JPH1037018A - Antibacterial cellulose regenerated fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial cellulose regenerated fiber having excellent humidity retention and combinedly having antibacterial property, antifungal property and acaricidal property without losing water absorbing property and feeling, etc., of the fiber itself. SOLUTION: This fiber is obtained by adding regenerated chitosan fine particles or regenerated acetylated chitosan fine particles having <=10μm particle diameter, and nitryl-based, pyridine-based, haloalkylthio-based, organic iodine- based, thiazole-based and benzimidazole-based antibacterial agents to cellulose viscose, and spinning the viscose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a regenerated cellulose fiber having excellent moisture retention, antibacterial property, antifungal property and anti-mite property without impairing the water absorption inherent in the regenerated cellulose fiber. The present invention provides fibers which are used as raw materials for yarns, knitted fabrics, nonwoven fabrics, papermaking and the like, and are widely used in the fields of clothing, sanitary materials, packaging materials, industrial materials, and agriculture.

[0002]

2. Description of the Related Art As a method for imparting antibacterial properties, antifungal properties, and anti-mite properties to fibers, a method of mixing and spinning chemicals in raw materials at the time of fiber production, or a method of processing into fibers is proposed. Have been. Examples of substances conventionally used to impart antibacterial properties include substances having metal ions such as silver, copper, and zinc, benzalkonium chloride, organosilicon-based quaternary ammonium salts, and hexamethylene biguanide hydrochloride. Also, examples of the substance that imparts antifungal properties include organic thiazolyl compounds and organic aromatic compounds such as benzimidazolyl compounds. Examples of the substance that imparts anti-mite properties include acaricides and repellents. . Then, a fiber having antibacterial properties, antifungal properties, and anti-mite properties has been obtained by kneading individual chemicals into the fibers or fixing them to the functional groups on the surface by chemical bonding.

[0003] However, bacteria, molds and ticks which are antibacterial, antifungal and anti-mite properties are completely different from the biological point of view, and substances having resistance to them are basically different. It is different. Therefore, bacteria, molds, ticks, and other fibers having resistance to them, such as antibacterial fibers, antifungal fibers, and anti-mite fibers, have been developed. No fibers have been developed.

[0004] The present applicant discloses in Japanese Patent Application Laid-Open No. Hei 4-289221 that a regenerated chitosan microparticle or a regenerated acetylated chitosan microparticle having a particle diameter of 10 µm or less is mixed and spun into viscose in regenerated cellulose fiber. By adding 0.5% by weight or more and 2.0% by weight or less to a regenerated cellulose fiber having antibacterial and deodorizing performance which is improved in dyeability and durable without impairing the original strength of the regenerated fiber, Also, in Japanese Patent Application No. 6-308109, a quaternary ammonium chloride chitosan fine particle having a particle diameter of 10 μm or less is mixed and spun in viscose, and 0.3 to
It has been disclosed that by containing 1.6% by weight, a regenerated cellulose fiber having a broad antibacterial spectrum can be obtained. These are chitosan-based microparticulates only mixed in viscose and spun regenerated cellulose fibers, which are mainly intended for antibacterial properties, not for antifungal properties, but for anti-mite properties. Also, it is already known that chitosan obtained from the exoskeleton of crabs, shrimps and insects has antibacterial and antifungal properties, but it cannot be said that the resistance to fungi having cellulolytic properties is sufficient. Mite control cannot be expected.

[0005] Regarding the antifungal property, there has been no fiber obtained by mixing an agent having an antifungal property such as an organic aromatic compound such as an organic thiazolyl compound or a benzimidazolyl compound into a fiber raw material and spinning. The performance can be exhibited by fixing these antifungal agents on the fibers, but the method of fixing them on the fibers makes it possible to obtain the inherent water absorption of the fibers,
The result is impaired moisture retention and texture, and there is a practical disadvantage.

