WO2018223743A1 - Silver-containing antibacterial product, and preparation method thereof - Google Patents

Abstract

Disclosed are a silver-containing antibacterial product and a preparation method thereof. The silver-containing antibacterial product contains a silver-containing alcohol amine chelate as an antibacterial ingredient obtained by mixing a silver-containing substance and an alcohol amine for reaction. The silver-containing alcohol amine chelate is uniformly distributed in and combined with the internal part and/or the surface of the product. The silver-containing product contains 0.01 to 10 weight% of silver by weight of the product, and the moisture absorption capability of the product is at least 6g/g. A silver-containing antibacterial dressing can be prepared from the silver-containing antibacterial product. The silver-containing antibacterial product exhibits an antibacterial activity on Staphylococcus aureus.

Description

[Invention name established by ISA according to Rule 37.2] Silver-containing antibacterial product and preparation method thereof Technical field

The invention relates to a silver-containing antibacterial product and a preparation method thereof, in particular to a silver-containing product containing a silver-containing alcohol amine chelate compound. The articles can be used in medical dressings and other antimicrobial fields.

Background technique

With the improvement of people's living standards and changes in eating habits, human disease spectrum presents some new features. Chronic exudative wounds such as venous ulcers, arterial ulcers, diabetic ulcers, traumatic ulcers, and pressure ulcers caused by diseases such as diabetes, pressure sores, hemorrhoids, and hypertension seriously affect people's health. Exudative wounds are a type of chronic wound that secretes large amounts of exudate, while the main components of exudates are pus, tissue fluid, and some necrotic tissues and cells. Therefore, the care of chronic exudative wounds should not only fully absorb the wound exudate, but also provide a warm and moist healing environment for wound healing. Anti-infective care should also be carried out on the wound in time.

At present, the antibacterial silver-containing substances used in the dressings on the market are mainly some organic and inorganic salts of silver, such as silver nitrate, silver chloride, silver hypochlorite, silver carbonate, silver acetate, sodium zirconium phosphate, etc. .

U.S. Patent No. 6,897,349 and European Patent No. 1,216,065 disclose the preparation of a silver-containing antibacterial material by dispersing silver chloride in the fibers during the preparation of the fibers. However, the material (chlorine) in the production of such wound dressings is highly corrosive to equipment.

Chinese patent CN1308509C discloses a silver-containing chitosan fiber having antibacterial action and a preparation method thereof, which comprises mixing silver compound particles having a particle diameter of about 1 micrometer, that is, sodium zirconium hydrogen phosphate (trade name: Alphasan) in spinning. In the silk solution, the silver compound contains silver in an amount of from 3.0 to 4.0% by weight. Because Alphasan itself has a limited amount of silver, the silver content of the product is also small. In addition, the particle size of Alphasan is too large, which is detrimental to fiber strength.

Ionic antibacterial dressings have a high efficiency in the use of silver, and most of the silver-containing antibacterial dressings on the market are mostly ionic. However, most of the silver compounds used in ionic silver-containing dressings are very low in water solubility, such as silver chloride, silver carbonate, etc., because of their low solubility in water, only a small amount of silver ions are ionized after water to reach equilibrium. When these small amounts of silver ions are consumed, the insoluble silver compound re-ionizes a small amount of silver ions, and the effect of sustained release of silver ions is achieved by such a dissolution balance. The use of a low-water-soluble ionic silver-containing dressing can release silver ions continuously, but it releases less silver ions after water contact, so relatively more silver compounds are still needed to achieve the desired antibacterial effect. In addition, the release of silver in this type of wound dressing is generally performed. The amount of silver released in 10 ml of wound simulating solution is only about 20 ppm in 10 ml of wound simulant, which affects its antibacterial effect and effect to some extent. Time, in addition, most of the ionic silver-containing dressings are not stable, and the silver-containing dressings will change color after being left for a period of time, affecting their acceptability as a commercial appearance.

In addition, studies have used silver-containing complexes as antibacterial agents, such as silver thiosulfate complexes and silver-ammonia complexes, but such silver-containing complexes are a class of inorganic chelate compounds that have good solubility in water. However, the solubility in organic solvents such as ethanol is poor, which is quite disadvantageous for products which are gelled by water, such as carboxymethyl cellulose fiber products, carboxyethyl cellulose fiber products, and acylated chitosan fibers. product.

Summary of the invention

In order to solve the above problems, in one aspect, the present invention discloses a silver-containing antibacterial article comprising a silver-containing alcohol amine chelate as an antibacterial component, and the silver-containing alcohol amine chelate compound is uniform. Distributing and incorporating to the interior and/or surface of the article, the article has a silver content of from 0.01 to 10% by weight, based on the weight of the article, and the article has a moisture absorption capacity of 6 g/g or more.

The silver-containing alcohol amine chelate of the present invention has different isomers according to the length of the alcohol amine carbon atom chain, and the alcohol amine is an organic substance containing an amino group and a hydroxyl group, for example, different carbon chain lengths. The structure of the silver-containing alcohol amine chelate is as follows:

And so on, including a series of isomers of different carbon chain lengths. The silver-containing alkamine chelate is a stable silver-centered chelate, and the silver ion and the alkanolamine molecule are chelated in a 1:2 form to form a soluble chelate. In the preparation, the alcohol amine can be gradually added dropwise to the dispersion of the silver-containing compound, and the dispersion of the silver-containing compound can be added dropwise to the alcohol amine until a uniform silver-containing alcohol amine chelate solution is obtained. The dispersion of the silver-containing compound means a precipitate, a colloid or a solution. If a soluble silver-containing compound (such as silver nitrate) is used as the starting material, it should preferably be converted into a slightly soluble, poorly soluble or insoluble silver-containing compound, and then thoroughly mixed with the alcohol amine until the precipitate just dissolves.

The silver-containing alcohol amine chelate of the present invention is obtained by thoroughly mixing a silver-containing substance with an alcohol amine, wherein the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3: 1. The silver-containing material is selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver acetate or silver oxalate, and the alcohol amine is an organic substance containing an amino group and a hydroxyl group.

Taking soluble silver nitrate as an example, silver nitrate is first reacted with an appropriate excess of sodium hydroxide to form a poorly soluble silver oxide precipitate, and then ethanolamine is gradually added dropwise until the formed silver oxide precipitate just dissolves, thereby obtaining a clear and transparent Silver-containing ethanolamine chelate solution.

AgNO ₃ +NaOH->Ag ₂ O+NaNO ₃ +H ₂ O

Taking insoluble silver acetate and ethanolamine as an example, a soluble silver-containing ethanolamine chelate is obtained after the reaction.

In one embodiment, the silver-containing antimicrobial article of the present invention is a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material, which can be obtained as follows:

(1) immersing the fiber, fabric or polyurethane material in a solvent selected from the group consisting of ethanol, water or a combination thereof;

(2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate, the silver-containing substance being selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or a silver oxalate; the alcohol amine is an organic substance containing an amino group and a hydroxyl group, wherein the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1;

(3) adding the silver-containing alcohol amine chelate to the mixture of the step (1), so that the fiber, fabric or polyurethane material is immersed at 25-80 ° C for 1-120 minutes, and then taken out and dried to obtain a A silver-containing antibacterial product is described.

