JPH0892820A - Method for producing chitin fiber and film - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] 10 to 48% by weight of caustic soda is added to chitin in a solution form to produce alkaline chitin, which is crushed and crushed and carbon disulfide is added under reduced pressure. Then, a chitin xanthate reaction of chitin is carried out to form chitin xanthate, crushed ice is added to dissolve the chitin xanthate to produce chitin viscose, and then chitin viscose alone or cellulos viscose is mixed. Then, spinning is carried out by a conventional wet spinning method of viscose rayon and a conventional method for producing cellophane to produce chitin alone or a mixed fiber with cellulose and a film. [Effect] It has excellent antibacterial properties and great dyeing property to acid dyes. Therefore, it can be used in various applications for medical purposes or for blending with other fibers, and the film can also be used in various applications for medical purposes or as a film.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing chitin viscose using chitin as a raw material, and recycle obtained by spinning a chitin viscose or a stock solution obtained by mixing the chitin viscose with cellulose viscose. The present invention relates to a textile product having improved dyeability, which comprises chitin or recycled chitin and recycled cellulose, and further hygiene materials, fiber materials having an antibacterial effect, chitin-related fibers and films useful for daily sundries and the like. .

[0002]

Chitin has a chemical structure similar to that of cellulose. That is, chitin is one in which the hydroxyl group at the C-2 position of the glucose residue of cellulose is substituted with an aminoacetyl group, and is considered to be a kind of cellulose derivative. Therefore, various attempts have heretofore been made to form chitin into fibers in the same manner as cellulose. That is, chitin is dissolved in a trichloroacetic acid solution to produce a chitin dope, and acetone,
A method of wet spinning at a temperature of 40 to 55 ° C. using a coagulating liquid composed of methanol or ethanol (JP-A-57-57).
171712), (JP-A-58-214512),
(JP-A-5-25289). However, although chitin has a chemical structure similar to that of cellulose,
Its properties are significantly different from cellulose. Therefore, conventionally, it was impossible to produce, for example, a uniform chitin viscose by the same production method as that of cellulose.

[0003]

As mentioned above, chitin is considered to be one of the derivatives of cellulose, but the presence of an aminoacetyl group in the chitin molecule makes it possible to compare chemicals with, for example, chemical substances. Therefore, the utilization of chitin has been remarkably lower than that of cellulose. However, since chitin has hydroxyl groups in the molecule like cellulose, it has been attempted to make the chitin into a viscose, but as described above, under the same conditions as the viscose of the cellulose. Chitin viscose could not be done. That is, a freezing method is adopted for the conversion of chitin into a viscose, which destroys the micelle structure of chitin and prevents deacetylation of chitin by caustic soda as much as possible, and xanthogenation of alkali chitin for the production of chitin viscose. The chitin viscose can be produced by improving the reactivity of the chitin, but in that case, the chitin formation into a viscose requires a long-term freezing step at a low temperature under alkaline dipping of the chitin at a low temperature. did. Therefore, although it was possible to make chitin into a viscose only in the laboratory by the above method, there was a problem that it was industrially extremely difficult. Therefore, the inventors of the present invention have made extensive studies on the industrial production method of chitin viscose, and as a result, the present invention shows that ordinary cellulose
The present invention succeeds in making chitin into a viscose by improving the usual viscose production process without using the above-mentioned freezing process using a viscose production facility. Ordinary cellulose from chitin viscose produced by the present invention or a stock solution of chitin viscose and cellulose viscose prepared by viscose conversion of chitin
The purpose of the present invention is to produce a chitin fiber by spinning by a Sviscoose spinning method, or to produce a film by an ordinary production method of a Vicoce method cellulose film (abbreviated as cellophane).

[0004]

According to the present invention, 10 to 48% by weight, preferably 25 to 40% by weight, of caustic soda in solution is used in an amount equal to or more than the weight of chitin, preferably 2 to 20 times by weight. Add and add 1 at a temperature of 10 to 60 ° C, preferably 15 to 35 ° C.
Stir for 0 minutes or more, preferably 15 to 150 minutes, and then squeeze and grind to a weight of 1 to 10 times, preferably 2 to 5 times the weight of the raw material chitin. Then, 10 to 80% by weight of the raw material chitin,
Preferably 40 to 50% by weight of carbon disulfide is added under reduced pressure and 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 based on the chitin weight of the obtained chitin xanthate is added, and the mixture is stirred and dissolved at room temperature 5 to 30 ° C. for at least 30 minutes. A method for producing chitin viscose, wherein chitin viscose produced alone or the chitin viscose and cellulose viscose produced by a conventionally known method are mixed at an arbitrary weight ratio, and the pressure is reduced. A method for producing a fiber of chitin alone or a mixed fiber with cellulose, which is defoamed under air and spun by a wet spinning method of a normal viscose rayon, and a conventional viscose cellulosic film. Chitin alone or cellulose produced by law - is to provide a process for producing the mixed film with the scan.

