WO2016206638A1

WO2016206638A1 - Wound dressing containing silver chelate fiber

Info

Publication number: WO2016206638A1
Application number: PCT/CN2016/087192
Authority: WO
Inventors: 王晓东; 陶炳志; 莫小慧; 姜猛进; 徐建军; 宋永娇
Original assignee: 佛山市优特医疗科技有限公司
Priority date: 2015-06-25
Filing date: 2016-06-25
Publication date: 2016-12-29
Also published as: CN104958779B; CN104958779A

Abstract

A wound dressing containing silver chelate fibers has a single-layer structure or a multi-layer structure. The wound dressing having a single-layer structure is manufactured by blending and spinning silver chelate fibers and silver-free fibers. The wound dressing having a multi-layer structure comprises a silver chelate fabric and a silver-free fabric, and the silver chelate fabric is manufactured by blending and spinning silver chelate fibers and silver-free fibers. The weight of the silver-free fibers is 5-95 wt% of the total weight of the wound dressing. The silver chelate fibers contained in the wound dressing has a silver content of 1-35 wt%. The wound dressing has an areal weight of 25-750 g/m², moisture absorption of 5 g/100 cm² and above and wet strength of 0.3 N/cm and above.

Description

Wound dressing containing chelated silver fiber

Technical field

The present invention relates to a dressing, and in particular to a wound dressing comprising a chelated silver fiber.

Background technique

In the care of chronic wounds, the choice of a dressing that effectively absorbs wound exudate and prevents wound infection is a key factor in the treatment of chronic wounds. Due to the long healing period of chronic wounds, it is easy to cause wound infection during the treatment process, especially ulcerative wounds are most prone to microbial infection, which prolongs the healing time of the wound. Therefore, it is a wound dressing that can be antibacterial for a long time. One of the keys to chronic wound healing.

At present, there are two main types of antibacterial wound dressings. The first one is a fabric made of natural antibacterial materials such as chitosan fibers, and the second is an antibacterial or gel material (such as fiber). A fabric made of a silver material and/or polyhexamethylene biguanide (PHMB) or the like. Because the second wound dressing can meet the requirements of sterilization and moisture absorption required for wound healing, it has been widely promoted and applied.

The current silver-containing dressings are mainly divided into two major categories, namely metal-type silver-containing dressings and ionic silver-containing dressings. The silver in the metallic silver-containing dressing is present in the dressing as a metal element, such as a silver plated material or a nanosilver particle. While the silver in the ionic silver-containing dressing is present in the dressing as silver ions and forms a silver compound or complex with other components of the dressing; in the case of liquids such as wound exudates, the ionic silver-containing Silver ions in the dressing will be released. The silver elemental or silver ions in the silver-containing dressing reduce the activity of the bacterial bioactive enzyme by destroying the bacterial cell membrane or the enzyme protein in the bacterial body, thereby realizing the antibacterial effect of the silver-containing dressing.

U.S. Patent No. 7,385,101 B2 discloses an antibacterial textile material suitable for use in a wound dressing and a wound dressing thereof which is obtained by mixing a textile fiber having a metallic silver coating on the surface with alginate fibers by a nonwoven method. A wound dressing having a silver content of up to 8 wt% and having a long-term antibacterial effect. However, this dressing metallic silver coating has a low silver element release rate which reduces the antimicrobial effect of the wound dressing. Moreover, such textile fibers with a metallic silver coating have poor hygroscopicity, which makes the wound dressing described above unfavorable for wound healing.

Chinese Patent Application No. 200510084006.2 discloses a nano silver antibacterial dressing and a preparation method and application thereof. The invention adopts a padding method to coat a coating liquid containing nano silver on a fabric to prepare a nano silver content of 0.05-2.9 wt%. Dressing. The nano silver antibacterial dressing has obvious ability to kill or inhibit pathogenic bacteria when treating infectious wounds, and can accelerate wound healing. However, the silver in the above nanosilver antibacterial dressing is elemental silver, and its silver release rate Lower, the treatment of chronic wound infections, especially the severe wound infections common in ulcer wounds, is ineffective and cannot meet the needs of the market.

Chinese patent application CN101187153A discloses a simple method for rapidly adding silver ion sterilization to calcium alginate fibers by immersing calcium alginate fibers in a mixture of a silver ion-containing compound and a carboxymethylcellulose nanopowder. The surface of the calcium alginate fiber adsorbs silver-containing substances. However, this adsorption is physical adsorption, and the silver-containing substance is easily detached during the subsequent processing of the fiber, which results in a low silver content of the dressing prepared by the above simple method, resulting in an unsatisfactory antibacterial effect of the dressing.

European Patent EP 1 882 482 B1 discloses a method of immersing fibers in a solution containing silver ions, which is also of the ionic silver type. However, this method requires the use of an organic solvent during the treatment, and the residue of the organic solvent in the dressing prepared by the method causes the dressing to have an adverse effect on the human body. In addition, the dressing prepared by this method has a particularly low wet strength, which is detrimental to the overall removal of the wound dressing during replacement.

Polyhexamethylene biguanide (PHMB) is an environmentally friendly polymer disinfectant with excellent bactericidal effect, fast action, stable nature and easy to dissolve in water.

Chinese Patent Application No. 201010538137.4 discloses a fibrous wound dressing having an antibacterial effect and a preparation method thereof, which is a fabric made of fibers coated with a polyhexamethylene biguanide solution, and the prepared dressing has both antibacterial properties. Performance, moisture absorption and moisturizing properties, has a significant therapeutic effect on chronic wounds. However, the surface of the dressing coated with PHMB will be sticky, which is not conducive to the use of medical personnel.

Therefore, the development of a highly hygroscopic, high-humidity and long-term antibacterial wound dressing is currently a difficult problem to be solved in the treatment of chronic wounds.

Summary of the invention

An object of the present invention is to provide a wound dressing containing a chelated silver fiber, which has the characteristics of long-term antibacterial function and high hygroscopicity and high wet strength, thereby solving the problem of insufficient wound dressing performance for treating chronic wounds. problem.

Another object of the present invention is to provide a method of preparing the above wound dressing containing chelating silver fibers.