[0006] Regarding mite prevention, acaricides and repellents are fixed to fibers, but the durability of the effect and the safety to the human body have been pointed out.
Therefore, fibers that impart antifungal properties and anti-mite properties to the fibers as described above, retain the inherent water absorption, moisture retention, and texture of the fibers and have practically sufficient performance and safety have not been developed. It is.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a fiber without impairing its inherent properties such as water absorption and texture.
An object of the present invention is to provide an antibacterial regenerated cellulose fiber having excellent moisturizing properties and having antibacterial properties, antifungal properties and anti-mite properties.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides a regenerated chitosan microparticle having a particle diameter of 10 μm or less, or a regenerated acetylated chitosan microparticle, a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent, and a thiazole antibacterial agent. And a benzimidazole-based antibacterial agent added to cellulose viscose, and the viscose is spun to obtain an antibacterial cellulose regenerated fiber. The fiber of the present invention has a synergistic effect of antibacterial and antifungal effects by simultaneously mixing and containing these multiple drugs, and has a broader antibacterial spectrum and broader antibacterial effect than the individual effects of each drug. Mold spectrum,
It is possible to develop anti-mite properties.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The particle size used in the present invention is 10
In order to obtain regenerated chitosan microparticles having a particle size of μm or less or regenerated acetylated chitosan microparticles, the present applicant has disclosed in
It is preferably prepared by the method disclosed in JP-A-2-62827 and JP-A-62-100534. That is, chitosan is dissolved in an acidic aqueous solution to obtain a chitosan acidic aqueous solution, and the aqueous solution is added to a basic aqueous solution by means of dropping or the like to coagulate and regenerate to obtain regenerated chitosan, or the regenerated chitosan is dissolved in a polar solvent such as methanol or ethanol. The regenerated acetylated chitosan acetylated with acetic anhydride or the like is thoroughly washed with water until it becomes neutral, and then the regenerated chitosan or the regenerated acetylated chitosan is further atomized, whereby the regenerated chitosan microparticles or regenerated acetylated Chitosan microparticles can be obtained efficiently.

[0010] For the expression of antibacterial properties and the improvement of moisture retention of fibers,
Since the intramolecular amino group of chitosan greatly contributes, the degree of acetylation when acetylating regenerated chitosan into regenerated acetylated chitosan leaves about 20% of amino groups, that is, the degree of deacetylation does not fall below 20%. It is preferable to do so.

For atomization, a usual spray dryer can be used. In order to atomize by spray-drying, it is preferred to use a conventional wet pulverizer such as a homogenizer, which is previously pulverized and dispersed to use as a milky suspension having an average particle diameter of 50 μm or less. The suspension thus obtained is discharged and dried in a high-temperature atmosphere together with pressurized air discharged from the periphery of the nozzle. At this time, the suspension is further atomized by shrinkage.
The temperature in the high-temperature atmosphere may be any temperature as long as it is sufficient to dry the object to be dried, and can be freely selected in the range of 100 to 180 ° C. The particle size of the obtained fine particles can be arbitrarily adjusted by appropriately adjusting the discharge amount and the applied air pressure when discharging into a high-temperature atmosphere, but it is possible to surely obtain a dried product having a desired uniform particle size. It is preferable to further classify to obtain.

The nitrile antibacterial used in the present invention is preferably a haloaryl nitrile compound, more preferably a haloisophthalonitrile compound. As the haloisophthalonitrile compound, 2, 4, 5, 6
-Tetrachloroisophthalonitrile, 5-chloro-2,
4,6-trifluoroisophthalonitrile and the like can be mentioned.

The pyridine antibacterial agent used in the present invention is preferably a halogenated pyridine derivative, a pyridinethiol-1-oxide compound or the like, and more preferably a sulfonylhalopyridine compound, a pyridinethiol-1-oxide compound. And the like.

Examples of the halogenated pyridine derivative include 2-chloro-6-trichloromethylpyridine,
-Chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridylmethanol, and sulfonylhalopyridine compounds 2,2,5,6-tetrachloro-4-methylsulfonylpyridine, 2,3,5-trichloro-
4- (n-propylsulfonyl) pyridine and the like, and as the pyridinethiol-1-oxide compound,
2-pyridinethiol-1-oxide sodium, 2-
Pyridinethiol-1-oxide zinc, di (2-pyridinethiol-1-oxide) and the like can be mentioned.

Preferred examples of the haloalkylthio antibacterial agent used in the present invention include haloalkylthiophthalimide compounds, haloalkylthiotetrahydrophthalimide compounds, haloalkylthiosulfamide compounds, haloalkylthiosulfimide compounds and the like.

