is defoamed and then spun by a conventional wet spinning method of a viscos method rayon, and a method of producing a usual viscos method cellulose film. Chitin alone or cellulose produced by law - is to provide a process for producing the mixed film with the scan.

[0005] In general, chitin is present as an organic skeletal material of arthropods, annelids and molluscs, and is particularly remarkably present in the exoskeleton of arthropods. The raw material chitin used in the present invention is obtained by finely pulverizing the legs of a snow crab and removing calcium, protein, and other trace components by treating them with a dilute hydrochloric acid and caustic soda solution for a short time. An example of the analysis value is as follows. Moisture 5.0% Ash 0.08% Residual protein 0.05% Viscosity 450 CPS Particle size 60 mesh pass (mePass) Here, the viscosity is determined by using a N, N dimethylacetamide-lithium chloride composite solvent at a concentration of 0.4. %, Values measured at 20 ° C.

[0006] The raw material chitin does not necessarily need to be derived from red snow crab, but according to the study of the present inventors, chitin derived from snow crab has a high viscosity measured as described above and is considered to have strong glucosidic bonds. For this reason, it has high chemical and physical stability and is suitable for producing the chitin fiber of the present invention. The smaller the amount of ash and residual protein, the higher the quality of the fiber, but the value is preferably 0.5% or less. The particle size has a close relationship with the obtained fiber, but when mixed spinning with cellulos viscos, it can be arbitrarily selected according to the mixing ratio of cellulos viscos. Also, the particle size is related to the time of alkali chitinization, the progress of deacetylation in the following immersion step of chitin,
Preferably, a 30 mesh pass or less is suitable.

Next, the details of the manufacturing process of the present invention will be described. (1) Immersion step Caustic soda used for the raw material chitin is used as a solution at a concentration of 10 to 48% by weight. If the concentration of caustic soda is less than 10% by weight, sufficient alkali chitin for xanthate formation of chitin cannot be obtained, and if the concentration of caustic soda is more than 48% by weight, deacetylation of chitin in addition to alkali chitinization. Viscosities progress rapidly, and a viscos suitable for spinning the desired fiber cannot be obtained. (2) Squeezing and crushing process When the squeezing of alkali chitin is less than twice, it is difficult to squeeze with a normal squeezing machine, and the squeezing is limited to two times. become,
When by-products are excessively generated in the viscosifying process and mixed with cellulose biscos, the quality of the mixed viscos is deteriorated, and the upper limit of pressing is four times. When powdered chitin is used, the pulverizing step is omitted. (3) Sulfidation and dissolution process Carbon disulfide in an amount of 10 to 80% by weight with respect to the raw material chitin is added at room temperature under reduced pressure in the same manner as in the case of the production of cellulose biscoice, and the mixture is stirred for at least 10 minutes. A xanthogenation reaction of chitin is performed. If the amount of carbon disulfide added is less than 10% by weight, chitin xanthate having good solubility in water cannot be obtained, and if it exceeds 80% by weight, unreacted carbon disulfide and by-products due to the reaction between caustic soda and the like will be obtained. Are produced in large quantities, and satisfactory biscos cannot be obtained. Furthermore, the crushed ice added for the biscosification of chitin xantate is 2 to 30 times the amount of chitin xantate, and if it is less than 2 times, the content of chitin is high, and the temperature drop during melting is not sufficient, A sufficiently stable chitin viscos cannot be obtained due to large deacetylation of chitin. In this case, the amount of crushed ice to be added is limited to 20 times the amount of chitin in the chitin biscoose and the cooling temperature during melting. At least 3 lysis
Stir for at least 0 minute, preferably for 2 to 10 hours to completely dissolve. In this case, the melting temperature drops to around freezing point,
The thawing step also has the effect of the conventional freezing step. (4) Filtration and Aging Steps Filtration is performed in exactly the same manner as in the case of the conventional production of cellulos biscos, and ripening to a viscosity suitable for spinning alone or mixed with cellulose biscos and film formation. Through the above steps, a chitin viscos capable of spinning and film formation similar to that of cellulose viscos is obtained.

Next, the present invention will be described by way of examples.

Example 1 40 g of chitin powder (manufactured by Sanei Kogyo Co., Ltd.) having a viscosity of 120 CPS (measured in the same manner as described above)
A 50% by weight aqueous solution of caustic soda was added and stirred at room temperature. The produced alkaline chitin was pressed to 4 times the weight of chitin. 1. Carbon disulfide on pressed alkaline chitin
4 ml was added under reduced pressure, and the mixture was stirred and reacted for 3 hours.
90 g of crushed ice was added to the obtained chitin zante and dissolved with stirring to obtain chitin biscote. The chitin viscos had a falling ball viscosity of 72 seconds and a chitin content of 5%.

