WO2012106983A1

WO2012106983A1 - Antibacterial fibrous dressing containing nano-sized metal and preparation method thereof

Info

Publication number: WO2012106983A1
Application number: PCT/CN2012/070378
Authority: WO
Inventors: 王晓东; 莫小慧; 史福军
Original assignee: 佛山市优特医疗科技有限公司; 南方医科大学珠江医院
Priority date: 2011-02-11
Filing date: 2012-01-16
Publication date: 2012-08-16
Also published as: CN102631699A

Abstract

An antibacterial fibrous dressing containing nano-sized metal and a preparation method thereof. On the surfaces of the fibers of the dressing are distributed nano-sized metal particles in an amount of 0.5 to 10 wt%. The dressing can persistently release sufficient amounts of nano-sized metal particles to provide long term and effective antibacterial capability, suitable for use as a dressing for chronic wounds.

Description

Antibacterial fiber type dressing containing nano metal and preparation method thereof

Technical field

The present invention relates to an antimicrobial fiber-containing dressing containing nano-metals and a method of preparing the same. Background technique

It is well known that silver and copper, especially silver, have long been recognized to have effective antibacterial properties, particularly for killing some bacteria that are common in the care of chronic wounds. Moreover, the sterilization effect of silver on certain antibiotic-resistant bacteria has been shown. At present, the most common antibacterial silver-containing dressings are divided into ionic and nano-metal types. Silver ion technology is used to provide silver ions to the wound dressings through a silver compound, while nano-metal technology is used to make nano-metals. Metals such as nanosilver particles are applied to the wound dressing.

In the preparation of antibacterial fiber-based wound dressings, the prior art mainly employs the following two methods. One is to dissolve (or dissolve) the antimicrobial agent into the interior of the fibrous polymer material by blending the antimicrobial agent in the spinning solution and retaining it in the finished fiber.

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.

Chinese Patent No. CN1308509C discloses a silver-containing chitosan fiber having an antibacterial action and a preparation method thereof, which comprises mixing a silver compound particle having a particle diameter of 1 μm or less, that is, sodium zirconium hydrogen phosphate (trade name: Alphasan), in spinning. In the solution, the silver compound contains silver in an amount of from 3.0 to 4.0% by weight.

Chinese Patent No. CN1060235C discloses a bacteriostatic propylene fiber and a method for producing the same, which comprises forming a fiber by mixing and spinning a bacteriostatic masterbatch with polypropylene, the fiber containing 500-1000 ppm by weight of a bacteriostatic agent.

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

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. But the method is to make With a colloidal protective agent, a colloidal protective dose of up to 2% by weight can be used. All of these colloidal protective agents 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 turn 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.

The second is to apply the antibacterial agent to the surface of the fiber or fabric, i.e., to the surface of the fiber or fabric, or to the surface of the fiber or fabric.

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

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.

Chinese Patent Application No. CN1066783A discloses a method of preparing an antibacterial material containing an antibacterial metal by forming an antibacterial material containing an antibacterial metal of silver, copper or the like and an alloy thereof by a physical method such as vapor deposition.

US Patent No. 7,462,753 discloses a nanosilver wound dressing having a four-layer structure, the first layer being composed of a hydrophilic cloth, the second layer being composed of an activated carbon cloth impregnated with nanosilver, and the third layer being super A nonwoven fabric composed of a water-absorbent polymer is formed, and the fourth layer is composed of a pore-like fabric covering the third layer.

European Patent EP 1095179 discloses a method of making a nonwoven fabric for a wound dressing which utilizes a lamination process to composite alginate webs on both sides of a silver coated fibrous web.

U.S. Patent No. 7,385,101 discloses an antibacterial textile material suitable for use in a wound dressing and a wound dressing thereof which is obtained by mixing a textile fiber having a metallic silver coating on the surface with alginate fibers by a nonwoven method. .

A silver-containing medical dressing is prepared by blending silver-containing fibers with non-silver-containing fibers, and the resulting wound dressing contains 0.01 to 5.0% by weight of silver ions, as disclosed in U.S. Patent No. 2,003,088, 346, and European Patent Application No. 1,319,842.