In order to achieve the above object, an aspect of the invention provides a wound dressing comprising a chelated silver fiber, the wound dressing being a single layer structure or a multilayer structure, wherein

The single layer structure wound dressing is made by blending silver fiber with silver fiber without blending;

The multi-layered wound dressing comprises a chelated silver fabric and a silver-free fabric, and the wound dressing is prepared by first forming a fabric by blending silver fibers with silver fibers, and then fabricating the above. The prepared chelated silver fabric is compounded on the silver-free fabric prepared above;

The weight of the silver-free fiber is from 5 to 95% by weight based on the total weight of the wound dressing.

In the above technical solution, the blending method includes a weaving and a non-woven method, wherein the weaving method includes a weaving, knitting, and the like.

In the above-described multi-layered wound dressing, the chelated silver fabric may be placed on the inner layer (ie, the wound contact layer), the intermediate layer, or the outer layer (ie, away from the wound layer) of the wound dressing as needed. When the chelated silver fabric is disposed as a wound contact layer, the silver ions released from the chelated silver fabric can kill microorganisms in the wound; when the chelated silver fabric is placed away from the wound layer The microorganism can be blocked outside the wound to prevent wound infection; when the chelated silver fabric is set as the intermediate layer, the purpose of killing both the microorganisms in the wound secretion and blocking the invasion of microorganisms outside can be achieved. Whether the chelated silver fabric is disposed as a wound contact layer, an intermediate layer, or away from the wound layer, the layers may be disposed in an island shape.

In addition, the wound dressing of the above multilayer structure may include a sheet material layer including but not limited to a polyurethane film, a hydrogel film, a release film, in addition to the chelated silver fabric and the silver-free fabric. Wait.

In general, for wounds with more serious infections, a wound dressing containing more silver is needed to ensure that the wound dressing can release enough silver ions to kill the microorganisms, especially for those who need to leave the wound dressing in the wound. In the case of a long time, such as 7 days or even 14 days, the total amount of silver ions in the wound dressing becomes the key to effectively eliminate wound infection. Therefore, in order to meet the antibacterial requirements, it is necessary to have a higher silver ion content in the wound dressing. The method for preparing a silver dressing containing wound dressing according to the present invention can make the silver content of the chelated silver fiber in the wound dressing of the present invention up to 35 wt%, that is, the quality of the silver ion in the chelated silver fiber. The score can be up to 35wt%. Since silver ions in the chelated silver fiber can be released in contact with water, the silver content of the chelated silver fiber generally does not need to be 35 wt% from the viewpoint of practical use and production cost. For slightly infected wounds or to prevent wound infections, the wound dressing used may contain less silver. In some wound dressing embodiments, the chelated silver fibers have a silver content of from 1 to 20% by weight. In some wound dressing embodiments in which the silver ion distribution is more uniform in some of the chelated silver fibers, the chelated silver fibers have a silver content of from 1 to 10% by weight.

Chelation refers to the formation of two or more central ions simultaneously with certain polydentate ligands. Coordination key. Generally, such polydentate ligands are ligands containing nitrogen (N), oxygen (O) and sulfur (S). A chelate is a compound in which two or more coordinate bonds are formed by metal ions with other molecules. The chelated silver fiber is bonded to the fiber by means of a chemical bond to satisfy the requirement that the silver material is stable and not easy to fall off. Since chelation can combine a large amount of silver ions on a specific fiber, the purpose of increasing the silver content of the fiber and the dressing can be achieved. Unlike general physical adsorption, such as surface coating, chelation is a chemical bond. After silver ions are chelated with fibers, they are generally not easily detached from the fibers during subsequent processing.

In the above technical solution, the fiber chelated with silver ions in the chelated silver fiber is polyacrylonitrile fiber (PAN fiber) or polyacrylonitrile/polyvinyl alcohol blend fiber (PAN/PVA fiber). The nitrile group (-CN) in these fibers has a good chelation with silver ions.

In addition, some pretreatment of these fibers prior to chelation of silver can result in better chelation of the fibers with silver ions, including but not limited to amidoxime treatment, polyamine treatment, micro Hole extraction treatment and surface hydrophilic treatment. These pretreatments will be described in more detail below in the present invention. These post-treatments of these fibers after chelation of the silver may improve the fiber/dressing properties, such as hygroscopicity and dressing color change, to facilitate wound care, including but not limited to carboxymethylation, Acylation treatment, alkyl sulfonation treatment, ammonia solution infiltration treatment, and surface oil/emulsifier treatment. These post-processing will be described in more detail below in the present invention.

In order to further increase the efficiency of chelated silver, it is necessary to select fibers having a certain fineness and length. In some preferred embodiments, the polyacrylonitrile fibers or polyacrylonitrile/polyvinyl alcohol blend fibers have a fineness (i.e., linear density) of from 0.1 to 10 dtex and a length of from 3 to 125 mm.

In the above technical solution, the silver-free fiber may be selected from the group consisting of alginate fiber, chemically modified polyacrylonitrile fiber, chitosan fiber, chemically modified chitosan fiber, cellulose fiber, chemically modified cellulose. Fiber, polyvinyl alcohol fiber, chemically modified polyvinyl alcohol fiber, polyester fiber, polypropylene fiber, polyethylene fiber, polyamide fiber, protein fiber, bicomponent fiber.

In view of the high requirements of the wound dressing for moisture absorption properties, in general, the silver-free fiber is preferably a gel fiber. The main feature of the gel fiber is that the fiber has no appearance difference with other fibers in a dry state, but after encountering a liquid such as water, a wound exudate or the like, the gel fiber can absorb a large amount of water, so that the fiber The cross section expands, or the entire fiber becomes colloidal, and the fiber has a high hygroscopicity but a large loss of strength after moisture absorption. In some preferred absorbent dressing embodiments, the silver-free fiber is selected from the group consisting of alginate fibers, chemically modified cellulose fibers (such as carboxymethyl cellulose fibers or carboxyethyl cellulose fibers), and chemistry. Modified chitosan fiber (acylated chitosan fiber or carboxymethyl chitosan fiber). In still other wound dressing embodiments, the silver-free fiber is a bicomponent fiber, one of which is a low melting fiber, and the fabric (mainly a nonwoven fabric) made from the bicomponent fiber is treated by a hot oven. The bicomponent fibers are sintered at the cross-contact so that the strength, especially the wet strength, of the entire wound dressing can be significantly improved.

