WO2015165400A1 - 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法 - Google Patents

含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法 Download PDF

Info

Publication number
WO2015165400A1
WO2015165400A1 PCT/CN2015/077792 CN2015077792W WO2015165400A1 WO 2015165400 A1 WO2015165400 A1 WO 2015165400A1 CN 2015077792 W CN2015077792 W CN 2015077792W WO 2015165400 A1 WO2015165400 A1 WO 2015165400A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
thiosulfate
fiber
fabric
group
Prior art date
Application number
PCT/CN2015/077792
Other languages
English (en)
French (fr)
Inventor
陶炳志
王晓东
姜猛进
Original Assignee
佛山市优特医疗科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 佛山市优特医疗科技有限公司 filed Critical 佛山市优特医疗科技有限公司
Publication of WO2015165400A1 publication Critical patent/WO2015165400A1/zh

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/04—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by pouring or allowing to flow on to the surface of the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B9/00—Solvent-treatment of textile materials
    • D06B9/04—Successively applying two or more different solvent-based treating materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them

Definitions

  • the present invention relates to a moisture absorbing silver-containing article, and more particularly to a silver-containing article comprising a silver thiosulfate complex or a silver ammonia complex.
  • the articles can be used in medical dressings and other antimicrobial fields.
  • 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.
  • 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.
  • the material (chlorine) in the production of such wound dressings is highly corrosive to equipment.
  • Citride 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.
  • 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.
  • most of the silver compounds used in ionic silver-containing dressings are very low in water solubility, such as silver chloride, silver carbonate, etc., due to their low solubility in water, After water, only a small amount of silver ions are ionized to reach a dissolution 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 dissolution equilibrium. .
  • 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.
  • 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 less stable, and the silver-containing dressing will discolor after a period of time, affecting its acceptability as a commercial appearance.
  • the present invention discloses a moisture absorbing silver-containing antibacterial article comprising a silver thiosulfate complex or a silver ammonia complex as an antibacterial component, the thiosulfuric acid.
  • the silver complex or silver ammonia complex is evenly distributed and bonded to the interior and/or surface of the article, the article having a silver content of from 0.01 to 10% by weight, based on the weight of the article, and the article having a moisture absorption capacity of 6 g/ g or more.
  • the silver thiosulfate complex of the present invention is Ag 2 S 2 O 3 and/or comprises [Ag(S 2 O 3 )] 5- and/or [Ag 2 (S 2 O 3 ) 3 ] 4-
  • the complex is preferably a complex containing [Ag 2 (S 2 O 3 ) 3 ] 4- .
  • the silver thiosulfate complex may be present in the interior and/or surface of the article in the form of a precipitate of Ag 2 S 2 O 3 , or may comprise [Ag(S 2 O 3 )] 5- and/or [Ag The soluble complex of 2 (S 2 O 3 ) 3 ] 4 is present in the interior and/or surface of the article.
  • the silver-ammonia complex of the present invention is [Ag(NH 3 ) 2 ] + which is present in the interior and/or surface of the article in the form of a soluble complex.
  • Silver thiosulfate complex and silver ammonia complex are a kind of stable silver-based complex.
  • silver and thiosulfate can be coordinated with different ratios. Combines to form a complex.
  • polar carrier particles in the preparation of conventional silver thiosulfate complexes to prevent aggregation of the silver thiosulfate complex.
  • ammonia water must be gradually added dropwise to a solution of a sparingly soluble, poorly soluble or insoluble silver-containing compound until the silver-containing compound is just dissolved to prevent an excess of ammonia from forming an unstable azide compound.
  • a soluble silver-containing compound such as silver nitrate
  • the silver thiosulfate complex of the present invention is obtained by adding a substance providing silver ions to a soluble thiosulfate, wherein the molar ratio of thiosulfate to silver ion is S 2 O 3 2- /Ag + is 1: 1 to 8:1, preferably from 1.1:1 to 3:1, the silver ion-providing substance is selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate, silver acetate or silver oxalate;
  • the thiosulfate is selected from sodium thiosulfate or potassium thiosulfate.
  • the silver-ammonia complex of the present invention is obtained by gradually dropping ammonia water into a solution of a sparingly soluble, poorly soluble or insoluble silver-containing compound until the silver-containing compound is just dissolved. If a soluble silver-containing compound (such as silver nitrate) is used as a raw material, it should be converted into a slightly soluble, insoluble or insoluble silver-containing compound, and then gradually add ammonia water until the precipitate just dissolves, thereby obtaining a silver-ammonia complex. Wherein the molar ratio of ammonia molecule to silver ion NH 3 /Ag + is 2:1.
  • the process of producing a silver thiosulfate complex is as follows: silver nitrate reacts with sodium thiosulfate to form silver thiosulfate precipitate, and the resulting silver thiosulfate is formed. The precipitate can be further reacted with an excess of sodium thiosulfate to form a soluble complex:
  • the process of producing a silver-ammonia complex is as follows: silver nitrate reacts with a suitable excess of sodium hydroxide to form a poorly soluble silver oxide precipitate, and then gradually adds ammonia water thereto until the formed silver oxide precipitate just dissolves, thereby obtaining a clear and transparent Silver ammonia complex solution:
  • insoluble silver salts such as silver carbonate, silver sulfate, and the like may also react with thiosulfate or aqueous ammonia to produce a silver thiosulfate complex and a silver ammonia complex, respectively.
  • insoluble silver carbonate with sodium thiosulfate and ammonia Take the reaction of insoluble silver carbonate with sodium thiosulfate and ammonia as an example:
  • a soluble silver thiosulfate complex containing [Ag(S 2 O 3 )] 5- and/or [Ag 2 (S 2 O 3 ) 3 ] 4- is present in the same solution and is a very stable structure, even if added Chloride ions also do not produce silver chloride precipitation. Similarly, [Ag(NH 3 ) 2 ] + is also a very stable structure, and silver chloride precipitation does not occur even if chlorine ions are added.
  • the silver-containing antimicrobial article of the present invention may be a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material, which may be prepared as follows:
  • a substance providing silver ions to the soluble thiosulfate to obtain a silver thiosulfate complex selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate Silver acetate or silver oxalate;
  • the soluble thiosulfate is selected from the group consisting of sodium thiosulfate or potassium thiosulfate; wherein the molar ratio of thiosulfate to silver ion is S 2 O 3 2- /Ag + is 1:1 ⁇ 8:1, preferably 1.1:1 to 3:1;
  • step 3 adding the silver thiosulfate complex to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-70 ° C for 1-120 minutes, and then taken out and dried to obtain the silver-containing Antibacterial products.
  • 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:
  • the silver-containing compound is selected from the group consisting of silver sulfate, Silver chloride, silver carbonate, silver oxide, silver acetate or silver oxalate; wherein the molar ratio of ammonia molecule to silver ion NH 3 /Ag + is 2:1;
  • step 1) adding the silver ammonia complex to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-70 ° C for 1-120 minutes, and then taken out and dried to obtain the silver-containing antibacterial product.
  • 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:
  • thiosulfate solution selected from the group consisting of sodium thiosulfate or potassium thiosulfate, the solvent being selected from the group consisting of ethanol, water or The combination;
  • 3) dispersing a substance providing silver ions 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, and acetic acid.
  • silver or silver oxalate, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;
  • step 2) adding the silver ion-containing solution or dispersion to the mixture of the step 2) at 25-70 ° 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 thiosulfate to silver ion S 2 O 3 2- /Ag + is 1:1 to 8:1, preferably 1.1:1 to 3:1.
  • 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:
  • thiosulfate solution selected from the group consisting of sodium thiosulfate or potassium thiosulfate, the solvent being selected from the group consisting of ethanol, water or The combination;
  • step 4 adding the thiosulfate solution to the mixture of the step 2) at 25-70 ° 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 thiosulfate to silver ion S 2 O 3 2- /Ag + is 1:1 to 8:1, preferably 1.1:1 to 3:1.
  • 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:
  • a silver-containing compound selected from the group consisting of silver nitrate sulfate, silver chloride, silver carbonate, silver oxide, silver acetate or silver oxalate, the solvent Selected from ethanol, water or a combination thereof;
  • step 3 adding ammonia water to the mixture of the step 2) at 25-70 ° C until the silver-containing compound is dissolved, and allowed to stand for 1-120 minutes, and then taken out and dried to obtain the silver-containing antibacterial product.
  • concentration of the ammonia water is 5-25% by weight, and the molar ratio of the ammonia molecule to the silver ion NH 3 /Ag + is 2:1.
  • 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.
  • Silver-containing alginate fiber, silver-containing acylated chitosan fiber, silver-containing carboxymethyl chitosan fiber, silver-containing carboxymethyl cellulose fiber, silver-containing carboxyethyl cellulose fiber and silver-containing sulfonyl fiber Colloids can form after water absorption and are therefore particularly suitable for making wound dressings.
  • the silver-containing fibers have a linear density of from 1 to 10 dtex and a fiber length of from 5 to 125 mm.
  • 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 fabrics.
  • the silver-containing fabric can be a woven, knitted or nonwoven fabric having a basis weight of from 12 to 280 grams per square meter.
  • the silver-containing polyurethane material is a silver-containing polyurethane film having a thickness of 0.1 to 1 mm or a silver-containing polyurethane sponge having a thickness of 1 to 10 mm.
  • the silver-containing antimicrobial article of the present invention is a silver-containing fiber and can be prepared as follows:
  • the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;
  • a substance providing silver ions to the soluble thiosulfate to obtain a silver thiosulfate complex selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate Silver acetate or silver oxalate;
  • the soluble thiosulfate is selected from the group consisting of sodium thiosulfate or potassium thiosulfate; wherein the molar ratio of thiosulfate to silver ion is S 2 O 3 2- /Ag + is 1:1 ⁇ 8:1, preferably 1.1:1 to 3:1;
  • the silver-containing antibacterial article obtained by the above step 4) can be further modified by carboxymethylation, carboxyethylation, acylation or sulfonylation to increase its hygroscopic property or gelation property.
  • the silver-containing antimicrobial article of the present invention is a silver-containing fiber and can be prepared as follows:
  • the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;
  • the silver-containing compound is selected from the group consisting of silver sulfate and chlorine Silver, silver carbonate, silver oxide, silver acetate or silver oxalate; wherein the molar ratio of ammonia molecule to silver ion NH 3 /Ag + is 2:1;
  • the silver-containing antibacterial article obtained by the above step 4) can be further modified by carboxymethylation, carboxyethylation, acylation or sulfonylation to increase its hygroscopic property or gelation property.
  • the alginate fiber may be a high mannuronic acid type, a high guluronate type or a mannuronic acid/guluronic acid mixed type fiber.
  • the alginate fiber may be calcium alginate fiber or calcium alginate/sodium fiber.
  • the chitosan fiber may have a degree of deacetylation of greater than 80%.
  • the silver-containing fiber of the present invention can be processed by a weaving, knitting or non-woven process to obtain a silver-containing antibacterial fabric having a silver content of 0.01-10%, based on the weight of the silver-containing antibacterial fabric.