Examples of the haloalkylthiophthalimide compound include N-fluorodichloromethylthiophthalimide and N-trichloromethylthiophthalimide, and examples of the haloalkylthiotetrahydrophthalimide compound include N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide. , N-trichloromethylthiotetrahydrophthalimide and the like.

The haloalkylthiosulfamide compounds include N-trichloromethylthio-N- (phenyl) methylsulfamide, N-trichloromethylthio-
N- (4-chlorophenyl) methylsulfamide, N-
(1-fluoro-1,1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N-
(1,1-difluoro-1,2,2-trichloroethylthio) -N- (phenyl) methylsulfamide and the like, and as the haloalkylthiosulfimide compound,
N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfimide, N, N-dichlorofluoromethylthio-N'-phenylsulfimide, N, N
-Dimethyl-N '-(p-tolyl) -N'-(florodichloromethylthio) sulfimide.

As the organic iodine antibacterial agent used in the present invention, preferably, an iodosulfone compound, an iodide unsaturated aliphatic compound and the like are mentioned, and more preferably, an iodosulfonylbenzene compound can be mentioned.

The iodosulfonyl compound includes:
Iodosulfonylbenzene compounds such as diiodomethyl-p-tolylsulfone, 1-diiodomethylsulfonyl-4-methylbenzene, 1-diiodomethylsulfonyl-4-chlorobenzene, and the like;
As the iodinated unsaturated aliphatic compound, 3-iodo-2-
Propargyl butylcarbamic acid, 4-chlorophenyl-3-iodopropargyl formal, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo-1-
Propene, 2,3,3-triiodoallyl alcohol and the like can be mentioned.

Preferred examples of the thiazole antibacterial agent used in the present invention include an isothiazolin-3-one compound and a benzthiazole compound.
An isothiazolin-3-one compound can be exemplified.

The above isothiazolin-3-one compounds include 1,2-benzisothiazolin-3-one,
(N-octyl) -4-isothiazolin-3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,
5-dichloro-2-cyclohexyl-4-isothiazolin-3-one and the like. Examples of the benzthiazole compound include 2- (4-thiocyanomethylthio) benzthiazole, 2-mercaptobenzthiazole sodium,
Zinc 2-mercaptobenzthiazole and the like can be mentioned.

The benzimidazole antibacterial agent used in the present invention is preferably a benzimidazole carbamic acid compound, a sulfur atom-containing benzimidazole compound, a cyclic compound derivative of benzimidazole, or the like, and more preferably benzimidazole. Carbamic acid compounds, thiazolylbenzimidazole compounds and the like.

The above-mentioned benzimidazole carbamate compounds include methyl 1H-2-benzimidazole carbamate, 1-butylcarbamoyl-2-methyl benzimidazole carbamate and 6-benzoyl-1H-2.
-Methyl benzimidazole carbamate, 6- (2-
Thiophenecarbonyl) -1H-2-benzimidazole methyl carbamate and the like.

The sulfur atom-containing benzimidazole compounds include 1H-2-thiocyanomethylthiobenzimidazole and 1-dimethylaminosulfonyl-2.
-Cyano-4-bromo-6-trifluoromethylbenzimidazole and the like.

The cyclic compound derivatives of benzimidazole include 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole, 2- (1- (3,5-dimethyl) Pyrazolyl))-1H-benzimidazole, 2- (2-furyl) -1H-benzimidazole and the like.

The above nitrile antibacterial agent, pyridine antibacterial agent, haloalkylthio antibacterial agent, organic iodine antibacterial agent,
Thiazole antibacterial agents, benzimidazole antibacterial agents,
One or two or more of these antibacterial agents may be selected and used as a mixture. Further, even one of the six antibacterial agents described above does not exhibit the effect expected to be lacking. The particle size of the mixture obtained by mixing the selected antibacterial agents is 10 μm in order to prevent clogging during spinning as in the case of the regenerated chitosan microparticles or regenerated acetylated chitosan microparticles.
m or less is preferable. As a method of adjusting the particle size to 10 μm or less, there is a method of mixing individual antibacterial agent particles finely pulverized with a pulverizer or the like to 10 μm or less, a method of pulverizing after mixing each antibacterial agent, and the like. May be used.