As mentioned above, gel fiber is an ideal wound dressing material, but because it is gelled with water, it cannot be directly prepared from a silver fiber solution by infiltrating the fiber; and because of the gel fiber After the water, the fiber cross-section expands or the entire fiber becomes colloidal, and the wet strength of the gel fiber is relatively small. Therefore, the present invention particularly proposes a wound dressing containing chelating silver fibers in a preferred embodiment, which is prepared by blending a chelated silver fiber with a silver-free gel fiber, which solves the pure gel. Fiber dressings are not capable of directly loading silver and insufficient wet strength, while the wound dressings containing chelated silver non-gel fibers have some of the characteristics of gel fibers such as moisture absorption properties and gel properties.

In the above preferred embodiment, in order to prevent the gel properties and hygroscopic properties of the wound dressing from being lowered by the blending of the chelated silver non-gel fibers, it is necessary to control the ratio of the chelated silver non-gel fibers. In order for the wound dressing to have a significant gel effect, even though the wound dressing is capable of effectively absorbing liquids such as water, wound exudates and forming a gel, in some wound dressing embodiments, the weight of the gel fibers is The wound dressing is 50-95 wt% of the total weight. In some preferred absorbent dressing embodiments, the gel fibers have a weight of from 70 to 95% by weight based on the total weight of the wound dressing.

Additionally, the thickness (gram weight) of the wound dressing provided by the present invention can be selected based on the degree of infection of the wound and the amount of secretion. If the wound secretion is more, you can use a more important wound dressing, so that the hygroscopicity and wet strength of the dressing can be higher; if the wound secretion is not much, you can use a small weight dressing, so The dressing is relatively soft due to its low thickness. In general, the wound dressings provided herein have a basis weight of from 25 to 750 g/m ² .

In order to increase the strength of the wound dressing described above, it is also possible to add reinforcing threads, yarns and filaments to the wound dressing.

Another aspect of the present invention provides a method of preparing the above-described wound dressing containing a chelated silver fiber, the method comprising the steps of:

(1) adding silver-containing material to deionized water to obtain a silver-containing solution, wherein the concentration of silver ions in the silver-containing solution is 0.01-30% by weight;

(2) Soaking polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber in step (1) The obtained silver-containing solution is kept for 5 to 600 minutes, and the temperature of the silver-containing solution is maintained at 10 to 65 ° C, wherein the ratio of the weight of the fiber to the weight of the silver-containing solution (or the bath ratio) is 1: 5-1:1000;

(3) rinsing the fiber obtained in the step (2), and drying or drying it to obtain a chelated silver fiber;

(4) preparing the silver-containing fabric by blending the chelated silver fiber obtained in the step (3) with the silver-free fiber;

(5) The silver-containing fabric obtained in the step (4) is cut into a sheet shape, which is then packaged and sterilized to obtain the wound dressing containing the chelating silver fibers.

According to the target silver content of the chelated silver fiber, the parameters such as the soaking time and the temperature of the silver-containing solution in the step (2) can be further controlled. Generally, the higher the concentration of silver ions in the silver-containing solution, the higher the silver content in the chelated silver fibers. The relationship between the bath ratio in step (2), the temperature of the silver-containing solution, and the soaking time as well as the silver content of the fiber is also the same. The initial pH of the silver-containing solution can be controlled between 4 and 7.

The present invention provides a method for preparing the above-described wound dressing containing silver fiber, in particular, a method in which silver is chelated, and the silver content of the chelated silver fiber can be easily controlled by controlling the above parameters.

In some embodiments of the above preparation method, the step (2) further comprises a step (2a), the step (2a) is a pretreatment of the fiber used in the step (2), the pretreatment being one of the following treatments Kind or more:

Amidoxime treatment;

Polyamine treatment;

Microporous extraction treatment; and

The surface is hydrophilic.

In the step (2a), the amidoxime treatment is to reduce the structural nitrile group (-C=N) of the fiber used in the step (2) to an amino group-containing thiol-C(NH ₂ )=N. (OH), whereby the nitrogen and oxygen atoms in this structure form a chelate ring with the silver ions. For example, a polyacrylonitrile/polyvinyl alcohol blend fiber obtained by blending polyacrylonitrile fibers and polyvinyl alcohol fibers is subjected to amidoxime treatment to obtain an amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber ( PAO/PVA fiber).

A typical guanamine deuteration treatment is to soak a polyacrylonitrile fiber or a polyacrylonitrile/polyvinyl alcohol blend fiber in an aqueous solution containing hydroxylammonium hydrochloride and anhydrous sodium carbonate. Thus, the polyacrylonitrile fiber or the polyacrylonitrile/polyvinyl alcohol blend fiber is deuterated by amidoxime. The temperature of the amidoxime treatment is 20-90 ° C, and the soaking time is 10 min -5 h. During the amidoximation treatment, The pH of the above aqueous solution is generally from 5 to 8, and the bath ratio (i.e., the ratio of the weight of the fiber to the weight of the aqueous solution) is between 1:1 and 1:150. The length of the amidoxime treatment affects the degree of guanamine deuteration, which in turn affects the amount of chelated silver. In general, the longer the amidoxime treatment time, the higher the degree of guanamine deuteration and the higher the efficiency of chelation of silver ions. The same principle applies to explaining the bath ratio during processing.

Polyacrylonitrile (PAN, Polyacrylonitrile) fiber may not be suitable for amidoxime treatment, and its amidoximation reaction conditions are difficult to control and the efficiency of chelation of silver is not high. Polyacrylonitrile fibers are more suitable for treatment with polyamines to achieve an increase in the amount of chelated silver and chelated silver. In some preparation method examples, the specific method of the polyamine treatment is to react the polyacrylonitrile fiber with ethylenediamine (EDA) at 50-150 ° C and under a catalyst (such as aluminum chloride) to obtain a chelate. A silver-containing polyamine polyacrylonitrile (PAEA) fiber, that is, 1,N-ethylenediamino-polyacrylonitrile.

After the microporous treatment of the polyacrylonitrile/polyvinyl alcohol blend fiber and then the amidoxime treatment, the blended fiber has a higher efficiency of chelation silver. A typical microporous treatment is to first add polyethylene glycol 1000 to the spinning solution, and then extract it with ethanol, and the resulting blended fibers will have some very fine pores inside. This fiber is then subjected to amidoxime treatment to sequester more silver ions.

In addition, the hydrophilic treatment of the surface of the fiber used in the step (2) before the chelating silver treatment is also advantageous for silver ion chelation.