It can be seen that in the prior art, the method of using silver ions or nano silver particles as an antibacterial agent to be provided into the wound dressing used may be to mix and retain the silver compound or the nano silver particles in the spinning solution. In the fiber, or silver ion or nano silver particles The antimicrobial agent is applied to the surface of the fiber or fabric to penetrate or adhere to the surface of the fiber or fabric. However, the production method of the antibacterial fibrous dressing in which the metal compound or the nano metal particles are added to the spinning solution so that the entire fiber structure has metal ions or nano metal particles uniformly distributed has a long production cycle, which is disadvantageous for reducing the production cost. In addition, the method for producing an antibacterial fiber-based dressing in which metal particles or even nano-metal particles are applied to the surface of a fiber or fabric is a padding method, a dipping method, and a vapor deposition method, and metal particles, even nano metal particles, are adsorbed only on fibers. Or the surface layer of the fabric is easily peeled off from the surface of the fiber or fabric and cannot be used for the sol fiber.

In order to solve the above problems, the present invention employs spraying a nano metal particle, preferably a nano silver particle, onto a surface of a fiber or fabric by a spraying method. Due to the high surface potential of nano-metals, in order to reduce the surface energy, the surface atoms of the particles and the exposed groups on the surface of the fibers (such as hydroxyl groups and carboxyl groups) are closely adsorbed by approximate chemical bonds and van der Waals forces, and the nanoparticles also interact with certain fiber surfaces. Electrostatic adsorption is formed, and physical grooves, slits, and the like on the surface of the fiber may also form an incorporation of the nanoparticles, and also adhere the particles to the surface of the fiber. Through the above action, the nano metal finally adheres relatively firmly to the surface of the fiber or fabric after spraying, and at the same time, since the nano metal particles adhere only to the surface of the fiber or the fabric, it does not affect the internal structure of the fiber or the fabric. For wound dressings, the general frequency of replacement is 24 hours, and the longer is 7 days or even 21 days, but it will not last longer than 21 days. Therefore, the dressing made by spraying method does not affect the antibacterial effect of the dressing.

This method is particularly suitable for wound dressings made from sol fibers. This material is no different from normal fibers under normal conditions, but the fibers become colloidal when exposed to water or aqueous solutions. This material is very valuable as a wound dressing. First, this material generally has a very high moisture absorption performance, generally can absorb 1000%-2000% of water; Second, once the material is absorbed into water, the dressing has excellent moisture retention and can keep the wound for a long time. There is a humid microclimate. The sol fibers generally used as wound dressings include alginate fibers, carboxymethyl chitosan fibers, acylated chitosan fibers, carboxymethyl cellulose fibers, and water-insoluble cellulose sulfonate fibers. Wait.

The general spraying is to use water as a medium to disperse the nano metal particles in an aqueous solution. However, this method is not feasible for partially highly soluble fiber dressings such as carboxymethyl chitosan fibers, acylated chitosan fibers, carboxymethyl cellulose fibers or cellulose sulfonate fibers. These fibers become colloidal when in contact with water, even after spraying a small amount of nano-aqueous solution. After drying, the fiber or dressing is very hard and not soft enough to be applied to the wound and can no longer be used as a wound dressing. In particular, we have studied the spraying of such fiber dressings, that is, using organic solvents as a medium, such as acetone, alcohol, etc., to solve these problems. As long as a certain proportion of the nano-metal is dispersed in an organic solvent by an appropriate method, the solution is sprayed on the surface of the fiber or fabric. The organic solvent can be volatilized in a subsequent process to cause the nanometal to be applied to the surface of the fiber or fabric.

Of course, aqueous spraying can be used for materials that are not highly sol or even sol.

Accordingly, it is an object of the present invention to efficiently distribute a relatively high content of nano metal particles uniformly on the surface of a fiber or fabric to obtain an antimicrobial fibrous wound dressing containing a high concentration of nano metal particles. Summary of the invention

The present invention provides an antimicrobial fiber-based wound dressing containing nano metal, and a method of preparing the wound dressing.

Since the particle size of the nano metal particles used in the present invention is generally about 5-10 nm, which is less than one thousandth of the fiber diameter, the particle size of the silver compound particles used in the prior art (for example, CN1308509C and EP1849464A1) It accounts for 5-10% of the fiber diameter and is difficult to apply to the fiber surface. And because the nano metal particles are extremely small, they can be uniformly distributed on the surface of the fiber after being sprayed onto the surface of the fiber.

In the dressing of the present invention, the content of the nano metal particles is from 0.5 to 10% by weight, preferably from 0.6 to 9% by weight, most preferably from 0.8 to 8% by weight.

The nano metal particles used in the present invention have a particle diameter of from 1 nm to 500 nm, preferably from 1 nm to 400 nm.

The nano metal particles used in the present invention are nano silver particles or nano copper particles or nano zinc particles.

