JP3279882B2 - Method for producing chitosan-given fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a chitosan-provided fiber.
And a method for producing the same .

[0002]

2. Description of the Related Art Textile products are widely used in the fields of clothing, bedding, intellectuals, materials, and the like. However, with the sophistication of consumer needs, further various functions are required. One of the required functions is antibacterial and deodorant.

With respect to imparting antibacterial properties to fibers, a method of binding silver ions or copper ions to fibers as an antibacterial agent is disclosed in Japanese Patent Application Laid-Open No. 52-92000, and the fiber surface is chemically modified. JP-A-3-213652 discloses a method for bonding a specific metal such as, for example, a method in which a fiber surface is modified with hydroxylamine and then chemically bonded to a metal such as copper or aluminum.

In the method of attaching a low molecular weight organic antibacterial agent to fibers, it has been proposed to use 2,4,4'-trichloro-2'-hydroxy-diphenyl ether as an antibacterial agent as disclosed in JP-A-69-144678. Kaisho 59-15
No. 7,376, JP-A-59-230588, etc., the use of 3,4,4'-trichlorocarbanilide is disclosed in JP-A-1-266277, JP-A-2-112.
No. 474, for example.

[0005] In addition, in the method of attaching a specific deodorant to fibers, ferrous sulfate / ascorbic acid and ferric phthalocyanine are used as deodorants in the method of attaching a deodorant to fibers. No. 42 (1986),
p. 50, Journal of the Textile Society of Japan, No. 41 (1985), p. 26
7.

[0006] Among these methods, however, the method of bonding metals, depending on the metal, reveals a color unique to the metal, impairs the quality of the fiber product, and limits the use of the fiber product. Evaluation is low. In addition, in the method using a low-molecular organic antibacterial agent or a specific deodorant, since the antibacterial agent and the deodorant are held by a physical bond instead of a chemical bond, they are exposed, stained, dropped off by washing, etc. It is not satisfactory in terms of durability.

[0007]

SUMMARY OF THE INVENTION The present invention has been made based on such a situation, and an object of the present invention is to provide a chitosan-given fiber which has no coloring and is durable and has an excellent antibacterial deodorizing function. Another object is to stably obtain such fibers.

[0008]

According to the present invention, 1 × 10 ^{−5 is provided.}
Fiber having acidic group of ~ 1500 × 10 ⁻⁵ eq / g
To an aqueous acid solution containing 0.1 to 20% by weight of an acid
Impregnated with a chitosan solution containing 0.1 to 10% by weight
Method for producing chitosan-added fiber characterized by treating
In the law.

[0009]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The chitosan-provided fiber of the present invention is a fiber to which chitosan having an antibacterial deodorizing function is firmly fixed and provided.

The fiber to which chitosan is added is a fiber having an acidic group, and examples of the acidic group include a carboxyl group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group. The fiber has 1 × 10 ^{−5 to} 1500 × 10 ⁻⁵ equivalent / g in the base polymer. Moreover, one acidic group is added by chemical modification of the fiber surface.
It may be a fiber introduced from × 10 ^{−5 to} 1500 × 10 ⁻⁵ equivalent / g. The amount of acidic group in the fiber can be appropriately controlled by the copolymerization amount of the acidic group-containing component, the degree of modification, and the like.

As the fiber having an acidic group, a polyester fiber whose base polymer is made of polyester, polyamide or acrylonitrile-based polymer, for example, a sulfonic acid group-containing polyester polymer obtained by copolymerizing sulfoisophthalic acid or the like with polyethylene terephthalate; Carboxylic acid group-containing acrylonitrile-based polymer obtained by copolymerizing acrylic acid, methacrylic acid, itaconic acid and the like with acrylonitrile, and sulfonic acid group-containing acrylonitrile-based polymer obtained by copolymerizing methallyl sulfonate, parasulfophenyl methallyl ether and the like with acrylonitrile And acrylic fibers.

When the base polymer of the acrylic fiber is produced by radical polymerization or redox polymerization in combination with a reducing agent using a persulfate as a polymerization initiator, the obtained polymer includes the polymerization initiator An acrylic fiber comprising an acrylonitrile-based polymer obtained by such a polymerization method may be used, since it has a sulfonic acid group or a sulfuric ester group at the terminal of the polymer chain, which results in an acrylic fiber having an acidic group. Further, the amount of the acidic group of the obtained acrylic fiber can be determined by dissolving in a solvent such as dimethylformamide or the like, and after cation exchange, by a non-aqueous neutralization titration method.

The chitosan in the present invention is a polysaccharide having a glucosamine unit as a main constituent unit, and is obtained by deacetylating chitin present in the shell of crab, shrimp, etc. Form a polyion complex with the group.

