WO2023005035A1 - 一种海藻酸盐医用纤维及其制备方法和应用 - Google Patents

一种海藻酸盐医用纤维及其制备方法和应用 Download PDF

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WO2023005035A1
WO2023005035A1 PCT/CN2021/127247 CN2021127247W WO2023005035A1 WO 2023005035 A1 WO2023005035 A1 WO 2023005035A1 CN 2021127247 W CN2021127247 W CN 2021127247W WO 2023005035 A1 WO2023005035 A1 WO 2023005035A1
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alginate
solution containing
chitosan
sodium alginate
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English (en)
French (fr)
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李喆
杜柘彬
徐畅
吕向国
孙卫华
张晓雨
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江苏国望高科纤维有限公司
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • 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
    • A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28—Polysaccharides or their derivatives
    • 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
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow

Definitions

  • the invention relates to the technical field of medical fibers, in particular to an alginate medical fiber and its preparation method and application.
  • Alginate fiber is a new type of marine biomass fiber, which has been widely used in medical wound dressings.
  • alginate dressings are prepared from calcium alginate fibers through non-woven processing.
  • Alginate can absorb wound exudate Liquid (also very useful for wounds with moderate to severe exudate), forms a gel and covers the wound, keeps the wound moist and promotes healing; at the same time releases calcium to the wound, thereby helping the wound to stop bleeding; and the alginic acid dressing They are so lightweight that most alginate dressings are able to absorb many times their weight in fluid; in addition, alginate dressings can be rinsed off with saline so the dressing can be removed without interfering with granulation tissue healing, which makes changing The medicine is almost painless.
  • Alginate dressings currently on the market can be divided into two categories: surface dressings and wound fillings.
  • Surface dressings are generally made of non-woven fabrics, and wound fillings can be made by cutting non-woven fabrics into long and narrow strips. It can also be processed into tops after carding, and then cut and packaged to form the final product.
  • the existing alginic acid dressings still have the following problems, which make it difficult to meet the actual needs of the application range and application effect. Wound epithelialization and other aspects have an effect, and cannot significantly and effectively promote wound healing; the duration of auxiliary wound healing is short; Sodium zirconium phosphate silver seaweed fiber is obtained by wet spinning by mixing sodium zirconium silver phosphate dispersion with sodium alginate spinning solution.
  • the antibacterial sodium zirconium silver phosphate seaweed fiber can release silver ions, It has a good antibacterial effect, but the fiber strength is not high and the spinnability is poor.
  • the analysis may be the spinning under the condition that the inorganic particles and the alginate solution are mixed heterogeneously.
  • the purpose of the present invention is to overcome one or more deficiencies in the prior art, and provide an improved method for preparing alginate medical fibers that can effectively promote or assist in accelerating wound healing and have excellent mechanical properties.
  • the synthesized alginate medical fiber can not only make the antibacterial effect run through the whole process of wound healing, but also have the functions of promoting angiogenesis and promoting re-epithelialization, so as to effectively promote or assist in accelerating the wound healing process , At the same time, it can also overcome the problems of poor strength and poor spinnability of the existing alginate medical fibers.
  • the present invention also provides an alginate medical fiber prepared by the above method.
  • the present invention also provides the aforementioned alginate medical fiber used as short fiber for the preparation of non-woven medical dressing.
  • a preparation method of alginate medical fiber comprising: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, which is then wet-spun, Then respectively go through the treatment in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw and dry; wherein, in the chitosan solution containing copper ions, the content of copper ions is 0.05-0.2mol/L; In the sodium alginate solution containing silver ions, the silver ion content is 0.1-0.5mol/L; the first coagulation bath is an aqueous solution containing calcium ions and zinc ions, and the second coagulation bath is an aqueous solution containing calcium ions. ethanol in water.
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 5-20: 100;
  • the molding of the main fiber alginate fiber ensures better ion release performance and overall mechanical properties.