Next, the thus obtained particle diameter of 10 μm
The following regenerated chitosan microparticles or regenerated acetylated chitosan microparticles and nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents,
In order to simultaneously contain the thiazole antibacterial agent and the benzimidazole antibacterial agent in the cellulose regenerated fiber, as it is, or as an additional solution previously dispersed in water or an alkaline aqueous solution, or in an appropriate amount of cellulose viscose to be added What is necessary is just to disperse it into an additive solution, mix it with cellulose viscose just before spinning, and spin it. As for the spinning conditions and the like at this time, ordinary production conditions for regenerated cellulose fibers are applied. The cellulose viscose used in the present invention generally has rayon viscose and polynosic viscose, and the antibacterial cellulose regenerated fiber of the present invention may have any shape such as staples and filaments. An inorganic pigment such as titanium oxide can be used together for dulling or the like.

Regenerated chitosan microparticles having a particle size of 10 μm or less or regenerated acetylated chitosan microparticles and nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents, thiazole antibacterial agents, benz The total amount of imidazole antibacterial agent added to cellulose is
0.3 to 2.0% by weight is preferred. If the amount is small, the desired antibacterial and antifungal properties cannot be obtained, and if the amount is large, the fiber strength decreases, which is not suitable for practical use.

The proportion of the regenerated chitosan microparticles or the regenerated acetylated chitosan microparticles in the mixture of the regenerated chitosan microparticles or the regenerated acetylated chitosan microparticles and the antibacterial agent is preferably 10 to 90%. 10
If it is less than 90%, sufficient antibacterial properties and fiber moisturizing properties cannot be obtained, and if it is more than 90%, desired antifungal properties and anti-mite properties cannot be obtained. Therefore, more preferably, the ratio of the regenerated chitosan microparticles or the regenerated acetylated chitosan microparticles is 20 to 80%. As is clear from the examples,
Regenerated chitosan microparticles, or those containing only a mixture of antibacterial agents without adding regenerated acetylated chitosan microparticles, the effect of the present invention cannot be expected, and the antibacterial cellulose regenerated fiber of the present invention has the above-described structure. As a result, the fiber has the inherent water absorbency, excellent moisture retention, and simultaneously has antibacterial properties, antifungal properties, and anti-mite properties not found in conventional antibacterial cellulose regenerated fibers.

[0030]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to this range.
The fineness, dry strength, wet strength, knot strength, hygroscopicity, antibacterial performance, antifungal performance, anti-mite performance, etc. were tested by the following methods. (1) Fineness, dry strength, wet strength, knot strength JIS L 1015 “Staple test method for chemical fibers” (2) Hygroscopicity Approximately 10 g of absolute dry weight of a sample is measured, and immediately measured at 35 ° C. and 90% relative humidity. The sample was allowed to stand for 60 minutes, and its weight was measured. (3) Antibacterial performance The antibacterial performance was measured according to the method for measuring the number of bacteria in the Antibacterial Product Processing Effect Test Manual of the Textile Sanitary Processing Council. The method is as follows.

<Bacterial Counting Method> Staphylo
coccus aureus, IFO 12732; Escherichia coli, IFO 13168, and E. in the following table), Pseudomonas aeruginos
a, IFO 3080; ) Is used as a test cell, and this is preliminarily cultured in a normal broth medium at 5 to 30 × 10 ⁵ cells / ml to prepare a test cell suspension. 0.2 ml of the suspension is uniformly inoculated to 0.2 g of a sample in a sterilized screw vial, and cultured at 35 to 37 ° C. for 18 hours, and then sterilized buffered saline is added to the container. 20ml
In addition, after vigorously shaking by hand 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 dilute 1 ml of each stage. Was placed in a sterile petri dish, and about 15 ml of a standard agar medium pour plate was attached to the same diluent to prepare two plates each. This is 35
After culturing at ~ 37 ° C for 24 hours, the number of growing colonies was counted,
The number of viable bacteria in the sample was calculated by multiplying the dilution factor.