In the chitosan-provided fiber of the present invention, the chitosan forms a polyion complex with the acidic group of the fiber and is ionically bonded, and the amount of chitosan is fixed to the fiber by 0.1 to 5% by weight. If the amount is less than 0.1% by weight, the antibacterial deodorizing function is insufficient, and if it exceeds 5% by weight, the physical quality of the base fiber is reduced by the polyion complex. The presence of the polyion complex can be confirmed by dissolving the chitosan-provided fiber with a solvent for the fiber serving as the base material and from the infrared absorption spectrum of the insoluble material.

Further, in the chitosan-provided fiber of the present invention, since chitosan forms a polyion complex with the acidic group of the fiber, the antibacterial deodorizing function of chitosan and the function of the acidic group of the fiber are exhibited, respectively. In addition, since the bonding strength is enhanced by having a large number of amino groups in the chitosan molecule, it exhibits a bonding strength comparable to that of a covalent bond and provides durability to the antibacterial deodorant function.

The chitosan-provided fiber of the present invention not only has excellent antibacterial properties, but also has an excellent deodorizing effect, in particular, by chemically reacting with aldehydes represented by acetaldehyde to remove aldehydes in the gas phase. Has performance. Further, the chitosan-provided fiber of the present invention has chitosan immobilized in an insolubilized state, has a durable antibacterial deodorizing function, and has a durability of the antibacterial deodorizing function, which can dissolve the chitosan-provided fiber into chitosan. It can also be confirmed from the fact that the antibacterial deodorizing function does not decrease even when immersion treatment is performed with an acid aqueous solution, for example, an acetic acid aqueous solution.

The chitosan-provided fiber of the present invention is produced by the following method. That is, 1 × 10 ^{−5 to} 1500 × 10
^-5 equivalents / g of a fiber having an acidic group,
Impregnation is performed with a chitosan solution in which 0.1 to 10% by weight of chitosan is dissolved in an aqueous acid solution containing 1% by weight.

In the method of the present invention, the fiber is preferably an acrylic fiber made of an acrylonitrile-based polymer obtained by redox polymerization using a persulfate alone or in combination with a reducing agent, or a sulfoisophthalate copolymer. Polyester fibers made of polyethylene terephthalate are used.

The chitosan in the chitosan solution includes:
Chitosan having any degree of deacetylation may be used as long as it is soluble in a dilute acid.
90% of chitosan is used, and the molecular weight of chitosan to be used is not particularly limited and can be selected from those having molecular weights of about tens of thousands to about one million. Can be

As the chitosan solution, an acid is used in an amount of 0.1 to 20.
A chitosan solution obtained by dissolving 0.1 to 10% by weight of chitosan in an aqueous acid solution containing 1% by weight is used. Examples of the acid in the acid aqueous solution include inorganic acids such as hydrochloric acid, and organic acids such as acetic acid, lactic acid, oxalic acid, and propionic acid. Chitosan is easily dissolved in such an aqueous acid solution, but has a chitosan concentration of 0.1% by weight.
When the amount is less than the above, the amount of chitosan added to the fiber is small, and a sufficient antibacterial deodorizing function cannot be provided. When the amount exceeds 10% by weight, the viscosity of the solution becomes too high, and it becomes difficult to impregnate the fiber.

For the impregnation of the fiber with the chitosan solution, methods such as spraying, dipping and coating are used. The temperature, time and the like in the impregnation treatment are not particularly limited, and the chitosan forms and bonds with the acidic group of the fiber and the polyion complex in a short time, and the chitosan adheres to the fiber. The amount of chitosan to be fixed is set based on the amount of acidic groups in the fiber and the concentration of chitosan in the chitosan solution, and is 0.1 to 5% by weight based on the fiber. After the impregnation treatment, washing and drying are performed as necessary.

As described above, according to the method of the present invention, a chitosan-fixed acrylic fiber can be stably obtained in a short time under a mild condition for forming a polyion complex. The method of the present invention can also be partially applied to fibers by printing or the like, depending on the form of the fiber, the intended use of the fiber product, and the like.

[0024]

The present invention will be described below in more detail with reference to examples. In addition, each evaluation in an Example was based on the following method.

Antibacterial test: The sample fiber was placed in an aqueous solution containing 2 × 10 ⁴ Staphylococcus aureus / ml in accordance with the Shake Flask Method, which is the standard for antibacterial and deodorized processed products of the Textile Sanitation Processing Council. The number of viable bacteria in the aqueous solution after the time shaking treatment is measured.

Deodorizing test: 1 g of a sample fiber is sealed in a 370 ml Erlenmeyer flask adjusted to an acetaldehyde concentration of 100 ppm, and after 60 minutes, the acetaldehyde concentration in the flask is measured.

Washing durability test: Using a home washing machine,
After washing the sample fiber according to JIS L0217 and 103, centrifugal dehydration and drying are performed, and an antibacterial test and a deodorant test are performed.

