WO2014086186A1

WO2014086186A1 - Antibacterial silver-containing fiber wound dressing and preparation method thereof

Info

Publication number: WO2014086186A1
Application number: PCT/CN2013/083631
Authority: WO
Inventors: 莫小慧; 王晓东
Original assignee: 佛山市优特医疗科技有限公司
Priority date: 2012-12-03
Filing date: 2013-09-17
Publication date: 2014-06-12
Also published as: CN103074703A

Abstract

The invention relates to an antibacterial silver-containing fiber wound dressing and a preparation method thereof, and in particular, the present invention relates to a silver-containing fiber wound dressing containing silver chloride particles, and a preparation method thereof. The silver-containing fiber wound dressing comprises silver-containing fibers. The silver chloride particles with the particle sizes in a range of 0.01-5 micrometers are uniformly distributed in the silver-containing fibers and on surfaces of the silver-containing fibers, and the silver content accounts for 0.01-10wt% of the weight of the wound dressing. As a wound treatment dressing, the silver-containing fiber wound dressing is capable of continuous releasing an enough amount of silver ions, which is especial suitable for chronic wound treatment, and can provide a long-term effective antibacterial function and effectively prevent wounds from being infected by various bacteria or other microbes.

Description

Antibacterial silver-containing fiber wound dressing and preparation method thereof

The invention relates to

The present invention relates to

Its preparation method. Background technique

Currently, silver used in antibacterial silver-containing dressings can be classified into metallic silver and ionic silver. Metallic silver exists in the form of elemental silver. Since metallic silver has a low solubility in water and other liquids, only a small amount of silver enters the solution after oxidation after contact with moisture, and its release rate is slow. In order to solve the above problems, most of the metallic silver medical dressings are nano silver dressings. Because of its small particle size and large specific surface area, nano silver is easy to release silver ions after entering the solution, and has superior antibacterial effect than metallic silver. A typical application example is CN102453968A. This patent application applies nanosilver directly to the wet spinning solution without the use of a colloidal protective agent, and utilizes the high viscosity of the spinning solution to uniformly disperse the nanosilver in the spinning dope and the fibers.

Chinese patent application CN1895683A discloses a nano silver antibacterial dressing and a preparation method thereof, which adopts a padding method to apply a coating liquid containing nano silver on a fabric to prepare a dressing having a nano silver content of 0.05-2.9% by weight. .

Chinese patent application CN1673425A describes a method comprising 0.1-1% by weight of nanosilver antibacterial viscose fiber, wherein nanosilver is added to the spinning dope. However, this method requires the use of a colloidal protective agent with a colloidal protective dose of up to 2% by weight. All of these colloidal protectants can only be present in the form of a suspension inside the fiber and not as part of the cross-linking of macromolecules in the fiber. This in fact reduces the proportion of the spinning polymer in the fiber, which in turn limits the maximum content of nanosilver, which can only achieve a 1% by weight nanosilver content.

Chinese patent CN100346840C discloses a composite nano antibacterial medical dressing which combines silver-containing nanoparticles on a nonwoven fabric or a carbon fiber adsorbent material, having a particle diameter of 1-15 nm.

Although the antibacterial effect of nano-silver dressings is obvious, the safety of nano-scale materials has not been completely determined. Therefore, the medical dressings containing ion silver are still used at present. Ionic silver is present in the form of a silver compound such as silver nitrate, silver sulfadiazine, silver chloride, Silver phosphate, etc., silver compounds can continuously release silver ions after contact with sodium ions in body fluids or wound exudates, and silver ions are released faster.

European Patent EP 1 849 464 and U.S. Patent No. 2007 275 043 describe a method of adding a silver compound (silver carbonate) to the interior of a fiber by blending a silver compound in a fiber spinning solution.

European Patent No. 1,330,565 B1 discloses a silver-containing antimicrobial fiber and a dressing thereof, which consists of calcium alginate, carboxymethylcellulose fibers and a silver compound (silver zirconium hydrogen phosphate) having a silver content of from 0.1 to 2% by weight.

The silver compound can be classified into a water-soluble silver compound and a water-insoluble silver compound. Water-soluble silver compounds, such as silver nitrate, have high solubility in water and easily ionize silver ions. However, since silver ions are highly oxidizing, it is easy to oxidize and blacken the carrier material after being combined with the dressing carrier material. The water-insoluble silver compound combines silver ions with suitable anions (such as chloride, carbonate, phosphate, etc.) into a water-insoluble silver compound, which is difficult to ionize silver ions and make silver more stable. Oxidation blackening of the carrier material during production is avoided. On the other hand, although the insoluble silver compound has low solubility in water, it can ionize a small amount of silver ions after being exposed to water. When these small amounts of silver ions are consumed, the insoluble silver compound immediately ionizes a small amount of silver ions. To achieve ionization balance, thereby achieving the effect of continuously releasing silver ions.