The effect is determined by comparing the regenerated chitosan microparticles or regenerated acetylated chitosan microparticles with a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent, and a thiazole antibacterial agent. Agent,
Based on the average number of bacteria of three samples without addition of the benzimidazole antibacterial agent and three samples of the addition sample, the difference between the increase and decrease was calculated by the following formula,
1.6 or more was determined to have an antibacterial effect.

[0033]

(Equation 1)

(4) Antifungal performance JIS Z 2911 "Mold resistance test" Wet test method The test cells were Aspergillus niger (Aspergillus niger)
niger, IFO 4414; ), Ketomium globosum (IFO 6347, hereinafter referred to as C.), Trichoderma viride (Tricho)
derma viride, IFO 5720; ) Were used. The results were determined by the following indication of mold resistance.

[0035]

[Table 1]

(5) Mite-preventing performance A sample is uniformly spread over the entire bottom surface of a plastic petri dish having a diameter of 4 cm and a height of 0.6 cm, and 0.05 g of a powder feed free of mites is placed on the sample. This is placed in the center of a plastic petri dish having a diameter of 9 cm and a height of 1.5 cm. Between these large and small petri dishes, approximately 3,000 viable mite culture media are introduced as the number of viable mites and spread uniformly. Put this on an adhesive sheet, put the adhesive sheet together in a 27 × 13 × 9 cm plastic container for food preservation, put saturated saline solution, cover the container and keep the humidity in the container at about 75%,
After being stored in a thermostat at 5 ° C. ± 1 ° C. and bred for one day and night, the mites were collected from the sample by a water washing method, counted, and the repellency was determined by applying the following formula. In addition, the test considered the variation and
Times.

[0037]

(Equation 2)

Example 1 Deacetylation degree 85% 500 g of chitosan having an average molecular weight of 42,000 was added to 250 g of acetic acid.
Was added to and dissolved in 7,750 g of water to obtain an aqueous solution of chitosan acetic acid. The viscosity of this solution at 20 ° C. was 3,400 cps as measured by a rotational viscometer. The acidic aqueous solution of chitosan was dropped into a 5% aqueous solution of caustic soda to solidify and regenerate in granular form.

After washing the coagulated product sufficiently with water until it becomes neutral, water is added in advance so that the final solid content concentration becomes 2 to 2.5%, and the mixture is rotated at 15,000 rpm for 3 minutes. The mixture was pulverized and dispersed three times to obtain a milky suspension. This was filtered through a 120-mesh sieve to remove coarse pieces, and the filtrate was discharged into a high-temperature atmosphere at 170 to 180 ° C at a flow rate of 18 ml / min with pressurized air of 3.0 kg / cm ² while stirring with a stirrer. The dried product was collected in a cyclone collector. The dried product is classified into an air classifier (manufactured by Seishin Enterprise Co., Ltd.)
Classification was performed using a trade name (Specdik 250) to obtain 300 g of regenerated chitosan fine granules having a particle size of 5 μm or less.

A commercially available mixture of a nitrile-based antibacterial agent, a pyridine-based antibacterial agent, a haloalkylthio-based antibacterial agent, an organic iodine-based antibacterial agent, a thiazole-based antibacterial agent, and a benzimidazole-based antibacterial agent is applied to the regenerated chitosan microparticles. Regenerated antibacterial and antifungal agent (manufactured by SENKAWA Co., Ltd., trade name KB9E, hereinafter abbreviated as antibacterial and antifungal agent A) 80 to 20 (weight ratio) of chitosan microparticles to antibacterial and antifungal agent A And 375 g of a mixture of the regenerated chitosan microparticles and the antibacterial antifungal agent A was obtained.

A mixture of the regenerated chitosan microparticles and the antibacterial and antifungal agent A was mixed with rayon viscose (cellulose 9.0%, total alkali 6.0%, total sulfur 2.5%) obtained by a conventional method. 15 liters, for cellulose
The regenerated chitosan microparticles and the antibacterial and antifungal agent A mixture dispersion liquid, which were previously dispersed in water so as to be added amounts of 0, 0.3, 0.5, 2.0, and 3.0% by weight, respectively, were prepared. Add,
After uniformly mixing with rayon viscose and defoaming, immediately use a nozzle of 0.09 mmφ × 100H and spinning speed 5
At 2 m / min, sulfuric acid 115 g / l, sodium sulfate 310
g / l, zinc sulfate 14 g / l, spinning in a spinning bath at a temperature of 53 ° C., drawing by a conventional two-bath tension spinning method, cutting to 32 mm, and performing a usual scouring and drying treatment to obtain a 3-denier antibacterial cellulose. Recycled fibers were obtained as Samples 1 to 5 without breakage. The fineness, dry strength,
Table 2 shows the results of measuring the wet strength, knot strength and hygroscopicity.
Table 3 shows the measurement results of the antibacterial performance, the antifungal performance, and the anti-mite performance.

