JP3424114B2 - Modified cellulose regenerated fiber and its production method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has antioxidative and antibacterial properties suitable for use in textile products such as woven fabrics, nonwoven fabrics and papermaking in the field of food packaging materials such as fresh fish and meat. The present invention relates to a modified cellulose regenerated fiber and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, research on antioxidants that digest oxygen and active oxygen, which adversely affect the freshness of foods, has been widely conducted, and butylhydroxytoluene, butylhydroxyanisole, ascorbic acid, α-tocopherol and the like have been investigated. Used as an antioxidant in foods. JP-A-8
Japanese Patent No. 325831 discloses a modified cellulose fiber containing an extract from a plant and a water-insoluble, non-sublimable alcohol. However, it is not intended to provide the fiber with antioxidant ability.

On the other hand, mixing the chitosan fine granules with cellulose viscose and spinning the mixture to prepare a cellulose regenerated fiber is disclosed by the applicant in Japanese Patent Publication No. 7-68648. Of cellulose regenerated fiber having antibacterial properties by mixing and spinning cellulose with a cellulose viscose solution, and Patent Document 2
Japanese Patent No. 571738 discloses a non-woven fabric having antibacterial, antifungal, and deodorizing properties using cellulose regenerated fibers obtained by mixing finely granular regenerated chitosan with a cellulose viscose solution and spinning the mixture. However, a modified cellulose regenerated fiber and its modified dispersion regenerated chitosan containing an antioxidant are dispersedly contained in the regenerated cellulose fiber to provide antioxidant ability and antibacterial performance, and long-term stabilization of the performance is achieved. The manufacturing method was unknown.

[0004]

In general, antioxidants are extremely unstable in air, and therefore long-term use of antioxidants is required for use in textile products for food packaging materials that are often exposed to air. Stability is required. However, it is difficult to maintain the antioxidant capacity for a long period of time by simply adding the antioxidant to the fiber by post-treatment, and it is sufficient to use the existing antioxidant auxiliary agent at the same time when treating. Durability is not obtained.
Similarly, if the antibacterial agent is simply applied to the fibers after the post-treatment, the antibacterial agent may fall off from the fibers, resulting in poor durability. INDUSTRIAL APPLICABILITY The present invention relates to a modified cellulose regenerated fiber which exhibits stable antioxidant and antibacterial effects for a long period of time when used in textile products such as woven fabrics, nonwoven fabrics and papermaking in the field of food packaging materials, etc. The purpose is to provide the law.

[0005]

DISCLOSURE OF THE INVENTION The present invention is a modification in which a regenerated cellulose fiber contains fine regenerated chitosan particles containing a pulverized product or extract of a plant tissue having an antioxidant ability. Modified cellulose characterized by adding and mixing regenerated cellulose and microparticulate regenerated chitosan containing pulverized product or extract of plant tissue having antioxidant ability to cellulose viscose solution, and spinning the solution. This is a method for producing regenerated cellulose fibers.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the cellulose viscose solution used for the modified cellulose regenerated fiber of the present invention, a usual rayon viscose solution (including a polynosic viscose solution) can be mentioned. It may be a mixture of titanium oxide and the like for the purpose of chemical conversion.

Examples of the pulverized product or extract of plant tissue having antioxidant ability as an antioxidant used in the present invention include vitamins typified by ascorbic acid and α-tocopherol, and catechin and flavonol. Representative flavonoids, tannins, β
-Containing carotenoids and terpenoids typified by carotene and lycopene, and lignans typified by sesamin, and specific examples including these include tea of the camellia family, mate of the ilex family, rose Family tea, tea walnuts, yellow mud, potatoes family Gymnema sylvestre, legume family Aspalathus linealis, and eucommia family Eucommia etc.
Pepper belonging to the crude drugs and spices, nutmeg of the Asteraceae family, cinnamon and laurel of the Lauraceae family, mustard and wasabi of the Brassicaceae family, fenugreek of the Leguminaceae family, cloves of the Aphiaceae family, allspice and eucalyptus, and dill of the aeriaceae family. , Celery seed, caraway, coriander, cumin, fennel, parsley and anise, garlic and onion of the lily family, cardamom of the ginger family, ginger and turmeric, perilla of the Labiatae family, basil, marjoram, oregano, sage, rosemary,
Thyme, Scutellaria, lavender and peppermint, red pepper and paprika of the Solanaceae family, Yukinoshita of the Asteraceae family, chamomile of the Asteraceae family, mugwort, marigold and sunflower,
Lemongrass of Poaceae, Peony of Peony, Vanilla of Orchidaceae, Salmon of Rutaceae, Lemon and Orange,
Examples include sesame seeds of the sesame family, peaches of the rose family, ume and apricots, and also those obtained by roasting or fermenting these. Among these, it is particularly preferable to use a crushed product or extract of tea, tea, rosemary, sage. It is also possible to use one kind or a combination of two or more kinds of pulverized products or extracts of plant tissues having such antioxidant ability. In the present invention, the particle size of the antioxidant needs to be made as small as possible in order to be contained in the finely granulated regenerated chitosan.