In some embodiments of the above preparation method, the step (3) further comprises a step (2b), the step (2b) is a post-treatment of the chelated silver fiber obtained in the step (2), the post-treatment is as follows One or more of the treatments:

Carboxymethylation;

Acylation treatment;

Alkyl sulfonation treatment;

Surface oil/emulsifier treatment;

Ammonia solution infiltration treatment; and

The sodium thiosulfate solution is infiltrated.

In the step (2b), the typical carboxymethylation treatment is to soak the chelating silver fiber through sodium hydroxide for 10-80 min, and then the fiber is placed in a sodium chloroacetate solution for 20-320 min, and the temperature is maintained at Between 15-75 ° C, then wash with alcohol and dry. The core of the carboxymethylation treatment is to use as low a concentration and temperature as possible, using as mild as possible The conditions are such that the pH of the solution is maintained above 7 throughout the process to minimize the loss of silver ions during processing. The above acylation treatment can be found in the introduction in WO2012/136082. The above alkyl sulfonation treatment can be found in the introduction in WO2012/061225.

The surface oil/emulsifier treatment of the chelated silver fibers is to increase the hydrophilicity of the fibers or to improve the antistatic properties of the fibers, thereby increasing the processability of the chelated silver fibers during subsequent processing.

In general, silver-containing fibers will change color when exposed to light, especially some ionic silver-containing fibers, which will turn black or gray when seen. In addition, the color of the fiber is also changed after the fiber is chelated. For example, the original color of the above fiber is white, and the color of the fiber becomes dark after chelation of silver, such as light gray, beige, gray, black, brown or even reddish brown. Clinically, it is generally undesirable to have the color of the wound dressing too deep, and in particular it is undesirable for the color of the wound dressing to be red or reddish brown.

The chelated silver fiber obtained in the above step (2) is substantially stable in color in the dry state, but the color changes and becomes deeper when it encounters water or wound secretion. The chelated silver fiber obtained by the treatment of the step (2) can be infiltrated with an ammonia solution to alleviate the degree of color change. The ammonia solution infiltration treatment treats the chelated silver fibers with an ammonium salt solution to further stabilize the color of the chelated silver fibers, particularly in the wet state. The chelated silver fiber after the ammonia solution infiltration treatment has a small color change in a wet state, and remains substantially gray or grayish black. The typical ammonia solution infiltration treatment is to first dissolve an ammonium salt such as ammonium chloride, ammonium acetate, ammonium carbonate or ammonium sulfate in water, and the concentration of the ammonium salt solution is 0.01-25% by weight, and the temperature of the ammonium salt solution is controlled. 10-55 ° C; then the chelated silver fiber prepared in step (2) is immersed in the solution, the soaking time is controlled at 1-60 min.

Another method for stabilizing the color of the wound dressing is to subject the chelated silver fiber obtained in step (2) to a sodium thiosulfate solution infiltration treatment. The treatment is to firstly configure a sodium thiosulfate solution having a concentration of 0.001-1.5 mol/L; then, the chelated silver fiber obtained in the step (2) is infiltrated into the solution, and the bath ratio of the infiltration is 1:5-1: 500, the treatment temperature is 15-55 ° C, and the soaking treatment time is 1-85 min. Among them, the solution can be stirred by the agitator during the infiltration process at a speed of 0-100 rad/min.

The chelated silver fiber in the wound dressing provided by the present invention does not substantially change in color under normal indoor illumination after the above-mentioned ammonia solution infiltration treatment or infiltration treatment with sodium thiosulfate solution. Even after a certain period of outdoor sunlight, the color of the above-mentioned chelated silver fiber or the wound dressing containing the chelated silver fiber is substantially unchanged, and the silver release rate of the fiber does not substantially change after sun exposure, as in Example 2. The data is shown.

Of course, it is also possible to combine polyacrylonitrile fibers and polyacrylonitrile/polyvinyl alcohol blend fibers. The silver-containing fiber is firstly made into a fabric by a blending method, and then the fabric is directly subjected to a chelation silver treatment to prepare a silver-containing fabric. Finally, the silver-containing fabric is cut, packaged and sterilized to prepare the chelated silver fiber. Wound dressing.

In view of this, a further aspect of the present invention provides a method of preparing the above-described wound dressing containing a chelated silver fiber, the method comprising the steps of:

(1) fabricating a polyacrylonitrile fiber or a polyacrylonitrile/polyvinyl alcohol blend fiber and a silver-free fiber by a blending method;

(2) adding silver-containing material to deionized water to obtain a silver-containing solution, wherein the concentration of silver ions in the silver-containing solution is 0.01-30% by weight;

(3) soaking the fabric obtained in the step (1) in the silver-containing solution prepared in the step (2) for 5 to 600 minutes, and maintaining the temperature of the silver-containing solution at 10 to 65 ° C, wherein the fabric a ratio of weight to the weight of the silver-containing solution (or bath ratio) of 1:5-1:1000 to obtain a silver-containing fabric;

(4) rinsing the silver-containing fabric obtained in the step (3), and drying or drying to obtain a chelated silver fabric;

(5) The chelated silver fabric obtained in the step (4) is cut into a sheet shape, which is then packaged and sterilized to obtain the wound dressing containing the chelating silver fibers.

In some embodiments of the above preparation method, before the step (1), the step (1a) is further included, and the step (1a) is a polyacrylonitrile fiber or a polyacrylonitrile/polyvinyl alcohol blend fiber used in the step (1). Pretreatment is performed, which is one or more of the following treatments:

Amidoxime treatment;

Polyamine treatment;

Microporous extraction treatment; and

The surface is hydrophilic.

In some embodiments of the above preparation method, the step (4) further comprises a step (3b), the step (3b) is a post-treatment of the silver-containing fabric obtained in the step (3), and the post-treatment is as follows One or more of:

Carboxymethylation;

Acylation treatment;

Alkyl sulfonation treatment;

Surface oil/emulsifier treatment;

Ammonia solution infiltration treatment; and

The sodium thiosulfate solution is infiltrated.

In some embodiments of the above two preparation methods, the amidoximation treatment specifically comprises the following steps:

(1) Soaking the polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber in an aqueous solution containing hydroxylamine hydrochloride and anhydrous sodium carbonate for 10-300 min, and the bath ratio of the soaking is 1:10-1 : 150, and the temperature of the solution is maintained at 20-90 ° C, the pH of the solution is maintained at 5-8;

(2) Drying the fibers after the immersion treatment.