In one embodiment, the silver-containing antimicrobial article of the present invention is a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material, which can be prepared as follows:

(1) dissolving an alcohol amine in a solvent, the alcohol amine being an organic substance containing an amino group and a hydroxyl group, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;

(2) immersing the fiber, fabric or polyurethane material in the alcohol amine solution of step (1);

(3) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;

(4) adding the silver ion-containing solution or dispersion to the mixture of the step (2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial agent. The article wherein the molar ratio of the alkanolamine to the silver ion is from 1:1 to 10:1, preferably from 1.5:1 to 3:1.

In another embodiment, the silver-containing antimicrobial article of the present invention is a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material, which can be obtained as follows:

(1) dispersing a silver-containing substance in a solvent to obtain a solution or dispersion containing silver ions selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;

(2) immersing a fiber, fabric or polyurethane material in the silver ion-containing solution or dispersion;

(3) dissolving an alcohol amine in a solvent selected from the group consisting of ethanol, water, or a combination thereof, the alcohol amine being an organic substance containing an amino group and a hydroxyl group;

(4) adding the step (3) alkanolamine solution to the mixture of the step (2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial article, wherein The molar ratio of the alkanolamine to the silver ion is from 1:1 to 10:1, preferably from 1.5:1 to 3:1.

In yet another embodiment, the silver-containing antimicrobial article of the present invention is a silver-containing fiber which can be prepared as follows:

(1) preparing a fiber spinning solution according to a conventional wet spinning method, the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;

(2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or Silver oxalate, the alcohol amine is an organic substance containing an amino group and a hydroxyl group, the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1;

(3) adding the silver-containing alcohol amine chelate to the spinning solution, and stirring uniformly to obtain a silver-containing spinning solution;

(4) Spinning and drying using the silver-containing spinning solution to obtain the silver-containing antibacterial article.

In one embodiment, the silver-containing fiber may be selected from the group consisting of silver-containing alginate fibers, silver-containing chitosan fibers, silver-containing acylated chitosan fibers, silver-containing carboxymethyl chitosan fibers, and silver-containing viscous fibers. Glue fiber, silver-containing lyocell fiber, silver-containing sea silk fiber, silver-containing carboxymethyl cellulose fiber, silver-containing carboxyethyl cellulose fiber, silver-containing sulfonyl fiber, silver-containing polypropylene fiber, silver-containing rayon Fiber or silver-containing nylon fiber. In one embodiment, the silver-containing fabric may be selected from the group consisting of silver-containing alginate fabrics, silver-containing chitosan fabrics, silver-containing chitosan fabrics, silver-containing carboxymethyl chitosan fabrics, and silver-containing pastes. Glue fiber fabric, silver-containing lyocell fabric, silver-containing seaweed fiber fabric, silver-containing carboxymethyl cellulose fabric, silver-containing carboxyethyl cellulose fabric, silver-containing sulfonyl fiber fabric, silver-containing polypropylene fabric, silver-containing Polyester fabric or silver-containing nylon fabric.

In one embodiment, the silver-containing fabric is a woven, knitted or nonwoven fabric having a basis weight of from 12 to 600 grams per square meter.

In one embodiment, the silver-containing antimicrobial article is a silver-containing polyurethane film or a silver-containing polyurethane sponge having a thickness of 0.1 to 1 mm and a silver-containing polyurethane sponge having a thickness of 1 to 10 mm.

In one embodiment, the silver-containing alginate fiber is a high mannuronic acid type, a high guluronate type or a mannuronic acid/guluronic acid mixed type fiber.

In one embodiment, the silver-containing alginate fiber is calcium alginate fiber or calcium alginate/sodium fiber.

In one embodiment, the silver-containing chitosan fiber has a degree of deacetylation of greater than 80%.

In one embodiment, the silver-containing fibers have a linear density of from 1 to 10 dtex and a fiber length of from 5 to 125 mm.

In one embodiment, the silver-containing antimicrobial article can be obtained by carboxymethylation, carboxyethylation, acylation or sulfonylation modification.

In one embodiment, the silver-containing antimicrobial article is subjected to a slitting, packaging, and sterilization process to form a silver-containing antimicrobial dressing having a silver content of 0.01-10% and a grammage of 12-600. g/m2.

In one embodiment, the silver-containing antimicrobial fabric is processed by a woven, knitted or nonwoven process having a silver content of from 0.01 to 10% and a basis weight of from 12 to 600 grams per square meter.

In one embodiment, the silver-containing antimicrobial fabric is processed from a silver-containing antimicrobial article by a woven, knitted or nonwoven process having a silver content of from 0.01 to 10% and a basis weight of from 12 to 600 grams per square meter.

In one embodiment, the silver-containing antibacterial dressing is prepared by a silver-containing antibacterial fabric by a slitting, packaging and sterilization process, and the silver-containing antibacterial dressing has a silver content of 0.01-10% and a gram weight of 12-600 g. / square meter.

In another aspect, the invention provides a method of making a silver-containing antimicrobial article. The silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, and the method comprises the following steps:

(1) immersing the fiber, fabric or polyurethane material in a solvent selected from the group consisting of ethanol, water or a combination thereof;

(2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or a silver oxalate; the alcohol amine is an organic substance containing an amino group and a hydroxyl group, wherein the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1;

(3) adding the silver-containing alcohol amine chelate to the mixture of the step (1), so that the fiber, fabric or polyurethane material is immersed at 25 to 80 ° C for 1 to 120 minutes, and then taken out and dried to obtain The silver-containing antibacterial article.

In one embodiment, the silver-containing antimicrobial article is a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material, and the method of preparing a silver-containing antimicrobial article includes the following steps:

(1) dissolving an alcohol amine in a solvent selected from the group consisting of ethanol, water, or a combination thereof, the alcohol amine being an organic substance containing an amino group and a hydroxyl group;

(2) immersing the fiber, fabric or polyurethane material in the alcohol amine solution of step (1);

(3) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;

(4) adding the solution or dispersion of the silver-containing substance to the mixture of the step (2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial agent. The article wherein the molar ratio of the alkanolamine to the silver ion is from 1:1 to 10:1, preferably from 1.5:1 to 3:1.

In one embodiment, the silver-containing antimicrobial article is a silver-containing fiber, and the method of preparing the silver-containing antimicrobial article is as follows:

(1) preparing a fiber spinning solution according to a conventional wet spinning method, the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;

(2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or Silver oxalate, the alcohol amine is an organic substance containing an amino group and a hydroxyl group, the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1; preferably 1.5:1 to 3:1;

(3) adding the silver-containing alcohol amine chelate to the spinning solution, and stirring uniformly to obtain a silver-containing spinning solution;

(4) Spinning and drying using the silver-containing spinning solution to obtain the silver-containing antibacterial article.

In one embodiment, the spinning obtained silver-containing antimicrobial article is obtained by carboxymethylation, carboxyethylation, acylation or sulfonylation modification. In the method of the present invention relating to the impregnation process, the resulting silver-containing alcohol amine chelate can be combined with a specific site of the article by electrostatic action to thereby obtain a silver-containing antimicrobial material containing a silver alcohol amine chelate.