  • the weight is 12-280 g/m2.
  • the silver-containing antibacterial fabric can be further subjected to a slitting, packaging and sterilization process to obtain a silver-containing antibacterial dressing, wherein the silver-containing antibacterial dressing has a silver content of 0.01-10%, based on the weight of the silver-containing antibacterial dressing.
  • the weight is 12-280 g/m2.
  • the silver-containing fabric or the silver-containing polyurethane material of the invention can be subjected to a slitting, packaging and sterilization process to obtain a silver-containing antibacterial dressing, wherein the silver-containing antibacterial dressing has a silver content of 0.01-10%, and contains silver antibacterial agent.
  • the weight of the dressing is 12-280 g/m2.
  • the hygroscopic silver-containing antibacterial product containing the silver thiosulfate complex or the silver ammonia complex of the invention not only has a remarkable antibacterial effect, but also has a rapid and obvious release of silver, and can quickly kill pathogenic microorganisms.
  • the silver thiosulfate complex is stable in acidic and alkaline environment, convenient to prepare, has certain optical stability, is not easy to change color, and can be widely used for the care of chronic exudative wounds.
  • the present invention provides a method of making a hygroscopic silver-containing antimicrobial article that incorporates a silver thiosulfate complex or a silver-ammonia complex onto a soft, hygroscopic article without the need for a carrier.
  • the silver-containing antibacterial article may be a silver-containing fiber, a silver-containing fabric, or a silver-containing polyurethane material.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves an impregnation process, which method can include:
  • a substance providing silver ions to the soluble thiosulfate to obtain a silver thiosulfate complex selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate Silver acetate or silver oxalate;
  • the soluble thiosulfate is selected from the group consisting of sodium thiosulfate or potassium thiosulfate; wherein the molar ratio of thiosulfate to silver ion is S 2 O 3 2- /Ag + is 1:1 ⁇ 8:1, preferably 1.1:1 to 3:1;
  • step 3 adding the silver thiosulfate complex to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-70 ° C for 1-120 minutes, and then taken out and dried to obtain the silver-containing Antibacterial products.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves an impregnation process, which method can include:
  • the silver-containing compound is selected from the group consisting of silver sulfate and chlorine Silver, silver carbonate, silver oxide, silver acetate or silver oxalate; wherein the molar ratio of ammonia molecule to silver ion NH 3 /Ag + is 2:1;
  • step 1) adding the silver ammonia complex to the mixture of step 1), so that the fiber, fabric or polyurethane material is immersed at 25-70 ° C for 1-120 minutes, and then taken out and dried to obtain the silver-containing antibacterial product.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves an impregnation process, which method can include:
  • thiosulfate solution selected from the group consisting of sodium thiosulfate or potassium thiosulfate, the solvent being selected from the group consisting of ethanol, water or The combination;
  • 3) dispersing a substance providing silver ions 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, and acetic acid.
  • silver or silver oxalate, the solvent being selected from the group consisting of ethanol, water, or a combination thereof;
  • step 2) adding the silver ion-containing solution or dispersion to the mixture of the step 2) at 25-70 ° 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 thiosulfate to silver ion S 2 O 3 2- /Ag + is 1:1 to 8:1, preferably 1.1:1 to 3:1.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves an impregnation process, which method can include:
  • thiosulfate solution selected from the group consisting of sodium thiosulfate or potassium thiosulfate, the solvent being selected from the group consisting of ethanol, water or The combination;
  • step 4 adding the thiosulfate solution to the mixture of the step 2) at 25-70 ° 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 thiosulfate to silver ion S 2 O 3 2- /Ag + is 1:1 to 8:1, preferably 1.1:1 to 3:1.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves an impregnation process, which method can include:
  • a silver-containing compound selected from the group consisting of silver sulfate, silver chloride, silver carbonate, silver oxide, silver acetate or silver oxalate, the solvent being selected From ethanol, water or a combination thereof;
  • concentration of the ammonia water is 5-25% by weight, and the molar ratio of the ammonia molecule to the silver ion NH 3 /Ag + is 2:1.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves a spinning process, which method can include:
  • the fiber being selected from the group consisting of alginate fibers Dimensions, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;
  • a substance providing silver ions to the soluble thiosulfate to obtain a silver thiosulfate complex selected from the group consisting of silver nitrate, silver sulfate, silver chloride, silver oxide, silver carbonate Silver acetate or silver oxalate;
  • the soluble thiosulfate is selected from the group consisting of sodium thiosulfate or potassium thiosulfate; wherein the molar ratio of thiosulfate to silver ion is S 2 O 3 2- /Ag + is 1:1 ⁇ 8:1, preferably 1.1:1 to 3:1;
  • the above method may further comprise: 5) subjecting the silver-containing antibacterial preparation obtained by the above step 4) to carboxymethylation, carboxyethylation, acylation or sulfonylation to modify, thereby increasing its moisture absorption property or gelatinization. performance.
  • the method of the present invention for preparing a hygroscopic silver-containing antimicrobial article involves a spinning process, which method can include:
  • the fiber being selected from the group consisting of alginate fibers, chitosan fibers, viscose fibers, lyocell fibers or sea ray fibers;
  • the silver-containing compound is selected from the group consisting of silver sulfate and chlorine Silver, silver carbonate, silver oxide, silver acetate or silver oxalate; wherein the molar ratio of ammonia molecule to silver ion NH 3 /Ag + is 2:1;
  • the above method relating to the spinning process may further comprise: 5) modifying the silver-containing antibacterial article obtained by the above step 4) by carboxymethylation, carboxyethylation, acylation or sulfonylation to thereby increase Hygroscopic properties or gelation properties.
  • the generated silver thiosulfate complex or the silver ammonia complex can be combined with a specific site of the product by electrostatic action, thereby obtaining a silver thiosulfate complex or a silver ammonia complex.
  • Silver-containing antibacterial material may be combined with a specific site of the product by electrostatic action, thereby obtaining a silver thiosulfate complex or a silver ammonia complex.
  • the fibers used may be staple fibers or filaments, and the filaments may be more advantageous for the impregnation treatment. If you use filaments, you can After impregnation, it is cut into staple fibers having a length of 5-125 mm for further processing.
  • the fabric used comprises alginate fabric, chitosan fabric, acylated chitosan fabric, carboxymethyl chitosan fabric, viscose fabric, lyocell fabric, Seaweed fabric, carboxymethyl cellulose fabric, carboxyethyl cellulose fabric, sulfonyl fiber fabric, polypropylene fabric, rayon fabric and nylon fabric.
  • These fabrics may be woven, knitted or non-woven, having a basis weight of between 12 and 280 grams per square meter.
  • the fabric After the fabric is processed by the method of the present invention, it may be further subjected to cutting, packaging and sterilization 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.
  • 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.
  • 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.
  • the hygroscopic silver-containing antibacterial article is a sol-formed article, such as silver-containing alginate fibers or fabrics, silver-containing carboxymethyl cellulose 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.
  • 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.
  • the hygroscopic silver-containing antibacterial article is a non-solile article, such as silver-containing polyester fiber or fabric, silver-containing polypropylene fiber or fabric, silver-containing lyocell fiber or fabric, silver-containing viscose fiber or fabric, Silver non-modified chitosan fiber or fabric and silver-containing polyurethane material, etc., can properly adjust the ratio between water and ethanol in the solvent, appropriately increase the proportion of water to reduce the proportion of ethanol, even the solvent can be composed entirely of water Therefore, the silver thiosulfate complex does not precipitate out of the system, and the utilization ratio of the silver thiosulfate complex is improved.
  • a silver thiosulfate complex solution or a silver ammonia complex solution may be directly added to the fiber spinning solution, and then 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 alginic acid Salt fiber, silver-containing chitosan fiber, silver-containing viscose fiber, silver-containing lyocell fiber or silver-containing sea silk fiber. Since the silver thiosulfate complex solution and the silver ammonia complex solution are very stable under normal conditions, they are very suitable for the preparation of these fibers.
  • the spinning liquid of these fibers is generally very viscous, it is advantageous to prevent precipitation and re-agglomeration of silver thiosulfate and silver ammonia, so that the silver-containing fibers can be directly woven after being uniformly stirred.
  • 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 12-280 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.
  • carboxymethylated, carboxyethylated, and sulfonyl cellulose can be obtained by carboxymethylation, carboxyethylation, or sulfonylation, respectively;
  • chitosan is carboxymethylated or Acylation can respectively give carboxymethylated chitosan or acylated chitosan.
  • the lyocell fiber according to the present invention means a cellulose fiber prepared by a solvent method.
  • 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 invention was tested using the BS: EN13726-1-2002 method, and the silver content was tested using an atomic absorption spectrometer.
  • the silver-containing antibacterial product containing the silver thiosulfate complex or the silver ammonia complex as an antibacterial component of the invention has a broad antibacterial spectrum and exhibits strong antibacterial activity against Gram-negative bacteria and Gram-positive bacteria. It is also rapid and light stable and can be widely used in chronic infectious exudative wounds such as diabetic foot, acne and some cave wounds. The healing of the wound provides a moist environment and an anti-infective barrier.
  • Figure 1 shows the zone of inhibition of the dressing containing 0.2% by weight of silver ions prepared in Example 13 after 1 day in a S. aureus culture dish.
  • Figure 2 shows the zone of inhibition of the dressing containing 0.2% by weight of silver ions prepared in Example 13 after 3 days in a S. aureus culture dish.
  • Figure 3 shows the zone of inhibition of the dressing containing 0.3% by weight of silver ions prepared in Example 18 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 18 after 3 days in a S. aureus culture dish.
  • Figure 5 shows the zone of inhibition of the dressing containing 0.53 wt% silver ions prepared in Example 22 after 1 day in a S. aureus culture dish.
  • Figure 6 shows the zone of inhibition of the dressing containing 0.53 wt% silver ions prepared in Example 22 after 3 days in a S. aureus culture dish.
  • Figure 7 shows the zone of inhibition of the dressing containing 0.3% by weight of silver ions prepared in Example 19 after 1 day in a S. aureus culture dish.
  • Figure 8 shows the zone of inhibition of the dressing containing 0.3% by weight of silver ions prepared in Example 19 after 3 days in a S. aureus culture dish.
  • the above preparation process is carried out at room temperature.
  • the silver oxide of (3)1 is slowly added to the sodium thiosulfate solution of 2, and while stirring, the precipitate of yellow thiosulfate immediately formed is dissolved by the sodium thiosulfate solution to obtain a silver thiosulfate material.
  • Solution, the final solution is grayish black;
  • the above preparation process is carried out at room temperature.
  • the silver oxide of (3)1 is slowly added to the sodium thiosulfate solution of 2, and while stirring, the precipitate of yellow thiosulfate immediately formed is dissolved by the sodium thiosulfate solution to obtain a silver thiosulfate material.
  • Solution, the final solution is grayish black;