In some embodiments of the above two preparation methods, the polyamine treatment specifically comprises the following steps:

(1) the polyacrylonitrile fiber or polyacrylonitrile / polyvinyl alcohol blend fiber is immersed in a polyamine solution, and the temperature of the solution is maintained at 50-150 ° C;

(2) The catalyst is added to the polyamine solution in step (1), the fiber and the polyamine are reacted under the action of a catalyst for 0.5-10 h;

(3) washing the fiber after the immersion treatment with alcohol, and drying the washed fiber;

Wherein the polyamine is preferably ethylenediamine.

In some embodiments of the above two preparation methods, the silver-containing substance may be selected from one or more of the following silver compounds: silver nitrate; silver chloride; silver sulfate; silver carbonate; silver acetate; silver lactate Silver bromide; and silver zirconium phosphate.

In theory, any water-soluble silver compound, or a silver compound released by silver ions in water, can be used to prepare silver ion aqueous solutions, such as silver nitrate, silver chloride, silver sulfate, silver carbonate, sodium zirconium phosphate. Etc. But the preferred silver compound is silver nitrate. Because silver nitrate is 100% water soluble. A relatively high utilization rate of silver material can be achieved. For example, silver nitrate has a silver content of 63.5 wt%, and all of the silver nitrate can be dissolved in an appropriate amount of water. Therefore, the configuration of 1000 mL of a solution containing 0.1 wt% of silver ions requires 1.57 g of silver nitrate. A typical sodium zinc zirconium phosphate product is Alphasan, which may have a silver content of 10%, but sodium zirconium phosphate does not release all silver ions, so an aqueous solution that achieves a concentration of 0.1% silver ions requires a large amount of silver-containing compounds, and It is necessary to continuously test the amount of silver in the solution. If it is insufficient, it is necessary to continue adding the silver-containing material until the desired concentration of silver ions is reached.

The method provided by the present invention uses deionized water as a solvent in the process of chelation of silver without using other dispersants and organic solvents. The silver-containing solution can be prepared by adding the above silver compound to deionized water in accordance with the required silver ion concentration.

Compared with the prior art, the wound dressing containing the chelating silver fiber provided by the present invention has high hygroscopicity and can reach 5g/100cm by controlling the selection of the blended fiber for preparing the above wound dressing and controlling the preparation process of the dressing. ² and above. In addition, compared with other absorbent dressings, the wound dressings provided by the present invention have a higher wet strength, generally above 0.3 N/cm; and the representative product of US Pat. No. 6,897,341 B2 is Aquacel Ag, which has a wet strength of only about 0.1 N/cm. . The wound dressings containing the chelating silver fibers provided by the present invention are mainly used for chronic wounds such as venous venous ulcers, pressure ulcers and diabetic foot ulcers, and other chronic ulcers.

DRAWINGS

1 is a inhibition zone of a wound dressing containing chelating silver-containing amidoxidinated polyacrylonitrile/polyvinyl alcohol blend fiber prepared in Example 1 of the present invention against Staphylococcus aureus at 24 hours;

2 is a inhibition zone of a wound dressing containing chelating silver-containing amidoxidinated polyacrylonitrile/polyvinyl alcohol blend fiber prepared in Example 3 of the present invention against Staphylococcus aureus at 24 hours;

3 is a bacteriostatic ring of a chelated silver melamine deuterated polyacrylonitrile/polyvinyl alcohol blend fiber prepared in Example 4 of the present invention against Staphylococcus aureus at 24 hours;

4 is a schematic view showing the structure of an island-shaped dressing containing chelating silver fibers prepared in Example 10 of the present invention, wherein: 41 is a polyurethane film, 42 is a silver-containing 5×5 island core, 43 is a silicone pad with a through hole, and 44 is Release film

Figure 5 is a schematic view of a wet dressing test method for a wound dressing provided by the present invention, wherein: 1 is a sample, 2 is a container, 3 is a liquid, and 4 is a sample holder.

detailed description

The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings and specific embodiments.

Example 1

Preparation of wound dressings containing chelating silver-containing amidoxidinated polyacrylonitrile/polyvinyl alcohol blend fibers

10 g of silver nitrate was dissolved in 5000 mL of deionized water, and after thorough dissolution, 500 g of amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber (ie, PAO/PVA fiber) having a fineness of 2 dtex and a length of 38 mm was placed. Soak in the above silver nitrate solution at room temperature for 9.5 h. After 2 washes, it is dried. The actual silver content of the above blended fibers was measured to be 17.9 wt%.

The prepared silver-containing PAO/PVA fiber was blended with 990 g of carboxymethyl cellulose fiber (length 50 mm, fineness 2.2 dtex), and then carded and needle-punched into a non-woven fabric (weight: 110 g/m ² ), and then packaged. Irradiation sterilization produces a wound dressing (sample) containing chelated silver fibers. The wound dressing was measured to have a hygroscopicity of 19 g/100 cm ² and a wet strength of 2.0 N/cm. The sample was then cut into 8× ¹⁰ mm ² small pieces and placed on a Petri dish coated with Staphylococcus aureus, and placed in an incubator at 37 ° C for 24 hours. The inhibition zone was observed as shown in Figure 1. It can be seen that there is a large amount of bacteria on the periphery of the bottom of the culture dish, and there is almost no bacterial growth at the bottom and the periphery of the sample, which proves that the silver ions in the dressing have killed the bacteria at the bottom and the periphery of the dressing, and produced a good antibacterial effect.

Example 2

Preparation of chelated silver amidoxime polyacrylonitrile/polyvinyl alcohol blend fibers

Prepare a silver nitrate solution according to the data in the following table, and maintain the temperature of the silver nitrate solution above 45 ° C, and a certain amount of amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber (fineness 4.5 dtex, The length is 100mm, and the color is milky white. It is placed in different concentrations of silver nitrate solution according to the weight in the table below. After washing for 3.5 hours, it is washed twice. After drying, the silver content of the fiber is measured and the results are shown in the following table.

