JPS591769A - Silver containing sterilizable cellulose fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to silver-containing permanently sterilized cellulose fibers.

It is known that when water is placed in a silver container, it becomes sterile. Therefore, as in the case of silver products, if water-insoluble silver or silver compounds are formed on the surface of the fibers, excellent sterilization properties similar to those of silver products can be obtained.

However, conventional methods in which silver or silver compounds are attached to the fiber surface have the disadvantage that their effectiveness quickly deteriorates due to their falling off, and those that are blended into the fiber stock solution during fiber production must be made of ultrafine powder. It does not enter the inside of the fiber uniformly, and what gets inside does not contribute to the bactericidal effect.
It has the disadvantage that in order to obtain a certain effect, it is necessary to use a larger amount of expensive compounds than necessary.

An object of the present invention is to provide a cellulose fiber containing water-insoluble silver or a silver compound and having excellent permanent bactericidal properties that overcomes these drawbacks. That is, the present invention involves bonding silver ions to the cation exchange groups of permanently sterilizing fibers containing water-insoluble scissors or silver compounds inside the fibers, particularly cellulose fibers having cation exchange ability, and converting the silver ions into water-insoluble Permanently sterilizing cellulose fibers or textile products containing cellulose fibers are produced by producing silver or silver compounds and incorporating them into the fibers.

The permanently sterilizing cellulose fiber of the present invention contains water-insoluble silver or a silver compound at a high concentration, particularly in the surface layer of the fiber, and exhibits excellent permanent sterilizing properties similar to those of metallic silver products.

Therefore, for example, in the case of fibers such as ordinary acrylic fibers that contain only acidic groups used as dyeing sheets, even if silver ions are bonded to the acidic groups in the fibers and then converted into water-insoluble steel or silver compounds, The amount of silver present in the surface layer of the fibers is extremely small and does not exhibit any bactericidal effect.

The cation exchange group of the cellulose fiber having cation exchange ability used in the present invention includes, for example, a sulfonic acid group, a carboxyl group, a hydroxyl group, and particularly a sulfonic acid group.

A carboxyl group is preferably used.

Further, it is preferable that the cation exchange group is present in the surface layer of the fiber as intensively as possible.

It can be obtained by dyeing with the cellulose direct dye having cation exchange ability of the present invention.

When cellulose fibers are dyed with anionic group-containing direct dyes, the dyes directly bind to the cellulose fibers, so the anionic groups can act as cation exchange groups, resulting in cellulose fibers with cation exchange ability. Can be converted. In this case, the anionic group-containing direct dye used is preferably a colorless direct dye, ie, a fluorescent dye.

On the other hand, as a method for dyeing cellulose fibers with an anionic group-containing direct dye, the usual method for dyeing cellulose fibers with direct dyes can be used as is, and a dip dyeing method, a vat steam method, a printing method, etc. are used.

In this case, the cation adsorption parameter of the resulting fiber tends to increase as the amount of anionic group-containing direct dye increases.

By treating the thus obtained cellulose fibers having cation exchange ability with an aqueous solution containing silver ions, fibers in which silver ions are bonded to anionic groups can be obtained. Note that as the aqueous solution containing silver ions used here, an aqueous solution of a water-soluble silver compound, such as silver nitrate, is preferably used.

At this time, the amount of silver ions bonded can be arbitrarily adjusted by adjusting the amount of anionic groups in the fiber or the concentration of the silver compound used. Next, cellulose fibers with cation exchange ability bound to silver ions are treated with an alkaline aqueous solution, so that the bound silver ions are converted to water-insoluble silver hydroxide, and the fibers are further heat-treated to dehydrate, thereby removing the surface layer of the fibers. Sterilizing cellulose fibers containing water-insoluble metallic silver in a portion are obtained.

As the alkaline aqueous solution used to convert Kushi ions into water-insoluble silver compounds, aqueous solutions of sodium hydroxide, sodium carbonate, sodium X carbonate, potassium hydroxide, lithium hydroxide, etc. are used, but industrially Aqueous solutions of sodium hydroxide and sodium carbonate are preferably used. Furthermore, by treating cellulose fibers with cation exchange ability with silver ions bonded to them with an aqueous hydrochloric acid solution to form silver chloride, and then reducing it with light, germicidal cellulose fibers containing water-soluble metallic silver inside the fibers can be produced. can get.

The bactericidal cellulose fiber of the present invention exhibits extremely excellent permanent bactericidal properties, and its bactericidal properties hardly decrease even after repeated regular home washing 20 times.

Even in aqueous solutions such as seawater containing large amounts of cations such as magnesium, the bactericidal properties hardly decrease.

On the other hand, if silver ions are simply bonded to the cation exchange groups of the cation exchange fibers, the silver ions are easily desorbed by an aqueous solution such as seawater containing large amounts of cations such as IJum and magnesium.

It is inevitable that the fibers will rapidly lose their bactericidal properties.

On the other hand, when it is converted into insoluble silver or silver compounds as in the present invention, those that adhere to the surface easily fall off, but those that have penetrated into the interior, even in the surface layer, aggregate during conversion and fall off. There is no. Therefore, permanent bactericidal properties can be obtained.