A method for preparing a silver-containing antimicrobial material is disclosed in U.S. Patent No. 6,897,349 and European Patent No. 1,216,065 B1, which first dissolves silver nitrate in an organic solvent and then reacts with a sodium chloride solution to form silver chloride, and disperses silver chloride on the surface of the fiber.

US 2010/0015208 A1 and the patent WO 2009/115804 A2 disclose a silver-containing fiber dressing and a preparation method thereof. After the fiber is made into a fabric, the silver nitrate solution and the sodium chloride solution are sequentially sprayed on the surface of the fabric, silver nitrate and Sodium chloride reacts to form silver chloride, which is deposited on the surface of the fiber.

Chinese patent CN101264335A discloses a preparation method of a bacterial cellulose membrane antibacterial dressing containing silver chloride nanoparticles, which sequentially immerses the bacterial cellulose membrane in a silver salt and a chloride salt solution, and reacts the silver salt and the chloride salt to obtain chlorine. The silver nanoparticles are obtained to obtain a bacterial cellulose film containing silver chloride nanoparticles, which can be used for an antibacterial dressing.

The above patents are based on the principle of reacting soluble silver salt with chloride salt to form silver chloride. The silver chloride is applied to the surface of the dressing by immersion or spraying to obtain silver chloride resistant. Bacterial dressings.

U.S. Patent No. 4,728,323 discloses a silver-containing antimicrobial dressing which employs a vapor phase coating or sputter coating method to deposit a silver salt, preferably silver chloride, on the surface of the dressing matrix material.

The silver chloride dressing described in the above patent, the silver chloride is only present on the surface of the dressing, the silver chloride particles fail to enter the interior of the dressing, and the silver is easily detached during the operation, resulting in a decrease in the antibacterial effect, although the silver ion on the surface of the dressing is higher than the inside of the dressing. Silver ions have a fast release time and a large amount of silver release, but correspondingly their silver release duration is short.

Therefore, in order to solve the problem of oxidative blackening of silver ions and achieve the effect of long-lasting release of silver ions, the present invention uses silver-insoluble silver compound as an antibacterial agent to directly disperse silver chloride particles uniformly in a spinning dope. Medium, and the resulting spinning dope is made into a silver-containing antibacterial fiber and a dressing thereof for the care of a chronic wound by a spinning process. In the silver-containing antibacterial fiber of the present invention, silver chloride particles are present inside and on the surface of the fiber. The technical effect of continuously releasing silver ions for 7 days can be achieved. Summary of the invention

In one aspect, the present invention provides a silver-containing fiber in which silver chloride particles having a particle diameter of 0.01 to 5 μm are uniformly distributed inside and on the surface of the silver-containing fiber, and the silver content is based on the weight of the silver-containing fiber. It is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

Since the silver chloride particles are insoluble silver compounds, when the particle size of the silver chloride particles is too large, the fibers are easily broken during the spinning process, and the particle size is too large to be uniform for the uniform dispersion of silver in the fibers. The silver chloride particles used in the present invention have a particle diameter of 0.01 to 5 μm. When the particle size of the silver chloride particle raw material is larger than 5 μm, the silver chloride particles may be ground to 0.01 to 5 μm by a ball milling process.

In one embodiment, the silver-containing fiber has a linear density of from 1 to 7 dtex, preferably from 1.5 to 3.0 dtex, and the silver-containing fiber has a length of from 10 to 125 mm, preferably from 20 to 78 mm.

In one embodiment, the silver-containing fiber may be a silver-containing alginate fiber, a silver-containing chitosan fiber, a silver-containing chitin fiber or a silver-containing cellulose fiber, wherein the silver-containing cellulose fiber is preferably contained Silver Lyocell fiber.

Preferably, the silver-containing fiber may be silver-containing alginate fiber, silver-containing sodium alginate fiber, silver-containing chitosan fiber or silver-containing chitin fiber. In one embodiment, the silver-containing fiber may also be a silver-containing carboxymethyl chitosan fiber, a silver-containing acylated chitosan fiber, or a silver-containing carboxymethyl cellulose fiber.

In another aspect, the present invention provides a silver fiber-containing wound dressing comprising one or more of the above silver-containing fibers.

In one embodiment, the silver-containing fibrous wound dressing may comprise the above-described silver-containing fibers and other non-silver-containing fibers blended therewith.

When the silver-containing fibrous wound dressing comprises a combination of different fibers, a wound dressing having a comprehensive function can be obtained. For example, when a silver-containing alginate fiber is blended with a silver-containing chitosan fiber, the wound dressing prepared has both hygroscopicity and hemostasis. Further, in order to further improve the moisture absorption property of the wound dressing, the silver-containing alginate fiber may be blended with the carboxymethyl cellulose fiber. In order to improve the wet strength of the wound dressing, the silver-containing carboxymethylcellulose fiber may be blended with unmodified cellulose fiber (Lyocell).