  • the silver oxide of (3)1 is slowly added to the sodium thiosulfate solution of 2, and while stirring, the precipitate of yellow thiosulfate immediately formed is dissolved by the sodium thiosulfate solution to obtain a silver thiosulfate material.
  • Solution, the final solution is grayish black;
  • the above preparation process is carried out at room temperature.
  • the above preparation process is carried out at room temperature.
  • Silver nitrate and ammonia water are prepared to obtain a silver ammonia complex solution:
  • Silver carbonate and ammonia water are prepared to obtain a silver ammonia mixture solution:
  • 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 6.1-6.2.
  • the inhibition zone of the dressing of the present embodiment after 1 day in the S. aureus culture dish is shown in Fig. 1; the dressing of the present embodiment is in the Staphylococcus aureus culture dish.
  • the inhibition zone after 3 days is shown in Figure 2. This indicates that the silver dressing containing silver thiosulfate has a certain inhibitory effect on Staphylococcus aureus.
  • acylated chitosan fiber 100 g was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver thiosulfate complex solution prepared in Example 2 was added to the above mixture to make an acylated shell.
  • the polysaccharide fiber is fully immersed in the solution at 40 ° C for 30 minutes, 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 120 gsm and a hygroscopicity of 20 g/100 cm 2 and a silver content of 0.5% by weight based on the weight of the dressing.
  • the pH of the dressing is 6.8-7.1.
  • 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 pH of the dressing is 4.3-6.8.
  • acylated chitosan nonwoven fabric 100 g was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver thiosulfate complex solution prepared in Example 4 was added to the above.
  • the acylated chitosan fabric is fully soaked in the solution for 30 minutes at room temperature, taken out, squeezed and dried, and then cut, packaged and sterilized to obtain a silver-containing chitosan dressing.
  • the weight is 100gsm.
  • the silver-containing acylated chitosan dressing had a hygroscopicity of 20 g/100 cm 2 and a silver content of 0.82% by weight based on the weight of the dressing.
  • the dressing has a pH of 6.9-7.0.
  • viscose woven fabric (gross weight 80 gsm) was immersed in 2500 ml of pure water at room temperature to sufficiently wet it, and then the silver thiosulfate complex solution prepared in Example 5 was added to the above mixture to make The viscose fiber fabric was fully soaked in a 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 15% by weight based on the weight of the dressing.
  • the pH of the dressing is 4.5-7.0.
  • a polyurethane film 100 g was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver thiosulfate complex solution prepared in Example 6 was added to the above mixture to obtain a polyurethane.
  • the film was fully soaked in a solution at 70 ° 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 5.1 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 the present embodiment after 1 day in the S.
  • aureus culture dish is shown in Fig. 3; the inhibition zone of the dressing of the present embodiment after 3 days in the S. aureus culture dish is shown in Fig. 4. This indicates that the silver dressing containing silver thiosulfate has a certain inhibitory effect on Staphylococcus aureus.
  • carboxymethyl modified cellulose fiber 100 g was immersed in 2500 ml of absolute alcohol at room temperature to sufficiently wet it, and then the silver ammonia complex solution prepared in Example 11 was added to the above mixture to obtain a carboxymethyl group.
  • the modified cellulose fiber is fully immersed in the solution for 5 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 modified cellulose dressing.
  • the silver-containing carboxymethyl-modified cellulose dressing had a basis weight of 125 g/m 2 (gsm), a hygroscopicity of 23 g/g, and a silver content of 0.3%, 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.
  • the inhibition zone of the dressing of this example after 1 day in the S. aureus culture dish is shown in Fig. 7; the inhibition zone of the dressing of this example after 3 days in the S. aureus culture dish is shown in Fig. 8. This indicates that the silver dressing containing silver thiosulfate has a certain inhibitory effect on Staphylococcus aureus.
  • the silver-containing polyurethane foam dressing had a hygroscopicity of 28 g/100 cm 2 and a silver content of 0.4% by weight based on the weight of the dressing.
  • the fiber was taken out, squeezed, and dried to obtain a silver-containing carboxymethyl-modified cellulose fiber having a hygroscopicity of 16 g/g and a silver content of 0.6% by weight.
  • 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 chitosan dressing had a basis weight of 135 gsm and a hygroscopicity of 21.4 g/100 cm 2 .
  • the silver content was 0.53 wt% based on the weight of the dressing.
  • the dressing has a pH of 6.9-7.1.
  • the inhibition zone of the dressing of the present embodiment after 1 day in the S. aureus culture dish is shown in Fig. 5; the inhibition zone of the dressing of the present embodiment after 3 days in the S. aureus culture dish is shown in Fig. 6.
  • 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 has a basis weight of 100 gsm, hygroscopicity. It is 16 g/100 cm 2 and the silver content is 0.63 wt% based on the weight of the dressing.
  • the pH of the dressing is 4.5-7.0.
  • the fiber was taken out, squeezed and dried to obtain a silver-containing carboxymethyl modified cellulose fiber having a hygroscopicity of 16 g/g and a silver content of 0.8% by weight.
  • 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 has a basis weight of 100 gsm, hygroscopicity. It was 16 g/100 cm 2 and the silver content was 0.91% by weight based on the weight of the dressing.
  • the pH of the dressing is 4.5-7.0.
  • 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 0.6% by weight based on the weight of the dressing.
  • the dressing has a pH of 6.1-6.2.
  • acylated chitosan nonwoven fabric 100 g was immersed in the above sodium thiosulfate solution, and allowed to stand for 10 minutes;
  • 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 25 g/100 cm 2 and a silver content of 0.53 wt% based on the weight of the dressing.
  • the dressing has a pH of 6.9-7.1.
  • 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 80 gsm.
  • the silver-containing viscose fiber dressing had a hygroscopicity of 11 g/100 cm 2 and a silver content of 0.63 wt% based on the weight of the dressing.
  • the dressing has a pH of 4.3-6.8.
  • the above materials are 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 5 g/100 cm 2 and a silver content of 0.6% by weight based on the weight of the dressing.
  • the above materials are 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 26 g/100 cm 2 and a silver content of 0.6% by weight based on the weight of the dressing.
  • 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 0.68% by weight based on the weight of the dressing.
  • the dressing has a pH of 6.1-6.5.
  • the above materials are 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 5 g/100 cm 2 and a silver content of 0.7% by weight based on the weight of the dressing.
  • the above materials are 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 1.0% by weight based on the weight of the dressing.
  • a calcium alginate fiber containing an antibacterial component of silver thiosulfate can be obtained, having a fiber fineness of 3 dtex and a length of 75 mm.
  • the non-woven fabric process can obtain a silver-containing fabric, and after cutting, packaging and sterilization, a calcium alginate silver-containing dressing can be obtained.
  • the weight of the dressing is 180 gsm, the hygroscopicity is 40 g/g, and the silver content is 2.8% according to the weight of the dressing. .
  • the dressing has a pH of 6.5-6.7.
  • 100 g of MG type sodium alginate powder is added to 1900 g of pure water and stirred well to obtain a suitable spinning solution, and then the silver ammonia complex solution prepared according to Example 11 is added to the spinning solution at room temperature, and the mixture is sufficiently stirred to be spun. Disperse evenly in the silk liquid, and then press the obtained silver-containing spinning solution through a metering pump to a spinneret, and then sequentially pass through a coagulation bath, hot water drawing, washing, drying, drying, crimping and cutting processes, and then Calcium alginate fiber containing an antibacterial component of a silver-ammonia complex having a fiber fineness of 3 dtex and a length of 75 mm.
  • the silver-containing fabric can be obtained, and then the calcium alginate silver-containing dressing can be obtained after slitting, packaging and sterilization.
  • the dressing weight is 170 gsm, the hygroscopicity is 45 g/g, and the silver content is 3.0 according to the weight of the dressing. %.
  • the pH of the dressing is 6.6-6.8.
  • chitosan powder 100 g is added to an appropriate amount of 2% aqueous acetic acid and stirred well, a suitable spinning solution is obtained according to a conventional method, and then the silver thiosulfate complex prepared according to Example 1 is added to the spinning solution at room temperature.
  • the solution is thoroughly stirred to be uniformly 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, drying, and curling.
  • a chitosan fiber containing a silver thiosulfate antibacterial component was obtained, and the fiber fineness was 2 dtex and the length was 60 mm.
  • the silver-containing fabric can be obtained through a conventional nonwoven process.
  • 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 is 7.0-7.3.
  • the silver thiosulfate complex solution prepared in accordance with Example 5 Adding the silver thiosulfate complex solution prepared in accordance with Example 5 to a conventional viscose spinning solution (solid content: 9%) at room temperature, stirring well to make it uniformly dispersed in the spinning solution, and then obtaining the obtained silver-containing solution.
  • the spinning solution is squeezed to the spinneret by a metering pump, and then passes through the coagulation bath, hot water drawing, washing, drying and cutting processes, and then the viscose fiber containing the antibacterial component of silver thiosulfate can be obtained, and the fiber fineness is obtained. 3dtex, length 55mm. .
  • the silver-containing viscose fiber can obtain a silver-containing fabric through a conventional non-woven fabric process.
  • a viscose fiber-containing silver dressing After slitting, packaging and sterilization, a viscose fiber-containing silver dressing can be obtained, the basis weight is 120 gsm, and the silver content is 3.05 by weight of the dressing. %, the hygroscopicity of the dressing is 10g/100cm 2 . The pH of the dressing is 4.5-6.8.
  • the silver ammonia complex solution prepared in accordance with Example 12 was added to a conventional viscose spinning solution (solid content: 9%) at room temperature, thoroughly stirred to uniformly disperse in the spinning solution, and the resulting silver-containing spun yarn was obtained.
  • a conventional viscose spinning solution solid content: 9%
  • the viscose fiber containing the antibacterial component of the silver ammonia complex can be obtained, and the fiber fineness is 3dtex.
  • the length is 55mm.
  • the silver-containing viscose fiber can obtain a silver-containing fabric through a conventional nonwoven process.
  • a viscose fiber-containing silver dressing After slitting, packaging and sterilization, a viscose fiber-containing silver dressing can be obtained, and the basis weight is 125 gsm. According to the weight of the dressing, the silver content is 3.2. %, the hygroscopicity of the dressing is 12g/100cm 2 . The pH of the dressing is 4.8-6.8.
  • the silver-containing chitosan fiber obtained in Example 36 is acylated or carboxymethylated with succinic anhydride or sodium chloroacetate to obtain an acylated chitosan or a carboxymethylated chitosan fiber, and a fiber.
  • the fineness is 2.1 dtex and the length is 55 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 has a basis weight of 120 gsm and a hygroscopicity of 23 g/100 cm 2 and a silver content of 0.85% by weight of the dressing.
  • the pH of the dressing is 6.8-7.0.
  • the silver-containing viscose fiber obtained in Example 37 or 38 was subjected to carboxymethylation reaction with sodium chloroacetate to obtain a carboxymethylated cellulose fiber having a fiber fineness of 3.1 dtex and a length of 50 mm, which was subjected to conventional nonwovens.
  • the cloth 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 120 gsm and a hygroscopicity of 26 g/100 cm 2 and a silver content of 2.5% by weight of the dressing.
  • the pH of the dressing is 4.8-7.0.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Epidemiology (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