In the method of the present invention relating to the impregnation process, the fibers used may be staple fibers or filaments, and the filaments may be more advantageous for the impregnation treatment. If filaments are used, they can be cut into staple lengths of 5-125 mm after impregnation for further processing.

In the method of the present invention relating to the impregnation process, the fabric used includes alginate fabric, chitosan fabric, acylated chitosan fabric, carboxyethyl cellulose fabric, sulfonyl fiber fabric, polypropylene fabric, and rayon fabric. And nylon fabric. These fabrics may be woven, knitted, or nonwoven having a basis weight between 12 and 600 grams per square meter. After the fabric is processed by the method of the present invention, it can be further cut, packaged and sterilized to prepare a silver-containing antibacterial dressing, wherein the silver-containing antibacterial dressing has a silver content of 0.01-10% by weight, including The weight of the silver antibacterial dressing.

In the dressing industry, a porous polyurethane material having a thickness of 1 mm or less is generally referred to as a film, and a porous polyurethane material having a thickness of 1 mm or more is referred to as a sponge. In the method of the present invention relating to the impregnation process, the polyurethane material used may be a polyurethane film having a thickness of 0.1 to 1 mm or a polyurethane sponge having a thickness of 1 to 10 mm. After the polyurethane material is processed by the method of the invention, it can be further cut, packaged and sterilized to prepare a silver-containing antibacterial dressing, wherein the silver-containing antibacterial polyurethane dressing has a silver content of 0.01-10% by weight. Based on the weight of the silver-containing antimicrobial dressing. In the method of the present invention relating to the impregnation process, if the hygroscopic silver-containing antibacterial article is a sol-formed article, such as silver-containing alginate fibers or fabrics, silver-containing carboxymethylcellulose fibers or fabrics, silver-containing Acylated chitosan fibers or fabrics, silver-containing carboxyethyl fibers or fabrics, silver-containing sulfonyl fibers or fabrics, since the sol fibers irreversibly form a gel in aqueous solution, the solvent used should be ethanol and water. Mixture to avoid the formation of an irreversible gel. Generally, the volume ratio of ethanol to water in the solvent can be greater than 1:1, and the solvent can be used in an amount of more than 30 times the weight of the hygroscopic silver-containing antimicrobial article. If the hygroscopic silver-containing antibacterial article is a non-solvent article, such as silver-containing rayon fibers or fabrics, silver-containing polypropylene fibers or fabrics, silver-containing lyocell fibers or fabrics, silver-containing viscose fibers or fabrics, Silver-containing non-modified chitosan fiber or fabric and silver-containing polyurethane material, etc., can properly adjust the ratio between water and ethanol in the solution, appropriately increase the proportion of water to reduce the proportion of ethanol, even the solvent can be all from water composition.

In the process of the present invention relating to the spinning process, the silver-containing alkamine chelate can be directly added to the fiber spinning solution and spun into a silver-containing fiber by a known spinning process. The method is suitable for wet or solvent-spun fibers such as silver-containing alginate fibers, silver-containing chitosan fibers, silver-containing viscose fibers, silver-containing lyocell fibers or silver-containing sea-hair fibers. Since silver-containing alkanolamine chelates are generally very stable, they are very suitable for the preparation of these fibers. In addition, since the spinning solutions of these fibers are generally very viscous, it is advantageous to prevent precipitation and re-agglomeration of the silver-containing chelate compound, so that the silver-containing fibers can be directly woven after being uniformly stirred.

Further, the silver-containing fiber obtained by the above method can also be prepared into a silver-containing fabric by woven, knitted or non-woven. These silver-containing fabrics can be cut, packaged and sterilized to further form a silver-containing antimicrobial dressing.

The silver-containing fiber, the silver-containing fabric, the silver-containing polyurethane material or the further silver-containing antimicrobial dressing prepared by the above method of the present invention has a silver content of 0.01 to 10% by weight, and comprises a silver fiber or a silver-containing fabric or a silver-containing polyurethane. The weight of the material or silver-containing antibacterial dressing is 12-600 g/m2.

The non-solifying fibers or fabrics produced by the process of the present invention can be further chemically modified to increase their moisture absorption properties or gel forming properties. For example, viscose fibers can be carboxymethylated, carboxyethylated or sulfonylated to give carboxymethylated cellulose, carboxyethylated cellulose, and sulfonyl cellulose; chitosan is carboxymethylated or Acylation can respectively give carboxymethylated chitosan or acylated chitosan.

The sterilization method of the present invention includes cobalt 60 irradiation, ethylene oxide, electron beam, high temperature and the like.

The hygroscopicity of the articles of the present invention was tested using the method of BS: EN13726-1-2002, and the amount of silver contained was tested by an atomic absorption spectrophotometer.

The hygroscopicity of the silver-containing antimicrobial articles (fiber, fabric or polyurethane materials) and silver-containing antimicrobial dressings referred to in the present invention are represented by two methods: g/g and g/100 cm ² . These two representations can be linked by the weight of the fabric or dressing. For example, a silver-containing chitosan dressing has a hygroscopicity of 23 g/g and a dressing weight of 130 gsm (g/m ² ). The hygroscopicity of the dressing can also be expressed as 23 g/g X 130 gsm X 10 ^-2 = 29.9 g / 100 cm ² .

The silver-containing alcohol amine chelate of the invention has a broad antibacterial spectrum as an antibacterial component, and exhibits strong antibacterial activity against gram-negative bacteria and gram-positive bacteria, and has a rapid effect and It has light stability and can be widely used in chronic infectious exudative wounds, such as diabetic foot, acne and some cave-type wounds, providing a moist environment and an anti-infective barrier for wound healing.

DRAWINGS

Figure 1 shows the zone of inhibition of the dressing containing 0.5% by weight of silver ions prepared in Example 22 after 1 day in a S. aureus culture dish.

Figure 2 shows the zone of inhibition of the dressing containing 0.55% by weight of silver ions prepared in Example 23 after 3 days in a S. aureus culture dish.

Figure 3 shows the zone of inhibition of the dressing containing 0.79 wt% silver ion prepared in Example 24 after 1 day in a S. aureus culture dish.

Figure 4 shows the zone of inhibition of the dressing containing 0.3% by weight of silver ions prepared in Example 26 after 3 days in a S. aureus culture dish.

Figure 5 shows the zone of inhibition of the dressing containing 0.8% by weight of silver ions prepared in Example 28 after 1 day in a S. aureus culture dish.

Figure 6 shows the zone of inhibition of the dressing containing 0.93% by weight of silver ions prepared in Example 33 after 3 days in a S. aureus culture dish.

Figure 7 shows the zone of inhibition of the dressing containing 0.83 wt% silver ions prepared in Example 36 after 1 day in a S. aureus culture dish.

