KR910000055B1 - Antimicrobial fabrics having improved susceptibility - Google Patents

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Description

Antimicrobial textile products with improved discoloration

1 is a graph showing the relationship between dialkylsulfosuccinate adhesion amount, whiteness and wicking of an organosilicon 1% owf treated cloth containing a fourth ammonium base.

The present invention relates to an antimicrobial fiber product, and more particularly, to provide an antimicrobial fiber product having improved durability while improving discoloration such as yellowing or yellowing of fluorescent dyes.

In the atmosphere, microorganisms such as molds and bacteria grow, causing harmful effects on textile products and the human body. For example, sweat and food are attached to a wide range of textile products such as medical products, bedding products, and interior products, and exterior products. Incubated. Hygiene problems such as discoloration, fiber embrittlement, or cause of bad odor are caused by the microorganisms and the discharges from the microorganisms. Of course, in socks, underwear, casual wear, bedding sheets, covers, and the like, the growth, propagation, and diffusion of bacteria adhered to fibers are of course harmful to human health.

Conventionally, in order to solve such a problem, an organic tin compound, an organic mercury compound, a method of treating with a halogenated phenolic compound, a method of treating with a quaternary ammonium base-containing cationic surfactant, and treating with a vinyl polymer having a quaternary ammonium base Methods are known. However, in the case of these known methods, a satisfactory method is not known because of the problem of toxicity to the human body, pollution of the treated waste liquid, lack of durability, problems of discoloration by treatment, and the like. In particular, cationic polymers having a quaternary ammonium salt group have been attracting attention due to less problems such as toxicity (for example, JP-A-56-45485). However, these processing agents have not only difficulties in durability, appearance and feel, but also defects such as loss of fluorescence or yellowing due to the fact that most of the optical brighteners are anionic group-containing dyes, especially when treated with fluorescent brighteners. Had

The present inventors have reached the present invention as a result of earnestly researching to solve such drawbacks, maintain excellent antimicrobial properties, improve antimicrobial durability, and obtain a white product that prevents whiteness or yellowing. That is, the present invention is a textile product treated with organosilicon having a quaternary ammonium base represented by the following general formula, wherein the quaternary ammonium cation in the organosilicon is at least partially treated by an anionic surfactant It is characterized by being blocked.

Where n is an integer between 16 and 20

The textile product according to the present invention maintains the excellent antimicrobial properties of the organosilicon having a quaternary ammonium base and at the same time improves laundry durability, prevents whiteness or yellowing by treatment, and improves absorbency. There are so many features that you can do. Another great feature is the excellent appearance and feel of the processed product.

(단, R : 알콕시기, 할로겐원자, 아실기, 1개는 히드록실기라도 좋다. R' : 치환기를 가지고 있어도 좋은 탄소원자수가 20이하의 2가의 탄화수소기 또는 산소원자, 질소원자를 함유하는 탄소원자수가 20이하의 2가의 탄화수소기라도 좋다. R" : 저급알킬기, R'" : 탄소원자수가 1 내지 20의 알킬기, 알케닐, 환상지방족 탄화수소기, 방향족기, 아르알킬기 또는 알카릴기이다. n : 1 내지 3의 정수, X : 음이온, 예컨대 염소원자, 브롬원자 등이다.)로 표시되는 오르가노실리콘이 예시된다.As the organosilicon having a quaternary ammonium salt group used in the present invention, organosilicon having a quaternized structure of a diorganopolysiloxane having a siloxane unit having a tertiary nitrogen-containing group such as a dialkyl substituted aminoalkyl group, a general formula

(Wherein R is an alkoxy group, a halogen atom, an acyl group, and one may be a hydroxyl group.) R 'is a divalent hydrocarbon group having 20 or less carbon atoms or an oxygen atom or a nitrogen atom which may have a substituent. A divalent hydrocarbon group having 20 or less carbon atoms may be used. R ″: lower alkyl group, R ′ ″: alkyl group having 1 to 20 carbon atoms, alkenyl, cycloaliphatic hydrocarbon group, aromatic group, aralkyl group or alkaryl group. organosilicon represented by n: an integer of 1 to 3, X: an anion such as chlorine atom, bromine atom, etc.).

Moreover, as the latter preferable compound,

(N: 16-20) is illustrated.