一种包含硫代硫酸银配合物或银氨配合物的可吸湿的含银抗菌制品，所述配合物均匀分布并结合于制品的内部和/或表面，以制品重量计，所述制品的含银量为0.01-10%重量%，所述制品的吸湿能力为6g/g以上。此外，还提供了制备方法及含银抗菌敷料。可应用于慢性感染性渗出性伤口。

Description

含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法 技术领域
本发明涉及一种可吸湿的含银制品，尤其是一种含有硫代硫酸银配合物或银氨配合物的含银制品。所述制品可以用于医用敷料和其他抗菌领域。
背景技术
随着人们生活水平的提高和饮食习惯的变化，人类的疾病谱呈现出一些新的特点。由糖尿病、压疮、褥疮和高血压等疾病引发的静脉性溃疡、动脉性溃疡、糖尿病性溃疡、创伤性溃疡、压力性溃疡等慢性渗出性伤口严重影响着人们的身体健康。渗出性伤口，顾名思义，是一类会分泌大量渗出液的慢性伤口，而渗出液的主要成分是一些脓液、组织液和一些坏死的组织和细胞。因此，慢性渗出性伤口的护理除了应该充分吸收伤口渗出液，为伤口愈合提供温暖和湿润的愈合环境，还应该及时对伤口进行抗感染护理。
目前，市场上应用在敷料中的抗菌性含银物质主要是一些银的有机盐和无机盐，例如硝酸银，氯化银，次氯酸银，碳酸银，醋酸银，磷酸锆钠银等等。
美国专利US6,897,349和欧洲专利EP1216065公开了制备含银抗菌材料的方法，该方法通过在制备纤维过程中，使氯化银分散于纤维之中。但这种伤口敷料的生产过程中材料(氯)对设备的腐蚀性很大。
中国专利CN1308509C公开了一种具有抗菌作用的含银甲壳胺纤维及其制备方法，该方法将粒径为1微米左右的银化合物颗粒，即银磷酸锆氢钠(商品名为Alphasan)混合于纺丝溶液中，该银化合物含银量为3.0-4.0重量％。由于Alphasan本身含银量有限，因此产品的含银量也很小。此外Alphasan的粒径太大，对纤维强度不利。
离子型抗菌敷料对银的使用效率较高，市场上主要含银抗菌敷料大都是离子型的。但是目前离子型含银敷料使用的银化合物大都是水溶性很低的，如氯化银、碳酸银等，由于它们在水中的溶解度低，遇 水后仅电离出少量的银离子便达到溶解平衡，当这些少量的银离子被消耗完后，不溶的银化合物才重新电离出少量的银离子，通过这样的溶解平衡达到持续释放银离子的效果。使用水溶性低的离子型含银敷料虽然可以持续地释放银离子，但其遇水后银离子释放量较少，因此仍然需要相对较多的银化合物才能实现需要的抗菌效果。此外，这种类型的伤口敷料银释放表现一般，以1％的含银量计算，在10ml伤口模拟液中24小时的银释放量只有20ppm左右，这在一定程度上影响了其抗菌效果和作用时间，除此之外，大多数的离子型的含银敷料不太稳定，放置一段时间后含银敷料会变色，影响了其作为商品的外观可接受性。
发明内容
为了解决上述问题，在一方面，本发明公开了一种可吸湿的含银抗菌制品，所述含银抗菌制品包含硫代硫酸银配合物或银氨配合物作为抗菌成分，所述硫代硫酸银配合物或银氨配合物均匀分布并结合于制品的内部和/或表面，以制品重量计，所述制品的含银量为0.01-10重量％，且所述制品的吸湿能力为6g/g以上。
本发明所述的硫代硫酸银配合物为Ag2S2O3和/或包含[Ag(S2O3)]5-和/或[Ag2(S2O3)3]4-的配合物，优选为包含[Ag2(S2O3)3]4-的配合物。所述硫代硫酸银配合物既可以以Ag2S2O3沉淀的形式存在于制品的内部和/或表面，也可以以包含[Ag(S2O3)]5-和/或[Ag2(S2O3)3]4-的可溶性配合物的形式存在于制品的内部和/或表面。本发明所述的银氨配合物为[Ag(NH3)2]+，其以可溶性配合物的形式存在于制品的内部和/或表面。
硫代硫酸银配合物和银氨配合物是一类稳定的以银为核心的络合物，在硫代硫酸银配合物中，银与硫代硫酸根可以以不同的配比以配位键结合形成配合物。在硫代硫酸银配合物的制备过程中，如果硫代硫酸根相对于银离子是过量的，则将残存大量的硫代硫酸盐和包含其他阴离子的盐，使硫代硫酸银配合物变得不纯净。此外，在常规的硫代硫酸银配合物的制备中需要使用极性的载体颗粒，以防止硫代硫酸银配合物的聚集。例如，当1当量的硝酸银或者醋酸银与2当量的硫代硫酸钠反应时，会产生1当量的硝酸钠或者醋酸钠废盐，这些废盐 的存在会导致银浓度降低，影响其抗菌效果。因此，在制备过程中，硫代硫酸根与银离子的配比非常关键，这直接决定了硫代硫酸银配合物的热稳定性和对极性物质的吸附能力。在银氨配合物中，银离子与氨分子以1:2的形式配位，从而形成可溶性银氨配合物。在制备时，必须将氨水逐渐滴加到微溶、难溶或不溶的含银化合物的溶液中，直至所述含银化合物刚好溶解，以免氨水过量而形成不稳定的叠氮化合物。如果以可溶性含银化合物(如硝酸银)为原料，则应先将其转化为微溶、难溶或不溶的含银化合物，然后逐渐滴加氨水，直至沉淀刚好溶解。
本发明的硫代硫酸银配合物通过将提供银离子的物质添加至可溶性硫代硫酸盐中而获得，其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾。本发明的银氨配合物通过将氨水逐渐滴加到微溶、难溶或不溶的含银化合物的溶液中，直至所述含银化合物刚好溶解而得到。如果以可溶性含银化合物(如硝酸银)为原料，则应先将其转化为微溶、难溶或不溶的含银化合物，然后逐渐滴加氨水，直至沉淀刚好溶解，从而得到银氨配合物，其中氨分子与银离子的摩尔比NH3/Ag+为2:1。
以可溶性的硝酸银分别与硫代硫酸钠或氨水的反应为例，产生硫代硫酸银配合物的过程如下：硝酸银与硫代硫酸钠反应生成硫代硫酸银沉淀，生成的硫代硫酸银沉淀可进一步与过量的硫代硫酸钠反应生成可溶性配合物：
AgNO3+Na2S2O3→Ag2S2O3+NaNO3
               不可溶
Ag2S2O3+Na2S2O3→Na4Ag2(S2O3)3
                   可溶
产生银氨配合物的过程如下：硝酸银与适当过量的氢氧化钠反应生成难溶的氧化银沉淀，然后向其中逐渐滴加氨水，直至所生成的氧化银沉淀刚好溶解，从而得到澄清透明的银氨配合物溶液：
AgNO3+NaOH→Ag2O+NaNO3+H2O
             不可溶
Ag2O+NH3·H2O→[Ag(NH3)2]OH
                  可溶
除了以上所述的可溶性的硝酸银之外，不可溶的银盐，如碳酸银、硫酸银等也可与硫代硫酸盐或氨水反应分别产生硫代硫酸银配合物和银氨配合物。以不可溶的碳酸银与硫代硫酸钠和氨水的反应为例：
Ag2CO3+Na2S2O3→Ag2S2O3+Na2CO3
               不可溶
Ag2S2O3+Na2S2O3→Na4Ag2(S2O3)3
                   可溶
Ag2CO3+NH3·H2O→[Ag(NH3)2]OH+Na2CO3
                   可溶
包含[Ag(S2O3)]5-和/或[Ag2(S2O3)3]4-的可溶性硫代硫酸银配合物共存于同一溶液中，是非常稳定的结构，即使加入氯离子也不会产生氯化银沉淀。同样地，[Ag(NH3)2]+也是非常稳定的结构，即使加入氯离子也不会产生氯化银沉淀。
在一个实施方案中，本发明的含银抗菌制品可为含银纤维、含银织物、或含银聚氨酯材料，其可如下制得：
1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
3)将所述硫代硫酸银配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
在一个实施方案中，本发明的含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其可如下制得：
1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、 水或它们的组合；
2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
3)将所述银氨配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
在另一实施方案中，本发明的含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其可如下制得：
1)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述硫代硫酸盐溶液中；
3)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
4)在25-70℃下将所述含银离子的溶液或分散体添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
在又一实施方案中，本发明的含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其可如下制得：
1)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述含银离子的溶液或分散体；
3)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
4)在25-70℃下将所述硫代硫酸盐溶液添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
在又一实施方案中，本发明的含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其可如下制得：
1)将含银化合物分散于溶剂中，从而获得含银化合物的分散体，所述含银化合物选自硝硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述含含银化合物的分散体中；
3)在25-70℃下将氨水添加至步骤2)的混合物中，直至所述含银化合物刚好溶解，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中所述氨水的浓度为5-25重量％，氨分子与银离子的摩尔比NH3/Ag+为2:1。
在一个实施方案中，所述含银纤维可选自含银海藻酸盐纤维、含银壳聚糖纤维、含银酰化壳聚糖纤维、含银羧甲基壳聚糖纤维、含银黏胶纤维、含银莱赛尔纤维、含银海丝纤维、含银羧甲基纤维素纤维、含银羧乙基纤维素纤维、含银磺酰基纤维、含银丙纶纤维、含银绦纶纤维或含银尼纶纤维。其中含银海藻酸盐纤维、含银酰化壳聚糖纤维、含银羧甲基壳聚糖纤维、含银羧甲基纤维素纤维、含银羧乙基纤维素纤维和含银磺酰基纤维在吸水后可以形成胶体(因此又称溶胶性纤维)，因此特别适合于制成伤口敷料。
在一个实施方案中，所述含银纤维的线密度为1-10dtex，纤维长度为5-125mm。
在一个实施方案中，所述含银织物可选自含银海藻酸盐织物、含银壳聚糖织物、含银酰化壳聚糖织物、含银羧甲基壳聚糖织物、含银 黏胶纤维织物、含银莱赛尔织物、含银海丝织物、含银羧甲基纤维素织物、含银羧乙基纤维素织物，含银磺酰基纤维织物、含银丙纶织物、含银绦纶织物或含银尼纶纤维织物。
在一个实施方案中，所述含银织物可为机织物、针织物或非织造物，所述含银织物的克重为12-280克/平方米。
在一个实施方案中，所述含银聚氨酯材料为厚度为0.1-1毫米的含银聚氨酯薄膜或厚度为1-10毫米的含银聚氨酯海绵。
在再一实施方案中，本发明的含银抗菌制品为含银纤维，并可如下制得：
1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
3)将所述硫代硫酸银配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
4)使用所述含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
此外，由如上步骤4)获得的含银抗菌制品可进一步进行羧甲基化、羧乙基化、酰化或磺酰基化以改性，从而增加其吸湿性能或成胶性能。
在再一实施方案中，本发明的含银抗菌制品为含银纤维，并可如下制得：
1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
3)将所述银氨配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
4)使用含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
此外，由如上步骤4)获得的含银抗菌制品可进一步进行羧甲基化、羧乙基化、酰化或磺酰基化以改性，从而增加其吸湿性能或成胶性能。
在一个实施方案中，所述海藻酸盐纤维可为高甘露醛酸型、高古洛糖醛酸型或甘露糖醛酸/古洛糖醛酸混合型纤维。优选地，所述海藻酸盐纤维可为海藻酸钙纤维或海藻酸钙/钠纤维。
在一个实施方案中，所述壳聚糖纤维的脱乙酰度可在80％以上。
本发明的含银纤维可经过机织、针织或者非织造工艺加工，从而制得含银抗菌织物，所述含银抗菌织物的含银量为0.01-10％，以含银抗菌织物重量计，克重为12-280克/平方米。所述含银抗菌织物可进一步经分切、包装和灭菌工序，从而制得含银抗菌敷料，所述含银抗菌敷料的含银量为0.01-10％，以含银抗菌敷料重量计，克重为12-280克/平方米。
本发明的含银织物或含银聚氨酯材料可经分切、包装和灭菌工序，从而制得含银抗菌敷料，所述含银抗菌敷料的含银量为0.01-10％，以含银抗菌敷料重量计，克重为12-280克/平方米。
实验证明，本发明的含硫代硫酸银配合物或银氨配合物的可吸湿的含银抗菌制品不仅具有显著的抗菌效果，而且银释放快速而明显，可以快速杀灭病原微生物。此外，硫代硫酸银配合物在酸性和碱性环境下稳定，配制方便，具有一定的光学稳定性，不易变色，可以广泛用于慢性渗出性伤口的护理。
在另一方面，本发明提供了制备可吸湿的含银抗菌制品的方法，所述方法无需载体即可将硫代硫酸银配合物或银氨配合物结合至柔软可吸湿的制品上。所述含银抗菌制品可为含银纤维、含银织物、或含银聚氨酯材料。
在一个实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及浸渍过程，所述方法可包括：
1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化 银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
3)将所述硫代硫酸银配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
在一个实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及浸渍过程，所述方法可包括：
1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
3)将所述银氨配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
在另一实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及浸渍过程，所述方法可包括：
1)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述硫代硫酸盐溶液中；
3)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
4)在25-70℃下将所述含银离子的溶液或分散体添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为 1.1:1～3:1。
在又一实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及浸渍过程，所述方法可包括：