[0042]

[Table 2]

[0043]

[Table 3]

As is apparent from Tables 2 and 3, the regenerated antibacterial cellulose regenerated fiber obtained by simultaneously adding the regenerated chitosan microparticles and the antibacterial antifungal agent A to rayon viscose and spinning have excellent hygroscopicity. Along with antibacterial performance, antifungal performance,
Sample 5 has excellent antibacterial performance, antifungal performance, and mite prevention performance, but has a large decrease in strength. Therefore, in practice, the amount of the mixture of the regenerated chitosan microparticles and the antibacterial and antifungal agent A is preferably 0.3 to 2.0% based on cellulose.

Example 2 500 g of chitosan having a degree of deacetylation of 90% and an average molecular weight of 54,000 was dissolved in 7,750 g containing 250 g of acetic acid to obtain an aqueous solution of chitosan acetic acid. The viscosity at 20 ° C. of this solution was 4,300 cps as measured by a rotational viscometer. This chitosan acidic solution was dropped into a 5% aqueous ammonia solution to coagulate and regenerate chitosan in a string form.

After the coagulated product was sufficiently washed with water until it became neutral, the coagulated product was treated with a homogenizer in the same manner as in Example 1 to obtain 1
The mixture was pulverized and dispersed three times at 5,000 rpm for 3 minutes each to obtain a milky suspension. This was filtered through a 100-mesh sieve, and the filtrate was stirred with a stirrer and discharged into a 175 ° C. high temperature atmosphere at a flow rate of 16 ml / min together with 4.0 kg / cm ² of pressurized air while maintaining a dispersed state. The dried product was collected by a cyclone collector. The dried product was classified in the same manner as in Example 1 to obtain 360 g of regenerated chitosan fine granules having a particle size of 5 μm or less.

With respect to the regenerated chitosan microparticles, the commercially available antibacterial and antifungal agent A used in Example 1 was used so that the regenerated chitosan microparticles and the antibacterial antifungal agent A became 80 to 20 (weight ratio). The mixture was added to obtain 450 g of a mixture of the regenerated chitosan microparticles and the antibacterial antifungal agent A.

A mixture of the regenerated chitosan microparticles and the antibacterial and antifungal agent A was mixed with polynosic viscose (cellulose 5.0%, total alkali 3.5%, total sulfur 3%) for each 15 parts.
Liters, 0,0.3,0.
A dispersion of the regenerated chitosan microparticles and the antibacterial and antifungal agent A mixture previously dispersed in water so as to have a mixing amount of 5, 2.0, and 3.0% by weight is added, and the mixture is uniformly mixed and defoamed. Immediately thereafter, using a nozzle of 0.07 mmφ × 500H, at a spinning speed of 32 m / min, 24 g / l of sulfur, 0.4 g / l of zinc sulfate,
The fiber is spun into a spinning bath of sodium sulfate 60 g / l at a temperature of 35 ° C., then stretched twice in a bath of 2 g / l sulfuric acid and 0.05 g / l of zinc sulfate at a temperature of 27 ° C., cut into 38 mm, and then cut into 1 g of sodium carbonate. / L, sodium sulfate 2g / l, temperature 6
After the treatment under the condition of 0 ° C., the treatment was again performed at 5 g / l of sulfuric acid and the temperature of 65 ° C., and the ordinary scouring and drying treatment was performed.
1.25-denier antibacterial cellulose regenerated fiber was produced as Samples 6 to 10 without thread breakage. The fineness, dry strength, wet strength, knot strength and hygroscopicity of these samples 6 to 10 were measured, and the results are shown in Table 4, and the measurement results of antibacterial performance, antifungal performance and mite prevention performance are shown in Table 5. .