The silver-containing fibrous wound dressing of the present invention can be obtained by blending the silver-containing fibers and optionally non-silver-containing fibers by a needle punching nonwoven process, a chemical bonding nonwoven process, a weaving process, or a knitting process. When needling the nonwoven process, a fiber length of _30-100mm; when using chemical bonding process nonwovens, fiber length may be _3-15mm; When weaving or knitting process, the fiber length may be 20 85mm.

In one embodiment, the silver fiber-containing wound dressing is a needle-punched nonwoven fabric, and the absorption amount of the solution A is 1200% or more, the longitudinal wet strength MD is not less than 0.3 N/cm, and the transverse wet strength CD is not less than 0.4 N/cm.

In another aspect, the invention provides a method of making a silver-containing fiber, the method comprising the steps of:

a) dissolving a portion of the polymer in a solvent to form a polymer spinning solution such that the viscosity of the polymer spinning solution reaches 50-2000 centipoise, wherein a portion of the polymer comprises 5-40 weights of the total polymer. %, the solvent is a polar solvent selected from water, acetic acid or a combination thereof; b) dispersing silver chloride particles in the polymer spinning solution, and continuously stirring to uniformly disperse the silver chloride particles;

C) dissolving the remaining polymer in the spinning solution obtained in step b), thereby obtaining a spinning dope, wherein the silver ion content is from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the weight of the polymer;

d) the spinning dope obtained in step c) is made into the silver-containing fiber by a spinning process Dimension.

In yet another aspect, the present invention provides another method of making silver-containing fibers, characterized in that the method comprises the steps of:

a) dispersing silver chloride particles in a solvent, maintaining agitation to uniformly disperse the silver chloride particles, thereby obtaining a silver chloride dispersion, wherein the solvent is a polar solvent selected from the group consisting of water, acetic acid or a combination thereof;

b) adding a polymer to the silver chloride dispersion obtained in step a) to obtain a spinning dope having a viscosity of from 3,000 to 30,000 centipoise, wherein the silver ion content is based on the weight of the polymer 0.01-10% by weight, preferably 0.1-5% by weight;

c) The spinning dope obtained in step b) is made into a silver-containing fiber by a spinning process. In the method of producing a silver-containing fiber of the present invention, the polymer is alginate, chitosan, chitin, cellulose. Preferably, the polymer is alginate, chitosan or chitin, wherein the alginate is preferably high mannuronic acid (M), high guluronic acid (G) or mannose Aldehydic acid/guluronic acid (M/G) mixed type.

In another aspect, the present invention provides a method of preparing a silver fiber-containing wound dressing, the method comprising the steps of:

a) the silver-containing fibers and optionally the non-silver-containing fibers obtained by the above method for preparing silver-containing fibers are blended and processed into a fabric by a nonwoven, woven or knitted process;

b) The fabric obtained in step a) is cut, sterilized, and packaged to obtain the silver-containing fibrous wound dressing.

In another aspect, the present invention provides a silver-containing fibrous wound dressing prepared by the above method for preparing a silver fiber-containing wound dressing.

The antibacterial agent silver chloride used in the present invention is added to the polymer spinning solution before the spinning process, and all or a part of the polymer raw material is added after being sufficiently dispersed uniformly, thereby ensuring uniform distribution of silver ions in the preparation. Silver-containing fiber structure inside and surface. When the antibacterial wound dressing made of such silver-containing fiber contacts the wound exudate, the silver ions in the silver chloride are first released from the surface of the dressing fiber, and the internal structure of the fiber is wetted, within the fiber structure. Silver ions are slowly released during wound care, allowing for effective silver ion concentrations to be maintained for long periods of time.

Accordingly, in yet another aspect, the present invention is also directed to the use of the silver-containing fibrous wound dressing in the care of wounds and surgical hemostasis, such as in the treatment of chronic wounds. As a wound dressing, The silver-containing fibrous wound dressing of the invention has the ability to continuously release a sufficient amount of silver ions, is particularly suitable for chronic wound treatment, and can provide long-term and effective antibacterial function, and can effectively prevent various bacteria or other microorganisms from being wounded. infection. DRAWINGS

Figure 1 is a graph showing the zone of inhibition of a silver-containing alginate dressing containing 0.1% by weight of silver ions in a 7-day culture dish in an E. coli dish.

Figure 2 is a graph showing the inhibition zone of a silver-containing chitosan dressing containing 0.5% by weight of silver ions in a B. subtilis culture dish for 7 days.

Figure 3 shows the zone of inhibition of a silver-containing sodium alginate dressing containing 1% by weight of silver ions in a Bacillus subtilis culture dish for 7 days.

Figure 4 shows the zone of inhibition of the silver-containing alginate dressing containing 3% by weight of silver ions in the ABC for 7 days.

