JPH04257301A - Antifungal and deodorizing leg product and its production - Google Patents

Abstract

PURPOSE:To obtain the title product with high safety to the skin, excellent in durability by impregnating a leg product with an acidic solution of chitosan containing both synthetic resin and crosslinking agent followed by treatment under heating. CONSTITUTION:The objective antifungal, deodorizing product such as polyamide socks can be obtained by the following process: a leg product is impregnated with an acidic solution (the concentration of an acid such as acetic acid is pref. 1-10wt.%) of chitosan (e.g. >=80%-deacetylated chitin) containing (A) a modified acid amide resin (its amount to be used being pref. 4-6wt.% based on the aqueous solution) and (B) a crosslinking agent such as epichlorohydrin (its amount to be used being 0.1-0.5wt. based on the aqueous solution) followed by treatment under heating. It is preferable that the present product be attached with >=0.2wt.% of the chitosan based on the fiber weight.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD This invention relates to leg products having antibacterial and deodorizing properties. More specifically, the present invention relates to a leg product using chitosan that is durable and has excellent antibacterial and deodorizing effects, and a method for producing the same.

0002

[Prior Art] Leg products such as pantyhose, socks, and tights are prone to sweat, especially in the areas that come into contact with shoes.
Antibacterial and deodorizing treatments have been applied because other metabolic waste products of the human body tend to accumulate and the odor thereof causes discomfort and is unsanitary.

Conventionally, as agents used for the above-mentioned antibacterial treatment, heavy metal compounds such as alkylamine derivatives, phenol derivatives, halogen derivatives, quaternary ammonium salts, biguanidine derivatives, furan derivatives, and organic mercury compounds have been used. , acrinol, and other pigments are used. However, the above-mentioned antibacterial treatment agents are not necessarily harmless to the human body, and therefore have a high possibility of causing skin disorders. Furthermore, the antibacterial treatment agent fell off from the textile product during washing, and the durability was also unsatisfactory.

[0004] In recent years, it has been proposed to use chitin-based materials to create fabrics with antibacterial and deodorizing properties that are free from the risk of skin damage (Japanese Patent Laid-Open Nos. 01-268127, 2001-10).
9959, Japanese Unexamined Patent Publication No. 02-307915, etc.), however, leg products have a problem in that they are not sufficiently durable against washing and the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a leg product that has durable antibacterial and deodorizing properties and is highly safe for the skin, and a method for producing the same.

[0006]

[Means for Solving the Problems] That is, one of the present inventions is as follows:
Another aspect of the present invention is a leg product having antibacterial and deodorizing properties, characterized in that chitosan is attached as the above-mentioned antibacterial and deodorizing treatment agent. A method for producing a leg product having antibacterial and deodorizing properties, characterized in that the leg product is impregnated in an acidic solution of chitosan containing a synthetic resin and a crosslinking agent and heat-treated.

The chitosan used in the present invention is a deacetylated compound of chitin, and preferably has a degree of deacetylation of 50 to 100%. Further, chitin-based substances such as carboxyl-modified chitin may also be used. Chitin is widely and abundantly present in nature, and is particularly contained in invertebrates and fungi as a complex with proteins. Especially among invertebrates, crustaceans such as shrimp and crabs, and beetles,
It is found in large amounts in insects such as crickets.

[0008] A method for producing chitin, which is a raw material for chitosan used in the present invention, from these raw materials is described, for example, in Journalof
Biological sciences Re
search, Vol 7, P168 (1954
), Journal of Organic C
hemistry, Vol 27, P1161 (
1962), and Fishery Technology
ogy, Vol. 11, P50 (1974) can be applied.

[0009] Chitin-based substances containing chitosan, which is a deacetylated compound of chitin, have excellent antibacterial properties against Escherichia coli, Trichophyton, Staphylococcus, etc., so they can impart antibacterial properties to textile products. It also has excellent biocompatibility and does not cause skin damage. In the antibacterial and deodorizing leg products of the present invention, this chitosan is used together with a synthetic resin and a crosslinking agent, and is fixed by heat treatment, which prevents it from falling off from textile products and significantly improves durability. It has become.

[0010] That is, in the leg product having antibacterial and deodorizing properties of the present invention, chitosan is firmly fixed inside and outside the textile product by impregnation and heat treatment, so it does not fall off even after multiple washings. Less is. Therefore, the antibacterial effect against Escherichia coli, Trichophyton, and others is sustained, and the proliferation of Staphylococcus aureus, which causes odor, can be suppressed. Furthermore, chitosan has excellent biocompatibility, making it extremely safe for skin.

[0011] Leg products as used in the present invention refer to all leg products such as support pantyhose, woolly pantyhose, tights, socks, insoles, and shoe lining fabrics. The materials constituting the leg products of this invention include synthetic fibers such as polyamide, polyester, and acrylonitrile, natural fibers such as cotton, linen, silk, and wool.
Furthermore, even if the polyurethane fiber is used for the purpose of imparting elasticity, the present invention is not limited thereto.