The chitosan used in the present invention is preferably a low molecular weight chitosan having an average molecular weight of 10,000 to 230,000. The modified cellulose regenerated fiber of the present invention can be obtained as follows. The method for obtaining finely particulate regenerated chitosan containing a pulverized product or extract of plant tissue having antioxidant ability is not particularly limited, but the following method is preferable. That is, chitosan is dissolved in an acidic aqueous solution of acetic acid, dichloroacetic acid, formic acid, etc., or a mixture thereof to obtain an acidic aqueous solution of chitosan, and the chitosan acidic aqueous solution is a pulverized product or extract of plant tissue having antioxidant ability. The substances are mixed and stirred, and the mixed aqueous solution is dropped into a basic solution composed of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, water of ethylenediamine, polar alcohol alone or a mixture thereof. Coagulated and regenerated by means to obtain regenerated chitosan granules containing a pulverized product or extract of plant tissue having antioxidant ability. After thoroughly washing this with water until it becomes neutral, the regenerated chitosan granules are pulverized and dispersed in advance by an ordinary wet pulverizer such as a homogenizer to obtain an average particle diameter of 50.
A milky suspension having a particle size of μm or less is prepared, and the suspension is discharged and dried in a high temperature atmosphere of 100 to 180 ° C. together with pressurized air discharged from the periphery of the nozzle, and is classified by a classifier to be antioxidant. A fine granular regenerated chitosan having a particle size of 10 μm or less, which contains a pulverized product or extract of a plant tissue having a function, is obtained.

As another method, chitosan is dissolved in the above acidic aqueous solution to prepare an acidic chitosan aqueous solution, and the chitosan acidic aqueous solution is mixed with a pulverized product or extract of plant tissue having an antioxidant ability, and the mixture is stirred. 100-200 with the mixed aqueous solution together with the pressurized air discharged from the periphery of the nozzle
It is discharged and dried in a high temperature atmosphere of 0 ° C. to obtain a chitosanate granule containing a pulverized product or extract of plant tissue having an antioxidant ability. It is neutralized and regenerated with the same basic aqueous solution as above, dried, and then classified with a classifier to obtain a pulverized product or extract of plant tissue having an antioxidant ability and having a particle size of 10 μm or less. Obtain fine granular regenerated chitosan.

The particle size of the fine granular chitosan containing the pulverized product or extract of the plant tissue having the antioxidant ability used in the above method is preferably 10 μm or less. If the particle size exceeds 10 μm, the yarn will be spun during spinning. It may cause breakage, which is not preferable.

Further, the compounding weight ratio of the pulverized product or extract of plant tissue having an antioxidant ability to chitosan is 1:
0.2-1 is preferable. If the blending weight ratio is less than 0.2, the antioxidant ability of the obtained fiber is low, and if it exceeds 1, the balance between chitosan and the antioxidant is lost, and the long-term stability of the antioxidant ability is lacking.

Next, in order to incorporate the above-mentioned finely granular regenerated chitosan into the regenerated cellulose fibers, the finely divided chitosan is added to and mixed with the cellulose viscose solution, or the solution is spun, or water or an alkaline aqueous solution is previously prepared. Alternatively, microparticulate regenerated chitosan is dispersed and mixed in an appropriate amount of cellulose viscose solution to be added to prepare an addition solution, which is added to the cellulose viscose solution at a blending amount immediately before spinning and spinning is performed. The spinning conditions for fiber formation at this time are the same as those for producing regenerated cellulose fibers from an ordinary cellulose viscose solution. The amount of regenerated chitosan in the form of fine particles containing a pulverized product or extract of plant tissue having antioxidative ability is preferably 0.5 to 3% by weight based on cellulose. If the added amount is less than 0.5% by weight, desired antioxidative ability and antibacterial performance are not imparted to the obtained fiber, and if it exceeds 3% by weight, the strength of the fiber decreases, which is not preferable. The modified cellulose regenerated fiber of the present invention may have any shape such as staple and filament.