  • the chitosan used in the chitosan solution containing copper ions has a weight average molecular weight of 1.0 ⁇ 10 6 -2.2 ⁇ 10 6 g/mol.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate, copper sulfate or copper acetate in the chitosan solution, and the chitosan solution is prepared by removing Chitosan with an acetylation degree greater than 95% is obtained by dissolving in 1-6wt% acid ester aqueous solution; wherein, the content of chitosan in the chitosan solution is 3-10wt%.
  • the weight average molecular weight of the sodium alginate used is 3.0 ⁇ 10 5 -6 ⁇ 10 5 g/mol.
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate, silver sulfate, silver phosphate or silver perchlorate in sodium alginate solution, and the alginate
  • the sodium solution is obtained by dissolving sodium alginate in water, wherein the sodium alginate content is 3-8 wt%.
  • the concentration of calcium ions is 0.1-0.3 mol/L
  • the concentration of zinc ions is 0.1-0.5 mol/L
  • the coagulation temperature of the first coagulation bath is 30-40 °C
  • the residence time is 3-6s.
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion.
  • the calcium ion concentration is 0.3-0.5 mol/L
  • the coagulation temperature of the second coagulation bath is 40-50°C
  • the residence time is 2-4s.
  • the second coagulation bath is obtained by dissolving calcium chloride in 50-70 wt% ethanol aqueous solution.
  • the washing bath is 80-90wt% ethanol aqueous solution.
  • an alginate medical fiber prepared by the above-mentioned preparation method.
  • each particle is in the fiber matrix and is not easy to fall off during use, which improves the durability and effectiveness of antibacterial, wound healing promotion or auxiliary acceleration.
  • the sodium alginate in the preparation process of alginate medical fiber, since sodium alginate can rapidly undergo ion exchange reactions with calcium ions, zinc ions, and copper ions; When the spinneret hole is squeezed into the coagulation bath, the thin stream formed by the blended spinning solution is rapidly coagulated and finally transformed into alginate medical fibers.
  • the sodium alginate contained in the blended spinning solution can quickly combine with calcium ions, Zinc ions and copper ions undergo an ion exchange reaction, thereby forming a chitosan-modified alginate fiber, and the fiber contains copper ions, silver ions, zinc ions, and calcium ions at the same time, and the alginate fiber of the present invention is obtained.
  • Salt medical fiber since sodium alginate can rapidly undergo ion exchange reactions with calcium ions, zinc ions, and copper ions;
  • alginic acid as a polymer carboxylic acid
  • sodium alginate can quickly undergo ion exchange reactions with calcium ions, zinc ions, copper ions, etc.
  • alginate as a polyanionic electrolyte, can produce electrostatic adsorption with chitosan of polycation electrolyte, and then in the preparation process, along with ion exchange and electrostatic adsorption, the interaction between alginate and chitosan is effectively improved Mechanical properties of alginate fibers.
  • alginate medical fiber silver ions are dispersed in alginic acid, which is similar to calcium ions and has a higher loading capacity, which can ensure the sustained release of the fiber for a long time during use. Copper ions, zinc ions, and calcium ions are combined with alginic acid in sequence.
  • a kind of above-mentioned alginate medical fiber is used as short fiber for the preparation of non-woven medical dressing, wherein, the fiber length of alginate medical fiber is 35-150mm, and the fineness is: 2.0-5dtex, the dry breaking strength is 2.5-3.5cN/dtex.
  • the alginate medical fiber of the present invention When the alginate medical fiber of the present invention is applied in skin wound covering dressings, it has good antibacterial properties, continuously releases silver ions, calcium ions, copper ions and zinc ions within 7-10 days, and is effective against Escherichia coli, golden yellow
  • the bactericidal rate of Staphylococcus, Candida albicans and Pseudomonas aeruginosa are all above 98%.
  • the alginate medical fiber of the present invention can also be used as a fiber raw material to be woven into a sheet, tube or special shape for use in oral repair, hernia repair, ureteral stent, nerve repair, hard tissue repair and other tissue repair fields.