[0012] The leg product of the present invention preferably has 80% or more of deacetylated chitin fixed to it in an amount of 0.05% or more based on the weight of the fiber. More preferably 0.2
It is preferable to use the above-mentioned adhesive. If a material with a low degree of deacetylation is used, or even if a material with a high degree of deacetylation is fixed, it is difficult to obtain durable antibacterial properties.

The method for manufacturing leg products of the present invention will be explained below. First, chitosan is dissolved in an aqueous solution of dilute acid. The acid concentration is preferably 1 to 10% by weight. The concentration of chitosan in the aqueous acid solution is determined by considering solubility, viscosity, etc., and is preferably 0.3 to 4% by weight. Acids include acetic acid,
Examples include lactic acid, formic acid, succinic acid, and gluconic acid, with formic acid being particularly preferred.

Next, in order to strengthen the adhesion of chitosan to the textile product, a synthetic resin and a crosslinking agent are used as a mixed impregnating treatment solution. In addition to modified acid amide resins, synthetic resins used in the production method of the present invention include synthetic resins that do not release formaldehyde, such as polyacrylate resins, polyurethane resins, and polyvinyl alcohols. The mixing ratio of the synthetic resin to the aqueous solution is preferably 1 to 10% by weight. Furthermore, 4 to 6% by weight is preferable. The proportion of synthetic resin to the textile product is preferably 0.1 to 6% by weight. More preferably, it is 0.2 to 3% by weight.

[0015] The crosslinking agents used in the production method of the present invention include epichlorohydrin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Epoxy compounds such as 2,4
-Isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate can be mentioned.

Furthermore, polyols such as ethylene glycol, trimethylolpropane, glycerin, and polyoxyethylene glycol, bisacrylamides such as N,N-methylenebisacrylamide, and polyepoxides obtained by reacting acrylic acid or methacrylic acid Examples include di- or triacrylic acid or methacrylic esters. The mixing ratio of the crosslinking agent to the aqueous solution is preferably 0.05 to 2% by weight. More preferably, it is 0.1 to 0.5% by weight.

[0017] The impregnation process is carried out using a normal dyeing machine such as a dyeing machine used for dyeing socks, at a bath ratio of 1:5 to 1:50.
It can be carried out in the same way as normal staining. The processing temperature is preferably room temperature to 70°C. If the temperature is 70° C. or higher, polymerization of the machining fluid will begin, resulting in a hard texture, and it will be impossible to reuse the deliquified product after removing excess fluid from the target pick-up rate, which is undesirable. Processing time is 10 minutes to 30 minutes
It is preferable to dehydrate after impregnation. The pick-up rate of the treatment solution for textile products depends on the chitosan concentration25
-130% is preferable, and 40-100% is more preferable. Next, heat treatment is performed. The heat treatment may be heat-sensitive or moist heat, but moist heat is preferable. The condition is 1
The preferred range is 00 to 140°C and 5 to 60 seconds. For pantyhose, socks, etc., a moist heat treatment method using a mold can be applied. Drying can be carried out under normal conditions and is not particularly limited.

[0018] The drying temperature is preferably 50 to 140°C. Drying at 100° C. to 130° C. with moist heat is more preferable because it can improve the adhesion between the resin and the textile product without impairing the texture, and further improves durability. It is convenient for pantyhose kings, socks, etc. because the steam set using a mold can be applied as is. Under these conditions, the durability performance aimed at by the present invention can be fully demonstrated, but it is also effective to use a fixing agent to increase the adhesion strength between chitosan and fibers. preferable.

The above-mentioned fixing agent is selected and used depending on the material of the fiber. For example, natural fibers other than wool such as cotton, linen, and rayon include polyamine type, polyvinylamine, polyacrylonitrile polymer, polycation type such as quaternized polyethyleneimine, and others. For polyester materials, there are alkylaryl polybricol ethers, etc., and in any case, 0.
A concentration of 5-1% by weight is preferred. For wool, examples include metal-containing synthetic tannin derivatives, and for nylon fibers, examples include tannic acid, phenolsulfonic acid formalin condensate, and the like.

[0020]

[Examples] This invention will be explained below with reference to Examples. The physical properties were evaluated using the following measurement method. 1) Antibacterial The number of bacteria was measured to evaluate the antibacterial property according to the following manual for the evaluation of the processing effect of antibacterial and deodorizing processed products: How to measure the number of bacteria (Textile Sanitary Processing Council, 1988).