Figure 5 shows the zone of inhibition of the silver-containing calcium alginate dressing containing 10% by weight of silver ions in the A. aureus culture dish for 7 days.

Figure 6 shows the zone of inhibition of the silver-containing chitin dressing containing 1.5% by weight of silver ions in E. coli culture dishes after 7 days.

Figure 7 shows the zone of inhibition of the silver-containing alginate dressing containing 0.01% by weight of silver ions in a P. aeruginosa culture dish for 7 days.

Figure 8 shows the inhibition zone of a silver-containing acylated chitosan dressing containing 0.5% by weight of silver ions in a B. subtilis culture dish after 7 days. detailed description

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

The calculation is as follows:

The dry weight of sodium alginate powder is 6kg, the water content is 8.6%, then the wet weight of sodium alginate powder is 6÷(l-8.6%)=6.56kg. If 5% sodium alginate solution is prepared, it needs 6÷5% water. X95%=114kg;

Taking 0.5% by weight of silver ions (based on the weight of the polymer) and 6 kg of dry sodium alginate powder as an example, the weight of silver ions is 6x0.5%=0.03kg _; since silver accounts for 75 times of silver chloride. If the amount is %, it is actually necessary to use silver chloride 0.03 ÷ 75% = 0.04 kg or 40 g.

The M/G type, G type and M type sodium alginate powder (pharmaceutical grade) used in the following examples were purchased from FMC Biopolymer, silver chloride (analytical grade) was purchased from Sinopharm Chemical Reagent Co., Ltd., chitosan, carapace The powder was purchased from Shanghai Yuanju Biotechnology Co., Ltd. Example 1

A silver-containing silver alginate fiber containing 0.1% by weight of silver ions and a wound dressing thereof were prepared.

1. Add 114 liters of water to the stirred vessel.

2. For products containing 0.1% by weight of silver ions and 6 kg of dry weight M/G type sodium alginate, according to the above calculation method, 8 g of silver chloride, 6.56 kg of sodium alginate powder and 114 liters of water are required.

3. Weigh 8 g of silver chloride (silver chloride particles nominally 0.5 μm) and 6.56 kg of M/G sodium alginate powder, first add 1.3 kg of seaweed to the stirred vessel containing 114 liters of water. Sodium powder, start the stirrer. After all the sodium alginate powder was dissolved, a sample was tested and the viscosity of the sodium alginate solution was 50 cps.

4. While stirring the stirrer, add 8 grams of silver chloride to evenly disperse the silver chloride in the solution.

5. While stirring the mixer continuously, slowly add the remaining sodium alginate powder to the stirred vessel.

6. After all the sodium alginate has been dissolved thoroughly, remove the agitated vessel from the agitator and allow the agitated mixture (ie, the spinning dope) to stand for about 24 hours for natural defoaming. At this time, silver chloride is uniformly distributed in the sodium alginate solution.

7. After most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to the conventional calcium alginate fiber extrusion process, that is, the sodium alginate is converted into calcium alginate through a spinning bath. The draw bath and the draw roll are stretched to align the molecular chains, clean, dry, oil, curl and cut.

8. The spun fibers are white with a silver content of about 0.1% by weight.

9. The resulting fiber is made into a nonwoven fabric using a conventional nonwoven process. The prepared cloth was cut into 10 x 10 cm and packaged in an aluminum foil pouch.

10. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-50 kGy to obtain a silver-containing silver alginate dressing containing 0.1% by weight of silver ions. Example 2

In order to observe the antibacterial property of the dressing, a certain amount of Escherichia coli was uniformly applied to the culture dish, and then the silver-containing silver alginate dressing obtained in Example 1 was cut into 2×2 cm and placed therein, and continuously cultured at a constant temperature of 37° C. After 7 days, the growth of bacteria on the plate was observed every day. Figure 1 shows the zone of inhibition of a silver-containing alginate dressing containing 0.1% by weight of silver ions in an E. coli dish for 7 days. It can be seen that the silver-containing calcium alginate dressing still has good antibacterial properties after 7 days. Example 3

Silver-containing chitosan fibers containing 0.5% by weight of silver ions and their wound dressings were prepared.

1. Calculate the weight of the chitosan raw material and the amount of silver chloride required according to the calculation method of alginic acid according to the moisture content of the chitosan raw material and the required solid content. For example, the moisture content of the chitosan raw material is 10% by weight, and the solid content of the spinning dope is 5% by weight. For the chitosan raw material powder containing 0.5% by weight of silver ions and 6 kg of dry weight, 0.04 kg of silver chloride, 6.67 kg of chitosan powder and 114 liters of a 2% by weight aqueous solution of acetic acid were required.