  • the present invention has the following advantages compared with the prior art:
  • the present invention innovatively selects the process raw materials, process and parameters, so that the prepared alginate medical fiber can regulate and release various trace elements, and through the preparation process of each raw material
  • the interaction of the existing alginate medical fiber overcomes the defects of low strength and easy fracture of the water-soluble fiber, improves the mechanical properties of the fiber, and also makes the various ions contained in the fiber: calcium ion, silver ion, Zinc ions and copper ions can be released in an orderly and effective amount according to the needs of each stage of wound healing, so that the alginate medical fiber prepared by the present invention can not only make the antibacterial effect throughout the whole process of wound healing, but also It has the effects of promoting angiogenesis and re-epithelialization, thereby effectively promoting or assisting in accelerating the wound healing process.
  • it can also overcome the problems of poor strength and poor spinnability of the existing alginate medical fibers, making it It can be applied to the preparation of nonwoven medical dressings.
  • Fig. 1 is the effect diagram of the ion release performance test of the medical dressing prepared by using the alginate medical fiber of Example 1 as the short fiber.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a deacetylation degree of 96% in 6wt% acid ester aqueous solution Obtain; Wherein, in the chitosan solution, the content of chitosan is 10wt%, and the weight average molecular weight of chitosan is 1.0 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.2mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the sodium alginate content is 8wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 3.0 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.5mol/L;
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 8: 100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.3mol/L, the concentration of zinc ions is 0.5mol/L, and the coagulation temperature of the first coagulation bath is 40°C, residence time is 6s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 70wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.5mol/L, the coagulation temperature of the second coagulation bath is 50°C, and the residence time is 4s;
  • the washing bath is 90 wt% ethanol aqueous solution.
  • Said alginate medical fiber has a spinning speed of 10m/s and a draw ratio of 2 times.
  • the fineness of the obtained fiber is 5.0dtex and the dry breaking strength is 3.5cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 7 days; and the bactericidal rate of Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa are all above 99%.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a degree of deacetylation of 97% in 5wt% acid ester aqueous solution Obtain; Wherein, in chitosan solution, the content of chitosan is 9wt%, and the weight-average molecular weight of chitosan is 1.4 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.18mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the content of sodium alginate is 7wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 3.5 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.4mol/L;
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 10:100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.3mol/L, the concentration of zinc ions is 0.4mol/L, and the coagulation temperature of the first coagulation bath is 40°C, residence time is 6s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 70wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.5mol/L, the coagulation temperature of the second coagulation bath is 50°C, and the residence time is 4s;
  • the washing bath is 90 wt% ethanol aqueous solution.
  • Said alginate medical fiber has a spinning speed of 12m/s and a draw ratio of 2 times.
  • the resulting fiber has a fineness of 4.5dtex and a dry breaking strength of 3.2cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 10 days; and the bactericidal rate to Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa is all above 99%.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in the chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a deacetylation degree of 98% in 4wt% acid ester aqueous solution Obtain; Wherein, in chitosan solution, the content of chitosan is 8wt%, and the weight-average molecular weight of chitosan is 1.8 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.15mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the content of sodium alginate is 6wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 4.0 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.3mol/L;
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 5: 100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.2mol/L, the concentration of zinc ions is 0.3mol/L, and the coagulation temperature of the first coagulation bath is 38°C, the residence time is 5s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 60wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.4mol/L, the coagulation temperature of the second coagulation bath is 48°C, and the residence time is 3s;
  • the washing bath is 85 wt% ethanol in water.
  • Said alginate medical fiber has a spinning speed of 14m/s and a draw ratio of 3 times.
  • the resulting fiber has a fineness of 4.0dtex and a dry breaking strength of 3.0cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 9 days; and the bactericidal rate of Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa are all above 98%.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a deacetylation degree of 99% in 3wt% acid ester aqueous solution Obtain; Wherein, in chitosan solution, the content of chitosan is 6wt%, and the weight-average molecular weight of chitosan is 2.0 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.1mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the content of sodium alginate is 5wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 4.5 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.2mol/L;
  • the volume ratio of the chitosan solution containing copper ions and the sodium alginate solution containing silver ions is 15: 100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.2mol/L, the concentration of zinc ions is 0.3mol/L, and the coagulation temperature of the first coagulation bath is 36°C, the residence time is 5s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 60wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.4mol/L, the coagulation temperature of the second coagulation bath is 40°C, and the residence time is 3s;
  • the washing bath is 85 wt% ethanol in water.