All samples were observed to be slightly grayish in color after 7 days of storage at room temperature in the dark. The fourth sample TP677D of the above sample was exposed to sunlight for 1 h, and it was observed that the color of the corresponding fiber did not substantially change after the sun exposure. The silver release rate was tested separately before and after exposure to sunlight, and the results are shown in the following table:

样品sample	日晒Sun exposure	24h银释放(ppm)24h silver release (ppm)	72h银释放(ppm)72h silver release (ppm)	168h银释放(ppm)168h silver release (ppm)
TP677DTP677D	无no	3939	5454	112112
TP677D TP677D		1h1h	4141	5858	116116

Example 3

Preparation of 100 g of amide containing chelating silver according to the method of TP677B in Example 2 The polyacrylonitrile/polyvinyl alcohol blend fiber was found to have a silver content of 9.5 wt%.

Then, the obtained silver-containing fiber is uniformly mixed with 900 g of silver-free alginate fiber (calcium sodium type G alginate, fineness 2.8 dtex, length 50 mm), and then carded and needle-punched to form a non-woven fabric (gram weight 200 g) /m ² ), then packaged, irradiated and sterilized. The silver content of the dressing was measured to be 0.89 wt%. The wound dressing was measured to have a hygroscopicity of 26 g/100 cm ² and a wet strength of 2.8 N/cm. The sample was then cut into 10 mm ² small pieces and placed on a Petri dish coated with Staphylococcus aureus, and placed in an incubator at 37 ° C for 24 h. The inhibition zone was observed as shown in Fig. 2. It can be seen that there is a large amount of bacteria on the periphery of the bottom of the culture dish, and there is almost no bacterial growth at the bottom and the periphery of the sample, which proves that the silver ions in the dressing have killed the bacteria at the bottom and the periphery of the dressing, and produced a good antibacterial effect.

Example 4

After dissolving 0.05 g of silver nitrate in 250 mL of deionized water and thoroughly dissolving at room temperature, 0.5 g of amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber (fineness 2 dtex, length 38 mm) was placed in the liquid at room temperature. Soak for 0.5h. After 2 washes, it is dried. The actual silver content of the fiber was measured to be 0.6% by weight.

The prepared fiber was cut short and spread to 1 cm ² , placed on a Petri dish coated with Staphylococcus aureus, and placed in an incubator at 37 ° C for 24 hours. The inhibition zone was observed as shown in FIG. 3 . It can be seen that there is a large amount of bacteria on the periphery of the bottom of the culture dish, and there is almost no bacterial growth at the bottom and the periphery of the sample, which proves that the silver ions in the fiber have killed the bacteria at the bottom and the periphery of the dressing, and produced a good antibacterial effect.

Example 5

100 g of silver nitrate was dissolved in 10 liters of deionized water, and after completely dissolved, 1 kg of amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber (PAO/PVA fiber) (fineness 3 dtex) was placed in the above nitric acid. Soak in silver solution for 9.5 h at room temperature. After 2 washes, it is dried. The actual silver content of the fiber was measured to be 18.9 wt%. The fibers were then cut into short fibers of length 51 mm.

The prepared silver-containing PAO/PVA fiber and carboxymethyl cellulose fiber were blended with 5wt% silver-containing PAO/PVA fiber and 95wt% carboxymethyl cellulose fiber, and combed and needled to make a weight of 120g/m ^{2 .} The non-woven fabric is then packaged and irradiated for sterilization. The wound dressing was measured to have a hygroscopicity of 25.5 g/100 cm ² , a wet strength of 2.3 N/cm, and a dressing containing silver content of 0.9 wt%.

The color of the dressing was observed to be light gray in the dry state. After standing for 24 hours under normal laboratory lighting, the color of the dressing was still light gray, with little change. The dressing was placed in solution A for 24 h and the color of the dressing was observed to be brown under normal laboratory illumination.

The 7-day silver release data for the dressing was tested as follows:

样品sample	24h银释放24h silver release	72h银释放72h silver release	168h银释放168h silver release
实施例5Example 5	3434	4242	6161

Example 6

The silver-containing fiber obtained in Example 4 was blended with M-type alginate fiber, uniformly mixed according to the ratio of 90 wt% silver-containing PAO/PVA fiber and 10 wt% alginate fiber, and carded and needle-punched to make a weight of 120 g/m. ² non-woven fabrics, then packaged, irradiated and sterilized. The wound dressing was measured to have a hygroscopicity of 11 g/100 cm ² , a wet strength of 13 N/cm, and a dressing containing silver content of 15% by weight.

Example 7

According to the TP677B method of Example 2, 100 g of amidated deuterated polyacrylonitrile/polyvinyl alcohol blend fiber containing silver chelate was prepared, and the fiber content of the fiber was measured to be 9.5 wt.

The prepared fiber is then subjected to a sodium thiosulfate solution infiltration treatment:

1) preparing a sodium thiosulfate solution at a concentration of 1 mol/L;

2) The above chelated silver fiber is placed in a sodium thiosulfate solution at a normal temperature, a bath ratio of 1:50;

3) The soaking treatment time is 15 min;

5) The solution was agitated with a stirrer during the process at a speed of 50 rad/min.

Then, the obtained silver-containing fiber was uniformly mixed with 900 g of silver-free carboxymethyl cellulose fiber (DS0.3, fineness 2.2 dtex, length 50 mm), and then carded and needle-punched to obtain a non-woven fabric (gram weight 120 g/ m ² ), then packaged, irradiated and sterilized. The silver content of the dressing was measured to be 0.8% by weight. The dressing had a hygroscopicity of 18 g/100 cm ² and a wet strength of 1.2 N/cm.

The color of the dressing was observed to be light gray. The dressing was packaged in a paper-plastic (transparent) package and the color of the dressing was still light gray after 24 hours of normal laboratory lighting. The dressing was cut into 5 x ⁵ cm ² pieces and placed in the A solution for 24 h. The color of the dressing was observed to be light gray under normal laboratory illumination. The color is slightly deeper than the dry state, but there is no reddish brown.

Example 8

The silver-containing fiber obtained in Example 4 was blended with the polypropylene fiber, uniformly mixed according to the ratio of 10% by weight of the silver-containing PAO/PVA fiber and 90% by weight of the polypropylene fiber, and carded and needle-punched to form a nonwoven fabric having a basis weight of 300 g/m ² . The nonwoven fabric was then compounded with a polyacrylate high-absorbent fiber nonwoven fabric (gram weight 200 g/m ² ), and then a polypropylene spunbond fabric (gram weight 25 g) was laminated on the silver-free side of the composite material. /m ² ). After packaging and irradiation sterilization, a three-layer fabric dressing is formed, the upper layer contains silver, the middle layer is highly hygroscopic, and the bottom layer protects the dressing. The total weight of the dressing was measured to be 525 g/m ² , the hygroscopicity was 52 g/100 cm ² , the wet strength was 19 N/cm, and the dressing contained silver content of 1.02%.