2. Weigh 0.04 kg of silver chloride (silver chloride particles nominally 0.5 μm) and 6.67 kg of chitosan powder.

3. Add 110 liters of 2% by weight aqueous acetic acid solution to the stirred vessel and start the stirrer.

4. After fully dispersing all the silver chloride particles in 4 liters of water, add the silver chloride aqueous dispersion to a stirred vessel containing the aqueous acetic acid solution, and continue to start the stirrer to uniformly disperse the silver chloride in the solution. .

5. Slowly add all the chitosan powder while the stirrer is stirring.

6. After fully dispersing the chitosan, remove the stirrer and allow the stirred mixture (ie, the spinning dope) to stand for about 24 hours for natural defoaming.

7. After most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to a conventional chitosan fiber extrusion process, that is, a tow bath of 5 wt% sodium hydroxide is used to form a tow, The molecular chains are rearranged, washed, dried, oiled, crimped and cut by drawing bath and draw roll stretching.

8. The spun fibers are light yellow in color and have a silver content of about 0.5% by weight.

9. The resulting fiber is made into a nonwoven fabric using a conventional nonwoven process. The cloth to be made Cut into 10x10cm and pack into aluminum foil bag.

10. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-40 kGy to obtain a silver-containing chitosan dressing containing 0.5% by weight of silver ions. Example 4

In order to observe the antibacterial property of the dressing, a certain amount of Bacillus subtilis was uniformly applied in the culture dish, and then the dressing obtained in Example 3 was cut into 2x2 cm and placed therein, and cultured at 37 ° C for 7 days at a constant temperature, observed daily. Bacterial growth on the plate. Figure 2 shows the zone of inhibition of silver-containing chitosan dressings containing 0.5% by weight of silver ions in Bacillus subtilis culture dishes after 7 days. It can be seen that the silver-containing chitosan dressing still has good antibacterial properties after 7 days. Example 5

A silver-containing sodium alginate fiber containing 1% by weight of silver ions and a wound dressing thereof were prepared.

1. Add 114 liters of water to the stirred vessel.

2. For products containing 1% by weight of silver ions and 6 kg of dry weight of G-type sodium alginate, according to the above calculation method, 0.08 kg of silver chloride, 6.56 kg of sodium alginate powder, and 114 liters of water are required.

3. Weigh 0.08 kg of silver chloride (silver chloride particles with a nominal particle size of 0.05 μm) and 6.56 kg of G-type sodium alginate powder. Add 0.08 kg of silver chloride to a stirred vessel containing 114 liters of water to start mixing. The silver chloride is uniformly dispersed in the solution. Add 1 kg of sodium alginate powder and continue to stir.

4. While stirring the mixer continuously, slowly add the remaining sodium alginate powder to the stirred vessel.

5. After all the sodium alginate has been sufficiently dispersed, the agitated vessel is taken out from the agitator, and the agitated mixture (i.e., the spinning dope) is allowed to stand for about 24 hours for natural defoaming. At this time, silver chloride was uniformly distributed in the sodium alginate solution.

6. After most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to the conventional calcium alginate sodium fiber extrusion process, that is, the sodium alginate is converted into calcium alginate through a spinning bath. Sodium, by molecular stretching, stretching, drying, oiling, crimping and cutting through a drawing bath and a pulling roll. 7. The spun fibers are white with a silver content of about 1% by weight.

8. The resulting fiber is made into a nonwoven fabric using a conventional nonwoven process. The prepared cloth was cut into 10 x 10 cm and packaged in an aluminum foil pouch.

9. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-50 kGy to obtain a silver-containing calcium alginate dressing containing 1% by weight of silver ions. Example 6

In order to observe the antibacterial property of the dressing, a certain amount of Bacillus licheniformis was uniformly coated in the culture dish, and then the dressing obtained in Example 5 was cut into 2×2 cm and placed therein, and continuously cultured at a constant temperature of 37° C. for 7 days, and the plate was observed every day. The growth of bacteria on the surface. Figure 3 shows the inhibitory zone of a silver-containing sodium alginate dressing containing 1% by weight of silver ions in a Bacillus licheniformis dish for 7 days. It can be seen that the silver-containing sodium alginate dressing still has good antibacterial properties after 7 days. Example 7

A silver-containing silver alginate fiber containing 3% by weight of silver ions and a wound dressing thereof were prepared.

1. Add 114 liters of water to the stirred vessel.

2. For products containing 3% by weight of silver ions and 6 kg of dry weight MG type sodium alginate, according to the above calculation method, 0.24 kg of silver chloride, 6.56 kg of sodium alginate powder, and 114 liters of water are required.

3. Weigh 0.24 kg of silver chloride (silver chloride particles with a nominal particle size of 1 μm) and 6.56 kg of MG type sodium alginate powder. First, add 1.9 kg of sodium alginate powder to a stirred vessel containing 114 liters of water. Start the blender. After the sodium alginate powder was completely dissolved, the sodium alginate solution was sampled and tested to have a viscosity of 500 cps.