Figure 8 shows the zone of inhibition of the dressing containing 2.8% by weight of silver ions prepared in Example 39 after 3 days in a S. aureus culture dish.

detailed description

Example 1

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver acetate) of 2:1:

(1) 0.32 ml of ethanolamine (16.6 mol / L) was first diluted with 30 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) weighing 0.46 g of silver acetate powder;

(3) slowly adding the above ethanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 2

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver acetate) of 2:1:

(1) Diluting 1.62 ml of ethanolamine (16.6 mol/L) with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) Weigh 2.3 g of silver acetate powder and disperse into 50 ml of absolute ethanol to form a suspension;

(3) slowly adding the above silver acetate suspension to an ethanol solution of ethanolamine, stirring while stirring, until silver acetate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 3

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver carbonate) of 2:1:

(1) 15.6 ml of ethanolamine (16.6 mol / L) was first diluted with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) weighing 7.6 g of silver carbonate powder;

(3) slowly adding the above ethanolamine solution to the silver carbonate with a rubber dropper, stirring while adding, until the silver carbonate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 4

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver sulfate) of 2:1:

(1) 18.3 ml of ethanolamine (16.6 mol / L) was first diluted with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) Weigh 8.6 g of silver sulfate powder and disperse into 50 ml of pure water to form a suspension;

(3) slowly adding the above silver sulfate suspension to an ethanol solution of ethanolamine, stirring while adding, until silver sulfate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 5

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver nitrate) of 2:1:

(1) Diluting 1.62 ml of ethanolamine (16.6 mol/L) with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) Weigh 2.34g of silver nitrate powder and add sodium hydroxide solution to form a black precipitate;

(3) slowly adding the above ethanolamine solution to the black precipitate with a rubber dropper, stirring while adding, until the black precipitate dissolves to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 6

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver acetate) of 5:1:

(1) 8.1 ml of ethanolamine (16.6 mol / L) was first diluted with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) Weigh 2.3 g of silver acetate powder and add to 50 ml of pure water to form a suspension;

(3) slowly adding the above silver acetate suspension to an ethanol solution of ethanolamine, stirring while adding, until silver acetate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 7

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver carbonate) of 5:1:

(1) 78 ml of ethanolamine (16.6 mol / L) was first diluted with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) weighing 7.6 g of silver carbonate powder;

(3) slowly adding the above ethanolamine solution to the silver carbonate with a rubber dropper, stirring while adding, until the silver carbonate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 8

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver sulfate) of 5:1:

(1) 91.5 ml of ethanolamine is first diluted with 300 ml of absolute ethanol to obtain an ethanolamine ethanol solution;

(2) weighing 8.6 g of silver sulfate powder;

(3) slowly adding the above ethanolamine solution to the silver sulfate with a rubber dropper, and stirring until the silver sulfate is dissolved to obtain a silver-containing ethanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 9

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of propanolamine to silver ion (silver acetate) of 2:1:

(1) 2.021 g of propanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of propanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder and dispersing into 60 ml of absolute ethanol to form a suspension;

(3) slowly adding the above silver acetate suspension to the ethanol solution of propanolamine, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing propanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 10

Preparation of a silver-containing alcohol amine chelate solution with a molar ratio of 1-methyl-ethanolamine to silver ion (silver acetate) of 2:1:

(1) 2.021 g of 1-methyl-ethanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 1-methyl-ethanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above 1-methyl-ethanolamine solution to the silver acetate with a plastic pipette, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing still to obtain a colorless transparent Solution

The above preparation process is carried out at normal temperature.

Example 11

Preparation of a silver-containing alcohol amine chelate solution with a molar ratio of 2-methyl-ethanolamine to silver ion (silver acetate) of 2:1:

(1) 2.021 g of 2-methyl-ethanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 2-methyl-ethanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder and dispersing into 50 ml of pure water to form a silver acetate suspension;

(3) slowly adding the above silver acetate suspension to an ethanol solution of ethanolamine, stirring while stirring, until silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 12

Preparation of a silver-containing alcohol amine chelate solution with a molar ratio of n-butanolamine to silver ion (silver acetate) of 2:1:

(1) 2.48 g of n-butanolamine is first diluted with 300 ml of absolute ethanol to obtain an ethanol solution of n-butanolamine;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above n-butanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing n-butanolamine chelate solution, and standing still to obtain a colorless transparent Solution

The above preparation process is carried out at normal temperature.

Example 13

Preparation of a silver-containing alcohol amine chelate solution with a molar ratio of 1-methyl-propanolamine to silver ion (silver acetate) of 2:1:

(1) 2.48 g of 1-methyl-propanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 1-methyl-propanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above 1-methyl-propanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing still to obtain no Color transparent solution;

The above preparation process is carried out at normal temperature.

Example 14

Preparation of a silver-containing alcohol amine chelate solution with a molar ratio of 2-methyl-propanolamine to silver ion (silver acetate) of 2:1:

(1) 2.48 g of 2-methyl-propanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 2-methyl-propanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above 2-methyl-propanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing still to obtain no Color transparent solution;

The above preparation process is carried out at normal temperature.

Example 15

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of 1,2-dimethylethanolamine to silver ion (silver acetate) of 2:1:

(1) 2.48 g of 1,2-dimethylethanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 1,2-dimethylethanolamine in ethanol;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above 1,2-dimethylethanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing still to obtain no Color transparent solution;

The above preparation process is carried out at normal temperature.

Example 16

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of methanolamine to silver ion (silver acetate) of 2:1:

(1) 1.31 g of methanolamine is first diluted with 300 ml of absolute ethanol to obtain a methanol solution of methanolamine;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above methanolamine solution to the silver acetate with a plastic pipette, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 17

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of ethanolamine to silver ion (silver acetate) of 2:1:

(1) Diluting 1.62 ml of ethanolamine (16.6 mol/L) with 300 ml of distilled water to obtain an aqueous solution of ethanolamine;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above ethanolamine solution to the silver acetate with a rubber dropper, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 18

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of propanolamine to silver ion (silver acetate) of 2:1:

(1) 2.021 g of propanolamine is first diluted with 300 ml of distilled water to obtain an aqueous solution of propanolamine;

(2) weighing 2.3 g of silver acetate powder;

(3) slowly adding the above-mentioned propanolamine solution to the silver acetate with a plastic pipette, stirring while stirring, until the silver acetate is dissolved to obtain a silver-containing propanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 19

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of propanolamine to silver ion (silver sulfate) of 2:1:

(1) 19.8 g of propanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of propanolamine in ethanol;

(2) weighing 8.6 g of silver sulfate powder;

(3) slowly adding the above-mentioned propanolamine solution to the silver sulfate with a plastic dropper, stirring while stirring, until the silver sulfate is dissolved to obtain a silver-containing propanolamine chelate solution, and standing to obtain a colorless transparent solution;

The above preparation process is carried out at normal temperature.

Example 20

Preparation of a silver-containing alcohol amine chelate solution having a molar ratio of 1,2-dimethylethanolamine to silver ion (silver sulfate) of 2:1:

(1) 24.43 g of 1,2-dimethylethanolamine is first diluted with 300 ml of absolute ethanol to obtain a solution of 1,2-dimethylethanolamine in ethanol;

(2) weighing 8.6 g of silver sulfate powder;

(3) slowly adding the above 1,2-dimethylethanolamine solution to the silver sulfate with a rubber dropper, stirring while stirring, until the silver sulfate is dissolved to obtain a silver-containing alcohol amine chelate solution, and standing still to obtain no Color transparent solution;

The above preparation process is carried out at normal temperature.