In general, chitin is present as an organic skeletal substance in arthropods, annelids and molluscs, and is particularly abundant in the exoskeleton of arthropods. The raw material chitin used in the present invention is obtained by finely powdering the legs of the blue crab, calcium, protein, and other trace components that are treated by dilute hydrochloric acid and caustic soda solution for a short period of time to be removed. An example of the analysis value is as follows. Water content 5.0% Ash content 0.08% Residual protein 0.05% Viscosity 450 CPS Particle size 60 mesh pass (me Pass) Here, the viscosity is N, N dimethylacetamide-lithium chloride composite solvent, concentration, 0.4 %, The value measured at 20 ° C.

The raw material chitin does not necessarily have to be derived from red snow crab, but according to the study of the present inventor, chitin derived from snow crab has a high viscosity measured by the above and a strong glucoside bond. Therefore, it is suitable for the production of the chitin fiber of the present invention because of its high chemical and physical stability. The smaller the amount of ash and the amount of residual protein, the better the quality of the fiber obtained, but the value is preferably 0.5% or less. The particle size is closely related to the obtained fiber, but in the case of mixing and spinning with cellulose viscose, it can be arbitrarily selected according to the mixing ratio of the cellulose viscose. The particle size is related to the time of alkali chitin formation and the progress of deacetylation in the following dipping step of chitin,
30 mesh pass or less is preferable.

Next, details of the manufacturing process of the present invention will be described. (1) Immersion step The caustic soda used in the raw material chitin is used in a solution form at a concentration of 10 to 48% by weight. When the concentration of caustic soda is less than 10% by weight, sufficient alkali chitin cannot be obtained for the conversion of chitin to xanthate. When the concentration of caustic soda is 48% by weight or more, the chitin is deacetylated in addition to the alkali chitin. Rapidly progresses, and a viscose suitable for spinning the target fiber cannot be obtained. (2) Compressing and crushing process When the amount of alkaline chitin is less than 2 times, it is difficult to squeeze with a normal compressor, and it is limited to 2 times, but when it exceeds 4 times, the amount of alkaline chitin is too large. become,
When by-products are excessively produced in the biscosing process and mixed with cellulose viscose, the quality of the mixed viscose is deteriorated, and the upper limit of pressing is 4 times. When powdered chitin is used, the crushing step is omitted. (3) Sulfurization and dissolution step 10 to 80% by weight of carbon disulfide with respect to the raw material chitin is usually added under reduced pressure at room temperature and stirred for at least 10 minutes or more in accordance with the case of the production of cellulose viscose. The chitin xanthogenization reaction is carried out. 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 is used in excess of 80% by weight, a by-product of the reaction between unreacted carbon disulfide and caustic soda is obtained. However, a satisfactory viscose cannot be obtained. Further, the crushed ice added for making the chitin xanthate into a viscose is 2 to 30 times the amount of chitin xanthate, and if the amount is less than 2 times, the chitin content is high and the temperature drop during melting is not sufficient. Since the deacetylation of chitin is large, a sufficiently stable chitin viscose cannot be obtained. In this case, the amount of crushed ice added is limited to 20 times as much as the amount of chitin contained in chitin viscose and the cooling temperature during melting. At least 3
Stir for 0 minute or longer, preferably 2 to 10 hours to completely dissolve. In this case, the melting temperature drops to about freezing point,
The thawing process also combines the effects of the conventional freezing process. (4) Filtration and aging step Filtration is carried out in the same manner as in the case of the conventional production of cellulose viscose, and aging is carried out alone or in a mixed spinning with cellulose viscose to a viscosity suitable for film formation. Through the above steps, a chitin viscose capable of spinning and film formation similar to cellulose viscose can be obtained.

Next, the present invention will be described with reference to examples.