The modified cellulose regenerated fiber of the present invention and the method for producing the same are applied to the viscose method, but it is naturally possible to apply the present invention to the copper ammonia method, the solvent method, the acetate method and the like. Is. When the modified cellulose regenerated fiber of the present invention is used to form a woven fabric, a non-woven fabric, a papermaking machine, etc., in addition to using the fiber alone, other fibers such as polyamide, polyacrylonitrile, polyvinyl alcohol, polyester, polypropylene, polyethylene are used. 1 or 2 of synthetic fibers such as, natural fibers such as cotton, silk, wool and pulp, and regenerated fibers such as rayon and acetate.
It is also possible to mix more than one seed.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to this range. The fibers obtained in this example were evaluated by the following methods.

Measurement method of dry strength, wet strength and knot strength of fiber Measured according to JIS L1015 "Stap test method of chemical fiber".

Measurement method of degree of antioxidant β-carotene 0.2 mg / l, linoleic acid 40 mg /
1, nonionic surfactant containing polyoxyethylene sorbitan monolaurate as a main component (manufactured by Atlas Powder Co.,
Brand name: Tween20) was added to 1 l of a solution containing 400 mg / l, 10 g of the sample immediately after production was added, and the mixture was allowed to react at 50 ° C. for 70 minutes with gentle stirring. -65), the absorbance at a wavelength of 470 nm was measured, and the antioxidant degree was calculated by the following formula. In addition, the antioxidant degree after 3 months and 6 months after production was stored at room temperature in the place where each sample was exposed to room light for 3 months and 6 months after production, and then the same operation as described above was performed. The degree of antioxidant was calculated.

[0017]

[Equation 1]

Method of measuring antibacterial performance The antibacterial performance of a sample immediately after production was measured by the method for measuring the number of bacteria in the antibacterial and deodorant finishing effect evaluation test manual of the Textile Products Sanitary Processing Council. The method is as follows. Bacterial count measuring method Staphylococcus aureus IFO12732 is used as a test bacterial cell, which is preliminarily cultured in a normal broth medium to a concentration of 5 to 30 × 10 ⁵ cells / ml to prepare a test bacterial suspension. 0.2 ml of the suspension was uniformly inoculated into 0.2 g of a sample in a sterilized screw vial, and after static culture at 35 to 37 ° C. for 18 hours, 20 ml of sterile buffered physiological saline was placed in the container. In addition, after shaking vigorously by hand for 25 to 30 times with an amplitude of about 30 cm to disperse the viable bacteria under test in the solution, make an appropriate dilution series with sterile buffered saline, and add 1 ml of the diluted solution at each step. Approximately 15 ml of pour plates of standard agar medium were placed in each sterile petri dish, and two plates were prepared for each of the same dilutions. This is 35-3
After culturing at 7 ° C. for 24 to 48 hours, the number of growing colonies was measured and the dilution ratio was multiplied to calculate the number of viable bacteria in the sample.
And its effect is the increase / decrease value in the following formula based on the average number of bacteria of non-additional sample of microparticulate regenerated chitosan containing pulverized product or extract of plant tissue with antioxidant ability and the addition sample sample The difference was determined, and 1.6 or more was determined to have an antibacterial effect.

[0019]

[Equation 2]

Example 1 500 g of chitosan having a degree of deacetylation of 92% and an average molecular weight of 40,000 was added to 250 g of acetic acid.
Dissolved in 7750 g of water containing water to prepare an aqueous chitosan acetic acid solution, and finely crushed sage powder of Lamiaceae (Kaneka Sun Spice Co., Ltd. (Excluding powder) 25
0 g was added and mixed with 4.0 kg / cm ² of pressurized air at a flow rate of 5 liters per hour into a high temperature atmosphere of 180 ° C. and dried to obtain granular chitosan acetate containing sage finely ground product. The dried product was collected by a cyclone collector.