In the dressings to which the present invention relates, the fibers used may be any fiber suitable for dressing and fabrics thereof, preferably alginate fibers or chitosan fibers or cellulose fibers.

(including cellulose fibers obtained by solvent spinning), the alginate fiber is high mannuronic acid (M) type or high guluronic acid (G) type or mannuronic acid / gulose Aldonic acid

(M/G) Mixed type. The alginate fiber is calcium alginate fiber or calcium alginate/sodium alginate Fiber. The chitosan fiber may be a chitosan fiber or a carboxymethyl chitosan fiber or an acylated chitosan fiber having a degree of deacetylation of 80% or more. The cellulose fiber may be a carboxymethyl cellulose fiber, a water-insoluble cellulose sulfonate fiber, a carboxymethyl solvent-spun cellulose fiber, or a water-insoluble solvent spinning. Cellulose sulfonate fibers.

The fibers used in the present invention are short fibers which can be cut to a length according to the structure of the wound dressing, said fibers having a length of from 3 to 100 mm.

The fibers used in the present invention have a certain linear density and degree of curl, and the fibers have a linear density of from 1 to 5 decitex, preferably from 1.5 to 3 decitex.

The dressings to which the present invention relates are fabrics produced by a needle punching nonwoven process or a chemical bond nonwoven process or a weaving process or a knitting process. If the needle-punched nonwoven process is used, the fiber length can be longer, 30-100mm. If the chemical bonding nonwoven process is used, the fiber length can be shorter, 3-15mm, if woven or knitted, fiber The length can be 20-85mm.

The present invention provides a method for producing an antimicrobial fiber containing nano metal. First, a nano metal material is dispersed in an aqueous solution or an organic solvent in a ratio. A low-frequency ultrasound system (25-50 Hz) can be used to make the dispersion process more efficient. The nanometal containing solution is then sprayed onto the surface of the fiber or fabric according to process conditions.

The concentration of the nano-solution is determined by the process conditions and materials, and the final content of the nano-metal in the fiber or fabric should be between 0.5 and 10% by weight.

In the case of a continuous spinning process, the spray flow rate is calculated according to the spinning speed and the fiber bundle density. If it is a loose fiber spray, the total amount of fiber is calculated. If it is a fabric, calculate the total weight and area of the fabric.

The invention provides a preparation method of an antibacterial fiber containing nano metal, which specifically comprises the following steps:

Dispersing the nano metal in an aqueous solution or an organic solution to prepare a solution containing the nano metal;

The obtained nano metal-containing solution is sprayed onto the continuously spun silk bundle according to the process conditions;

Curing and cutting the obtained fiber bundle;

The resulting fibers are processed into a fabric by a nonwoven, woven or knitted process. The invention also provides a preparation method of an antibacterial fiber containing nano metal, which specifically comprises the following steps:

The obtained nano metal-containing solution is sprayed on the prepared short fiber surface by the weight of the fiber;

The resulting fibers are processed into a fabric by a nonwoven, woven or knitted process.

The invention provides a preparation method of an antibacterial fabric containing nano metal, which comprises the following steps:

The obtained nano metal-containing solution is sprayed onto the surface of the fabric according to the weight of the fabric, and may be sprayed on one side or sprayed on both sides of the fabric;

The method for preparing a nanofiber-containing antibacterial wound dressing provided by the present invention further comprises the following steps: cutting the obtained fabric, packaging and sterilizing to obtain the dressing.

The nano metal particles used in the above respective methods provided by the present invention are nano silver particles or nano copper particles or nano zinc particles.

The particle size of the nano metal particles in the above methods provided by the present invention is

1匪 -500匪, preferably 1匪 -400匪.

Therefore, when the above spraying method is employed, since the charge of the nano metal particles is high, the nano silver adheres to the surface of the fiber and can withstand a general nonwoven process. In addition, since the wound dressing of the present invention is a fibrous fabric having nano metal particles distributed on the surface, the fibrous wound dressing has a capability of rapidly releasing a sufficient amount of nano metal particles as a wound dressing, which is particularly suitable for chronic wound treatment. ', can provide long-term and effective antibacterial function, can effectively prevent infection of wounds by various bacteria and microorganisms. DRAWINGS

Figure 1 is a graph showing the zone of inhibition of a dressing containing 0.5% by weight of nanosilver in an E. coli dish for 1 day.

Figure 2 is a view showing a dressing containing 0.5% by weight of nano silver in an E. coli dish for 7 days. After the inhibition zone.

Figure 3 is a graph showing the zone of inhibition of a dressing containing 10% by weight of nano-copper in an E. coli dish for 1 day.