[0009]

Example 2 A chitin yarn was produced from the chitin biscos obtained in Example 1 by a wet spinning method using an ordinary spinning bath. The chitin fiber after scouring and drying had a dry strength of 0.8 g / d and a dry elongation of 10%.

[0010]

EXAMPLE 3 23 g of the chitin biscoose (chitin content 5%) prepared in Example 1 was added to 240 g of cellulose-biscoose (cellulose content 9%) manufactured by a known method, followed by stirring and mixing. . After stirring, mixing and defoaming under reduced pressure, chitin fibers (chitin content 5%, cellulose content 95%) were wet-spun according to a conventional method for producing viscos fibers.
%). Dry strength of obtained fiber 2.4 g / d Dry elongation 16.7% Wet strength 1.9 g / d Wet elongation 24.3%
Met.

[0011]

Example 4 A chitin / cellulose film having the following qualities was obtained according to a conventional cellophane production method using a 1% chitin / cellulose mixed viscosite produced in the same manner as in Example 3. . Basis weight 35.3 g / m ³ Thickness 0.02 mm Tensile strength Vertical 1.9 kg / 15 mm Horizontal 0.9
Kg / 15mm Tensile elongation length 13.0% Horizontal 18%.

[0012]

【The invention's effect】

(A) In the present invention, chitin biscos can be produced using the biscos production equipment as it is by improving the production process of ordinary cellulose biscos from chitin biscos. Was mixed with cellulose biscos in various ratios to produce chitin fibers and chitin films usable for various purposes. (B) The chitin fiber or film of the present invention is particularly excellent in antibacterial properties, and the chitin fiber obtained in Example 3 has a difference in the increase or decrease in the number of bacteria of 4.5 before washing and after washing as measured by the bacterial count method. 5.1, which sufficiently meets the standards of the Textile Sanitary Processing Council (1.6 or higher). (C) Compared to fibers or films obtained from ordinary cellulos biscos, they are used not only as antibacterial agents but also as fibers or films which are dyed well with acid dyes by utilizing the cationic property of chitin. This cationic property can be applied not only to dyes but also to fibers having various chemical trapping powers (adsorption, reactivity, etc.). (D) Chitin fiber of the present invention (cellulose content of 0% or more;
(Less than 100%) is not only used alone. Cotton, silk,
Mixing with natural fibers such as hemp and wool, as well as synthetic fibers such as regenerated fibers, man-made fibers, polyester, nylon, acrylic, etc.
Can be used for blending. (E) Chitin fibers or films can be used for nonwoven fabrics or films as well as fiber products such as spun yarns, woven fabrics and knitted fabrics. In the case of non-woven fabrics or films, anti-bacterial surgical gowns for clothing, paper diapers, antibacterial wet tissue for daily miscellaneous goods, and soil-improving films for agricultural use, etc. It can be used as a bed cushion for bedding and the like, which has an effect of preventing the floor from falling, and a filter for industrial use, which has an antibacterial effect. (F) In the case of knitted fabrics, not only applications having the same effect as nonwoven fabrics, but also clothing items such as underwear, socks, T-shirts, etc., beddings, bed covers, cushions and other bedding products utilizing improved dyeability, and towels , Slippers, cloth bags and other daily necessities,
Further, it can be used for medical supplies such as gauze, hot tie, cloth for poultices, buns and plasters.

Claims (3)

(57) [Claims] 1. A solution of caustic soda having a concentration of 10 to 48% by weight to a raw material chitin, 2 to 20 times the weight of the chitin in a solution state, and stirring at a temperature of 10 to 60 ° C. Press and crush to 10 times the weight. Then, carbon disulfide in an amount of 10 to 80% by weight of the raw material chitin is added under reduced pressure, and the mixture is stirred at a temperature of 10 to 40 ° C. for at least 20 minutes to cause a xanthogelation reaction of chitin. Add 2 to 20 times the amount of crushed ice with respect to the weight of chitin and stir at room temperature for at least 30 minutes,
A method for producing chitin biscose, comprising dissolving. 2. The chitin viscos produced in claim 1 alone or the chitin viscos and a cellulose viscos produced by a conventionally known method are mixed at an arbitrary weight ratio and defoamed under reduced pressure. A method of producing chitin-only fibers or fibers comprising chitin and cellulose by spinning a conventional viscose method rayon by a wet spinning method. 3. The chitin viscos produced in claim 1 alone or a cellulose viscos produced by a conventionally known method is mixed at an arbitrary weight ratio, defoamed, and both are treated with ordinary biscos. -A method for producing a chitin film or chitin cellulos-film, characterized in that a film is formed and dried according to a method for producing a cellulohan.