  • Said alginate medical fiber has a spinning speed of 16m/s and a draw ratio of 5 times.
  • the resulting fiber has a fineness of 2.0dtex and a dry breaking strength of 2.5cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 7 days; and the bactericidal rate of Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa are all over 98%.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a deacetylation degree of 99% in 2wt% acid vinegar aqueous solution Obtain; Wherein, in the chitosan solution, the content of chitosan is 5wt%, and the weight-average molecular weight of chitosan is 2.2 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.08mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the content of sodium alginate is 4wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 5.0 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.1mol/L;
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 18:100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.1mol/L, the concentration of zinc ions is 0.2mol/L, and the coagulation temperature of the first coagulation bath is 32°C, the residence time is 4s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 50wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.4mol/L, the coagulation temperature of the second coagulation bath is 48°C, and the residence time is 2s;
  • the washing bath is 80 wt% ethanol aqueous solution.
  • Said alginate medical fiber has a spinning speed of 18m/s and a draw ratio of 4 times.
  • the resulting fiber has a fineness of 2.5dtex and a dry breaking strength of 2.8cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 8 days; and the bactericidal rate of Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa are all above 98%.
  • This example provides a preparation method of alginate medical fiber and the alginate medical fiber prepared by this method.
  • the preparation method of the alginate medical fiber comprises the following steps: mixing a chitosan solution containing copper ions with a sodium alginate solution containing silver ions to obtain a blended spinning solution, and then performing wet spinning, and then respectively passing through the first Treat in the first coagulation bath and the second coagulation bath, wash in the washing bath, draw, dry, and wind up to obtain alginate medical fiber.
  • the chitosan solution containing copper ions is prepared by dissolving copper nitrate in chitosan solution, and the chitosan solution is prepared by dissolving chitosan with a deacetylation degree of 99% in 1wt% acid ester aqueous solution Obtain; Wherein, in chitosan solution, the content of chitosan is 3wt%, and the weight-average molecular weight of chitosan is 1.8 * 10 6 g/mol; In the chitosan solution containing copper ion, the content of copper ion is 0.05mol/L;
  • the sodium alginate solution containing silver ions is prepared by dissolving silver nitrate in sodium alginate solution, and the sodium alginate solution is obtained by dissolving sodium alginate in deionized water, wherein the content of sodium alginate is 3wt%, and the seaweed
  • the weight average molecular weight of sodium alginate is 6 ⁇ 10 5 g/mol; in the sodium alginate solution containing silver ions, the silver ion content is 0.3mol/L;
  • the volume ratio of the chitosan solution containing copper ions to the sodium alginate solution containing silver ions is 20:100;
  • the first coagulation bath is obtained by dissolving calcium chloride and zinc chloride in water in proportion, and the control calcium ion concentration is 0.1mol/L, the concentration of zinc ions is 0.1mol/L, and the coagulation temperature of the first coagulation bath is 30°C, the residence time is 3s;
  • the second coagulation bath is obtained by dissolving calcium chloride in 50wt% ethanol aqueous solution, and the calcium ion concentration is controlled to be 0.3mol/L, the coagulation temperature of the second coagulation bath is 50°C, and the residence time is 2s;
  • the washing bath is 80 wt% ethanol aqueous solution.
  • Said alginate medical fiber has a spinning speed of 20m/s and a draw ratio of 3 times.
  • the resulting fiber has a fineness of 2.4dtex and a dry breaking strength of 2.8cN/dtex. It can continuously release silver ions, calcium ions, copper ions and zinc ions within 7 days; and the bactericidal rate of Escherichia coli, Staphylococcus aureus, Candida albicans and Pseudomonas aeruginosa are all over 98%.
  • Application test a series of experiments include the safety and effectiveness evaluation of the alginate medical fiber prepared by this patent.
  • the safety evaluation is carried out in accordance with the requirements of GB/T 16886 Biological evaluation of medical devices.
  • Effectiveness evaluation includes antibacterial performance, water vapor transmission performance and zoological evaluation.