4. While stirring the stirrer, add 0.24 kg of silver chloride to uniformly disperse the silver chloride in the solution.

6. After all the sodium alginate was sufficiently dispersed, the stirring vessel was taken out from the agitator, and the agitated mixture (i.e., the spinning dope) was allowed to stand for about 24 hours to carry out natural defoaming. At this time, silver chloride was uniformly distributed in the sodium alginate solution. 7. When most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to the conventional calcium alginate fiber extrusion process, that is, the sodium alginate is converted into calcium alginate through a spinning bath. The draw bath and the draw roll are stretched to align the molecular chains, clean, dry, oil, curl and cut.

8. The spun fibers are white with a silver content of about 3% by weight.

9. The fibers are made into a nonwoven fabric using a conventional nonwoven process. The prepared cloth was cut into 10 x 10 cm and packaged in an aluminum foil pouch.

10. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-50 kGy to obtain a silver-containing alginate dressing containing 3% by weight of silver ions. Example 8

In order to observe the antibacterial properties of the dressing, a certain amount of Bacillus licheniformis was uniformly coated in the culture dish, and then the dressing obtained in Example 7 was cut into 2x2 cm and placed therein, and cultured continuously at a constant temperature of 37 ° C for 7 days, and the plate was observed every day. The growth of bacteria on the surface. Figure 4 shows the inhibition zone of a silver-containing alginate dressing containing 3% by weight of silver ions in a Bacillus licheniformis dish for 7 days. It can be seen that the silver-containing alginate dressing still has good antibacterial properties after 7 days.

Example 9

A silver-containing silver alginate fiber containing 10% by weight of silver ions and a wound dressing thereof were prepared.

1. Add 114 liters of water to the stirred vessel.

2. For products containing 10% by weight of silver ions and 6 kg of dry weight M-type sodium alginate, according to the above calculation method, 0.8 kg of silver chloride, 6.56 kg of sodium alginate powder, and 114 liters of water are required.

3. Weigh 0.8 kg of silver chloride (silver chloride particles with a nominal particle size of 1 μm) and 6.56 kg of M-type sodium alginate powder. First, add 1.9 kg of sodium alginate powder to a stirred vessel containing 114 liters of water. Start the blender. After the sodium alginate powder was completely dissolved, the sodium alginate solution was sampled and tested to have a viscosity of 500 cps.

4. While stirring the stirrer, add 0.8 kg of silver chloride to disperse the silver chloride in the solution.

5. Slowly add the remaining seaweed to the stirred vessel while the stirrer is continuously stirred. Sodium powder.

6. After all the sodium alginate has been sufficiently dispersed, the stirring vessel is taken out from the agitator, and the agitated mixture (i.e., the spinning dope) is allowed to stand for about 24 hours to carry out natural defoaming. At this time, silver chloride was uniformly distributed in the sodium alginate solution.

7. When most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to the conventional calcium alginate fiber extrusion process, that is, the sodium alginate is converted into calcium alginate through a spinning bath. The draw bath and the draw roll are stretched to align the molecular chains, clean, dry, oil, curl and cut.

8. The spun fibers are white with a silver content of about 10% by weight.

10. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-50 kGy to obtain a silver-containing calcium alginate dressing containing 10% by weight of silver ions. Example 10

In order to observe the antibacterial property of the dressing, a certain amount of Staphylococcus aureus was uniformly applied in the Petri dish, and then the dressing obtained in Example 9 was cut into 2×2 cm and placed therein, and cultured at 37 ° C for 7 days at a constant temperature. Observe the growth of bacteria on the plate. Figure 5 shows the zone of inhibition of the silver-containing alginate dressing containing 10% by weight of silver ions in the S. aureus culture dish after 7 days. It can be seen that the silver-containing calcium alginate dressing still has better antibacterial properties after 7 days. Example 11

A silver-containing chitin fiber containing 1.5% by weight of silver ions and a wound dressing thereof were prepared.

1. Calculate the weight of the chitin raw material and the amount of silver chloride required based on the calculation method of alginic acid according to the moisture content of the chitin raw material and the required solid content. For example, the moisture content of the chitin raw material is 10% by weight, and the solid content of the spinning dope is 5% by weight. For a chitin raw material powder containing 1.5% by weight of silver ions and 6 kg of dry weight, 0.12 kg of silver chloride, 6.67 kg of chitin powder and 114 liters of a 2% by weight aqueous solution of acetic acid are required.

2. Weigh 0.12 kg of silver chloride (silver chloride particles nominally 0.05 μm) and 6.67 kg of chitin powder. 3. Add 110 liters of 2% by weight aqueous acetic acid solution to the stirred vessel and start the stirrer.

4. After fully dispersing all the silver chloride particles in 4 liters of water, add the silver chloride aqueous dispersion to a stirred vessel containing the aqueous acetic acid solution, and continue to start the stirrer to uniformly disperse the silver chloride in the solution. . Add 1 kg of chitin powder and continue to stir.