1)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述含银离子的溶液或分散体；
3)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
4)在25-70℃下将所述硫代硫酸盐溶液添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
在又一实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及浸渍过程，所述方法可包括：
1)将含银化合物分散于溶剂中，从而获得含银化合物的分散体，所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
2)将纤维、织物或聚氨酯材料浸渍于所述含含银化合物的分散体中；
3)在25-70℃下将所述氨水溶液添加至步骤2)的混合物中，直至所述含银化合物刚好溶解，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
其中所述氨水的浓度为5-25重量％，氨分子与银离子的摩尔比NH3/Ag+为2:1。
在再一实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及纺丝过程，所述方法可包括：
1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤 维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
3)将所述硫代硫酸银配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
4)使用所述含银纺丝液纺丝并烘干，从而得到含银抗菌纤维。
此外，上述方法还可包括：5)将由如上步骤4)获得的含银抗菌制品进行羧甲基化、羧乙基化、酰化或磺酰基化以改性，从而增加其吸湿性能或成胶性能。
在再一实施方案中，本发明的制备可吸湿的含银抗菌制品的方法涉及纺丝过程，所述方法可包括：
1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
3)将所述银氨配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
4)使用含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
此外，上述涉及纺丝过程的方法还可包括：5)将由如上步骤4)获得的含银抗菌制品进行羧甲基化、羧乙基化、酰化或磺酰基化以改性，从而增加其吸湿性能或成胶性能。在本发明的涉及浸渍过程的方法中，生成的硫代硫酸银配合物或银氨配合物可通过静电作用而与制品的特定位点结合，进而得到含有硫代硫酸银配合物或银氨配合物的含银抗菌性材料。
在本发明的涉及浸渍过程的方法中，所用的纤维可以是短纤，也可以是长丝，且长丝可更有利于浸渍处理加工。如果使用长丝，则可 在浸渍之后切断成长度为5-125毫米的短纤，以便于进一步加工。
在本发明的涉及浸渍过程的方法中，所用的织物包括海藻酸盐织物、壳聚糖织物、酰化壳聚糖织物、羧甲基壳聚糖织物、黏胶纤维织物、莱赛尔织物、海丝织物、羧甲基纤维素织物、羧乙基纤维素织物，磺酰基纤维织物、丙纶织物、绦纶织物和尼纶纤维织物。这些织物可以是机织物、针织物，或非织造物，其克重在12-280克/平方米之间。所述织物经本发明的方法处理之后，可进一步经过裁切，包装和灭菌后，从而制成含银抗菌敷料，所述含银抗菌敷料的含银量为0.01-10重量％，按含银抗菌敷料的重量计。
在敷料工业界，一般将厚度在1毫米以下的多孔聚氨酯材料称为薄膜，将厚度为1毫米以上的多孔聚氨酯材料称为海绵。在本发明的涉及浸渍过程的方法中，所用的聚氨酯材料可为厚度为0.1-1毫米的聚氨酯薄膜或厚度为1-10毫米的聚氨酯海绵。所述聚氨酯材料经本发明的方法处理之后，可进一步经过裁切、包装和灭菌后，从而制成含银抗菌敷料，所述含银抗菌聚氨酯敷料的含银量为0.01-10重量％，按含银抗菌敷料的重量计。在本发明的涉及浸渍过程的方法中，如果所述可吸湿的含银抗菌制品为溶胶性的制品，例如含银海藻酸盐纤维或者织物、含银羧甲基纤维素纤维或者织物、含银酰化壳聚糖纤维或者织物、含银羧乙基纤维或者织物、含银磺酰基纤维或者织物，由于溶胶性纤维在水溶液中会不可逆地形成凝胶，因此所用的溶剂应为乙醇和水的混合物，以避免形成不可逆的凝胶。一般来说，溶剂中乙醇与水的体积比可大于1:1，溶剂的用量可为可吸湿的含银抗菌制品重量的30倍以上。如果所述可吸湿的含银抗菌制品为非溶胶性的制品，例如含银涤纶纤维或者织物、含银丙纶纤维或者织物、含银莱赛尔纤维或者织物、含银粘胶纤维或者织物、含银非改性壳聚糖纤维或织物和含银聚氨酯材料等等，则可以适当调节溶剂中水和乙醇之间的比例，适当增加水的比例而减少乙醇的比例，甚至溶剂可全部由水组成，使得硫代硫酸银配合物不会从体系中析出，提高硫代硫酸银配合物的利用率。
在本发明的涉及纺丝过程的方法中，可将硫代硫酸银配合物溶液或银氨配合物溶液直接加到纤维纺丝液中，再通过公知的纺丝工艺纺成含银纤维。所述方法适用于湿法或溶剂法纺丝纤维，如含银海藻酸 盐纤维、含银壳聚糖纤维、含银黏胶纤维、含银莱赛尔纤维或含银海丝纤维。由于硫代硫酸银配合物溶液和银氨配合物溶液在一般状况下非常稳定，因此非常适合这些纤维的制备。此外，由于这些纤维的纺丝液一般都很黏稠，有利于防止硫代硫酸银和银氨的析出和再团聚，因此在搅拌均匀后即可直接纺织含银纤维。
此外，还可以将通过上述方法制得的含银纤维通过机织、针织或者非织造的方式制备成含银织物。这些含银织物可以经裁切、包装和灭菌，从而进一步制成含银抗菌敷料。
由本发明的上述方法制得的含银纤维、含银织物、含银聚氨酯材料或进一步的含银抗菌敷料的含银量为0.01-10重量％，以含银纤维或含银织物或含银聚氨酯材料或者含银抗菌敷料的重量计，克重为12-280克/平方米。
由本发明的方法制得的非溶胶性的纤维或织物可进一步进行化学改性处理，从而增加其吸湿性能或成胶性能。例如，黏胶纤维经过羧甲基化、羧乙基化或者磺酰化分别可以得到羧甲基化纤维素、羧乙基化纤维素和磺酰基纤维素；壳聚糖经过羧甲基化或者酰化分别可以得到羧甲基化壳聚糖或者酰化壳聚糖。
本发明所述的莱赛尔纤维是指用溶剂法制备的纤维素纤维。
本发明所述的灭菌方式包括钴60辐照、环氧乙烷、电子束和高温等。
本发明的制品的吸湿性使用BS:EN13726-1-2002方法测试，含银量用原子光谱吸收仪测试。
本发明所提及的可吸湿的含银抗菌制品(纤维、织物或聚氨酯材料)和含银抗菌敷料的吸湿性有两种表示方法：g/g和g/100cm2。这两种表示方法可以通过织物或者敷料的克重联系起来，例如，一种含银壳聚糖敷料的吸收性是21g/g，此敷料的克重是120gsm(g/m2)，则此敷料的吸收性也可以表示成21g/g x 120gsm x 10-2＝25.2g/100cm2。
本发明的含有硫代硫酸银配合物或银氨配合物作为抗菌成分的含银抗菌制品具有很广的抗菌谱，对格兰氏阴性菌和格兰氏阳性菌表现出很强的抗菌活性，而且作用迅速和具有光稳定性，可以广泛应用于慢性感染性渗出性伤口，例如糖尿病足、褥疮和一些洞穴型伤口，为 伤口的愈合提供一个湿润的环境和抗感染的屏障。
附图说明
图1显示为实施例13所制备的含有0.2重量％银离子的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈。
图2显示为实施例13所制备的含有0.2重量％银离子的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈。
图3显示为实施例18所制备的含有0.3重量％银离子的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈。
图4显示为实施例18所制备的含有0.3重量％银离子的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈。
图5显示为实施例22所制备的含有0.53重量％银离子的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈。
图6显示为实施例22所制备的含有0.53重量％银离子的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈。
图7显示为实施例19所制备的含有0.3重量％银离子的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈。
图8显示为实施例19所制备的含有0.3重量％银离子的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈。
具体实施方式
实施例1
硫代硫酸根与银离子的摩尔比为3:1的硫代硫酸银配合物溶液的配制：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)14.19g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的硝酸银溶液缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银配合物溶液，最后溶液呈灰黑色；
以上的配制过程在室温下进行。
实施例2
硫代硫酸根与银离子的摩尔比为3:1的硫代硫酸银配合物溶液的配制：
(1)3.864g碳酸银加到10ml纯水中，制得一定浓度的含碳酸银的溶剂①；
(2)14.19g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的碳酸银缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银配合物溶液，最后溶液呈灰黑色；
以上的配制过程在40℃下进行。
实施例3
硫代硫酸根与银离子的摩尔比为3:1的硫代硫酸银配合物溶液的配制：
(1)3.248g氧化银用10ml纯水溶解，制得一定浓度的含氧化银的溶剂①；
(2)14.19g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的氧化银缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在45℃下进行。
实施例4
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的硝酸银溶液缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在室温下进行。
实施例5
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的硝酸银溶液缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在50℃下进行。
实施例6
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的硝酸银溶液缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配备过程在70℃下进行。
实施例7
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)3.864g碳酸银加到10ml纯水中，制得一定浓度的含碳酸银的溶剂①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的碳酸银缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在60℃下进行。
实施例8
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)3.248g氧化银用10ml纯水溶解，制得一定浓度的含氧化银的溶剂①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的氧化银缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在70℃下进行。
实施例9
硫代硫酸根与银离子的摩尔比为2:1的硫代硫酸银配合物溶液的配制：
(1)3.248g氧化银用10ml纯水溶解，制得一定浓度的含氧化银的溶剂①；
(2)9.46g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的氧化银缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，得到硫代硫酸银材料溶液，最后溶液呈灰黑色；
以上的配制过程在室温下进行。
实施例10
硫代硫酸根与银离子的摩尔比为1.1:1的硫代硫酸银配合物溶液的配制：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)5.203g硫代硫酸钠用20ml纯水溶解，得到一定浓度的无色的硫代硫酸钠溶液②；
(3)①的硝酸银溶液缓慢加到②的硫代硫酸钠溶液中，边加边搅拌，开始时刚生成的黄色硫代硫酸银沉淀马上会被硫代硫酸钠溶液所溶解，当硫代硫酸钠逐渐消耗完毕，黄色的硫代硫酸银沉淀不会溶解而是沉淀下来，最后得到硫代硫酸银材料的浑浊溶液，溶液呈灰黑色；
以上的配制过程在室温下进行。
实施例11
硝酸银与氨水配制得到银氨配合物溶液：
(1)4.73g硝酸银用10ml纯水溶解，制得一定浓度的无色的硝酸银溶液①；
(2)1.113g氢氧化钠用20ml纯水溶解，得到一定浓度的无色的氢氧化钠溶液②；
(3)②的氢氧化钠溶液加到①的硝酸银溶液中，边加边搅拌，得到黑色的氧化银沉淀，然后往此混合物逐渐加入23％的浓氨水，边加边搅拌，直至沉淀全部溶解，得到澄清透明的银氨混合物溶液。
实施施12
碳酸银与氨水配制得到银氨混合物溶液：
4.73g碳酸银用10ml纯水混合，然后往此逐渐加入20％的浓氨水， 直至白色沉淀完全溶解，得到澄清透明的银氨配合物溶液。
实施例13
100g羧甲基改性纤维素纤维在室温下浸泡在2500ml无水酒精中，使其充分浸湿，然后将实施例1所制得的硫代硫酸银配合物溶液添加至上述混合物中，使羧甲基改性纤维素纤维在室温下在溶液中充分浸泡静置5分钟，取出挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银改性纤维素敷料。所述含银羧甲基改性纤维素敷料的克重为120克/平方米(gsm)，吸湿性为22g/g，含银量为0.2％，按含银敷料重量计。含银改性纤维素敷料的pH值为6.1-6.2本实施例的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈如图1所示；本实施例的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈如图2所示。这表明含硫代硫酸银的伤口敷料对金黄色葡萄球菌具有一定的抑制作用。
实施例14
100g酰化壳聚糖纤维在室温下浸泡在2500ml无水酒精中，使其充分浸湿，然后将实施例2所制得的硫代硫酸银配合物溶液添加至上述混合物中，使酰化壳聚糖纤维在40℃下在溶液中充分浸泡静置30分钟，取出挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银酰化壳聚糖敷料。所述含银酰化壳聚糖敷料的克重为120gsm，吸湿性为20g/100cm2，按敷料重量计，含银量为0.5重量％。敷料的pH值为6.8-7.1。
实施例15