The granular chitosan acetate containing the sage finely pulverized product was mixed with 1.5 l of a basic aqueous solution containing 10% by weight of sodium hydroxide, 30% by weight of ethanol and 60% by weight of water at room temperature. After stirring for 1 minute for neutralization, it was stirred at 1,500 rpm. p. The mixture was centrifuged at m for 10 minutes, and the supernatant was removed. This was repeatedly treated with water until it became neutral, dried, and then classified using an air classifier (manufactured by Seishin Enterprise Co., Ltd., trade name: Spedic 250), and a sage finely ground product was contained. 300 g of fine granular regenerated chitosan having a particle size of 10 μm or less was obtained. The microparticulate regenerated chitosan was added to 15 l of each polynosic viscose solution obtained by the conventional method (5.0% cellulose, 3.5% total alkali, 3.0% total sulfur) relative to cellulose.
Dispersion liquid of fine particulate regenerated chitosan containing sage finely pulverized product previously dispersed in water so as to be 2, 0.5, 1.0, 2.0, 3.0, 4.0% by weight. Was added and mixed with the polynosic viscose solution so as to be uniform, and immediately after defoaming, using a spinneret of 0.07 mm × 500 H, 22 g / l of sulfuric acid and 65 g / l of sodium sulfate at a spinning speed of 30 m / min. , Zinc sulfate 0.5 g / l, and spinning in a spinning bath at a temperature of 35 ° C. Then, it is stretched 2 times under the conditions of sulfuric acid 2 g / l, zinc sulfate 0.05 g / l, temperature 25 ° C., cut to 38 mm, and treated under the conditions of sodium carbonate 1 g / l, sodium sulfate 2 g / l, temperature 65 ° C. Done,
It was again treated with sulfuric acid at 5 g / l and a temperature of 60 ° C., and then subjected to ordinary scouring and drying to produce a modified cellulose regenerated fiber having a fineness of 1.25 denier and a fiber length of 38 mm (Sample Nos. 1 to 6).

Next, as a comparative example, a cellulose regenerated fiber prepared by mixing 2.0% by weight of sage finely pulverized product alone with cellulose instead of the finely granulated regenerated chitosan containing sage finely pulverized product ( Sample No. 7), a cellulose regenerated fiber (Sample No. 8) produced by mixing only 2.0% by weight of finely granulated regenerated chitosan containing no sage finely pulverized material with cellulose, and further ordinary polynosic fiber ( Sample No. 9) was obtained respectively. The obtained sample No. 1 to
No. 9, dry strength, wet strength, knot strength and immediately after production 3
The antioxidant degree and the antibacterial performance were measured after 6 months and 6 months, and the results are shown in Table 1.

[0023]

[Table 1]

From Table 1, the sample No. of the comparative example is shown. No. 7 does not have antibacterial properties because it contains only sage finely ground material,
In addition, the degree of antioxidant was low after 3 months and 6 months, and the sample No.
No. 8 has an extremely low antioxidant degree because the finely granulated chitosan does not contain finely ground sage. Sample No. Sample No. 1 has a low antioxidant degree because it has a small addition amount of 0.2% by weight of finely divided chitosan containing sage finely pulverized material to cellulose, and has no antibacterial performance. On the contrary, 6 is too much, 4.0% by weight, and the strength of the fiber is lowered, which is not preferable. The compounding weight ratio of chitosan and sage finely ground product is 1: 0.5, and the addition amount of the finely granulated regenerated chitosan containing sage finely ground product to cellulose of the polynosic viscose solution is 0.5 to 3% by weight. Sample No. 2-5 immediately after manufacturing 3
After 6 months and 6 months, it has a good degree of antioxidant and antibacterial properties,
Moreover, the physical properties of the fiber are also good.

Example 2 Instead of the sage finely ground product as the antioxidant of Example 1, a rosemary finely ground product of Lamiaceae (rosemary powder made by Kaneka Sun Spice Co., Ltd.) was further finely ground, Example 1 except that coarse powder was removed with a 400 mesh sieve)
Modified cellulose regenerated fibers were produced under the same conditions as those described above (Sample Nos. 10 to 15). As a comparative example, only finely crushed rosemary was added to 2.0% by weight of cellulose.
Cellulose regenerated fiber was produced by using (Sample No. 1).
6). The obtained sample No. For 10 to 16, the dry strength, the wet strength, the knot strength, and the antioxidant degree and the antibacterial performance immediately after production, and after 3 months and 6 months were measured, and the results are shown in Table 2.