Example 9

The silver-containing fiber obtained in Example 4 was blended with the bicomponent fiber, uniformly mixed according to the ratio of 5 wt% silver-containing PAO/PVA fiber, 55 wt% viscose fiber and 40 wt% ES fiber, and directly combed and heated (140 ° C). The net is made into a non-woven fabric with a weight of 35 g/m ² , and this non-woven fabric is compounded with a polyacrylate high-absorbent fiber nonwoven fabric (gram weight 200 g/m ² ), and then in the composite material. One side of the silver was needle-punched with a layer of alginate fiber (gram weight 85 g/m ² ). Then packaged, irradiated and sterilized. The total weight of the dressing was measured to be 320 g/m ² , the hygroscopicity was 48 g/100 cm ² , the wet strength was 14 N/cm, and the dressing contained silver in an amount of 0.1%.

Example 10

Preparation of island shaped dressings containing chelated silver fibers

The nonwoven fabric wound dressing of Example 3 was cut into 5 x ⁵ cm ² pieces and placed in the middle of a 10 x 10 cm ² transparent PU film. Since the film has a sticker, the nonwoven fabric can be fixed to the film. A 10 x 10 cm ² silicone pad was then placed over the film and nonwoven. The silicone pad itself is viscous and has a uniform distribution of pores throughout the thickness of the silicone pad, with a pore size between 1-3 mm. The release film is placed on the silicone pad, and then packaged and sterilized.

A schematic cross-sectional view of the dressing is shown in Fig. 4, wherein: 41 is a polyurethane film, 42 is a silver-containing 5x5 island core, 43 is a silica gel pad with a through-hole, and 44 is a release film.

Example 11

Ammonium solution infiltration treatment of chelated silver amidoxime polyacrylonitrile/polyvinyl alcohol blend fiber

The silver chelated guanamine-deuterated polyacrylonitrile/polyvinyl alcohol blend fiber prepared in Example 2 was immersed in an aqueous solution of ammonium chloride having a concentration of 15 wt%, the solution temperature was 37 ° C, the soaking time was 30 min, and then taken out. Washed and dried.

Example 12

Preparation of a wound dressing containing a chelate silver-containing polyamine polyacrylonitrile fiber

10 g of polyacrylonitrile fiber was placed in a 5000 mL ethylenediamine round bottom flask, the oil bath was preheated to 100-120 ° C, and the reaction mixture was transferred to an oil bath, and the reaction mixture was brought to 100 ° C, and chlorine was added. Aluminum, start timing, constant temperature reflux 1-5 h and then take out the fiber and rinse with deionized water, after drying to obtain PAEA fiber (ie 1, N-ethylenediamine-based polyacrylonitrile fiber);

Then, the obtained PAEA fiber was immersed in 1000 mL of a silver nitrate solution having a concentration of 1 g/L, soaked for 24 hours, washed with deionized water, and dried to obtain PAEA chelated silver fiber.

The actual silver content of the fiber was measured to be 9.9 wt%.

The prepared silver-containing PAEA fiber and carboxymethyl cellulose fiber were blended with 20 wt% silver-containing PAEA fiber and 80 wt% carboxymethyl cellulose fiber, and carded and needle-punched to obtain a non-woven fabric having a basis weight of 120 g/m ² . Cloth, then packaged, irradiated and sterilized. The hygroscopicity was measured to be 21.5 g/100 cm ² , the wet strength was 2.8 N/cm, and the dressing contained silver content of 1.7%.

Several main test methods used in the present invention:

The hygroscopicity test of all wound dressings in the examples of the present invention refers to the international standard BS EN13726-1 2002, Part 1 Aspects of Absorbency.

A solution was introduced as a test solution in the above standard. The solution A was a solution containing 8.298 g of sodium chloride and 0.368 g of calcium chloride dihydrate per liter of the solution.

All silver content is expressed in weight percent unless otherwise noted. All fiber blend ratios are also by weight.

In order to improve the accuracy of the wet strength test, in particular to be able to more accurately compare the wet strength of different samples, the test procedure for the following steps is performed on the wet strength of the wound dressing:

1) The wound dressing sample 1 was cut into strips of 2 cm width and the length was at least 7 cm. Preferably, a second sample is cut in a 10 x 10 cm ² wound dressing in a direction at an angle of 90 degrees to the first sample to ensure simultaneous longitudinal (MD) and transverse (CD) directions. .

2) A double-folded sample was placed in the container 2 in which the above-mentioned test solution 3 was prepared, and the A solution was used as the test liquid 3. The solution in the container has a height of 2 +/- 0.5 cm.

3) The folded portion of the sample was placed at the bottom of the sample holder 4 and allowed to stand for 30 seconds as shown in FIG.

4) Clamp the sample out of the container and place the ends of the tensile tester clamp at the top and bottom.

5) The distance between the two jaws of the tester is 50mm, and the running speed of the top jaw is 100mm/min.

6) Record the maximum force (N) of the damaged sample. Two samples from the same dressing (10 x 10 cm ² ) were tested at the same time, and the higher intensity values tested were CD and the lower intensity values were MD.

The average wet strength is the average of MD and CD.

The silver content and silver release of the dressing were tested by the atomic absorption spectrometer method specified in the Chinese Pharmacopoeia.

Claims

A wound dressing containing a chelated silver fiber, the wound dressing being a single layer structure or a multilayer structure, wherein

The single layer structure wound dressing is made by blending silver fiber with silver fiber without blending;

The multi-layered wound dressing comprises a chelated silver fabric and a silver-free fabric, and the wound dressing is prepared by first forming a fabric by blending silver fibers with silver fibers, and then fabricating the above. The resulting chelated silver fabric is composited on a silver-free fabric;