Example 21

100 g of carboxymethyl modified cellulose fiber was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 2 was added to the above mixture. The carboxymethyl modified cellulose fiber is fully immersed in the solution for 30 minutes at room temperature, taken out, squeezed and dried, and then subjected to a conventional nonwoven process, and cut, packaged and sterilized to obtain a silver-containing modification. Cellulose fiber. The silver-containing carboxymethyl modified cellulose dressing has a basis weight of 120 g/m 2 (gsm), a hygroscopicity of 22 g/g, and a silver content of 0.2%, based on the weight of the silver-containing dressing. The pH of the silver-containing modified cellulose dressing is from 6.1 to 6.2.

Example 22

100 g of the acylated chitosan fiber was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 2 was added to the above mixture to make an acyl group. The chitosan fiber is fully soaked in a solution at 40 ° C, taken out, squeezed and dried, and then subjected to a conventional nonwoven process, and cut, packaged and sterilized to obtain a silver-containing chitosan dressing. . The silver-containing chitosan dressing has a basis weight of 120 gsm and a hygroscopicity of 20 g/100 cm ² and a silver content of 0.5% by weight of the dressing. The pH of the dressing is 6.8-7.1. The inhibition zone of the dressing of this example after 1 day in the S. aureus culture dish is shown in Figure 1, which indicates that the wound dressing of the silver-containing alkamine chelate has a certain bacteriostatic effect on S. aureus.

Example 23

100 g of viscose fiber was immersed in 2500 ml of pure water at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 3 was added to the above mixture, and then the viscose fiber was allowed to be After fully immersing in the solution at 45 ° C for 120 minutes, taken out and squeezed and dried, after a conventional non-woven process, and cut, packaged and sterilized, a silver-containing viscose fiber dressing was obtained. The silver-containing viscose fiber dressing had a basis weight of 110 gsm and a hygroscopicity of 12 g/100 cm ² and a silver content of 0.55% by weight based on the weight of the dressing. The dressing has a pH of 4.3-6.8. The inhibition zone of the dressing of this example after 3 days in the S. aureus culture dish is shown in Figure 2, which indicates that the wound dressing of the silver-containing alcohol amine chelate has a certain bacteriostatic effect on Staphylococcus aureus.

Example 24

100 g of carboxymethyl chitosan nonwoven (gram weight 100 gsm) was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 6 was used. Adding to the above mixture, allowing the acylated chitosan fabric to be fully soaked in the solution at room temperature for 30 minutes, taking out and squeezing and drying, and then cutting, packaging and sterilizing to obtain a silver-containing acylated shell. Sugar dressing, weight is 100gsm. The silver-containing acylated chitosan dressing had a hygroscopicity of 20 g/100 cm ² and a silver content of 0.79 wt% based on the weight of the dressing. The pH of the dressing is 6.8-7.0. The inhibition zone of the dressing of this example after 1 day in the S. aureus culture dish is shown in Figure 3, which indicates that the wound dressing of the silver-containing alkamine chelate has a certain bacteriostatic effect on S. aureus.

Example 25

100 g of viscose fabric (gram weight of 80 gsm) was immersed in 2500 ml of pure water at room temperature to sufficiently wet it, and then the alcohol amine chelate solution prepared in Example 10 was added to the above mixture to make it sticky. The rubber fiber fabric was fully immersed in the solution at 60 ° C for 120 minutes, taken out, squeezed and dried, and then cut, packaged and sterilized to obtain a silver-containing viscose fiber dressing having a basis weight of 80 gsm. The silver-containing viscose fiber dressing had a hygroscopicity of 10 g/100 cm ² and a silver content of 1.5% by weight based on the weight of the dressing. The pH of the dressing is 5.0-7.0.

Example 26

100 g of a polyurethane film (thickness 0.8 mm) was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 12 was added to the above mixture. The polyurethane film was sufficiently immersed in the solution at 60 ° C for 90 minutes, taken out, squeezed and dried, and then cut, packaged and sterilized to obtain a silver-containing polyurethane film dressing. The silver-containing polyurethane film dressing had a hygroscopicity of 6 g/100 cm ² and a silver content of 0.3% by weight based on the weight of the dressing. The inhibition zone of the dressing of this example after 3 days in the S. aureus culture dish is shown in Figure 4, which indicates that the wound dressing of the silver-containing alkamine chelate has a certain bacteriostatic effect on Staphylococcus aureus.

Example 27

100 g of carboxymethyl modified cellulose fiber was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver-containing alcohol amine chelate solution prepared in Example 15 was added to the above mixture. The carboxymethyl modified cellulose fiber is fully soaked in the solution at room temperature for 35 minutes, taken out, squeezed and dried, and then subjected to a conventional nonwoven process, and cut, packaged and sterilized to obtain a silver-containing modification. Cellulose dressing. The silver-containing carboxymethyl modified cellulose dressing had a basis weight of 126 g/100 cm ² , a hygroscopicity of 24 g/g, and a silver content of 0.4%, based on the weight of the silver-containing dressing. The pH of the silver-containing modified cellulose dressing is from 6.1 to 6.2.

Example 28

100 g of polyurethane foam (thickness: 6 mm) was immersed in 2,500 ml of pure water at room temperature to sufficiently wet it, and then a silver-containing alcohol amine chelate solution prepared in accordance with Example 16 was added to the above mixture to obtain a polyurethane. The foam is fully soaked in the solution at room temperature for 100 minutes, taken out, squeezed and dried, and then cut, packaged and sterilized to obtain a silver-containing polyurethane foam dressing. The silver-containing polyurethane foam dressing had a hygroscopicity of 25 g/100 cm ² and a silver content of 0.8% by weight based on the weight of the dressing. The inhibition zone of the dressing of this example after 1 day in the S. aureus culture dish is shown in Figure 5, which indicates that the wound dressing of the silver-containing alcohol amine chelate has a certain bacteriostatic effect on Staphylococcus aureus.

Example 29

(1) Dissolving 16.2 ml of ethanolamine in 2500 ml of anhydrous alcohol to obtain an ethanolamine solution;

(2) 100 g of carboxymethyl modified cellulose fiber was immersed in the above ethanolamine solution, and allowed to stand for 10 minutes;

(3) 4.6 g of silver acetate was added to 10 ml of pure water and the resulting dispersion solution was added to the above-mentioned fiber-impregnated solution.

The above operations were all carried out at room temperature. The fiber was taken out, squeezed and dried to obtain a silver-containing carboxymethyl modified cellulose fiber having a hygroscopicity of 18 g/g and a silver content of 0.8% by weight.

Example 30

(1) dissolving 20 ml of ethanolamine in 2500 ml of anhydrous alcohol to obtain an ethanolamine solution;

(2) 100 g of acylated chitosan fiber was immersed in the above ethanolamine solution, and allowed to stand for 10 minutes;

(3) 5.3 g of silver acetate was added to 10 ml of pure water and the resulting dispersion solution was added to the above-mentioned fiber-impregnated solution. The above operations were all carried out at 50 °C.