[Example 1] 40 to 10 g of chitin powder (manufactured by Sanei Industry Co., Ltd.) having a viscosity of 120 CPS (measured in the same manner as above)
50 ml of a wt% caustic soda solution was added and the mixture was stirred at room temperature. The produced alkaline chitin was squeezed to 4 times the weight of chitin. Carbon disulfide in pressed alkaline chitin 2.
Add 4 ml under reduced pressure and stir for 3 hours to react.
90 g of crushed ice was added to the obtained chitin xanthate and dissolved while stirring to obtain chitin viscose. The chitin viscose 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 viscose 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 chitin viscose (chitin content 5%) prepared in Example 1 was added to 240 g of cellulos viscose (cellulos content 9%) prepared by a known method and mixed with stirring. . After stirring and mixing and defoaming under reduced pressure, a chitin fiber (chitin content: 5%, cellulose content: 95%) was prepared by a wet spinning method according to a general method for producing a viscose fiber.
%) Was obtained. Dry strength of the 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 cellulosic film having the following quality was obtained according to a conventional method for producing cellophane using a chitin / cellulose mixed viscose having a chitin content of 1% 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 / 15 mm Tensile elongation Vertical 13.0% Horizontal 18%.

[0012]

【The invention's effect】

(A) In the present invention, chitin viscose can be produced by improving the ordinary production process of cellulose viscose using chitin viscose, and the chitin viscose can be produced using the viscose production equipment as it is. Was mixed with cellulose viscose in various ratios to produce chitin fibers and chitin films which can be used for various purposes. (B) The chitin fiber or film of the present invention is particularly excellent in antibacterial property, and the chitin fiber obtained in Example 3 has a difference in bacterial count increase / decrease value of 4.5 before washing and It is 5.1, which sufficiently meets the criteria (1.6 or higher) of the Textile Products Sanitary Processing Council. (C) It is used as a fiber or film which is not only antibacterial as compared with a fiber or film obtained from ordinary cellulose viscose but which is also well dyed with an acid dye by utilizing the cationic property of chitin. Further, this cationic property is applicable not only to dyes, but also to fibers having various chemical capturing powers (adsorption, reactivity, etc.). (D) Chitin fiber of the present invention (cellulosic 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 recycled fibers, artificial fibers, synthetic fibers such as polyester, nylon and acrylic,
Mixed spinning can be used. (E) The chitin fiber or film can be used for non-woven fabric or film, as well as fiber products such as spun yarn, woven fabric and knitted fabric. In the case of non-woven fabrics or films, surgical clothes with antibacterial effect for clothes, paper diaper with anti-fogging effect for daily sundries, wet tissue with antibacterial effect, film with soil improvement effect for agriculture, etc. It can be used for bedclothes and the like for bedclothes, which has an effect of preventing floor slippage, and industrial filters, which have an antibacterial effect. (F) In the case of knitted fabrics, not only applications that have the same effects as non-woven fabrics, but also clothing items such as underwear, socks, T-shirts, etc. that utilize improved dyeability, sleepwear items such as bajamas, bed covers, cushions, and towels. , Daily goods such as slippers, cloth bags,
Further, it can be used as a gauze, a tie, a cloth for a poultice, a medical article such as a bun plaster and the like.

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[Procedure amendment]

[Submission date] December 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Method for producing chitin fiber and film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taro Kaji 26-20 Kamiyama-cho, Koyoen-me, Nishinomiya-shi

Claims (3)

[Claims] 1. A caustic soda solution having a concentration of 10 to 48% by weight is added to a raw material chitin in a solution form in an amount of 2 to 20 times the weight of chitin, and the mixture is stirred at a temperature of 10 to 60 ° C. Compress to 10 times weight and crush. Then, 10 to 80% by weight of 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 carry out a xanth gelation reaction of chitin. Then, the obtained chitin xanthate is obtained. 2-20 times the amount of crushed ice based on the weight of chitin, and stirred at room temperature for at least 30 minutes,
A method for producing chitin viscose, which comprises dissolving. 2. The chitin viscose produced in claim 1 alone or the chitin viscose and the cellulose viscose produced by a conventionally known method are mixed at an arbitrary weight ratio and defoamed under reduced pressure. A method for producing a chitin-only fiber or a fiber composed of chitin and cellulose, which comprises spinning by a conventional wet spinning method of a viscose rayon. 3. The chitin viscose prepared in claim 1 is mixed alone or the cellulose viscose prepared by a conventionally known method is mixed at an arbitrary weight ratio, and defoamed to obtain a normal viscose. -A method for producing a chitin film or a chitin cellulosic film, which comprises depositing a film according to a method for producing serohan and drying the film.