Acid resistance test: 10% by weight of acetic acid in sample fiber
After immersion in an aqueous solution for 1 hour, the plate is washed with running water until no acid is found, dried, and subjected to an antibacterial test and a deodorant test.

Example 1 93% by weight of acrylonitrile and 7% by weight of vinyl acetate redox-polymerized with a polymerization initiator consisting of sodium persulfate and sodium bisulfite
1 part by weight of an acrylic fiber (2 denier) having an acid group amount of 5 × 10 ⁻⁵ equivalent / g consisting of a sulfonic acid group and a sulfate ester group was added to a 5% by weight aqueous solution of acetic acid in Daichitosan (Dainichiseika Co., Ltd.). Was immersed in 40 parts by weight of a chitosan solution containing 5% by weight of a chitosan solution, and the fiber was taken out, washed with running water for 10 minutes, and dried at 85 ° C. The obtained fiber was cut, an aqueous solution of iodine / potassium iodide was dropped on the cross section, and the cross section was observed with a microscope. As a result, it was confirmed that chitosan was fixed to the surface layer of the fiber.
The obtained fibers were evaluated, and the results are shown in Table 1.

[0030]

[Table 1]

Example 2 93% by weight of acrylonitrile redox-polymerized with a polymerization initiator consisting of sodium persulfate and sodium bisulfite and methyl acrylate 7
Consists wt% of polymer, a carboxyl group, acrylic fibers (2 denier) of sulfonic acid group and an acid group amount 7 × 10 ^-5 eq / g consisting of sulfate group with 1 part by weight, acetic acid 5 wt% aqueous solution of the die chitosan (Chitosan, manufactured by Dainichi Seika) was immersed for 1 second in 40 parts by weight of a solution in which 5% by weight was dissolved, the fiber was taken out, washed with running water for 10 minutes, and dried at 85 ° C. The obtained fiber is cut, and the cross section thereof has iodine /
An aqueous solution of potassium iodide was dropped, and the cross section was observed with a microscope. As a result, it was confirmed that chitosan was fixed to the surface of the fiber and was present. The obtained fibers were evaluated, and the results are shown in Table 2.

[0032]

[Table 2]

Example 3 One part by weight of a polyester fiber (2 denier) having a sulfonic acid group amount of 1150 × 10 ^-5 equivalent / g and polyethylene acetate terephthalate copolymerized with 5-sodium sulfoisophthalic acid was mixed with 5 parts by weight of acetic acid. The solution was immersed for 1 second in 40 parts by weight of a solution in which 5% by weight of ditoxane (Chitosan, manufactured by Dainichi Seika Co., Ltd.) was dissolved in a 1% aqueous solution. The obtained fibers were evaluated, and the results are shown in Table 3.

[0034]

[Table 3]

(Comparative Example 1) A polymer composed of 93% by weight of acrylonitrile and 7% by weight of vinyl acetate polymerized using azobisisobutyronitrile as a polymerization initiator, and having an acidic group content of 0.1 × 10 ⁻⁵ equivalent / g of acrylic fiber (2 denier) in a 5% by weight aqueous solution of acetic acid and 5% by weight of a solution of dichitosan (Chitosan, manufactured by Dainichi Seika) 4
Immersed in 0 parts by weight for 1 second.
Washed for 85 minutes and dried at 85 ° C. The obtained fibers were evaluated, and the results are shown in Table 4.

[0036]

[Table 4]

[0037]

The chitosan-provided fiber according to the present invention has an excellent antibacterial and deodorizing function which is free from coloring and has excellent durability because chitosan forms a polyion complex with an acidic group of the fiber and is bonded to the fiber. It also has a good texture. Further, according to the method of the present invention, such a chitosan-given fiber can be obtained stably without impairing the performance of the base fiber.

Continued on the front page (72) Inventor Satoshi Ogasawara 4-160 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Research Center (72) Inventor Mitsuaki Shiozuki 4-60, Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Prefecture No. Mitsubishi Rayon Co., Ltd. Product Development Research Center (72) Inventor Takanori Yamanan 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Intraday Seika Chemicals Co., Ltd. (72) Inventor Shinya Tsuchida 1-7 Nihombashi Bakurocho, Chuo-ku, Tokyo -6 Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-3-215533 (JP, A) JP-A-8-284066 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) D06M 15/03

Claims (1)

(57) [Claims] 1. A fiber having an acidic group of 1 × 10 ^{−5 to} 1500 × 10 ⁻⁵ equivalent / g is prepared by adding acid to 0.1 to 20% by weight.
A method for producing a chitosan-given fiber, comprising impregnating a chitosan solution in which 0.1 to 10% by weight of chitosan is dissolved in a contained acid aqueous solution.