100g粘胶纤维在室温下浸泡在2500ml纯水中，使其充分浸湿，然后将实施例3所制得的硫代硫酸银配合物溶液添加至上述混合物中，然后使粘胶纤维在45℃下在溶液中充分浸泡静置120分钟，取出挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银粘胶纤维敷料。所述含银粘胶纤维敷料的克重为110gsm，吸湿性为12g/100cm2，按敷料重量计，含银量为0.55重量％。敷料的pH值为 4.3-6.8。
实施例16
100g酰化壳聚糖非织造织物(克重100gsm)在室温下浸泡在2500ml无水酒精中，使其充分浸湿，然后将实施例4所制得的硫代硫酸银配合物溶液添加至上述混合物中，使酰化壳聚糖织物在室温下在溶液中充分浸泡静置30分钟，取出挤干并烘干后，经切断、包装和灭菌后，得到含银酰化壳聚糖敷料，克重为100gsm。所述含银酰化壳聚糖敷料的吸湿性为20g/100cm2，按敷料重量计，含银量为0.82重量％。敷料的pH值为6.9-7.0。
实施例17
100g粘胶纤维针织物(克重80gsm)在室温下浸泡在2500ml纯水中，使其充分浸湿，然后将实施例5所制得的硫代硫酸银配合物溶液添加至上述混合物中，使粘胶纤维织物在60℃下在溶液中充分浸泡静置120分钟，取出挤干并烘干后，经切断、包装和灭菌后，得到含银粘胶纤维敷料，克重为80gsm。所述含银粘胶纤维敷料的吸湿性为10g/100cm2，按敷料重量计，含银量为15重量％。敷料的pH值为4.5-7.0。
实施例18
100g聚氨酯薄膜(厚度0.8毫米)在室温下浸泡在2500ml无水酒精中，使其充分浸湿，然后将实施例6中所制得的硫代硫酸银配合物溶液添加至上述混合物中，使聚氨酯薄膜在70℃下在溶液中充分浸泡静置90分钟，取出挤干并烘干后，再经切断、包装和灭菌后，得到含银聚氨酯薄膜敷料。所述含银聚氨酯薄膜敷料的吸湿性为5.1g/100cm2，按敷料重量计，含银量为0.3重量％。本实施例的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈如图3所示；本实施例的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈如图4所示。这表明含硫代硫酸银的伤口敷料对金黄色葡萄球菌具有一定的抑制作用。
实施例19
100g羧甲基改性纤维素纤维在室温下浸泡在2500ml无水酒精中，使其充分浸湿，然后将实施例11所制得的银氨配合物溶液添加至上述混合物中，使羧甲基改性纤维素纤维在室温下在溶液中充分浸泡静置5分钟，取出挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银改性纤维素敷料。所述含银羧甲基改性纤维素敷料的克重为125克/平方米(gsm)，吸湿性为23g/g，含银量为0.3％，按含银敷料重量计。含银改性纤维素敷料的pH值为6.1-6.2。本实施例的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈如图7所示；本实施例的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈如图8所示。这表明含硫代硫酸银的伤口敷料对金黄色葡萄球菌具有一定的抑制作用。
实施例20
100g聚氨酯泡沫(厚度5毫米)在室温下浸泡在2500ml纯水中，使其充分浸湿，然后将实施例7所制得的硫代硫酸银配合物溶液添加至上述混合物中，使聚氨酯泡沫在室温下在溶液中充分浸泡静置100分钟，取出挤干并烘干后，再经切断、包装和灭菌后，得到含银聚氨酯泡沫敷料。所述含银聚氨酯泡沫敷料的吸湿性为28g/100cm2，按敷料重量计，含银量为0.4重量％。
实施例21
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g羧甲基改性纤维素纤维浸泡在上述硫代硫酸钠溶液中，静置10分钟；
将4.73g硝酸银溶解于10ml纯水中然后将所得溶液加入至上述浸泡有纤维的溶液中。
以上操作均在室温下进行。
将纤维取出，挤干并烘干后，得到含银羧甲基改性纤维素纤维，其吸湿性为16g/g，含银量为0.6重量％。
实施例22
将5.203g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g酰化壳聚糖纤维浸泡在上述硫代硫酸钠溶液中，静置10分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入至上述浸泡有纤维的溶液中。以上操作均在50℃下进行。
将纤维取出，挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银酰化壳聚糖敷料。所述含银酰化壳聚糖敷料的克重为135gsm，吸湿性为21.4g/100cm2。按敷料重量计，含银量为0.53重量％。敷料的pH值为6.9-7.1。
本实施例的敷料在金黄色葡萄球菌培养皿1天后的抑菌圈如图5所示；本实施例的敷料在金黄色葡萄球菌培养皿3天后的抑菌圈如图6所示。这表明含硫代硫酸银的伤口敷料对金黄色葡萄球菌具有一定的抑制作用。
实施例23
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g粘胶纤维浸泡在上述硫代硫酸钠溶液中，静置70分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入至上述浸泡有纤维的溶液中。以上操作均在70℃下进行。
将纤维取出，挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银粘胶纤维敷料所述含银粘胶纤维敷料的克重为100gsm，吸湿性为16g/100cm2，按敷料重量计，含银量为0.63重量％。敷料的pH值为4.5-7.0。
实施例24
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g羧甲基改性纤维素纤维浸泡在上述硫代硫酸钠溶液中，静 置10分钟；
将3.864g碳酸银加到10ml纯水中然后加入至上述浸泡有纤维的溶液中。
以上操作均在40℃下进行。
将纤维取出，挤干并烘干后，得到含银羧甲基改性纤维素纤维，其吸湿性为16g/g，含银量为0.8重量％。
实施例25
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g粘胶纤维浸泡在上述硫代硫酸钠溶液中，静置70分钟；
将3.248g氧化银溶解于10ml纯水中，然后将所得溶液加入至上述浸泡有纤维的溶液中。以上操作均在70℃下进行。
将纤维取出，挤干并烘干后，经过常规非织造布工序，并切断、包装和灭菌后，得到含银粘胶纤维敷料所述含银粘胶纤维敷料的克重为100gsm，吸湿性为16g/100cm2，按敷料重量计，含银量为0.91重量％。敷料的pH值为4.5-7.0。
实施例26
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g羧甲基改性纤维素非织造织物(克重130gsm)浸泡在上述硫代硫酸钠溶液中，静置10分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入上述浸泡有织物的溶液中。
以上操作均在室温下进行。
把上述织物取出，挤干并烘干后，经切断、包装和灭菌后，得到含银羧甲基改性纤维素敷料，克重为130gsm。所述含银羧甲基改性纤维素敷料的吸湿性为21g/100cm2，按敷料重量计，含银量为0.6重量％。敷料的pH值为6.1-6.2。
实施例27
将5.203g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g酰化壳聚糖非织造织物(克重150gsm)浸泡在上述硫代硫酸钠溶液中，静置10分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入上述浸泡有织物的溶液中。
以上操作均在50℃下进行。
把上述织物取出，挤干并烘干后，经过切断、包装和灭菌后，得到含银酰化壳聚糖敷料，克重为140gsm。所述含银酰化壳聚糖敷料的吸湿性为25g/100cm2，按敷料重量计，含银量为0.53重量％。敷料的pH值为6.9-7.1。
实施例28
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g粘胶纤维针织物(克重80gsm)浸泡在上述硫代硫酸钠溶液中，静置100分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入上述浸泡有织物的溶液中。
以上操作均在70℃下进行。
把上述织物取出，挤干并烘干后，经切断、包装和灭菌后，得到含银粘胶纤维敷料，克重为80gsm。所述含银粘胶纤维敷料的吸湿性为11g/100cm2，按敷料重量计，含银量为0.63重量％。敷料的pH值为4.3-6.8。
实施例29
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g厚度为0.8mm的聚氨酯薄膜浸泡在上述硫代硫酸钠溶液中，静置60分钟；
将4.73g硝酸银溶解于10ml纯水溶中，然后将所得溶液加入上述浸泡有聚氨酯薄膜的溶液中。
以上操作均在70℃下进行。
把上述材料取出，挤干并烘干后，经切断、包装和灭菌后，得到含银聚氨酯薄膜敷料。所述含银聚氨酯薄膜敷料的吸湿性为5g/100cm2，按敷料重量计，含银量为0.6重量％。
实施例30
将5.203g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g厚度为5mm的聚氨酯泡沫浸泡在上述硫代硫酸钠溶液中，静置60分钟；
将4.73g硝酸银溶解于10ml纯水中，然后将所得溶液加入上述浸泡有聚氨酯泡沫的溶液中。
以上操作均在70℃下进行。
把上述材料取出，挤干并烘干后，经切断、包装和灭菌后，得到含银聚氨酯泡沫敷料。所述含银聚氨酯泡沫敷料的吸湿性为26g/100cm2，按敷料重量计，含银量为0.6重量％。
实施例31
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的无水酒精中，得到硫代硫酸钠溶液；
将100g羧甲基改性纤维素非织造织物(克重130gsm)浸泡在上述硫代硫酸钠溶液中，静置10分钟；
将3.864g碳酸银溶解于10ml纯水中，然后将所得溶液加入上述浸泡有织物的溶液中。
以上操作均在45℃下进行。
把上述织物取出，挤干并烘干后，经切断、包装和灭菌后，得到含银羧甲基改性纤维素敷料，克重为130gsm。所述含银羧甲基改性纤维素敷料的吸湿性为21g/100cm2，按敷料重量计，含银量为0.68重量％。敷料的pH值为6.1-6.5。
实施例32
将14.19g硫代硫酸钠溶解于20ml纯水中，然后加入到2500ml的纯水中，得到硫代硫酸钠溶液；
将100g厚度为0.8mm的聚氨酯薄膜浸泡在上述硫代硫酸钠溶液中，静置60分钟；
将3.248g氧化银溶解于10ml纯水溶中，然后将所得溶液加入上述浸泡有聚氨酯薄膜的溶液中。
以上操作均在70℃下进行。
把上述材料取出，挤干并烘干后，经切断、包装和灭菌后，得到含银聚氨酯薄膜敷料。所述含银聚氨酯薄膜敷料的吸湿性为5g/100cm2，按敷料重量计，含银量为0.7重量％。
实施例33
将4.73g碳酸银分散于20ml纯水中，然后加入到2500ml的纯水中，得到碳酸银混合物；
将100g厚度为0.8mm的聚氨酯薄膜浸泡在上述混合溶液中，静置15分钟；
将25％的浓氨水逐渐加到上述混合物溶液中，直至碳酸银完全溶解，再静置15分钟。
把上述材料取出，挤干并烘干后，经切断、包装和灭菌后，得到含银聚氨酯薄膜敷料。所述含银聚氨酯薄膜敷料的吸湿性为6g/100cm2，按敷料重量计，含银量为1.0重量％。
实施例34
100g MG型海藻酸钠粉末加入1900g纯水中充分搅拌得到合适的纺丝液，然后在室温下往此纺丝液中加入按照实施例3制备的硫代硫酸银配合物溶液，充分搅拌使其在纺丝液中分散均匀，然后将所得含银纺丝液经过计量泵挤压至喷丝板，然后依次经过凝固浴、热水牵伸、洗涤、干燥、烘干、卷曲和切断工序后，可以得到含有硫代硫酸银抗菌成分的海藻酸钙纤维，纤维细度为3dtex，长度为75毫米。经过常 规非织造布工序可以得到含银织物，再经分切、包装和灭菌后可以得到海藻酸钙含银敷料，敷料克重180gsm，吸湿性40g/g，按敷料重量计含银量2.8％。敷料的pH值为6.5-6.7。
实施例35
100g MG型海藻酸钠粉末加入1900g纯水中充分搅拌得到合适的纺丝液，然后在室温下往此纺丝液中加入按照实施例11制备的银氨配合物溶液，充分搅拌使其在纺丝液中分散均匀，然后将所得含银纺丝液经过计量泵挤压至喷丝板，然后依次经过凝固浴、热水牵伸、洗涤、干燥、烘干、卷曲和切断工序后，可以得到含有银氨配合物抗菌成分的海藻酸钙纤维，纤维细度为3dtex，长度为75毫米。经过常规非织造布工序可以得到含银织物，再经分切、包装和灭菌后可以得到海藻酸钙含银敷料，敷料克重170gsm，吸湿性45g/g，按敷料重量计含银量3.0％。敷料的pH值为6.6-6.8。
实施例36
100g壳聚糖粉末加入适量的2％醋酸水溶液中充分搅拌，按照常规方法得到合适的纺丝液，然后在室温下往此纺丝液中加入按照实施例1所制备的硫代硫酸银配合物溶液，充分搅拌使其在纺丝液中分散均匀，将所得含银纺丝液经过计量泵挤压至喷丝板，然后依次经过凝固浴、热水牵伸、洗涤、干燥、烘干、卷曲和切断工序后，可以得到含有硫代硫酸银抗菌成分的壳聚糖纤维，纤维细度为2dtex，长度为60mm。经过常规非织造布工序可以得到含银织物，分切、包装和灭菌后可以得到壳聚糖含银敷料，按敷料重量计，含银量为1.05％，敷料克重120gsm，敷料吸湿性14g/100cm2。敷料的pH值为7.0-7.3。
实施例37
在室温下往常规黏胶纺丝液(固含量9％)中加入按照实施例5所制备的硫代硫酸银配合物溶液，充分搅拌使其在纺丝液中分散均匀，再将所得含银纺丝液经过计量泵挤压至喷丝板，然后依次经过凝固浴、热水牵伸、洗涤、烘干和切断工序后，可以得到含有硫代硫酸银抗菌 成分的粘胶纤维，纤维细度3dtex，长度为55mm。。所述含银粘胶纤维经过常规非织造布工序可以得到含银织物，分切、包装和灭菌后可以得到粘胶纤维含银敷料，克重为120gsm，按敷料重量计，含银量3.05％，敷料吸湿性10g/100cm2。敷料的pH值为4.5-6.8。
实施例38
在室温下往常规黏胶纺丝液(固含量9％)中加入按照实施例12所制备的银氨配合物溶液，充分搅拌使其在纺丝液中分散均匀，再将所得含银纺丝液经过计量泵挤压至喷丝板，然后依次经过凝固浴、热水牵伸、洗涤、烘干和切断工序后，可以得到含有银氨配合物抗菌成分的粘胶纤维，纤维细度3dtex，长度为55mm。所述含银粘胶纤维经过常规非织造布工序可以得到含银织物，分切、包装和灭菌后可以得到粘胶纤维含银敷料，克重为125gsm，按敷料重量计，含银量3.2％，敷料吸湿性12g/100cm2。敷料的pH值为4.8-6.8。
实施例39
把由实施例36制得的含银壳聚糖纤维，与丁二酸酐或者氯乙酸钠进行酰基化或者羧甲基化反应，得到酰化壳聚糖或者羧甲基化壳聚糖纤维，纤维细度为2.1dtex，长度为55mm，经过常规非织造布工序可以得到含银织物，分切、包装和灭菌后可以得到改性壳聚糖含银敷料。所述含银改性壳聚糖敷料的克重为120gsm，吸湿性为23g/100cm2，按敷料重量计，含银量为0.85％。敷料的pH值为6.8-7.0。
实施例40
把由实施例37或38制得的含银黏胶纤维，与氯乙酸钠进行羧甲基化反应，得到羧甲基化纤维素纤维，纤维细度3.1dtex，长度为50mm，经过常规非织造布工序可以得到含银织物，分切、包装和灭菌后可以得到改性纤维素纤维含银敷料。所述改性纤维素含银敷料克重为120gsm，吸湿性为26g/100cm2，按敷料重量计，含银量2.5％。敷料的pH值为4.8-7.0。