5. Slowly add the remaining chitin powder while the stirrer is stirring.

6. After all the chitin powder has been sufficiently dispersed, the stirrer is taken out and the agitated mixture (ie, the spinning dope) is allowed to stand for about 24 hours for natural defoaming.

7. When most of the bubbles in the spinning dope disappear, the obtained spinning dope is formed into a tow according to a conventional chitin fiber extrusion process, that is, a spinning bath of 5 wt% sodium hydroxide, through a drawing bath. The draw rolls are stretched to rearrange, clean, dry, oil, curl and cut the molecular chains.

8. The spun fibers are white with a silver content of about 1.5% by weight.

10. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-40 kGy to obtain a silver-containing chitin dressing containing 1.5% by weight of silver ions. Example 12

In order to observe the antibacterial property of the dressing, a certain amount of Escherichia coli was uniformly coated in the Petri dish, and then the dressing obtained in Example 11 was cut into 2×2 cm and placed therein, and cultured continuously at a constant temperature of 37° C. for 7 days, and the plate was observed every day. The growth of bacteria on the surface. Figure 6 shows the zone of inhibition of the silver-containing chitin dressing containing 1.5% by weight of silver ions in E. coli dishes for 7 days. It can be seen that the silver-containing chitin dressing still has good antibacterial properties after 7 days. Example 13

A silver-containing silver alginate fiber containing 0.01% by weight of silver ions and a wound dressing thereof were prepared.

1. Add 114 liters of water to the stirred vessel.

2. For products containing 0.01% by weight of silver ions and 6 kg of dry weight M-type sodium alginate, according to the above calculation method, 0.8 g of silver chloride, 6.56 kg of sodium alginate powder, and 114 liters of water are required.

3. Weigh 0.8g of silver chloride (the nominal particle size of silver chloride particles is 0.05 microns) and 6.56 One kilogram of M-type sodium alginate powder, 0.8 g of silver chloride was added to a stirred vessel containing 114 liters of water, and a stirrer was started to uniformly disperse silver chloride in the solution. Add 1 kg of sodium alginate powder and continue to stir.

6. After most of the bubbles in the spinning dope disappear, the obtained spinning dope is prepared according to the conventional calcium alginate sodium fiber extrusion process, that is, the sodium alginate is converted into calcium alginate through a spinning bath. Sodium, by molecular stretching, stretching, drying, oiling, crimping and cutting through a drawing bath and a pulling roll.

7. The spun fibers are white with a silver content of about 0.01% by weight.

9. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-50 kGy to obtain a silver-containing alginate dressing containing 0.01% by weight of silver ions. Example 14

In order to observe the antibacterial property of the dressing, a certain amount of Bacillus licheniformis was uniformly applied in the culture dish, and then the dressing obtained in Example 13 was cut into 2×2 cm and placed therein, and cultured continuously at a constant temperature of 37° C. for 7 days, and the plate was observed every day. The growth of bacteria on the surface. Figure 7 shows the inhibition zone of a silver-containing alginate dressing containing 0.01% by weight of silver ions in a Bacillus licheniformis dish for 7 days. It can be seen that the silver-containing alginate dressing still has good antibacterial properties after 7 days.

Example 15

Silver-containing acylated chitosan fibers and wound dressings thereof.

The silver-containing chitosan fibers containing 0.5% by weight of silver ions in Example 3 were acylated to obtain silver-containing acylated chitosan fibers containing 0.5% by weight of silver ions.

1. Weigh 1.6 kg of succinic anhydride, dissolve in 16 liters of absolute ethanol, stir until diced The acid anhydride was completely dissolved to obtain a succinic anhydride-ethanol solution having a concentration of 0.1 g/ml.

2. According to the weight ratio of the anhydride to the modified chitosan fiber: 2:1, 800 g of the silver-containing chitosan fiber of Example 3 was weighed, soaked in absolute ethanol for 30 minutes, and then dehydrated.

3. Place the silver-containing chitosan fiber in a succinic anhydride-ethanol solution and heat in a 70 ° C water bath for 45 minutes.

4. After stopping the reaction, the fiber was taken out, dehydrated, and the reaction solution remaining on the fiber was washed with absolute ethanol.

5. The washed fibers are oiled, dried, crimped and cut to obtain silver-containing acylated chitosan fibers.

6. The resulting fiber is made into a nonwoven fabric using a conventional nonwoven process. The prepared cloth was cut into 10 x 10 cm and packaged in an aluminum foil pouch.