[0026]

[Table 2]

From Table 2, it is shown that chitosan and the finely pulverized product of rosemary are mixed in a weight ratio of 1: 0.5, and the finely granulated regenerated chitosan containing the finely pulverized product of rosemary is 0 relative to the cellulose of the polynosic viscose solution. Sample No. added in the range of 5 to 3% by weight. Nos. 11 to 14 have a good degree of antioxidant, are stable for a long period of time, have antibacterial properties, and have good fiber physical properties.

Example 3 Chitosan having a degree of deacetylation of 92% and an average molecular weight of 40,000 was added to 250 g of acetic acid.
A water solution of chitosan acetic acid was dissolved in 7,750 g of water containing water, and the water solution was divided into 5 equal parts, each containing catechin of tea of the camellia family, which is an antioxidant, and oolong tea extract powder (manufactured by Suntory Ltd., trade name : Pure oolong powder) and oolong tea extract for chitosan 10, 20, 50, 10
It was added so as to be 0.150% by weight and mixed with stirring.
Each mixed solution was treated in the same manner as in Example 1 to obtain 5 kinds of fine granular regenerated chitosan each containing oolong tea extract and having a particle size of 10 μm or less, 60 g each. The microparticulate regenerated chitosan containing the respective oolong tea extracts was added to 15 liters of the same polynosic viscose solution as that used in Example 1 so as to be 2.0% by weight based on cellulose. A modified cellulose regenerated fiber having a fineness of 1.25 denier and a fiber length of 38 mm was obtained by the same operation as in Example 1 (Sample Nos. 17 to 21). Then, as a comparative example, instead of the finely granulated regenerated chitosan containing the oolong tea extract, only the oolong tea extract was added to the cellulose of the polynosic viscose solution at a blending amount of 2% by weight, and the same as above. A cellulose regenerated fiber was manufactured by the operation (Sample No. 22). The obtained sample No. 17-
No. 22, dry strength, wet strength, knot strength and immediately after production,
After 3 months and 6 months, measure the degree of antioxidant and antibacterial performance,
The results are shown in Table 3.

[0029]

[Table 3]

From Table 3, sample No. Sample No. 17 has a low antioxidant degree because the compounding weight ratio of the oolong tea extract to chitosan is as low as 1: 0.1. 21 has a ratio of 1:
Since it is too much as 1.5, the antioxidant degree becomes low after 3 months and 6 months, which is not preferable. In addition, the sample No. of the comparative example. No. 22 has only an oolong tea extract which is an antioxidant and does not contain regenerated chitosan, and therefore has a low antioxidant degree and no antibacterial performance. The compounding weight ratio of chitosan and oolong tea extract is 1: 0.2 to 1: 1.
Sample No. 2 in which the amount of regenerated chitosan containing oolong tea extract contained in the polynosic viscose solution in the range of 0 was 2.0 wt%. 18-2
0 is excellent in antioxidant degree immediately after production, 3 months, 6 months later,
It has antibacterial properties and is good without deterioration of the physical properties of the fiber.