[0021] The following bacteria were suspended in sterilized liquid broth, 0.2 ml of this liquid was inoculated onto a 0.2 g test piece (the number of bacteria was approximately 280,000), and after culturing at a temperature of 37°C for 18 hours. , take it out. Measure the number of viable bacteria on the test piece before and after culturing,
Calculate the increase/decrease value and difference in the number of bacteria using the following formula. Test bacteria: Staphylococcus aureus
cus aureus ATCC 6539 (IFO
12732) Test piece sample: 0.2g Culture temperature/time: 37°C x 18 hours Washing method: JIS 0217,103
Number of viable bacteria on test piece after 18 hours of culture Increase/decrease in number of bacteria = Log1
0 ──────────────────
Number of viable bacteria immediately before culturing (number of planted bacteria) Difference in bacterial count increase/decrease = bacterial count increase/decrease value of unprocessed sample - bacterial count increase/decrease value of processed sample A standard white cloth was used as the unprocessed sample.

2) Safety of skin disorders A patch test was conducted using a panel of 20 adult men and women in accordance with the Japan Industrial Skin Hygiene Association's patch test evaluation method (Kawagi) based on microscopic observation, and the evaluation was made in accordance with the following method. After applying the test sample and control sample to the inner side of the upper arm of a healthy person for 24 hours, the sample was removed and examined with the naked eye after 30 minutes.If there were no abnormalities, a lump specimen was prepared and the depression was examined using a stereomicroscope. Observe the skin groove (B-stage). For depressed skin grooves, the emphasis is on the reactivity symbol (+).
When subtracting the test regime irritation index from the control irritation index, the results are 0B (negative), 1B to 2B (semi-negative), and 3B (semi-positive) in descending order of skin irritation sensitivity.
, 4B (positive).

[0023]

[Examples 1 and 2, Comparative Examples 1 and 2] Woolly pantyhose made of nylon 66 fibers were used as textile products. After dyeing, processing was carried out under the following conditions. Acetic acid 2
% aqueous solution, add 3% by weight of 80% or more deacetylated chitin (trade name Daichitosan, manufactured by Dainichi Seika Co., Ltd.),
After swelling for 4 hours, a completely dissolved chitosan solution was prepared using a disperser. 7 parts of the above chitosan solution, 4 parts of modified acid amide resin (trade name: Riken Resin RJ-36, manufactured by Miki Riken Co., Ltd.), 4 parts of a reactive special silicone derivative (trade name: Parasolve 272, manufactured by Ohara Palladium Co., Ltd.), epoxy silicone compound (trade name: Dainippon Ink Co., Ltd.) 0.1 part of Dick Silicone Softner #200 (trade name, manufactured by Kagaku Kogyo Co., Ltd.) was dispersed in 84.9 parts of water.

Next, woolly pantyhose was added to this treatment solution at a bath ratio of 1:10 using a drum dyeing machine for 40 minutes.
℃ for 15 minutes, and the fixation rate was 0.02% by weight (Comparative Example 2) and 0.05% by weight using a Centor dehydrator.
(Example 1) The pickup rate is 24% and 0.
．． Pickup rate 48 to be 1% by weight (Example 2)
% excess liquid was removed. Continue using the mold at 125°C.
After performing a moist heat heat treatment for 15 seconds, it was dried.

An antibacterial property test (bacterial count measurement method) and a skin damage safety test were conducted on the woolly pantyhose to which chitosan had been fixed and which were not subjected to antibacterial and deodorizing treatment (Comparative Example 1). The results are shown in Table 1.

[0026]

[Example 3] Woolly pantyhose were processed under the same conditions as in Example 2, except that the heat treatment was carried out using dry heat at 125° C. for 2 minutes. The results are shown in Table 1.

[0027]

[Example 4, Comparative Example 3] Nylon 66 as a textile product
The treatment was carried out under the same conditions as in Example 2 using support pantyhose made of polyurethane fibers and polyurethane fibers. (Example 5) Support pantyhose to which chitosan was fixed and support pantyhose to which chitosan was not fixed (
The physical properties of Comparative Example 3) were evaluated. The results are shown in Table 1.

[0028]

[Example 5, Comparative Example 4] Cotton, acrylic,
The same treatment as in Example 2 was performed using women's socks (Example 5) made of nylon fiber blend yarn and polyurethane filament yarn. The obtained women's socks and the untreated socks (Comparative Example 4) were subjected to an antibacterial test (bacteria count measurement method) and a skin damage safety test before and after washing. The results are shown in Table 1.

[0029] As is clear from Table 1, the products processed with chitosan and synthetic resin and heat treated in the examples have antibacterial properties, have little loss of effectiveness after washing, and are excellent in durability. .

[0030]

[Table 1]

[0031]

[Effects of the Invention] The antibacterial and deodorizing leg product of the present invention has excellent durability compared to conventional products, and
It has no possibility of causing skin damage to the wearer and has high industrial utility value.

Claims (2)

[Claims] 1. A leg product having antibacterial and deodorizing properties, characterized in that chitosan is attached as the antibacterial and deodorizing treatment agent. 2. A method for producing a leg product having antibacterial and deodorizing properties, which comprises impregnating the leg product in an acidic solution of chitosan containing a synthetic resin and a crosslinking agent and heat-treating the leg product. manufacturing method.