[0049]

[Table 4]

[0050]

[Table 5]

As is clear from Tables 4 and 5, the antibacterial cellulose regenerated fiber of polynosic obtained by simultaneously adding the chitosan microparticles and the antibacterial and antifungal agent A to the polynosic viscose and spinning the fiber has excellent hygroscopicity. In addition to having the antibacterial performance, antifungal performance and mite prevention performance, Sample 10 exhibits excellent antibacterial performance, antifungal performance and mite prevention performance, but has a large decrease in strength. Therefore, in practice, the amount of the mixture of the regenerated chitosan microparticles and the antibacterial and antifungal agent A is preferably 0.3 to 2.0% based on cellulose.

Example 3 500 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.
Was added to and dissolved in 7,750 g to obtain an aqueous solution of chitosan acetic acid. The viscosity of this solution at 20 ° C. was 3,400 cps as measured by a rotational viscometer. This chitosan acidic solution was dropped into a 5% aqueous solution of caustic soda, and solidified and regenerated in granular form.

After the coagulated product was sufficiently washed with water until it became neutral, it was repeatedly pulverized and dispersed three times at 15,000 rpm for 3 minutes to obtain a milky suspension as in Example 1. This was filtered through a 120-mesh sieve to remove coarse pieces, and the filtrate was discharged together with 3.0 kg / cm ² of pressurized air at a flow rate of 16 ml / min into a high-temperature atmosphere of 170 to 180 ° C. while stirring with a stirrer. The dried product was collected by a cyclone collector. The dried product was classified using an air classifier (trade name: Spedick 250, manufactured by Seishin Enterprise Co., Ltd.) and 300 g of regenerated chitosan fine particles having a particle diameter of 5 μm or less were classified.
I got

The commercially available antibacterial and antifungal agent A used in Example 1 was added to the regenerated chitosan microparticles, and the mixture ratio (weight ratio) of the regenerated chitosan microparticles and the antibacterial antifungal agent A was added.
(Regenerated chitosan microparticles / antibacterial antifungal agent A) 0/10
0, 10/90, 20/80, 50/50, 80/2
It was adjusted to be 0, 90/10, 100/0.

A mixture of the regenerated chitosan microparticles and the antibacterial and antifungal agent A was mixed with rayon viscose (9.0% cellulose, 6.0% total alkali,
A mixture of each regenerated chitosan microparticles and antibacterial and antifungal agent A, which were dispersed in water in advance so that the amount of addition was 2.0% by weight with respect to cellulose in 15 liters of each of 15 liters. The dispersion was added, uniformly mixed with rayon viscose, defoamed, spun in the same manner as in Example 1, stretched by a usual two-bath tension spinning method, cut into 38 mm, and then subjected to a usual scouring and drying treatment. Then, 3 denier antibacterial regenerated cellulose fibers were produced as Samples 11 to 17 without breakage. The fineness, dry strength, wet strength, knot strength and hygroscopicity of these samples 11 to 17 were measured, and the results are shown in Table 6, and the measurement results of antibacterial performance, antifungal performance and mite prevention performance are shown in Table 7. .

[0056]

[Table 6]

[0057]

[Table 7]

As is clear from Tables 6 and 7, the antibacterial cellulose regenerated fiber obtained by simultaneously adding the regenerated chitosan microparticles and the antibacterial and antifungal agent A to rayon viscose and spinning have excellent hygroscopicity. Along with antibacterial performance, antifungal performance,
Although it has both anti-mite properties, Sample 11 has low hygroscopicity and Sample 17 has inferior mold resistance. Therefore, in practice, the ratio of the regenerated chitosan microparticles in the mixture of the regenerated chitosan microparticles and the antibacterial antifungal agent A is 2.0% by weight of the mixture of the regenerated chitosan microparticles and the antibacterial antifungal agent A based on the weight of cellulose. In this case, 10% to 90% is preferable.