The fiber is taken out, squeezed and dried, and then subjected to a conventional nonwoven process, and cut, packaged, and sterilized to obtain a silver-containing chitosan dressing. The silver-containing acylated chitosan dressing had a basis weight of 135 gsm and a hygroscopicity of 22 g/100 cm ² and a silver content of 0.6% by weight based on the weight of the dressing. The dressing has a pH of 6.5.

Example 31

(1) 20.21 g of 1-methyl-ethanolamine is first diluted with 3000 ml of absolute ethanol to obtain a solution of 1-methyl-ethanolamine in ethanol;

(2) immersing 100 g of viscose fiber in the above alcohol amine solution and allowing to stand for 70 minutes;

(3) 23 g of silver acetate was dissolved in 50 ml of pure water, and then the resulting solution was added to the above-mentioned fiber-impregnated alcohol amine solution. The above operations were all carried out at 65 °C.

(4) The fiber is taken out, squeezed and dried, and then subjected to a conventional nonwoven fabric process, and cut, packaged and sterilized to obtain a silver-containing viscose fiber dressing. The silver-containing viscose fiber dressing had a basis weight of 100 gsm and a hygroscopicity of 16 g/100 cm ² and a silver content of 0.7% by weight based on the weight of the dressing. The dressing has a pH of 5.5.

Example 32

(1) Dissolving 110 ml of ethanolamine in 2500 ml of anhydrous alcohol to obtain an ethanol solution of an alkanolamine;

(2) 100 g of carboxymethyl modified cellulose fiber was immersed in the above alcohol amine solution, and allowed to stand for 10 minutes;

(3) 20 g of silver sulfate was added to 10 ml of pure water and then added to the above-mentioned solution in which the fibers were soaked.

The above operations were all carried out at 45 °C. The fiber was taken out, squeezed and dried to obtain a silver-containing carboxymethyl modified cellulose fiber having a hygroscopicity of 17 g/g and a silver content of 0.9% by weight.

Example 33

(1) Dissolving 30 ml of ethanolamine in 2500 ml of pure water to obtain an ethanolamine solution;

(2) immersing 100 g of viscose fiber in the above ethanolamine solution and allowing to stand for 70 minutes;

(3) 3.323 g of silver oxide was dissolved in 10 ml of pure water, and then the resulting solution was added to the above-mentioned fiber-impregnated solution. The above operations were all carried out at 70 °C.

The fiber is taken out, squeezed and dried, and then subjected to a conventional nonwoven process, and cut, packaged, and sterilized to obtain a silver-containing viscose fiber dressing. The silver-containing viscose fiber dressing had a basis weight of 110 gsm and a hygroscopicity of 18 g/gsm and a silver content of 0.93 wt% based on the weight of the dressing. The pH of the dressing is 5. The inhibition zone of the dressing of this example after 3 days in the S. aureus culture dish is shown in Figure 6, which indicates that the wound dressing of the silver-containing alkamine chelate has a certain bacteriostatic effect on Staphylococcus aureus.

Example 34

(1) 80 ml of ethanolamine is added to 2500 ml of absolute ethanol to obtain an ethanolamine solution;

(2) 100 g of carboxymethyl modified cellulose nonwoven (gram weight 130 gsm) was soaked in the above ethanolamine solution, and allowed to stand for 10 minutes;

(3) 9.12 g of silver carbonate was dissolved in 10 ml of pure water, and then the resulting solution was added to the above solution soaked in the fabric.

The above operations were all carried out at room temperature. The above fabric was taken out, squeezed and dried, and then cut, packaged and sterilized to obtain a silver-containing carboxymethyl modified cellulose dressing having a basis weight of 130 gsm. The silver-containing carboxymethyl modified cellulose dressing had a hygroscopicity of 21 g/100 cm ² and a silver content of 0.7% by weight based on the weight of the dressing. The dressing has a pH of 6.3.

Example 35

(1) dissolving 20.23 ml of ethanolamine into 2500 ml of anhydrous alcohol to obtain an ethanolamine solution;

(2) 100 g of acylated chitosan nonwoven (gram weight 135 gsm) was immersed in the above ethanolamine solution, and allowed to stand for 10 minutes;

(3) 5.6 g of silver acetate was added to 10 ml of pure water, and the resulting solution was added to the above-mentioned fabric-impregnated solution.

The above operations were all carried out at 50 °C. The above fabric was taken out, squeezed and dried, and after cutting, packaging and sterilization, a silver-containing chitosan dressing was obtained, and the basis weight was 140 gsm. The silver-containing acylated chitosan dressing had a hygroscopicity of 26 g/100 cm ² , a silver content of 0.6% by weight based on the weight of the dressing, and a dressing pH of 6.8.

Example 36

(1) immersing 100 g of viscose woven fabric (gram weight 100 gsm) in the above propanolamine solution, and letting stand for 30 minutes;

(2) 5.3 g of silver acetate was added to 10 ml of pure water, and then the resulting solution was added to the above-mentioned fabric-impregnated solution.

The above operations were all carried out at 65 °C. The above fabric was taken out, squeezed and dried, and after cutting, packaging and sterilization, a silver-containing viscose fiber dressing was obtained, and the basis weight was 100 gsm. The silver-containing viscose fiber dressing had a hygroscopicity of 12 g/100 cm ² and a silver content of 0.83 wt% based on the weight of the dressing. The dressing has a pH of 6.8. The inhibition zone of the dressing of this example after 1 day in the S. aureus culture dish is shown in Figure 7, which indicates that the wound dressing of the silver-containing alcohol amine chelate has a certain bacteriostatic effect on Staphylococcus aureus.

Example 37

(1) dissolving 20.23 ml of ethanolamine into 2500 ml of anhydrous alcohol to obtain an ethanolamine solution;

(2) 100 g of a polyurethane film having a thickness of 0.8 mm is immersed in the above ethanolamine solution, and allowed to stand for 50 minutes;

(3) 5.6 g of silver acetate was added to 10 ml of pure water, and the resulting solution was added to the above-mentioned fabric-impregnated solution.

The above operations were all carried out at 60 °C. The above-mentioned fabric is taken out, squeezed and dried, and after being cut, packaged and sterilized, a silver-containing polyurethane film dressing is obtained. The silver-containing polyurethane film dressing had a hygroscopicity of 8 g/100 cm ² and a silver content of 0.6% by weight based on the weight of the dressing.

Example 38

(1) dissolving 20.23 ml of ethanolamine into 2500 ml of anhydrous alcohol to obtain an ethanolamine solution;

(2) 100 g of a polyurethane foam having a thickness of 5 mm was immersed in the above ethanolamine solution, and allowed to stand for 50 minutes;

(3) 5.6 g of silver acetate was added to 10 ml of pure water, and the resulting solution was added to the above-mentioned fabric-impregnated solution.