Example 4 500 g of chitosan having a degree of deacetylation of 82% and an average molecular weight of 45,000 was added to 250 g of acetic acid.
A water solution of chitosan acetic acid was dissolved in 7,750 g of water containing, and 250 g of green tea extract powder (manufactured by Citymex, trade name: green tea polyphenol CTP95) containing catechin of tea of the camellia family as an antioxidant was added to the aqueous solution,
After stirring, the aqueous solution was dropped into a 5% aqueous sodium hydroxide solution to obtain a regenerated chitosan granular material containing a green tea extract. The granules were sufficiently washed with water until they became neutral, and then water was added in advance so that the solid content concentration became 3.0% to prepare a dispersion liquid, which was then pulverized and dispersed (manufactured by Nittetsu Kogyo Co., Ltd.). , Trade name: Cavitron) 10,000 rpm.
p. m was supplied at a flow rate of 800 l / h, and this was repeated 7 times to obtain a milky suspension. While stirring the suspension with a stirrer, it was discharged with a pressurized air of 5.0 kg / cm ² at a flow rate of 20 l per hour into a high temperature atmosphere of 170 ° C. to be dried, and fine particles containing a green tea extract. The dried product of regenerated chitosan was collected in a cyclone collector.
The dried product was classified using an air classifier (manufactured by Seishin Enterprise Co., Ltd., trade name: Spedic 250) to obtain 300 g of regenerated chitosan having a particle diameter of 10 μm or less and containing a green tea extract. The fine granular regenerated chitosan containing this green tea extract was added to 15 l of each rayon viscose solution (cellulose 9.0%, total alkali 6.0%, total sulfur 2.5%) obtained by the conventional method. In contrast, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0
A dispersion of microparticulate regenerated chitosan containing a green tea extract previously dispersed in water so as to have a weight% was uniformly mixed with a rayon viscose solution, and immediately after defoaming, it was adjusted to 0.
Using a spinneret of 09mm x 100H, spinning speed 55
Sulfuric acid 110 g / l, sodium sulfate 300 at m / min
g / l, zinc sulphate 15 g / l, spinning in a spinning bath at a temperature of 50 ° C. and stretching by a normal two-bath tension spinning method, 51 mm
After slicing, cut into regular scouring and drying to obtain a fineness of 3.0 denier,
Modified cellulose regenerated fibers having a fiber length of 51 mm were manufactured (Sample Nos. 23 to 28).

Next, as a comparative example, the above sample No. In place of the finely granulated regenerated chitosan containing the green tea extract used in Example 26, a cellulose regenerated fiber (Sample No. 29) produced by mixing only the green tea extract and a finely granulated regenerated chitosan were mixed. Produced cellulose regenerated fiber (Sample N
o. 30) and ordinary rayon recycled fiber (Sample No. 3)
1) respectively. The obtained sample No. 23 to 31, dry strength, wet strength, knot strength and immediately after production, 3 months later,
The antioxidant degree and antibacterial performance were measured after 6 months, and the results are shown in Table 4.

[0033]

[Table 4]

From Table 4, the blending weight ratio of chitosan and green tea extract is 1: 0.5, and the addition amount of the finely granulated regenerated chitosan containing the green tea extract is 0 with respect to the cellulose of the rayon viscose solution. 5 to 3% by weight of sample No. 24-
No. 27 has an excellent degree of antioxidant immediately after production, and after 3 months and 6 months, has an antibacterial property, and has little deterioration in the physical properties of the fiber.

Example 5 Chitosan having a degree of deacetylation of 87% and an average molecular weight of 37,000 was added to 250 g of acetic acid.
Is dissolved in 7,750 g of water containing water to obtain an aqueous chitosan acetic acid solution, and the aqueous solution is divided into 5 equal parts, each of which is a tea extract powder containing catechin of the family Rosaceae (manufactured by Suntory Ltd.,
(Trade name: Santencha S powder) was added to chitosan so that the amount of the tea extract was 10, 20, 50, 100, and 150% by weight, respectively, and the mixture was stirred and mixed. Then add 5 of each aqueous solution.
% Aqueous sodium hydroxide solution to obtain regenerated chitosan granules containing the beet extract. The granules were sufficiently washed with water until each became neutral, and then water was added to the granules in advance so that the solid content concentration became 3.0% to prepare a dispersion liquid, which was then pulverized and dispersed (Nittetsu Kogyo Co., Ltd.). (Product name: Cavitron)
By 10,000 r. p. 800 l / h at m rpm
It is supplied at a flow rate of
A milky suspension was obtained. While stirring the suspension with a stirrer, a regenerated chitosan containing the beet extract is dried by being discharged into a high-temperature atmosphere of 170 ° C. at a flow rate of 20 l per hour together with pressurized air of 5.0 kg / cm ^2. The dried product was collected by a cyclone collector. The dried product is a wind classifier (manufactured by Seishin Enterprise Co., Ltd., trade name: Spedick 25).
0) was used to obtain 60 g of finely granular regenerated chitosan having a particle diameter of 10 μm or less and containing the above-mentioned wt% of tea extract. 15 g of each of the same polynosic viscose solutions as used in Example 1 of the finely granulated regenerated chitosan containing this tea extract were evenly mixed so that the compounding amount was 2% by weight with respect to cellulose. The mixture was mixed with the solution and the modified cellulose regenerated fiber having a fineness of 1.25 denier and a fiber length of 38 mm was manufactured by the same operation as in Example 1 (Sample Nos. 32 to 36).