This compound forms a film on the fiber, or the latter compound reacts with active hydrogen present in the fiber to introduce quaternary ammonium cation, which has excellent bactericidal and bactericidal effects against various molds and bacteria. have. Examples include fungi such as black mold, blue mold, yeast fungus, ketomium, cobweb fungus, Escherichia coli, Staphylococcus aureus, Corynebacterium bacteria, Gram-negative bacteria, Bacillus spp. Many bacteria such as genus have bactericidal and bactericidal effects.

Fiber materials to which the subject matter of the present invention is not particularly limited are natural fibers such as cotton, hemp, wool, and silk, regenerated fibers such as viscose rayon and ammonium copper ammonium, semisynthetic fibers such as acetate, and pro-acrylonitrile. Examples thereof include single or mixed fibers of synthetic fibers such as mixed fibers, polyamides, acrylics, polyesters, polyolefins, composite fibers, and yarns, knitted fabrics, nonwoven fabrics, rugs, towels, socks, and sewing articles made of these fibers. Moreover, the composite product of these fibers and another material may be sufficient.

The fiber product treated with the organosilicon has excellent antimicrobial properties and maintains good durability against general home washing or dry cleaning, but it is treated with harsh bacterial treatment such as 50 ppm of effective chlorine in a hospital at 70 ° C. for 10 minutes. The durability of the effect is still insufficient for the high temperature treatment in the autoclave. Furthermore, in the case of the white matter, in particular, fluorescent dyes of cellulose fibers, the whiteness decreases or the yellowing is accelerated as time passes by treatment with this compound, and the product quality and product value are remarkably damaged. .

Although it is not decided about this reason, it is thought that the compatibility of a processing agent and fluorescent dye is bad. Furthermore, when treated with the organosilicon, it becomes hydrophobic and therefore not suitable for processing of towels, sheets, underwear and the like. In the present invention, these drawbacks are solved at once.

The amount of the organosilicon imparted is usually 0.1 to 3% by weight, preferably 0.5 to 1% by weight, based on the weight of the fiber in solid content. The treatment method may be any of liquid treatment, pad drying, spray drying treatment, pad steam treatment, and the like, and may be heat treated again as desired. However, the liquid extraction process is particularly good. The treatment conditions are usually in a bath ratio of 1: 5 to 100 at room temperature to 80 ° C., preferably at 40 to 70 ° C. for at least 30 minutes, followed by hot air drying at 80 ° C. or higher.

(GAF Co. 올레일-n-메틸타우린나트륨염) 에어로졸 OT

(American cyanamid Co. 디옥틸술포숙시네이트), 고급알코올 인산에스테르염 등이 예시되고 단독 또는 2종이상의 병용이라도 좋다.In the present invention, it is usually essential to treat the organosilicon-treated fiber product with an anionic surfactant. As the anionic surfactant to be used, for example, higher fatty acids, higher fatty acid salts, soaps, sulfuric acid ester salts of higher alcohols, higher alkyl sulfonates, sulfated oils, sulfated fatty acid esters, sulfated olefins, alkylbenzene sulfonates, alkylnaphthalene sulfonates, Paraffin sulfonate

(GAF Co. oleyl-n-methyltaurine sodium salt) aerosol OT

(American cyanamid Co. dioctylsulfosuccinate), a higher alcohol phosphate ester salt, etc. are illustrated and may be used individually or in combination of 2 or more types.

The amount of the anionic surfactant used is at least one part, preferably at least 50%, more preferably all of the cationic groups possessed by the organosilicon. Moreover, by using 1.5 times or more of blocking amount of a cationic group, effects, such as water absorption and a sweat absorption, can also be improved further. In the present invention, the order in which the treatment agents are applied is also important, and it is impossible to obtain excellent effects even when used in the same bath. The treatment method with an anionic surfactant may also be arbitrarily used, such as an immersion method and a pad method. However, when organosilicon treatment is carried out by submersion (immersion) method, after the organosilicon is adsorbed to the fiber, an anionic surfactant and salts and other preparations are added to the residual bath for several minutes to several ten minutes. It is preferable to process. Therefore, it is a big advantage that the processing operation is simple and a special device is unnecessary.

On the other hand, in the pad method or the continuous method, it is desirable to pad dry with an anionic surfactant treatment liquid after pad drying with an organosilicon liquid. However, the present invention is not limited to these treatment methods, and for example, the pre-process may be performed by the dipping method and the post-process by the pad method, or vice versa. The present invention is illustrated by the following examples.

