WO2005038122A1 - Process for preparing textile containing silver - Google Patents

Abstract

The present invention relates to the use of solution of H4Ag206, particularly, to a simple process for preparing textile containing silver having antibacterial properties. The Process of the present invention includes following steps: 1) preparing the solution containing H4Ag2O6; 2) impregnating, leaching, spraying or coating the textile using obtained solution of H4Ag2O6; then 3) drying the wet textile. The method of the present invention greatly reduced the process of production, thus enlarged productivity and saved cost of production.

Description

 Method for preparing silver-containing textile

The invention relates to the use of H ₄ Ag ₂ 0 ₆ solution, in particular to its application in the production of silver-containing antibacterial textiles. The invention also relates to a simplified manufacturing method for silver-containing antibacterial textiles. Background technique

'Silver-containing textiles with antibacterial properties are a well-known product in the prior art. In the art, there are various methods for preparing silver-containing textiles, but most of them use a reducing agent to reduce silver nitrate to elemental silver, and then use an oxidant to reduce the reduced elemental silver or further oxidize to silver oxide. For example, Jiang Jianhua's Chinese patent CN1034090C discloses a method for manufacturing a long-acting broad-spectrum antibacterial fabric. The method includes dissolving silver nitrate in ammonia water, adding glucose to reduce it, and then using high temperature until the fabric appears brown-black and yellow-brown. International application WO03 / 14627 by Zhu Hongjun et al. Discloses an anti-aggregation nano silver antibacterial textile and a preparation method thereof. The method is to dissolve silver nitrate in ammonia water to obtain [Ag (NH ₃ ) ₂ ] +, [Ag (NH ₃ ) ₂ ] + is reduced to elemental silver and fixed on the fabric, and then the silver-containing fabric is further oxidized with an oxidizing agent to obtain a silver-containing antibacterial fabric.

 Liu Xiangwen's Chinese patent application CN1395828A discloses a rapid assembly method for nano silver antibacterial particles in the field. The method is to spray or paint silver nitrate directly on the surface of the fabric, and then treat the reducing agent or light to obtain an antibacterial silver-containing fabric.

U.S. Patent No. 6,364,420 B1 discloses a method for preparing a silver-containing fabric by immersing the fabric in an aqueous solution containing dissolved silver nitrate, and after soaking for a period of time, removing the fabric and immersing it in hot sodium hydroxide-containing solution In an aqueous solution of sodium persulfate and sodium sulphate, the solution is heated to 95-100 ° C, to obtain the desired silver-containing fabric. This method involves two impregnations. The first impregnation is to impregnate the monovalent silver ions between the fibers of the fabric or on the fibers during deposition. The second impregnation is to oxidize the monovalent silver ions to silver peroxide (Ag ₄ 0 ₄ ), So that the fabric contains silver peroxide and has antibacterial properties.

Chinese patent application CN1214867A, which has been assigned to the applicant, discloses a method for preparing a silver-containing fungicide. The method includes the following steps: 1) taking silver oxide and adding steam Distilled water; 2) after stirring for 15-60 minutes, add concentrated acid dropwise so that the pH value is 2-3.5; 3) clarify for at least 2 hours, pour out the clear solution; 4) add hydrogen peroxide to the precipitate, Then, a fungicide containing H ₄ Ag ₂ 0 ₆ was obtained. The feature of this method is to use silver oxide, such as silver oxide or silver peroxide, as a raw material instead of the commonly used silver nitrate, so that the step of reducing silver ions to elemental silver is avoided. Summary of the invention

The invention is based on the use of the bactericide obtained from the Chinese patent application CN1214867A. The present invention uses a bactericide containing H ₄ Ag ₂ 0 ₆ to prepare a silver-containing antibacterial fabric, which greatly simplifies the process flow, thereby saving production costs. Therefore, an object of the present invention is to provide an application of a fungicide containing H ₄ Ag ₂ 0 ₆ , and more particularly, it is an object of the present invention to provide a simplified method for producing an antibacterial textile containing silver. The method of the invention avoids a series of disadvantages caused by high-temperature oxidation, greatly saves energy, and therefore reduces production costs.

 Therefore, the present invention provides a method for preparing a silver-containing textile. The method includes the following steps:

1) preparing a solution containing H ₄ Ag ₂ 0 ₆ ;

2) impregnating, rinsing, spraying or coating the fabric with the obtained H ₄ Ag ₂ 0 ₆ solution; then

 3) Dry the wet textile. detailed description

In one aspect, the invention relates to the use of high-valent silver ion solutions. The high-valent silver ion solution of the present invention is a H ₄ Ag ₂ 0 ₆ solution, wherein the silver ions are in a positive tetravalent oxidation state. A method for preparing the solution has been disclosed in Chinese patent application CN1214867A. It is obtained by using silver oxide, such as silver oxide or silver peroxide as a raw material, adding hydrogen peroxide in an acidic medium, and the total content of silver ions in the obtained solution is 1-5000 ppm. In addition, a high-valent silver ion solution can also be obtained by dissolving silver oxide in persulfate. The total silver ion content in the obtained solution is 1-500 ppm. This method is disclosed in Chinese patent application CN1149389A. The high-valent silver ion solution obtained by the above two methods can be used in the present invention.