The silver-containing sterilizing cellulose fiber of the present invention can be spun, knitted, and woven in the same manner as ordinary fibers, and can be blended, knitted, interwoven, etc. with other types of fibers to produce permanently sterilized fiber products, if necessary. . Further, after blending, interweaving, or interweaving, the above-mentioned treatment may be used to bond silver ions and generate silver or silver compounds. For example, it can be applied to 1-inch rears for clothing such as surgical gowns for hospitals, sheets, curtains, carpets, and work clothes for food and pharmaceutical manufacturing factories. Furthermore, it can be applied to uses such as sterilizing water filters and sterilizing air filters.

The present invention will be explained below with reference to Examples. Measurement of cation adsorption parameters and bactericidal properties and washing were carried out in the following manner.

■ Cation adsorption parameters The test sample was dyed with C, I basic violet 1 under the following conditions, and the dye adsorption amount (m-mo) for the test sample was
l/kP) and calculate the cation adsorption parameter using the following formula.

Cation adsorption parameters (m-n1o1/kyfib
sr) = Dyeing amount of test sample - Dyeing amount of control sample * Control sample: Original sample used to create the test sample■ Staining conditions c, r Pe-'yy Bio L/t) 1 20%
owp acetic acid 0.5%owp sodium acetate 0.5%owp bath ratio
1:50 Temperature x Time 30'C The bactericidal effect is determined by the presence or absence of growth.

(Bactericidal effect) O: No bacterial growth is observed around the sample, and a halo is generated.

△: No halo is generated around the sample, but no bacterial growth is observed on the sample surface.

×: Growth of bacteria on the sample surface is observed.

■ Washing Using a household electric washing machine, wash for 15 minutes in a 30°C aqueous solution containing neutral detergent Zabu (manufactured by Kao Soap Co., Ltd.) I P/43, then rinse under running water for 5 minutes, dehydrate, and dry. .

For repeated washing, the above operation is repeated.

Example-1 Fluorescent dye Hakkol B, which has direct dyeability, is used to directly dye a refined plain fabric with a basis weight of 180 P/rl made of 100% cotton.
E (C,I Fluorescent BrlghZ
g Agent85 (manufactured by Showa Kagaku Co., Ltd.) 0 to 5.0 chiw
f. After being immersed in an aqueous solution at 60° C. containing 40% OVF of Glauber's salt for 30 minutes, the fabrics were washed with water and dried to obtain cotton fabrics with different dyed amounts of fluorescent dyes and different cation adsorption parameters.

Subsequently, these cotton fabrics were immersed in an aqueous solution at 40° C. containing 10% silver nitrate ovrf for 30 minutes, washed with water, dehydrated, and dried to obtain silver ion bonded cotton fabrics.

Next, this silver ion bond-treated cotton fabric was soaked with 0.1w of hydrochloric acid.
After immersing in an aqueous solution containing t% at 40° C. for 30 minutes, the fabric was washed with water, dehydrated, and dried to obtain a silver-containing treated cotton fabric.

The cation adsorption parameters of cotton fabrics dyed with different amounts of the fluorescent dyes described above and the relationship between washing frequency and bactericidal properties of silver-containing treated cotton fabrics were measured, and the following results were obtained.

” From the above results, as shown in Comparative Example 1, fluorescent dye Hakk
Cotton fabrics not treated with ol BK do not exhibit bactericidal properties, and samples dyed with Hakkol BE do not exhibit permanent bactericidal properties if the concentration of Hakkol BE used is low and the amount of dyeing is small.

In this case, the permanent sterilizing property is closely related to the cation adsorption parameter, and it can be seen that when the cation adsorption parameter is set to 0.2 or more, excellent sterilizing property is exhibited even after repeated washing up to 20 times.

Example-2 Fluorescent dye Mlkeph with direct dyeability was applied to a jersey knitted fabric made using a blended yarn consisting of 50% cotton and 50% acrylic fiber Ponnel Vl 7B2d (manufactured by Mitsubishi Rayon Co., Ltd.).
or BS (C,I FluoresaentBr1
gh'Fing Agent 90 (manufactured by Mitsui Toatsu) 5%
After being immersed for 30 minutes in an aqueous solution at 60° C. containing 40% OWF of Glauber's Salt, the sample was washed with water and dried, and the cation adsorption parameter was measured and a value of 0.5 was obtained. Subsequently, this fluorescent dye dyed blended knitted fabric was treated with silver nitrate lO%6wf.
After 30 minutes of immersion treatment in an aqueous solution at 40°C containing A knitted cotton/acrylic fiber blend fabric was obtained.

In order to determine the permanent bactericidal properties of this knitted fabric, we measured its bactericidal properties after washing it 20 times and twisting it. As a result, no growth of Staphylococcus aureus was observed around the sample, indicating that it had excellent permanent bactericidal properties. .

Claims (1)

[Claims] Silver ions are bonded to the cation exchange groups of cellulose fibers dyed with an anionic group-containing direct dye and have a cation exchange ability with a cation adsorption parameter of 0.2 or more, and water-insoluble silver or silver compounds are further extracted from the silver ions. A silver-containing sterilizing cellulose fiber produced by producing and incorporating the silver-containing cellulose fiber into the fiber, or a textile product containing the fiber.