  • the alginate medical fiber (according to Example 1) prepared by this patent is respectively evaluated for cytotoxicity, guinea pig delayed contact sensitization, and skin irritation.
  • the intracellular toxicity test is tested in accordance with GB/T 16886-5 "Biological Evaluation of Medical Devices Part 5: In Vitro Cytotoxicity Test”; the delayed contact sensitization test in guinea pigs is tested in accordance with GB/T 16886-10 Part 10: Stimulus and Delayed Type Hypersensitivity Test” was tested, using the maximal test Magnusson and Kligman method.
  • the skin irritation test was tested in accordance with GB/T 16886-10 "Biological Evaluation of Medical Devices Part 10: Irritation and Delayed Type Hypersensitivity Test".
  • Example 1 of the present invention has a cytotoxicity of less than grade 2, no skin sensitization, no intradermal irritation, and good biological safety.
  • the alginate medical fiber sample of Example 1 was tested for antibacterial performance by AATCC-100, and the antibacterial rate was 99%; after 10 days of continuous use, the antibacterial performance was tested by AATCC-100, and the antibacterial rate was 99%.
  • a medical dressing was prepared.
  • the dressing product was soaked in simulated body fluid PBS, and the contents of silver ions, zinc ions, copper ions and calcium ions released in the simulated body fluid were tested by atomic absorption spectrometer, and the test lasted for 6 days.
  • the test time points were 3h, 6h, 9h, 12h, 24h, 48h, 72h, 96h, 120h, 144h.
  • Ion release rate ion content in simulated body fluid at different time points/total ion content in medical dressings.
  • the test results are shown in Figure 1. During use, silver ions and calcium ions will release a large amount quickly in a short period of time.
  • the release rate can be slower in the middle and late stages but can maintain the ability of sustained release in the middle and late stages; in the early stage of wound healing, calcium ions (Ca 2+ ) are considered to help wounds stop bleeding and promote re-epithelialization, followed by calcium ions It can also play a role in stabilizing the biofilm in the middle and late stages of wound healing. Therefore, it is required that calcium ions be released quickly to a greater extent in the initial stage to meet the purpose of wound hemostasis and promote re-epithelialization.
  • zinc ions are an essential component of enzymes that maintain protein structural integrity and regulate gene expression. Participate in the regulation of immunity, cell growth and migration, and play a key role in wound healing. Therefore, it requires zinc ions to be able to run through the entire wound healing process, and to meet the release of a large amount in the early stage and to have a good sustained release ability in the middle and late stages .
  • copper ions can induce the expression of vascular endothelial growth factor, promote angiogenesis, and maintain the stability of collagen.
  • the frequency of release especially in the middle and late stages, needs to maintain a better release speed to meet the proliferation and remodeling of the wound.
  • the test results in Figure 1 show that the alginate medical fiber made by the present invention can fully meet the various stages of the above wound During the healing process, the effective release amount and frequency of ions meet the needs of each stage of wound healing.