The invention relates to the preparation of silver-containing antibacterial textiles using a high-valent silver solution. The method of the present invention includes the following steps: 1) preparing a solution containing H ₄ Ag ₂ 0 ₆ ;

2) impregnating, rinsing, spraying or coating textiles with the resulting H ₄ Ag ₂ 0 ₆ solution; and

3) Dry the wet textile.

 Textiles which can be used in the method of the present invention include natural textile materials and synthetic textile materials. The natural textile materials that can be used in the present invention can be cotton, wool, linen, chitosan and silk, preferably cotton, such as gauze, yarn, cotton non-woven fabric, and the like. The synthetic textile material that can be used in the present invention refers to synthetic fibers, that is, a type of rayon, including, but not limited to, viscose, polyester, nylon, rayon, and acetate fibers. One of them can be used alone. Blended textiles of the above products can be used, either in the form of fabrics or in the form of fibers or yarns. The textile used in the present invention may be a knitted fabric, a woven fabric, a non-woven fabric, or a yarn.

In the method of the invention, the textile is impregnated, rinsed, sprayed or coated with a H ₄ Ag ₂ 0 ₆ solution. The method used is conventional in the art. The wetted textile is then allowed to dry. The time for dipping, rinsing, spraying or coating textiles with H ₄ Ag ₂ 0 ₆ solution varies according to the type of textile. For example, if it is a cotton fabric with good water absorption, the impregnation time can be short, only 1 second, and for synthetic fibers with poor water absorption such as viscose, the impregnation time is longer, which can be more than 30 seconds. The drying method may be a method commonly used in the art, and is generally dried at 50-250 ° C, or may be directly irradiated with sunlight or irradiated with ultraviolet rays.

With the method of the invention, the silver content of the textile can be controlled by controlling the silver ion concentration of the high-valent silver ion solution. The silver content of the textile obtained by the method of the present invention can be as high as 120 μ _§ / π ² . The specific silver content also depends on the type of textile, such as the tightness of the fabric weaving, or whether it is a natural or synthetic fabric. Examples

 Hereinafter, the present invention will be specifically described through examples.

Example 1

A solution of H ₄ Ag ₂ 0 _{6 was} prepared according to the method of CN1214867A, so that the silver ion concentration in the obtained solution was 1000 ppm. At room temperature, a piece of 38 g / m ² cotton nonwoven fabric was taken, immersed in the above solution for 5 minutes, and then taken out, and then the silver-containing cotton nonwoven fabric was dried at 50 ° C. The silver content on the cotton non-woven fabric was measured to be 36.5 g / _C m ² . Example 2 A silver-containing cotton nonwoven fabric was prepared in the same manner as in Example i, except that the concentration of the H ₄ Ag ₂ 0 ₆ solution was 3000 ppm. The silver content on the cotton non-woven fabric was measured to be 75.8 g / cm ² . Example 3 '

A silver-containing cotton nonwoven fabric was prepared in the same manner as in Example 1, except that the concentration of the H ₄ Ag ₂ 0 ₆ solution was 4000 ppm. The silver content on the cotton non-woven fabric was measured to be 86.8 g / cm ² . Example 4

The H ₄ Ag ₂ 0 ₆ solution was prepared according to the method of CN1149389A, so that the silver ion concentration in the obtained solution was 500 ppm. At room temperature, take a piece of cotton non-woven fabric, immerse it in the above solution for 30 seconds, take it out, and then dry the silver-containing cotton non-woven fabric at 50 ° C. The silver content on the cotton nonwoven fabric was measured to be 16.7 g / cm ² . Example 5

The H ₄ Ag ₂ 0 ₆ solution was prepared according to the method of CN1149389A, so that the silver ion concentration in the obtained solution was 500 ppm. At room temperature, take a piece of cotton non-woven fabric, rinse it with the above solution for 1 minute, take it out, and then dry the silver-containing cotton non-woven fabric at 50 ° C. The silver content on the cotton nonwoven fabric was measured to be 17.0 g / cm ² . Example 6

The H ₄ Ag ₂ 0 ₆ solution was prepared according to the method of CN1149389A, so that the silver ion concentration in the obtained solution was 500 ppm. At room temperature, take a piece of cotton non-woven fabric, rinse it with the above solution for 5 minutes, take it out, and then dry the silver-containing cotton non-woven fabric at 50 ° C. The silver content on the cotton nonwoven fabric was measured to be 17.6 g / cm ² . Examples 7-9

The silver-containing cotton nonwoven fabrics of Examples 7-9 were prepared in the same manner as in Example 4, except that the concentration of the H ₄ Ag ₂ 0 ₆ solution was 50 ppm. The cotton non-woven fabrics were impregnated for 30 seconds, 1 minute, and 5 minutes, respectively. The silver content on the cotton non-woven fabric was measured to be 4.8 g / cm ² , 5.1 g / cm, 5.5 g / cm. Examples 10-11