7. The obtained nonwoven fabric was sterilized by gamma irradiation of 25-40 kGy to obtain a silver-containing acylated chitosan dressing containing 0.5% by weight of silver ions. Example 16

In order to observe the antibacterial property of the dressing, a certain amount of Bacillus subtilis was uniformly coated in the culture dish, and then the dressing obtained in Example 15 was cut into 2x2 cm and placed therein, and cultured at 37 ° C for 7 days at a constant temperature, observed daily. Bacterial growth on the plate. Figure 8 shows the zone of inhibition of silver-containing acylated chitosan dressings containing 0.5% by weight of silver ions in Bacillus subtilis culture dishes for 7 days. It can be seen that the silver-containing chitosan dressing still has good antibacterial properties after 7 days.

Claims

Claims:

1. A silver-containing fiber, characterized in that silver chloride particles with a particle size of 0.01-5 microns are evenly distributed inside and on the surface of the silver-containing fiber, and the silver content is 0.01-10 based on the weight of the silver-containing fiber. % by weight, preferably 0.1-5% by weight.

2. The silver-containing fiber according to claim 1, characterized in that the linear density of the silver-containing fiber is 1-7 dtex, preferably 1.5-3.0 dtex, and the length of the silver-containing fiber is 10-125 mm, preferably 10-125 mm. 20-78mm.

3. The silver-containing fiber according to claim 1 or 2, characterized in that the silver-containing fiber is silver-containing alginate fiber, silver-containing chitosan fiber, silver-containing chitin fiber or silver-containing cellulose fiber, The silver-containing fiber is preferably silver-containing calcium alginate fiber, silver-containing calcium sodium alginate fiber, silver-containing chitosan fiber or silver-containing chitin fiber, and the silver-containing cellulose fiber is preferably silver-containing Lyocell fiber.

4. The silver-containing fiber according to claim 1 or 2, characterized in that the silver-containing fiber is silver-containing carboxymethyl chitosan fiber, silver-containing acylated chitosan fiber or silver-containing carboxymethyl cellulose. fiber.

5. A silver-containing fiber wound dressing, characterized in that the silver-containing fiber wound dressing includes one or more silver-containing fibers as described in any one of claims 1 to 4.

6. The silver-containing fiber wound dressing according to claim 5, characterized in that the wound dressing is made of the silver-containing fiber and optional non-silver-containing fiber after being blended through a needle-punched nonwoven process and chemical bonding. Made by nonwoven process, woven process or knitting process.

7. The silver-containing fiber wound dressing according to claim 5, characterized in that the silver-containing fiber wound dressing is a needle-punched nonwoven fabric with an absorption capacity of solution A of more than 1200% and a longitudinal wet strength MD Not less than 0.3N/cm, transverse wet strength CD not less than 0.4 N/cm.

8. A method for preparing silver-containing fibers, characterized in that the method includes the following steps: a) dissolving a part of the polymer in a solvent to form a polymer spinning solution, so that the viscosity of the polymer spinning solution reaches 50 -2000 centipoise, wherein part of the polymer accounts for 5-40% by weight of the entire polymer, and the solvent is a polar solvent selected from water, acetic acid or a combination thereof; b) Dispersing silver chloride particles in the into the polymer spinning liquid, and continue stirring to evenly disperse the silver chloride particles;

c) Dissolve the remaining polymer in the spinning solution obtained in step b) to obtain a spinning solution, in which the silver ion content is 0.01-10% by weight based on the weight of the polymer, preferably 0.1-5% by weight;

d) Use the spinning solution obtained in step c) to produce the silver-containing fiber through a spinning process.

9. A method for preparing silver-containing fibers, characterized in that the method includes the following steps: a) Disperse silver chloride particles in a solvent, and keep stirring to uniformly disperse the silver chloride particles, thereby obtaining silver chloride Dispersion, wherein the solvent is a polar solvent selected from water, acetic acid or a combination thereof;

b) Add the polymer to the silver chloride dispersion obtained in step a) to obtain a spinning dope. The viscosity of the spinning dope is 3000-30000 centipoise, and the silver ion content is based on the weight of the polymer. 0.01-10% by weight, preferably 0.1-5% by weight;

c) The spinning solution obtained in step b) is made into silver-containing fibers through a spinning process.

10. The method according to claim 8 or 9, wherein the polymer is alginate, chitosan, chitin, or cellulose, and the polymer is preferably alginate, chitosan or chitin, The alginate is preferably a high mannuronic acid type, a high guluronic acid type or a mannuronic acid/guluronic acid mixed type.

11. A method of preparing a silver-containing fiber wound dressing, characterized in that the method includes the following steps:

a) The silver-containing fiber and the optional non-silver-containing fiber prepared by the method according to any one of claims 8-10 are blended and processed into a woven fabric through a non-woven, woven or knitting process. b) Cut, sterilize, and package the fabric obtained in step a) to obtain the silver-containing fiber wound dressing.

12. The use of the silver-containing fiber wound dressing according to any one of claims 5-7 in wound care and surgical hemostasis, such as the care of chronic wounds.