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Abstract

本发明公开了一种海藻酸盐医用纤维及其制备方法和应用，该制备方法包括：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥；第一凝固浴为含有钙离子与锌离子的水溶液，第二凝固浴为含有钙离子的乙醇水溶液；及上述制成的海藻酸盐医用纤维作为短纤维用于制备非织造医用敷料的用途；也可以作为纤维原料编织成片状、管状或特殊形状，用于口腔修复、疝修复、输尿管支架、神经修复、硬组织修复等组织修复领域。本发明海藻酸盐医用纤维能够兼具有效促进或辅助加速伤口愈合以及优异的力学性能等优点。

Description

一种海藻酸盐医用纤维及其制备方法和应用 技术领域
本发明涉及医用纤维技术领域，具体涉及一种海藻酸盐医用纤维及其制备方法和应用。
背景技术
海藻酸盐纤维是一种新型的海洋生物质纤维，已经在医用创伤敷料方面被广泛应用，例如海藻酸敷料是由海藻酸钙纤维经非织造加工制备得到的，海藻酸盐能够吸收伤口渗出液(对于中度至重度渗液的伤口也非常有用)，形成凝胶并覆盖在伤口，使伤口保持湿润的环境，促进愈合；同时向伤口释放钙，从而帮助伤口止血；而且海藻酸敷料的质量非常轻，大多数海藻酸敷料都能够吸收相当于自身重量很多倍的液体；此外，藻酸盐敷料还可以用生理盐水冲洗掉，这样的敷料去除时不会干扰肉芽组织愈合，这使得换药几乎无痛。
现在市场上的海藻酸敷料可分为二大类：表面用敷料和伤口充填物，表面用敷料一般由非织造布工艺制成，伤口充填物既可把非织造布切割成狭长的条子而制成，也可在梳棉后把纤维加工成毛条，经切割包装而形成最终产品。但是现有的海藻酸敷料却还存在着如下一些问题，使其应用范围与应用效果难以满足现实需求，例如存在着：目前的医用敷料功能单一，难以有效实现抗菌的同时对伤口的血管生成、创面上皮化等方面发生作用，无法对伤口的愈合做出明显且有效地促进作用；辅助伤口愈合的持续时间短；采用的原料与工艺不匹配，或者是顾此失彼，如有人提出的一种抗菌性磷酸锆钠银海藻纤维，通过将磷酸锆钠银分散液与海藻酸钠纺丝液混合，经湿法纺丝得到，其所制得的抗菌性磷酸锆钠银海藻纤维虽然可以释放银离子，具有良好的抗菌效果，但是纤维强度不高，可纺性差，分析可能是无机颗粒与海藻酸盐溶液为非均相混合情况下进行的纺丝。
发明内容
本发明的目的是克服现有技术中的一个或多个不足，提供一种改进的能够制备出兼具有效促进或辅助加速伤口愈合、优异力学性能的海藻酸盐医用纤维的方法，该方法制成的海藻酸盐医用纤维不仅可以使得抗菌效果贯穿伤口愈合的整个过程，而且还 能兼具促进血管生成、促进再上皮化等功效，从而在伤口愈合过程中起到有效地促进或辅助加速作用，同时还能克服现有海藻酸盐医用纤维的强度差，可纺性差的问题。
本发明同时还提供了一种上述方法制成的海藻酸盐医用纤维。
本发明同时还提供了一种上述海藻酸盐医用纤维作为短纤维用于非织造医用敷料的制备。
为达到上述目的，本发明采用的一种技术方案是：
一种海藻酸盐医用纤维的制备方法，所述制备方法包括：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥；其中，所述含有铜离子的壳聚糖溶液中，铜离子的含量为0.05-0.2mol/L；所述含有银离子的海藻酸钠溶液中，银离子含量为0.1-0.5mol/L；所述第一凝固浴为含有钙离子与锌离子的水溶液，所述第二凝固浴为含有钙离子的乙醇水溶液。
根据本发明的一些优选方面，所述含有铜离子的壳聚糖溶液与所述含有银离子的海藻酸钠溶液的体积比为5-20∶100；在该比例范围内，能够较好地确保主体纤维海藻酸盐纤维的成型，保证较好地离子释放性能以及整体的力学性能。
根据本发明的一些优选方面，所述含有铜离子的壳聚糖溶液中，采用的壳聚糖的重均分子量为1.0×10 6-2.2×10 6g/mol。
根据本发明的一些优选且具体的方面，所述含有铜离子的壳聚糖溶液通过将硝酸铜、硫酸铜或醋酸铜溶于壳聚糖溶液中制得，所述壳聚糖溶液通过将脱乙酰度大于95％的壳聚糖溶解于1-6wt％的酸醋水溶液中得到；其中，所述壳聚糖溶液中，壳聚糖的含量为3-10wt％。
根据本发明的一些优选方面，所述含有银离子的海藻酸钠溶液中，采用的海藻酸钠的重均分子量为3.0×10 5-6×10 5g/mol。
根据本发明的一些优选且具体的方面，所述含有银离子的海藻酸钠溶液通过将硝酸银、硫酸银、磷酸银或过氯酸银溶于海藻酸钠溶液中制得，所述海藻酸钠溶液通过将海藻酸纳溶解在水中得到，其中海藻酸钠含量为3-8wt％。
根据本发明的一些优选方面，所述第一凝固浴中，钙离子浓度为0.1-0.3mol/L，锌离子的浓度为0.1-0.5mol/L，第一凝固浴的凝固温度为30-40℃，停留时间为3-6s。
根据本发明的一些具体方面，所述第一凝固浴通过将氯化钙与氯化锌按比例溶解 在水中得到。
根据本发明的一些优选方面，所述第二凝固浴中，钙离子浓度为0.3-0.5mol/L，第二凝固浴的凝固温度为40-50℃，停留时间为2-4s。
根据本发明的一些具体方面，所述第二凝固浴通过将氯化钙溶解于50-70wt％的乙醇水溶液中得到。
根据本发明的一些具体方面，所述的洗涤浴为80-90wt％的乙醇水溶液。
本发明提供的又一技术方案：一种上述所述的制备方法制成的海藻酸盐医用纤维。本发明中，各颗粒在纤维基体中，在使用时不易脱落，提升了抗菌、伤口愈合的促进或辅助加速作用的持久性与有效性。