Claims (31)

  1. 一种可吸湿的含银抗菌制品，其特征在于，所述含银抗菌制品包含硫代硫酸银配合物或银氨配合物作为抗菌成分，所述硫代硫酸银配合物或银氨配合物均匀分布并结合于制品的内部和/或表面，以制品重量计，所述制品的含银量为0.01-10重量％，且所述制品的吸湿能力为6g/g以上。
  2. 根据权利要求1所述的可吸湿的含银抗菌制品，其特征在于，所述硫代硫酸银配合物为Ag2S2O3和/或包含[Ag(S2O3)]5-和/或[Ag2(S2O3)3]4-的配合物，优选为包含[Ag2(S2O3)3]4-的配合物。
  3. 根据权利要求1所述的可吸湿的含银抗菌制品，其特征在于，所述硫代硫酸银配合物通过将提供银离子的物质添加至可溶性硫代硫酸盐中而获得，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1。
  4. 根据权利要求1所述的可吸湿的含银抗菌制品，其特征在于，所述银氨配合物通过将氨水滴加至含银化合物中，直至所述含银化合物刚好溶解，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1。
  5. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述含银抗菌制品如下制得：
    1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
    2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化 银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
    3)将所述硫代硫酸银配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
  6. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述含银抗菌制品如下制得：
    1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
    2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
    3)将所述银氨配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
  7. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述含银抗菌制品如下制得：
    1)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述硫代硫酸盐溶液中；
    3)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    4)在25-70℃下将所述含银离子的溶液或分散体添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
    其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
  8. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述含银抗菌如下制得：
    1)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述含银离子的溶液或分散体中；
    3)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
    4)在25-70℃下将所述硫代硫酸盐溶液添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
    其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
  9. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述含银抗菌制品如下制得：
    1)将含银化合物分散于溶剂中，从而获得含银化合物的分散体，所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述含含银化合物的分散体中；
    3)在25-70℃下将氨水添加至步骤2)的混合物中，直至所述含银化合物刚好溶解，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
    其中所述氨水的浓度为5-25重量％，氨分子与银离子的摩尔比NH3/Ag+为2:1。
  10. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维，其特征在于，所述含银抗菌制品如下制得：
    1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
    2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
    3)将所述硫代硫酸银配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
    4)使用所述含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
  11. 根据权利要求1所述的可吸湿的含银抗菌制品，所述含银抗菌制品为含银纤维，其特征在于，所述含银抗菌制品如下制得：
    1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
    2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
    3)将所述银氨配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
    4)使用含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
  12. 根据权利要求5-9中任一项所述的可吸湿的含银抗菌制品，其特征在于，所述含银抗菌制品为含银纤维，所述含银纤维选自含银海藻酸盐纤维、含银壳聚糖纤维、含银酰化壳聚糖纤维、含银羧甲基壳聚糖纤维、含银黏胶纤维、含银莱赛尔纤维、含银海丝纤维、含银羧甲基纤维素纤维、含银羧乙基纤维素纤维、含银磺酰基纤维、含银丙纶纤维、含银绦纶纤维或含银尼纶纤维。
  13. 根据权利要求5-9中任一项所述的可吸湿的含银抗菌制品，其特征在于，所述含银抗菌制品为含银织物，所述含银织物选自含银海藻酸盐织物、含银壳聚糖织物、含银酰化壳聚糖织物、含银羧甲基壳聚糖织物、含银黏胶纤维织物、含银莱赛尔织物、含银海丝织物、含银羧甲基纤维素织物、含银羧乙基纤维素织物，含银磺酰基纤维织物、含银丙纶织物、含银绦纶织物或含银尼纶纤维织物。
  14. 根据权利要求13所述的可吸湿的含银抗菌制品，其特征在于，所述含银织物为机织物、针织物或非织造物，所述含银织物的克重为12-280克/平方米。
  15. 根据权利要求5-9中任一项所述的可吸湿的含银抗菌制品，其特征在于，含银抗菌制品为含银聚氨酯材料，所述含银聚氨酯材料为厚度为0.1-1毫米的含银聚氨酯薄膜或厚度为1-10毫米的含银聚氨酯海绵。
  16. 根据权利要求10或11所述的可吸湿的含银抗菌制品，其特征在于，所述海藻酸盐纤维为高甘露醛酸型、高古洛糖醛酸型或甘露糖醛酸/古洛糖醛酸混合型纤维。
  17. 根据权利要求10或11所述的可吸湿的含银抗菌制品，其特征在于，所述海藻酸盐纤维为海藻酸钙纤维或海藻酸钙/钠纤维。
  18. 根据权利要求10或11所述的可吸湿的含银抗菌制品，其特征在于，所述壳聚糖纤维的脱乙酰度在80％以上。
  19. 根据权利要求5-11中任一项所述的可吸湿的含银抗菌制品，其特征在于，所述含银纤维的线密度为1-10dtex，纤维长度为5-125mm。
  20. 一种可吸湿的含银抗菌制品，其特征在于，其由如权利要求10或11所述的可吸湿的含银抗菌制品进行羧甲基化、羧乙基化、酰化或磺酰基化改性而制得。
  21. 一种含银抗菌敷料，其特征在于，所述含银抗菌敷料由权利要求13或15所述的含银抗菌制品经分切、包装和灭菌工序制得，所述含银抗菌敷料的含银量为0.01-10％，以含银抗菌敷料重量计，克重为12-280克/平方米。
  22. 一种含银抗菌织物，其特征在于，其由如权利要求10、11、12和20中任一项所述的可吸湿的含银抗菌制品经过机织、针织或者非织造工艺加工制得，所述含银抗菌织物的含银量为0.01-10％，以含银抗菌织物重量计，克重为12-280克/平方米。
  23. 一种含银抗菌敷料，其特征在于，其由如权利要求22所述的含银抗菌织物经分切、包装和灭菌工序制得，所述含银抗菌敷料的含银量为0.01-10％，以含银抗菌敷料重量计，克重为12-280克/平方米。
  24. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述方法包括：
    1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
    2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比 S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
    3)将所述硫代硫酸银配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
  25. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述方法包括：
    1)将纤维、织物或聚氨酯材料浸渍在溶剂中，所述溶剂选自乙醇、水或它们的组合；
    2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
    3)将所述银氨配合物添加至步骤1)的混合物中，使得纤维、织物或聚氨酯材料在25-70℃下浸渍1-120分钟，然后取出烘干，从而获得所述含银抗菌制品。
  26. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述方法包括：
    1)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述硫代硫酸盐溶液中；
    3)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    4)在25-70℃下将所述含银离子的溶液或分散体添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗 菌制品，
    其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
  27. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述方法包括：
    1)将提供银离子的物质分散于溶剂中，从而获得含银离子的溶液或分散体，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述含银离子的溶液或分散体中；
    3)将可溶性硫代硫酸盐溶解于溶剂中，从而获得硫代硫酸盐溶液，所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾，所述溶剂选自乙醇、水或它们的组合；
    4)在25-70℃下将所述硫代硫酸盐溶液添加至步骤2)的混合物中，并静置1-120分钟，然后取出烘干，从而获得所述含银抗菌制品，
    其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选为1.1:1～3:1。
  28. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维、含银织物或含银聚氨酯材料，其特征在于，所述方法包括：
    1)将含银化合物分散于溶剂中，从而获得含银化合物的分散体，所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银，所述溶剂选自乙醇、水或它们的组合；
    2)将纤维、织物或聚氨酯材料浸渍于所述含含银化合物的分散体中；
    3)在25-70℃下将氨水添加至步骤2)的混合物中，直至所述含银化合物刚好溶解，并静置1-120分钟，然后取出烘干，从而获得所述 含银抗菌制品，
    其中所述氨水的浓度为5-25重量％，氨分子与银离子的摩尔比NH3/Ag+为2:1。
  29. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维，其特征在于，所述方法包括：
    1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
    2)将提供银离子的物质添加至可溶性硫代硫酸盐中，从而获得硫代硫酸银配合物，所述提供银离子的物质选自硝酸银、硫酸银、氯化银、氧化银、碳酸银、醋酸银或草酸银；所述可溶性硫代硫酸盐选自硫代硫酸钠或硫代硫酸钾；其中硫代硫酸根与银离子的摩尔比S2O3 2-/Ag+为1:1～8:1，优选1.1:1～3:1；
    3)将所述硫代硫酸银配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
    4)使用所述含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
  30. 一种制备可吸湿的含银抗菌制品的方法，所述含银抗菌制品为含银纤维，其特征在于，所述方法包括：
    1)按照常规纺丝方法制备纤维纺丝液，所述纤维选自海藻酸盐纤维、壳聚糖纤维、黏胶纤维、莱赛尔纤维或海丝纤维；
    2)将氨水逐渐滴加至含银化合物中，直至含银化合物刚好溶解，从而获得银氨配合物，所述氨水的浓度为5-25重量％；所述含银化合物选自硫酸银、氯化银、碳酸银、氧化银、醋酸银或草酸银；其中氨分子与银离子的摩尔比NH3/Ag+为2:1；
    3)将所述银氨配合物添加至所述纺丝液，并搅拌均匀，从而得到含银纺丝液；
    4)使用含银纺丝液纺丝并烘干，从而得到所述含银抗菌制品。
  31. 根据权利要求29或30所述的制备可吸湿的含银抗菌制品的方法，其还包括：
    5)将步骤4)获得的含银抗菌制品进行羧甲基化、羧乙基化、酰化或磺酰基化以改性。
PCT/CN2015/077792 2014-04-30 2015-04-29 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法 WO2015165400A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201410182491 2014-04-30
CN201410182491.6 2014-04-30
CN201410264337.3A CN104083800B (zh) 2014-04-30 2014-06-13 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法
CN201410264337.3 2014-06-13