Example 4 500 g of chitosan having a degree of deacetylation of 87% and an average molecular weight of 45,000 was added to acetic acid 250
g of water containing 7,300 g of a chitosan acetic acid aqueous solution having a viscosity of 3,300 cps at 25 ° C. This was dropped into a basic aqueous solution composed of 10% caustic soda and 20% water under a pressure from a hole having a pore diameter of 0.25 mm by a predetermined amount to be solidified and regenerated in a granular form. This was sufficiently washed until it became neutral to obtain regenerated chitosan granules. This with ethanol 4
After substitution twice, use equimolar acetic anhydride at room temperature for 24 hours.
After reacting for an hour, wash with ethanol and water,
In order to cut the ester bond with N caustic soda, the mixture was reacted at room temperature for 1 hour and washed with water to obtain 5.0 l of regenerated acetylated chitosan having a degree of deacetylation of 25%.

To 5.0 liters of the regenerated acetylated chitosan, 4.75 liters of water was added, and the mixture was mixed with a homogenizer to obtain 17.
Crushing twice for 5 minutes at 000 rpm, and
75 liters were added to obtain a dispersion having a concentration of 3.47%.
This was discharged and dried at a flow rate of 14 ml / min together with 3.6 kg / cm ² of pressurized air into a high-temperature atmosphere of 18 ° C., and the dried product was collected in a cyclone collector. Classification was performed by a classifier to obtain 200 g of regenerated acetylated chitosan microparticles having a particle diameter of 5 μm or less.

To the regenerated acetylated chitosan microparticles, the commercially available antibacterial and antifungal agent A used in Example 1 was mixed with the regenerated acetylated chitosan microparticles and the antibacterial and antifungal agent A at a ratio of 80: 2.
0 (weight ratio) to obtain 250 g of a mixture of the regenerated acetylated chitosan microparticles and the antibacterial antifungal agent A.

This was added to and mixed with polynosic viscose in the same manner as in Example 2, spun and subjected to the same treatment.
Antibacterial cellulose regenerated fibers of 1.25 denier x 38 mm were produced and produced as samples 18 to 22 without thread breakage, respectively. The fineness, dry strength, wet strength, knot strength and hygroscopicity of Samples 18 to 22 were measured, and the results are shown in Table 8, and the measurement results of antibacterial performance, antifungal performance, and anti-mite performance are shown in Table 9.

[0063]

[Table 8]

[0064]

[Table 9]

As is clear from Tables 8 and 9, the antibacterial cellulose regenerated fiber obtained by mixing the regenerated acetylated chitosan microparticles and the antibacterial antifungal agent A, and simultaneously adding the mixture to polynosic viscose and spinning was excellent. While having hygroscopicity, it also has antibacterial performance, antifungal performance, and anti-mite performance. Sample 22 exhibits excellent antibacterial performance, anti-fungal performance, and anti-mite performance, but has a large decrease in strength. Therefore, in practice, the amount of the mixture of the regenerated acetylated chitosan microparticles and the antibacterial antifungal agent A is as follows when the ratio of the mixture of the regenerated acetylated chitosan microparticles and the antibacterial antifungal agent A is 80:20 (weight ratio). The content is preferably 0.3 to 2.0% based on cellulose.

[0066]

As is clear from the above examples, according to the present invention, regenerated chitosan microparticles or regenerated acetylated chitosan microparticles having a particle size of 10 μm or less in regenerated cellulose fibers, nitrile antibacterial agents, Pyridine antibacterial agent,
A haloalkylthio antibacterial agent, an organic iodine antibacterial agent, a thiazole antibacterial agent and a benzimidazole antibacterial agent are simultaneously contained in cellulose in an amount of 0.3 to 2.0% (by weight) with respect to cellulose. Alternatively, by adding 10 to 90% of the total amount of the antibacterial agent mixed with the regenerated acetylated chitosan microparticles, the cellulose regenerated fiber has excellent hygroscopicity without impairing the inherent properties and texture of the regenerated cellulose fiber. In addition, it is possible to provide an antibacterial cellulose regenerated fiber having both antibacterial performance, antifungal performance, and anti-mite performance.

Claims (2)

[Claims] 1. The cellulose regenerated fiber has a particle diameter of 10 μm.
It is characterized by containing the following regenerated chitosan microparticles, a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent, a thiazole antibacterial agent, and a benzimidazole antibacterial agent. Antibacterial cellulose regenerated fiber. 2. The regenerated antibacterial cellulose fiber according to claim 1, wherein the regenerated chitosan microparticles are regenerated acetylated chitosan microparticles.