The weight of the silver-free fiber is from 5 to 95% by weight, preferably from 50 to 95% by weight, more preferably from 70 to 95% by weight, based on the total weight of the dressing.
The wound dressing containing chelating silver fibers according to claim 1, wherein the silver ion in the chelated silver fibers has a mass fraction of from 1 to 35 wt%, preferably from 1 to 20 wt%, more preferably from 1 to 10 wt%.
The wound dressing containing chelating silver fibers according to claim 1, wherein the silver-free fiber is selected from the group consisting of alginate fibers, chemically modified polyacrylonitrile fibers, chitosan fibers, and chemical modification. Chitosan fiber, cellulose fiber, chemically modified cellulose fiber, polyvinyl alcohol fiber, chemically modified polyvinyl alcohol fiber, polyester fiber, polypropylene fiber, polyethylene fiber, polyamide fiber, protein fiber, and double group The fiber, preferably a gel fiber, more preferably a chemically modified chitosan fiber, a chemically modified cellulose fiber, and an alginate fiber.
The wound dressing containing chelating silver fibers according to claim 1 or 3, wherein the fibers chelating with the silver ions in the chelating silver fibers are polyacrylonitrile fibers or polyacrylonitrile/polyvinyl alcohol blend fibers. .
The wound dressing containing chelating silver fibers according to claim 4, wherein the polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber is subjected to one or more of the following before chelation with silver ions Pretreatment:

Amidoxime treatment;

Polyamine treatment;

Microporous extraction treatment; and

The surface is hydrophilic.
The wound dressing containing chelating silver fibers according to claim 5, wherein the amidoximation treatment comprises the steps of:

1) The polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber is immersed in an aqueous solution containing hydroxylamine hydrochloride and anhydrous sodium carbonate for 10-300 min, and the bath ratio of the soaking is 1:10-1: 150, and maintaining the temperature of the solution at 20-90 ° C, maintaining the pH of the solution at 5-8;

2) Dry the fibers after the immersion treatment.
A wound dressing comprising a chelating silver fiber according to claim 5, wherein said polyamine treatment comprises the steps of:

1) immersing the polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber in a polyamine solution, and maintaining the temperature of the solution at 50-150 ° C;

2) The catalyst is added to the polyamine solution in the step (1), the fiber and the polyamine are reacted under the action of the catalyst for 0.5-10 h;

3) washing the fiber after the immersion treatment with alcohol, and drying the washed fiber;

Wherein the polyamine is preferably ethylenediamine.
The wound dressing containing chelating silver fibers according to claim 4, wherein the polyacrylonitrile fiber or polyacrylonitrile/polyvinyl alcohol blend fiber is subjected to one or more of the following after sequestration with silver ions Post processing:

Carboxymethylation;

Acylation treatment;

Alkyl sulfonation treatment;

Surface oil/emulsifier treatment;

Ammonia solution infiltration treatment; and

The sodium thiosulfate solution is infiltrated.
The wound dressing containing chelating silver fibers according to claim 4, wherein the polyacrylonitrile fibers or polyacrylonitrile/polyvinyl alcohol fiber blend fibers have a length of from 3 to 1.25 mm and a linear density of from 0.1 to 10 dtex.
A method of preparing a silver dressing-containing wound dressing according to claim 4, the method comprising the steps of:

(1) adding silver-containing material to deionized water to obtain a silver-containing solution, wherein the concentration of silver ions in the silver-containing solution is 0.01-30% by weight;

(2) soaking the polyacrylonitrile fiber or the polyacrylonitrile/polyvinyl alcohol blend fiber in the silver-containing solution prepared in the step (1) for 5 to 600 minutes, and maintaining the temperature of the silver-containing solution at 10-65 °C, Wherein the ratio of the weight of the fiber to the weight of the silver-containing solution is 1:5-1:1000;

(3) rinsing the fiber obtained in the step (2), and drying or drying it to obtain a chelated silver fiber;

(4) preparing the silver-containing fabric by blending the chelated silver fiber obtained in the step (3) with the silver-free fiber;

(5) The silver-containing fabric obtained in the step (4) is cut into a sheet shape, which is then packaged and sterilized to obtain the wound dressing containing the chelating silver fibers.
The method according to claim 10, further comprising a step (2a) before the step (2), wherein the step (2a) is a pretreatment of the fiber used in the step (2), the pretreatment being as follows One or more of:

Amidoxime treatment;

Polyamine treatment;

Microporous extraction treatment; and

The surface is hydrophilic.
The method according to claim 10, further comprising the step (2b) before the step (3), the step (2b) of post-treating the chelated silver fiber obtained in the step (2), the post-treatment Is one or more of the following treatments:

Carboxymethylation;

Acylation treatment;

Alkyl sulfonation treatment;

Surface oil/emulsifier treatment;

Ammonia solution infiltration treatment; and

The sodium thiosulfate solution is infiltrated.
A method of preparing a silver dressing-containing wound dressing according to claim 4, the method comprising the steps of:

(1) fabricating a polyacrylonitrile fiber or a polyacrylonitrile/polyvinyl alcohol blend fiber and a silver-free fiber by a blending method;

(2) adding silver-containing material to deionized water to obtain a silver-containing solution, wherein the concentration of silver ions in the silver-containing solution is 0.01-30% by weight;

(3) soaking the fabric obtained in the step (1) in the silver-containing solution prepared in the step (2) 5-600min, and maintaining the temperature of the silver-containing solution at 10-65 ° C, wherein the ratio of the weight of the fabric to the weight of the silver-containing solution is 1:5-1:1000, to obtain a silver-containing fabric;

(4) rinsing the silver-containing fabric obtained in the step (3), and drying or drying to obtain a chelated silver fabric;

(5) The silver-containing fabric obtained in the step (4) is cut into a sheet shape, which is then packaged and sterilized to obtain the wound dressing containing the chelating silver fibers.
The method according to claim 13, wherein the step (1a) is further included before the step (1), and the step (1a) is a combination of the polyacrylonitrile fiber or the polyacrylonitrile/polyvinyl alcohol used in the step (1). The pre-treatment of the mixed fibers is one or more of the following treatments:

Amidoxime treatment;

Polyamine treatment;

Microporous extraction treatment; and

The surface is hydrophilic.
The method according to claim 13, wherein the step (3b) is further included before the step (4), and the step (3b) is post-processing the silver-containing fabric obtained in the step (3), and the post-treatment is One or more of the treatments:

Carboxymethylation;

Acylation treatment;

Alkyl sulfonation treatment;

Surface oil/emulsifier treatment;

Ammonia solution infiltration treatment; and

The sodium thiosulfate solution is infiltrated.
The method according to claim 10 or 13, wherein the silver-containing substance is selected from one or more of the following silver compounds: silver nitrate; silver chloride; silver sulfate; silver carbonate; silver acetate; silver lactate Silver bromide; and silver zirconium phosphate.