The silver-containing cotton nonwoven fabrics of Examples 10-11 were prepared in the same manner as in Example i, except that the concentration of the H ₄ Ag ₂ 0 ₆ solution was 20 ppm. The cotton non-woven fabric impregnation time is 1 minute and 5 minutes, respectively. The silver content on the cotton non-woven fabric was measured to be 2.3 μ _§ / οπι \ 2.6 g / cm ² . Example 12

A solution of H ₄ Ag ₂ 0 _{6 was} prepared according to the method of CN1149389A, and the silver ion concentration in the solution was diluted to 500 pm. At room temperature, take a piece of viscose non-woven fabric, soak it in the solution for 1 minute, and take it out. After extrusion, it is dried at 170 ° to obtain a silver-containing viscose non-woven fabric. ² . Example 13

As in Example 5, a viscose PET blended nonwoven fabric was used instead of the full viscose nonwoven fabric, and the obtained silver-containing viscose blended nonwoven fabric had a silver content of 18.9 g / cm ² . Example 14

Same as in Example 5, gauze was used instead of cotton non-woven fabric, and the obtained silver-containing gauze had a silver content of 8.5 g / cm ² ₀

As in Example 5, a piece of cotton non-woven fabric was taken, soaked in the solution for 1 minute, and after being squeezed, it was dried under light for 4 hours. The silver content was 16.1 g / cm ² . Experimental example

 The samples of Examples 1-12 and blank samples were used to perform the bacteriostasis test according to AATCC test method 100-1999. The test bacteria was Staphylococcus aureus. The calculation method of bacteriostatic rate is as follows:

Bacteriostatic rate = [(CA) / C] X 100% Among them: A indicates the number of bacteria after 24 hours of incubation after inoculation of the drug-containing sample; C indicates the number of viable bacteria at "0" contact time after inoculation of the blank sample.

Cotton blank control samples were cultured for 24 hours after inoculation, and the number of live bacteria was 4.5 X 10 ^{8; the} number of live bacteria inoculated with "0" contact time was 6.8 X 10 ⁷ ; the former was 6.6 times that of the latter. Table 1 shows the experimental results of the present invention.

 Table 1

从实验结果可以看出，由本发明方法生产的含银抗菌织物具有良好 的抗菌性能。 由此可以得出结论， 用本发明方法可以生产出含银抗菌 纺织品。

It can be seen from the experimental results that the silver-containing antibacterial fabric produced by the method of the present invention has good antibacterial properties. It can be concluded from this that the method of the present invention can produce silver-containing antibacterial textiles.

Claims

Rights request 1. Application of H ₄ Ag ₂ 0 ₆ solution in the manufacture of silver-containing antibacterial textiles. 2. The use according to claim 1, characterized in that the textile is a knitted fabric, a woven fabric, a non-woven fabric or a yarn or a mesh. 3. The use according to claim 1, wherein the textile is a natural textile, a synthetic textile or a mixture thereof. 4. The application according to claim 3, characterized in that the natural textile is cotton, wool, linen, silk, chitosan or a mixed textile thereof; the synthetic textile comprises polyester, nylon, polyethylene and acetate fiber Or their blends. 5. The application according to claim 1, wherein the textile is a cotton non-woven fabric. 6. The application according to claim 1, wherein the textile is gauze. 7. The application according to claim 1, wherein the textile is a yarn. 8. The application according to claim 1, wherein the textile is a mesh film. 9. A method for manufacturing a silver-containing textile, the method comprising: 1) preparing a solution containing ¾Ag ₂ 0 ₆ ; 2) impregnating, rinsing, spraying or coating textiles with the resulting H ₄ Ag ₂ 0 ₆ solution; and 3) Dry the wet textile. 10. The method according to claim 8, wherein the concentration of the H ₄ Ag ₂ 0 ₆ solution is 1-5000 ppm. 11. The method according to claim 8, wherein the drying and drying temperature is 50 ° C-250 ° C, and the time is 2 minutes to 30 minutes. 12. The method according to claim 8, characterized in that it can be dried by sunlight or ultraviolet radiation. 13. The method according to claim 8, wherein the textile is a knitted fabric, a woven fabric, a non-woven fabric, a yarn, or a mesh. 14. The method of claim 8, wherein the textile is a natural textile, a synthetic textile, or a mixture thereof. 15. The method of claim 13, wherein the natural textile is cotton, wool, linen, silk, or a mixed textile thereof; the synthetic textile includes viscose, polyester, nylon, polyethylene, and acetate fibers Or their blends. 16. The method according to claim 8, wherein the textile is a cotton non-woven fabric. 17. The method according to claim 8, wherein the textile is gauze. 18. The method according to claim 8, wherein the textile is a yarn. 19. The method according to claim 8, wherein the textile is a mesh film. 20. A silver-containing antibacterial textile manufactured by the method of claim 8.