The above operations were all carried out at 60 °C. The above fabric is taken out, squeezed and dried, and after being cut, packaged and sterilized, a silver-containing polyurethane foam dressing is obtained. The silver-containing polyurethane foam dressing had a hygroscopicity of 26 g/100 cm ² and a silver content of 0.6% by weight based on the weight of the dressing.

Example 39

100 g of MG type sodium alginate powder was added to 1900 g of pure water and stirred well to obtain a suitable spinning solution, and then the silver-containing alcohol amine chelate solution prepared in accordance with Example 2 was added to the spinning solution at room temperature, and the mixture was thoroughly stirred. It is uniformly dispersed in the spinning solution, and then the obtained silver-containing spinning solution is extruded to a spinneret through a metering pump, and then sequentially passed through a coagulation bath, hot water drawing, washing, drying, drying, crimping and cutting processes. A calcium alginate fiber having an antibacterial component of a silver-containing alcohol amine chelate compound having a fiber linear density of 3 dtex and a length of 75 mm can be obtained. After the conventional non-woven fabric process, the silver-containing alginate fabric can be obtained, and then the calcium alginate silver-containing dressing can be obtained after slitting, packaging and sterilization. The dressing weight is 180gsm, the hygroscopicity is 40g/g, and the weight of the dressing is included. The amount of silver was 2.8% by weight. The dressing has a pH of 6.6. The inhibition zone of the dressing of this example after 3 days in the S. aureus culture dish is shown in Fig. 8, which indicates that the wound dressing of the silver-containing alkamine chelate has a certain bacteriostatic action against Staphylococcus aureus.

Example 40

100 g of chitosan powder is added to an appropriate amount of 2% acetic acid solution and stirred well, a suitable spinning solution is obtained according to a conventional method, and then the silver-containing alcohol amine chelate prepared according to Example 6 is added to the spinning solution at room temperature. The solution is fully stirred to make it evenly dispersed in the spinning solution, and the obtained silver-containing spinning solution is extruded to a spinneret through a metering pump, and then sequentially passed through a coagulation bath, hot water drawing, washing, drying, and drying. After the crimping and cutting steps, a chitosan fiber containing an antibacterial component of a silver-containing alcohol amine chelate compound having a fiber fineness of 2 dtex and a length of 60 mm can be obtained. The silver-containing fabric can be obtained through a conventional nonwoven process. After cutting, packaging and sterilizing, a chitosan-containing silver dressing can be obtained. According to the weight of the dressing, the silver content is 1.05%, the dressing weight is 120gsm, and the dressing moisture absorption is 14g. /100cm ² . The pH of the dressing was 7.2.

Example 41

Adding the silver-containing alcohol amine chelate solution prepared according to Example 8 to the conventional viscose fiber spinning solution (solid content 9%) at room temperature, stirring well to disperse evenly in the spinning solution, and then The obtained silver-containing spinning solution is extruded to a spinneret through a metering pump, and then passes through a coagulation bath, a hot water drawing, washing, drying and cutting process to obtain a viscose fiber containing an antibacterial component of an alcohol amine chelate. The fiber fineness is 3dtex and the length is 50mm. The silver-containing viscose fiber can obtain a silver-containing fabric through a conventional nonwoven process. After slitting, packaging and sterilization, a viscose fiber-containing silver dressing can be obtained, and the basis weight is 120 gsm. The silver content is based on the weight of the dressing. 3.06%, the dressing moisture absorption is 10g/100cm ² . The pH of the dressing was 5.6.

Example 42

The silver-containing chitosan fiber obtained in Example 40 is acylated or carboxymethylated with succinic anhydride or sodium chloroacetate to obtain an acylated chitosan or a carboxymethylated chitosan fiber. The fineness is 2.1 dtex and the length is 60 mm. The silver-containing fabric can be obtained through a conventional nonwoven process, and the modified chitosan silver-containing dressing can be obtained after slitting, packaging and sterilization. The silver-containing modified chitosan dressing had a basis weight of 125 gsm and a hygroscopicity of 22 g/100 cm ² and a silver content of 0.9% by weight based on the weight of the dressing. The dressing has a pH of 7.

Example 43

The silver-containing viscose fiber obtained in Example 41 was subjected to carboxymethylation reaction with sodium chloroacetate to obtain a carboxymethylated cellulose fiber having a fiber fineness of 3.3 dtex and a length of 50 mm, which was passed through a conventional nonwoven fabric. The process can obtain a silver-containing fabric, and the modified cellulose fiber silver-containing dressing can be obtained after slitting, packaging and sterilization. The modified cellulose silver-containing dressing has a basis weight of 123 gsm and a hygroscopicity of 26 g/100 cm ² and a silver content of 2.5% by weight of the dressing. The dressing has a pH of 6.5.

Claims (21)

A silver-containing antibacterial article, characterized in that the silver-containing antibacterial article comprises a silver-containing alcohol amine chelate as an antibacterial component, and the structural formula of the silver-containing alcohol amine chelate is as follows:

Wherein n is an integer and R ^- is NO ₃ ^- , CO ₃ ^2- , Cl ^- , SO ₄ ^2- or Ac ^- ; The silver-containing alcohol amine chelate is uniformly distributed and bonded to the interior and/or surface of the article. The article has a silver content of 0.01 to 10% by weight based on the weight of the product, and the absorbent capacity of the article is 6g / g or more. The silver-containing antimicrobial article according to claim 1, wherein the silver-containing alcohol amine chelate compound comprises an isomer thereof. The silver-containing antibacterial article according to claim 1, wherein the silver-containing alcohol amine chelate is obtained by sufficiently mixing a silver-containing substance with an alcohol amine selected from the group consisting of silver nitrate, Silver sulfate, silver carbonate, silver chloride, silver oxide, silver acetate or silver oxalate; the alcohol amine is an organic substance containing an amino group and a hydroxyl group; wherein the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1 Preferably, it is from 1.5:1 to 3:1. The silver-containing antibacterial article according to claim 1, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the silver-containing antibacterial product is prepared as follows: 1) immersing the fiber, fabric or polyurethane material in a solvent selected from the group consisting of ethanol, water or a combination thereof; 2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver; the alcoholamine is an organic substance containing an amino group and a hydroxyl group, wherein the molar ratio of the alkanolamine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1; 3) adding the silver-containing alcohol amine chelate to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-80 ° C for 1-120 minutes, and then taken out and dried to obtain the above-mentioned Silver antibacterial products. The silver-containing antibacterial article according to claim 1, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the silver-containing antibacterial product is prepared as follows: 1) dissolving an alcohol amine in a solvent, the alcohol amine being an organic substance containing an amino group and a hydroxyl group, the solvent being selected from the group consisting of ethanol, water, or a combination thereof; 2) immersing the fiber, fabric or polyurethane material in the alcohol amine solution of step 1); 3) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or silver oxalate The solvent is selected from the group consisting of ethanol, water, or a combination thereof; 4) adding the silver ion-containing solution or dispersion to the mixture of the step 2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial product. The molar ratio of the alkanolamine to the silver ion is from 1:1 to 10:1, preferably from 1.5:1 to 3:1. The silver-containing antibacterial article according to claim 1, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the silver-containing antibacterial product is prepared as follows: 1) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or silver oxalate The solvent is selected from the group consisting of ethanol, water, or a combination thereof; 2) immersing a fiber, fabric or polyurethane material in the silver ion-containing solution or dispersion; 3) dissolving the alcohol amine in a solvent, the alcohol amine being an organic substance containing an amino group and a hydroxyl group, the solvent being selected from the group consisting of ethanol, water, or a combination thereof; 4) adding the alcohol amine solution of the step 3) to the mixture of the step 2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial product, wherein the alcoholamine The molar ratio to the silver ions is from 1:1 to 10:1, preferably from 1.5:1 to 3:1. The silver-containing antibacterial article according to claim 1, wherein the silver-containing antibacterial article is a silver-containing fiber, characterized in that the silver-containing antibacterial article is prepared as follows: 1) preparing a fiber spinning solution according to a conventional wet spinning method, the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers; 2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver, the alcohol amine is an organic substance containing an amino group and a hydroxyl group, the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1; 3) adding the silver-containing alcohol amine chelate to the spinning solution, and stirring uniformly, thereby obtaining a silver-containing spinning solution; 4) Spinning and drying using the silver-containing spinning solution to obtain the silver-containing antibacterial article. The silver-containing antibacterial article according to any one of claims 4 to 7, wherein the silver-containing antibacterial article is a silver-containing fiber selected from the group consisting of silver-containing alginate fibers and a silver-containing shell. Glycan fiber, silver-containing chitosan fiber, silver-containing carboxymethyl chitosan fiber, silver-containing viscose fiber, silver-containing lyocell fiber, silver-containing sea silk fiber, silver-containing carboxymethyl cellulose fiber , silver-containing carboxyethyl cellulose fiber, silver-containing sulfonyl fiber, silver-containing polypropylene fiber, silver-containing rayon fiber or silver-containing nylon fiber. The silver-containing antibacterial article according to any one of claims 4 to 6, wherein the silver-containing antibacterial article is a silver-containing fabric selected from the group consisting of silver-containing alginate fabrics and silver-containing shells. Glycan fabric, silver-containing chitosan fabric, silver-containing carboxymethyl chitosan fabric, silver-containing viscose fabric, silver-containing lyocell fabric, silver-containing seaweed fabric, silver-containing carboxymethyl fiber Plain fabric, silver-containing carboxyethyl cellulose fabric, silver-containing sulfonyl fiber fabric, silver-containing polypropylene fabric, silver-containing rayon fabric or silver-containing nylon fabric. The silver-containing antimicrobial article according to claim 9, wherein the silver-containing fabric is a woven fabric, a knitted fabric or a nonwoven fabric, and the silver-containing fabric has a basis weight of 12 to 600 g/m 2 . The silver-containing antibacterial article according to any one of claims 4 to 7, wherein the silver-containing antibacterial article is a silver-containing polyurethane material, and the silver-containing polyurethane material is silver-containing having a thickness of 0.1 to 1 mm. Polyurethane film or silver-containing polyurethane sponge with a thickness of 1-10 mm. The silver-containing antibacterial product according to claim 8, wherein the silver-containing alginate fiber is a high mannuronic acid type, a high guluronate type or a mannuronic acid/guluronic acid mixed type. fiber. The silver-containing antimicrobial article according to claim 8, wherein the silver-containing alginate fiber is calcium alginate fiber or calcium alginate/sodium fiber. The silver-containing antimicrobial article according to claim 8, wherein the silver-containing chitosan fiber has a degree of deacetylation of 80% or more. The silver-containing antibacterial article according to any one of claims 4 to 7 or 12 to 14, wherein the silver-containing fiber has a linear density of from 1 to 10 dtex and a fiber length of from 5 to 125 mm. A silver-containing antibacterial dressing, characterized in that the silver-containing antibacterial dressing is obtained by a slitting, packaging and sterilization process of the silver-containing antibacterial product according to any one of claims 9 to 11, the silver-containing The antibacterial dressing has a silver content of 0.01-10%, and a grammage of 12-600 g/m2 based on the weight of the silver-containing antibacterial dressing. A method for preparing a silver-containing antibacterial article, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the method comprises: 1) immersing the fiber, fabric or polyurethane material in a solvent selected from the group consisting of ethanol, water or a combination thereof; 2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver; the alcoholamine is an organic substance containing an amino group and a hydroxyl group, wherein the molar ratio of the alkanolamine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1; 3) adding the silver-containing alcohol amine chelate to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-80 ° C for 1-120 minutes, and then taken out and dried to obtain the Silver-containing antibacterial products. A method for preparing a silver-containing antibacterial article, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the method comprises: 1) dissolving an alcohol amine in a solvent selected from the group consisting of ethanol, water or a combination thereof, the alcohol amine being an organic substance containing an amino group and a hydroxyl group; 2) immersing the fiber, fabric or polyurethane material in the alcohol amine solution of step 1); 3) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or silver oxalate The solvent is selected from the group consisting of ethanol, water, or a combination thereof; 4) adding the silver ion-containing solution or dispersion to the mixture of the step 2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial product. The molar ratio of the alkanolamine to the silver ion is from 1:1 to 10:1, preferably from 1.5:1 to 3:1. A method for preparing a silver-containing antibacterial article, wherein the silver-containing antibacterial article is a silver-containing fiber, a silver-containing fabric or a silver-containing polyurethane material, wherein the method comprises: 1) dispersing a silver-containing substance in a solvent to obtain a silver ion-containing solution or dispersion selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or silver oxalate The solvent is selected from the group consisting of ethanol, water, or a combination thereof; 2) immersing a fiber, fabric or polyurethane material in the silver ion-containing solution or dispersion; 3) dissolving an alcohol amine in a solvent selected from the group consisting of ethanol, water or a combination thereof, the alcohol amine being an organic substance containing an amino group and a hydroxyl group; 4) adding the alcohol amine solution of the step 3) to the mixture of the step 2) at 25-80 ° C, and allowing to stand for 1-120 minutes, and then taking out and drying to obtain the silver-containing antibacterial article, wherein the alcoholamine The molar ratio to the silver ions is from 1:1 to 10:1, preferably from 1.5:1 to 3:1. A method for preparing a silver-containing antibacterial article, the silver-containing antibacterial article being a silver-containing fiber, characterized in that the method comprises: 1) preparing a fiber spinning solution according to a conventional wet spinning method, the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers; 2) adding a silver-containing substance to the alcohol amine to obtain a silver-containing alcohol amine chelate selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or oxalic acid Silver, the alcohol amine is an organic substance containing an amino group and a hydroxyl group, the molar ratio of the alcohol amine to the silver ion is 1:1 to 10:1, preferably 1.5:1 to 3:1; 3) adding the silver-containing alcohol amine chelate to the spinning solution, and stirring uniformly, thereby obtaining a silver-containing spinning solution; 4) Spinning and drying using the silver-containing spinning solution to obtain the silver-containing antibacterial article. The method of preparing a silver-containing antimicrobial article according to claim 20, further comprising: modifying the silver-containing antimicrobial article obtained in the step 4) by carboxymethylation, carboxyethylation, acylation or sulfonylation.

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