Figure 4 is a graph showing the zone of inhibition of the dressing containing 10% by weight of nano-copper in an E. coli dish for 7 days.

Figure 5 is a graph showing the inhibition zone after 1 day in a S. aureus culture dish containing a 1% by weight nanosilver dressing.

Figure 6 is a graph showing the inhibition zone after 7 days in a S. aureus culture dish containing a 1% by weight nanosilver dressing. 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. Example 1

A method of preparing an antimicrobial chitosan fiber containing 0.5% nanosilver and a wound dressing thereof:

1. In the usual chitosan spinning process, the dry weight of the tow is calculated, for example, 6 g/m.

2. Check the line speed in meters/minutes, for example, 20 m/min. The total dry weight of the filament bundle per minute is obtained, ie 120 g/min.

3. Prepare the amount of water required for the solution, which can be sprayed onto the surface of the tow during the spinning process. The higher the silver concentration in the solution, the better. In this example, the prepared nano silver-containing solution has a concentration of 20%, and the silver particles have a nominal particle diameter of 5 nm.

4. The nanosilver powder (particle size 5 nm, D95=3.7-6.9) was first dispersed in an aqueous solution using an ultrasound system (25-50 Hz) containing 20% by weight of nanosilver.

5. Adjust the moving speed of the nozzle so that the spraying speed is about 3 g / min, and spray the solution evenly on the surface of the tow as the tow passes.

6. The tow will be dried, crimped and cut into short fibers of 50 mm length. The spun fibers are off-white, and wherein the nanosilver content is about 0.5% by weight.

7. The fibers are made into a nonwoven fabric using a conventional nonwoven process. The prepared cloth was cut into lOxlOcm and packaged in a paper bag. The resulting dressing will be sterilized by gamma irradiation of 25-40 kGy. 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 dressing obtained in Example 1 was cut into 2×2 cm, and continuously cultured at 37 ° C for 7 days, observed daily. Bacterial growth on each plate. Figure 1 shows the zone of inhibition of a dressing containing 0.5% by weight of nanosilver in an E. coli dish for 1 day. Figure 2 shows the zone of inhibition of a dressing containing 0.5% by weight of nanosilver in an E. coli dish for 7 days. It can be seen that the dressing containing 0.5% by weight of nanosilver still has good antibacterial properties after 7 days. Example 3

Method for preparing antibacterial calcium alginate fiber containing 10% nano copper and its wound dressing:

1. Calculate the dry weight of the tow in the usual calcium alginate spinning process, for example, 11.5 g

/Meter.

2. Check the line speed in meters/minutes, for example, 22 m/min. The total dry weight of the tow per minute is obtained, which is 253 g/min.

3. Since calcium alginate can be gelled with water, use acetone or other organic solvents as the medium. Prepare 500 grams of acetone liquid and 200 grams of nano-copper powder (copper-silver particles range in size from 10-40 nm).

4. The nano copper powder was first dispersed in an acetone solution using an ultrasonic system (25-50 Hz), and the solution contained 40% by weight of nano copper.

5. Adjust the nozzle so that the spray speed is approximately 63 g/min. The solution is sprayed evenly onto the surface of the tow as it passes.

6. The tow will be dried, crimped and cut into short fibers of 50 mm length. The spun fibers were grayish white and had a copper content of about 10% by weight.

7. 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 a paper bag. The resulting dressing will be sterilized by gamma irradiation of 25-40 kGy. Example 4

In order to observe the antibacterial properties of the dressing, a certain amount of Escherichia coli was evenly coated in the Petri dish, and then the dressing obtained in Example 3 was cut into 2 X 2 cm, respectively, at a constant temperature. The cells were continuously cultured at 37 ° C for 7 days, and the growth of the bacteria on each plate was observed every day. Figure 3 shows the zone of inhibition of a dressing containing 10% by weight of nano-copper in an E. coli dish for 1 day. Figure 4 shows the zone of inhibition of a dressing containing 10% by weight of nano-copper in an E. coli dish for 7 days. It can be seen that the dressing containing 10% by weight of nano-copper still has good antibacterial properties after 7 days. Example 5

A method of preparing a wound dressing comprising an antibacterial modified cellulose fiber of 1% nanosilver:

1. Flatly lay a fabric of 1 square meter and a weight of 120 g/m2 on a flat surface;

2. Weigh 180 g of acetone and 20 g of nano-silver aqueous solution containing 20% of nano-silver and mix to prepare a solution. The nano silver particles have a nominal particle size of 100 nm and an actual particle size distribution of 50-150 nm;

3. Spray about 30 grams of the solution onto one side of the carboxymethyl cellulose fabric. The resulting fabric contained 0.5% by weight of nanosilver.