本发明中，在海藻酸盐医用纤维的制备过程中，由于海藻酸钠能够迅速与钙离子、锌离子、铜离子发生离子交换反应；当共混纺丝液经湿法纺丝即经过计量泵从喷丝孔被挤到凝固浴中时，共混纺丝液形成的细流就被迅速凝固并最终转化为海藻酸盐医用纤维，其中，共混纺丝液含有的海藻酸钠能够迅速与钙离子、锌离子、铜离子发生离子交换反应，进而形成了壳聚糖改性的海藻酸盐纤维，而且该纤维内部同时含有铜离子、银离子、锌离子、钙离子，即获得了本发明的海藻酸盐医用纤维。
同时，由于海藻酸作为一种高分子羧酸容易与不同的阳离子发生离子交换反应，如在纺丝的过程中，海藻酸钠能够迅速与钙离子、锌离子、铜离子等发生离子交换反应，且海藻酸盐作为聚阴离子电解质，能够与聚阳电解质的壳聚糖产生静电吸附作用，进而在制备过程中，伴随着离子交换与静电吸附作用，海藻酸盐与壳聚糖的相互作用有效提高了海藻酸盐纤维的力学性能。
此外，上述制成的海藻酸盐医用纤维中，银离子分散在海藻酸中，与钙离子相似，有较高的负载量，可以保证纤维在使用时较长时间的持续释放。铜离子、锌离子、钙离子依次与海藻酸结合。
本发明提供的又一技术方案：一种上述所述的海藻酸盐医用纤维作为短纤维用于非织造医用敷料的制备，其中，海藻酸盐医用纤维的纤维长度为35-150mm，纤度为：2.0-5dtex，干态断裂强度为2.5-3.5cN/dtex。
本发明的海藻酸盐医用纤维在皮肤创面覆盖敷料中应用时，具有良好的抗菌性能，在7-10天内持续释放银离子、钙离子、铜离子和锌离子，并对对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
本发明的海藻酸盐医用纤维，也可以作为纤维原料编织成片状、管状或特殊形状，用于口腔修复、疝修复、输尿管支架、神经修复、硬组织修复等组织修复领域。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明基于目前海藻酸盐医用纤维存在的缺陷，创新地对工艺原料、工艺过程以及参数进行选择，使得制成的海藻酸盐医用纤维能够调节释放多种微量元素，并通过制备过程中各原料的相互作用，克服了现有海藻酸盐医用纤维这种水溶性纤维强度低，容易断裂的缺陷，提高了纤维的力学性能，同时还使得该纤维中含有的各离子：钙离子、银离子、锌离子和铜离子能够按照伤口愈合的各个阶段所需进行有序且有效量地释放，进而使得本发明制备的海藻酸盐医用纤维不仅可以使得抗菌效果贯穿伤口愈合的整个过程，而且还能兼具促进血管生成、促进再上皮化等功效，从而在伤口愈合过程中起到有效地促进或辅助加速作用，同时还能克服现有海藻酸盐医用纤维的强度差，可纺性差的问题，使其可应用于非织造医用敷料的制备。
附图说明
图1为采用实施例1的海藻酸盐医用纤维作为短纤维制备得到的医用敷料的离子释放性能测试效果图。
具体实施方式
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。
下述中，如无特殊说明，所有的原料可以来自商购或者按照本领域常规方法制成。
实施例1
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖 溶液通过将脱乙酰度为96％的壳聚糖溶解于6wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为10wt％，壳聚糖的重均分子量为1.0×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.2mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为8wt％，采用的海藻酸钠的重均分子量为3.0×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.5mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为8∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.3mol/L，锌离子的浓度为0.5mol/L，第一凝固浴的凝固温度为40℃，停留时间为6s；
第二凝固浴为通过将氯化钙溶解于70wt％的乙醇水溶液中得到，且控制钙离子浓度为0.5mol/L，第二凝固浴的凝固温度为50℃，停留时间为4s；
洗涤浴为90wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为10m/s，拉伸倍数为2倍，得到纤维的纤度为：5.0dtex，干态断裂强度为3.5cN/dtex。可以在7天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在99％以上。
实施例2
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将脱乙酰度为97％的壳聚糖溶解于5wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为9wt％，壳聚糖的重均分子量为1.4×10 6g/mol；含有铜离 子的壳聚糖溶液中，铜离子的含量为0.18mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为7wt％，采用的海藻酸钠的重均分子量为3.5×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.4mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为10∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.3mol/L，锌离子的浓度为0.4mol/L，第一凝固浴的凝固温度为40℃，停留时间为6s；