Publications (1)

Publication Number Publication Date
WO2015165400A1 true WO2015165400A1 (zh) 2015-11-05

Family

ID=51631622

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/077792 WO2015165400A1 (zh) 2014-04-30 2015-04-29 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法

Country Status (2)

Country Link
CN (1) CN104083800B (zh)
WO (1) WO2015165400A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112012009A (zh) * 2020-08-27 2020-12-01 中物院成都科学技术发展中心 一种超疏水杀菌材料及其制备方法
CN112211005A (zh) * 2020-09-18 2021-01-12 青岛大学 一种难燃强抗菌的海洋多糖聚合物涂层材料
CN114293363A (zh) * 2021-12-30 2022-04-08 广东宝创环保新材料制品有限公司 一种基于银锌组合物的聚丙烯抗菌纤维及其制备方法

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104645928B (zh) * 2013-11-25 2018-03-06 北京三聚环保新材料股份有限公司 银系脱汞剂的制备方法
CN104083800B (zh) * 2014-04-30 2016-05-04 佛山市优特医疗科技有限公司 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法
AU2016256436B2 (en) * 2015-04-28 2020-10-22 Convatec Technologies Inc. Antibacterial nanofibres
CN105709262A (zh) * 2016-03-16 2016-06-29 张家港耐尔纳米科技有限公司 一种载银抗菌敷料及其制备方法
CN106729931A (zh) * 2016-11-23 2017-05-31 苏州大学 一种载银甲壳胺医用敷料的制备方法
CN107158030A (zh) * 2017-06-08 2017-09-15 佛山市优特医疗科技有限公司 一种新型含银抗菌制品及其制备方法
CN113082283A (zh) * 2017-08-17 2021-07-09 太原理工大学 一种抗菌敷料及其制备方法
CN108029701A (zh) * 2017-12-15 2018-05-15 吴晓军 一种见光不变色的银离子抗菌剂
CN107927921B (zh) * 2017-12-29 2019-12-31 欧莱特（福建）健康科技有限公司 磁疗内衣
CN108210976A (zh) * 2018-02-05 2018-06-29 广东泰宝医疗器械技术研究院有限公司 一种抗菌硅酮复合泡沫敷贴的制备方法
CN109468832B (zh) * 2018-11-08 2021-08-03 珠海鑫康源新材料科技有限公司 银纤维排汗透湿面料及其制备方法
CN111493722A (zh) * 2020-05-30 2020-08-07 青岛玉竹叶纸品科技有限责任公司 抗菌湿纸巾及其制备方法
CN112897472B (zh) * 2021-02-03 2022-09-06 晋大纳米科技（厦门）有限公司 一种耐高温耐光照的络合银溶液的制备方法、络合银溶液及抗菌产品
CN112813677A (zh) * 2021-03-01 2021-05-18 饶恒 一种抗菌纺织物及泡棉等发泡产品的加工工艺
CN116065384A (zh) * 2023-01-17 2023-05-05 上海洁宜康化工科技有限公司 含银抗菌液体组合物、其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781851A (zh) * 2010-02-05 2010-07-21 洪桂焕 聚氨酯抗菌柔软涂层剂及其制备方法
CN104083800A (zh) * 2014-04-30 2014-10-08 佛山市优特医疗科技有限公司 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005337465B8 (en) * 2005-10-21 2011-08-04 Argentum International, Llc Medical device
CN101708341B (zh) * 2009-12-11 2012-07-18 东华大学 载银细菌纤维素水凝胶抗菌敷料制备方法及其制品
CN102373618B (zh) * 2011-11-18 2013-07-31 张家港耐尔纳米科技有限公司 一种载银海藻酸纤维及其制备方法
CN102677454B (zh) * 2012-06-06 2014-04-16 山东大学 一种在含纤维素材料上负载银纳米颗粒的方法
CN103074703A (zh) * 2012-12-03 2013-05-01 佛山市优特医疗科技有限公司 抗菌性含银纤维类伤口敷料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781851A (zh) * 2010-02-05 2010-07-21 洪桂焕 聚氨酯抗菌柔软涂层剂及其制备方法
CN104083800A (zh) * 2014-04-30 2014-10-08 佛山市优特医疗科技有限公司 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GAO, XIAOHONG ET AL.: "Antibacterial in-situ treatment of silk fabrics with nano silver", JOURNAL OF TEXTILE RESEARCH, vol. 34, no. 8, 31 August 2013 (2013-08-31), pages 100 - 104, ISSN: 0253-9721 *
QIN, YIMIN: "Different methods of adding silver into wound dressings", JOURNAL OF TEXTILE RESEARCH, vol. 27, no. 12, 31 December 2006 (2006-12-31), pages 109 - 112, ISSN: 0253-9721 *
ZHANG, WENZHENG: "The research and development of silver antibacterial material", NEW CHEMICAL MATERIALS, 31 December 1997 (1997-12-31), pages 20 - 22, ISSN: 1006-3536 *
ZHAO, LIANG: "Study on the silver metal composite material wound membrane", CHINESE MASTER'S THESES FULL-TEXT DATABASE, MEDICINE AND HEALTH SCIENCES, 15 May 2012 (2012-05-15), pages E080 - 19, ISSN: 1674-0246 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112012009A (zh) * 2020-08-27 2020-12-01 中物院成都科学技术发展中心 一种超疏水杀菌材料及其制备方法
CN112211005A (zh) * 2020-09-18 2021-01-12 青岛大学 一种难燃强抗菌的海洋多糖聚合物涂层材料
CN112211005B (zh) * 2020-09-18 2023-01-31 青岛大学 一种难燃强抗菌的海洋多糖聚合物涂层材料
CN114293363A (zh) * 2021-12-30 2022-04-08 广东宝创环保新材料制品有限公司 一种基于银锌组合物的聚丙烯抗菌纤维及其制备方法

Also Published As

Publication number Publication date
CN104083800B (zh) 2016-05-04
CN104083800A (zh) 2014-10-08

Similar Documents

Publication Publication Date Title
WO2015165400A1 (zh) 含硫代硫酸银配合物或银氨配合物的可吸湿的含银制品及其制备方法
CN102453968B (zh) 含纳米金属的抗菌性纤维、织物和伤口敷料及其制备方法
US9869037B2 (en) Method of producing a swellable polymer fibre
EP2842580B1 (en) Silvery antibacterial fibre, texture, and wound dressing, and preparation method thereof
KR101377569B1 (ko) 항균성 창상 피복재 및 그 제조방법
CA2924965C (en) Cellulose fibres
US6471982B1 (en) Wound dressing
WO2012106983A1 (zh) 含有纳米金属的抗菌性纤维类敷料及其制备方法
WO2012136082A1 (zh) 酰化壳聚糖伤口敷料、其制备方法及其应用
WO2003009810A2 (en) Silver alginate foam compositions
WO2014086186A1 (zh) 抗菌性含银纤维类伤口敷料及其制备方法
ES2633789T3 (es) Fibras de polisacáridos para apósitos para heridas
CN107456321B (zh) 一种纳米银抗菌卫生巾及其生产方法
WO2018223743A1 (zh) 一种含银抗菌制品及其制备方法
JP4826382B2 (ja) 抗菌性セルロース繊維及び皮膚接触用繊維製品
CN1308509C (zh) 一种具有抗菌作用的含银甲壳胺纤维及制备方法
JPH01270871A (ja) 創傷用包帯
CN114959946A (zh) 一种凝胶型持久抗菌海藻酸钙纤维及其制备方法
WO2021070915A1 (ja) 抗菌性シート状構造体
GB2588442A (en) Antimicrobial material

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15786461

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15786461

Country of ref document: EP

Kind code of ref document: A1