4. Turn the fabric over and spray the other side with the same share as in item 3 above. The resulting fabric had a total nanosilver content of about 1% by weight.

5. Before proceeding to the next step, ensure that the solvent is completely volatilized or the fabric is completely dry.

6. The fabric is cut into lO X lOcm and packaged into a paper bag. The resulting dressing will be sterilized by epoxy acetam. Example 6

In order to observe the antibacterial properties of the dressing, a certain amount of Staphylococcus aureus was uniformly applied in the Petri dish, and then the dressing obtained in Example 5 was cut into 2 X 2 cm, and continuously cultured at a constant temperature of 37 °C. Days, observe the growth of bacteria on each plate every day. Figure 5 shows the zone of inhibition of the dressing containing 1% by weight of nanosilver in the S. aureus culture dish after 1 day, and Figure 6 shows the dressing containing 1% by weight of nanosilver in the S. aureus culture dish after 7 days. Inhibition zone. It can be seen that the dressing containing 1% by weight of nanosilver still has good antibacterial properties after 7 days.

Claims

Claim

An antibacterial fibrous dressing comprising nano metal, characterized in that: the surface of the fibrous dressing is uniformly sprayed with nano metal, and the fiber is a sol fiber.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1, wherein the surface of the sol fiber is uniformly sprayed with an adhering nano metal.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1, wherein the content of the nano metal particles is from 0.5 to 10% by weight, preferably from 0.6 to 9% by weight, most preferably from 0.8 to 8. weight%.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the nano metal particles have a particle diameter of from 1 nm to 500 nm, preferably from 1 nm to 400 nm.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the nano metal particles are nano silver particles or nano copper particles or nano zinc particles.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the fiber is alginate fiber or chitosan fiber or cellulose fiber.

The nano metal-containing antimicrobial fiber-based dressing according to claim 6, wherein the alginate fiber is a high mannuronic acid type, a high guluronic acid type or a mannuronic acid/ Gluuronic acid mixed fiber.

The nano metal-containing antimicrobial fiber-based dressing according to claim 6, wherein the alginate fiber is calcium alginate fiber or calcium alginate/sodium fiber.

The nano metal-containing antimicrobial fiber-based dressing according to claim 6, wherein the chitosan fiber is a carboxymethyl chitosan fiber or an acylated chitosan fiber.

The nano metal-containing antimicrobial fiber-based dressing according to claim 6, wherein the cellulose fiber is carboxymethyl cellulose fiber or water-insoluble cellulose sulfonate fiber, Carboxymethyl solvent-spun cellulosic fibers or water-insoluble solvent-spun cellulose sulfonate fibers.

The nano metal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the fiber-based dressing is a woven fabric, a knitted fabric or a nonwoven fabric.

12. A method of preparing a nanometal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the method comprises the steps of:

Dispersing the nano metal particles in an aqueous solution or an organic solvent; then spraying on the surface of the continuously spun fiber tow;

Curing and cutting the fiber tow;

The obtained fiber is made into a nonwoven fabric by a non-woven process, cut into a block, and package sterilized.

13. A method of preparing a nanometal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the method comprises the steps of:

Dispersing the nano metal particles in an aqueous solution or an organic solvent; and then spraying the surface on the surface of the short fiber that has been cut;

14. A method of preparing a nano metal-containing antimicrobial fiber-based dressing according to claim 1 or 2 or 3, wherein the method comprises the steps of:

Dispersing the nano metal particles in an aqueous solution or an organic solvent; and then spraying the surface on the surface of the already made fabric;

The dressing obtained after spraying is cut into pieces and sterilized by packaging.

The method for preparing a nano metal-containing antimicrobial fiber-based dressing according to any one of claims 12 to 14, wherein the particle size of the nano metal particles is 1匪-500匪, preferably 1匪-400匪.

The method for producing a nano metal-containing antimicrobial fiber-based dressing according to any one of claims 12 to 14, wherein the nano metal particles are nano silver particles or nano copper particles or nano zinc particles.

The method for preparing a nano metal-containing antimicrobial fiber-based dressing according to any one of claims 12 to 14, wherein the fiber is alginate fiber, carboxymethyl chitosan fiber, acylation A chitosan fiber, a carboxymethylcellulose fiber, a water-insoluble cellulose sulfonate fiber, or the above-mentioned fiber in which a non-sol fiber is blended as a reinforcing fiber.