Next, as a comparative example, a cellulose regenerated fiber was prepared in the same manner as above except that only 2.0% by weight of the tea extract was added to the cellulose instead of the finely granulated regenerated chitosan containing the tea extract. Was manufactured (Sample No. 3)
7). The obtained sample No. For 32 to 37, the dry strength, the wet strength, the knot strength, and the antioxidant degree and the antibacterial performance immediately after the production, and after 3 months and 6 months were measured, and the results are shown in Table 5.

[0037]

[Table 5]

From Table 5, the addition ratio of chitosan and fine tea granulated regenerated chitosan containing cellulose extract to the cellulose of the polynosic viscose solution is 1: 0.2 to 1.0 in the compounding weight ratio of chitosan and beetroot extract. 2.0% by weight of sample N
o. 33 to 35 have a good antioxidant degree immediately after production, after 3 months, and after 6 months, are stable for a long time, and have antibacterial properties,
Moreover, the deterioration of the physical properties of the fiber is small, which is good.

[Example 6] Green tea extract powder of tea of the Camellia family (manufactured by Citymex, trade name: green tea polyphenol CTP95) and powder of green tea extract of rose family of Rosaceae (trade name: Santencha S) Powder) to weight ratio 1:
1 to obtain a mixture of green tea extract and beetroot tea extract.
Modified cellulose regenerated fibers were produced in the same manner as in Example 1 except that the mixture was used as the antioxidant instead of the sage finely ground product of Example 1 (Sample Nos. 38 to 43).

Next, in place of the finely granulated regenerated chitosan containing the mixture of the green tea and the tea extract used above as a comparative example, only the mixture of the green tea and the tea extract was added to 2.0% by weight of cellulose. % Regenerated cellulose fibers were produced in the same manner as described above except that they were added to polynosic viscose (Sample No. 44). The obtained sample No. 38-44
The dry strength, the wet strength, the knot strength, and the antioxidant degree and the antibacterial performance immediately after the production, and after 3 months and 6 months were measured, and the results are shown in Table 6.

[0041]

[Table 6]

From Table 6, it can be seen that the blending weight ratio of the mixture of the chitosan / green tea / herring tea extract was 1: 0.5, and the mixture of the green tea / herring tea extract to the cellulose of the polynosic viscose solution contained a minute amount. Sample No. 1 containing 0.5 to 3% by weight of granular regenerated chitosan. 39 to 42 have a good antioxidant degree, are stable for a long period of time, have an antibacterial property, have a small decrease in fiber physical properties and are good, and even if two kinds of plant tissue extracts are mixed, the effect is excellent. It is clear that .

[0043]

EFFECTS OF THE INVENTION As is clear from the above-mentioned Examples, microparticulate regenerated chitosan containing the pulverized product or extract of the plant tissue having the antioxidant ability of the present invention is added to and mixed with the cellulose viscose solution. The cellulose regenerated fiber obtained by the production method of spinning the solution is obtained by dispersing and containing finely granular regenerated chitosan containing a pulverized product or an extract of plant tissue having an antioxidant ability in the cellulose regenerated fiber. A modified cellulosic regenerated fiber that retains its antioxidant ability for a long period of time without impairing the original properties of the regenerated fiber and has antibacterial properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-325831 (JP, A) JP-A-8-144121 (JP, A) JP-A-9-119016 (JP, A) JP-A-5- 321017 (JP, A) JP 10-331070 (JP, A) Japanese Patent Publication 7-68648 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) D01F 1/00-9 / 04 C09K 15/00-15/34

Claims (2)

(57) [Claims] 1. A modified cellulosic regenerated fiber, characterized in that microparticulate regenerated chitosan containing a pulverized product or extract of a plant tissue having an antioxidant ability is dispersed and contained in a cellulosic regenerated fiber. . 2. A modification characterized in that finely granulated regenerated chitosan containing a pulverized product or extract of plant tissue having antioxidant ability is added to and mixed with a cellulose viscose solution, and the solution is spun. Method for producing regenerated cellulose fibers.