Example 1

The fourth ammonium base-containing organosilicon 1.2% owf, expressed in the following equation, is divided into 10 minutes while the refined, bleached, and fluorescently-dyed cotton price knit is rotated in a water of 1:20 using a wince dye. After the addition, the temperature was raised to 50 ° C. for 15 minutes, and then treated at that temperature for 15 minutes, followed by the addition of 1.2% owf of soap for 15 minutes, followed by centrifugal dehydration, followed by drying at 120 ° C. by a short loop dryer. Was done. Moreover, the sample which does not add soap as a comparative product was also created. The whiteness, light resistance, and durability of these treated fabrics were compared. Whiteness was evaluated by measuring L, a, and b with a colorimeter made by Nippon Denshi Color. The light resistance was irradiated for 1, 3, 5 hours with a photometer and the color fading was compared.

The durability was evaluated by testing antibacterial activity of the samples treated at 70 ° C. × 10 minutes with 50 times of home washing and 50 ppm of sodium hypochlorite solution by the JIS.Z.2911-1976 mold resistance test method. The results are shown in Table 1. Antibacterial cloths without added soap have a higher b value and poor whiteness as compared to untreated cloths (fluorescently dyed). It is easy to discolor in a short time also in the photometer irradiation test. The antibacterial test results showed that the antibacterial activity was good at 50 times of home washing, but the antimicrobial activity was clearly lowered at 70 ° C. × 10 minutes treatment with 50 ppm sodium hypochlorite solution.

On the other hand, the antibacterial cloth added with soap has no decrease in whiteness and no difference in light resistance as compared to the unprocessed cloth. In addition, even after treatment with sodium hypochlorite, excellent antibacterial durability was recognized.

[Table 1]

Example 2

Refined, preset and dyed polyester jersey was immersed in the aqueous solution of organosilicon containing ammonium base containing 1% owf in Example 1, heated at 60 ° C. for 20 minutes, and then sulfated fatty acid ester was treated with 1%. When owf was added and then dehydrated and dried for 10 minutes, the antimicrobial endurance was compared with the addition of sulfated fatty acid in the same manner as in Example 1, and the latter did not deteriorate even under the treatment of sodium hypochlorite. I could confirm that it does not.

Example 3

Paste, bleach, coat and fluorescein-dyed cotton fabrics are padded with 1.5% by weight solution of an organosilicone-containing organosilicon containing quaternary ammonium base, represented by the following formula, and wiped with mashglu About 1% owf of ganosilicone was attached to perform antimicrobial processing.

It was then padded and dried by a solution containing 0 to 5% by weight of dialkylsulfosuccinate. The relationship between the adhesion amount of the dialkyl sulfosuccinate and the whiteness (b value) and the water absorbency was examined to obtain the result as shown in FIG. In addition, the water absorbency was evaluated by dropping and diffusing water droplets on the treated cloth held horizontally (wicking time).

Undialkylsulfosuccinate treatment is high in b value and poor in whiteness. The absorbency is also bad. The adhesion amount of the dialkyl sulfosuccinate reached equilibrium at 1% owf of the same amount as the organosilicon, so that good whiteness was obtained. In addition, the wiking property also improved with the increase in the amount of the anionic surfactant used. Again, the antimicrobial test of these treated fabrics was carried out by bioassay.

Bioassay refers to the bacterial solution containing a certain number of Gram-negative bacteria, soaked in the cloth, and left for a certain time at the same temperature as the body temperature. The tendency is to be reduced, but reduced in antimicrobial fabrics.

The antimicrobial processed fabric according to the present invention exhibited a reduction rate of 95% or more regardless of the deposition amount of the dialkyl sulfosuccinate, thereby obtaining a good antimicrobial effect. Here, however, the durability of the antimicrobial properties was not a problem in 50 times of home washing, but as in Example 1, the adhesion amount of the dialkyl sulfosuccinate was 0.5% owf or less at 70 ° C. × 10 minutes treatment with a 500 ppm hypochlorous OH solution. The reduction rate of was less than 50% and the effect of post-treatment was also recognized here.

Claims (1)

In a fiber product treated with organosilicon having a quaternary ammonium base represented by the following general formula, wherein the quaternary ammonium cation in the organosilicon is at least partially blocked by treatment with an anionic surfactant. Antimicrobial fiber product with improved discoloration.

Where n is an integer between 16 and 20

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