第二凝固浴为通过将氯化钙溶解于70wt％的乙醇水溶液中得到，且控制钙离子浓度为0.5mol/L，第二凝固浴的凝固温度为50℃，停留时间为4s；
洗涤浴为90wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为12m/s，拉伸倍数为2倍，得到纤维的纤度为：4.5dtex，干态断裂强度为3.2cN/dtex。可以在10天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在99％以上。
实施例3
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将脱乙酰度为98％的壳聚糖溶解于4wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为8wt％，壳聚糖的重均分子量为1.8×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.15mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶 液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为6wt％，采用的海藻酸钠的重均分子量为4.0×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.3mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为5∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.2mol/L，锌离子的浓度为0.3mol/L，第一凝固浴的凝固温度为38℃，停留时间为5s；
第二凝固浴为通过将氯化钙溶解于60wt％的乙醇水溶液中得到，且控制钙离子浓度为0.4mol/L，第二凝固浴的凝固温度为48℃，停留时间为3s；
洗涤浴为85wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为14m/s，拉伸倍数为3倍，得到纤维的纤度为：4.0dtex，干态断裂强度为3.0cN/dtex。可以在9天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
实施例4
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将脱乙酰度为99％的壳聚糖溶解于3wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为6wt％，壳聚糖的重均分子量为2.0×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.1mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为5wt％，采用的海藻酸钠的重均分子量为4.5×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为 0.2mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为15∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.2mol/L，锌离子的浓度为0.3mol/L，第一凝固浴的凝固温度为36℃，停留时间为5s；
第二凝固浴为通过将氯化钙溶解于60wt％的乙醇水溶液中得到，且控制钙离子浓度为0.4mol/L，第二凝固浴的凝固温度为40℃，停留时间为3s；
洗涤浴为85wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为16m/s，拉伸倍数为5倍，得到纤维的纤度为：2.0dtex，干态断裂强度为2.5cN/dtex。可以在7天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
实施例5
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将脱乙酰度为99％的壳聚糖溶解于2wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为5wt％，壳聚糖的重均分子量为2.2×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.08mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为4wt％，采用的海藻酸钠的重均分子量为5.0×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.1mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为18∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.1mol/L，锌离子的浓度为0.2mol/L，第一凝固浴的凝固温度为32℃，停留时间为4s；
第二凝固浴为通过将氯化钙溶解于50wt％的乙醇水溶液中得到，且控制钙离子浓度为0.4mol/L，第二凝固浴的凝固温度为48℃，停留时间为2s；
洗涤浴为80wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为18m/s，拉伸倍数为4倍，得到纤维的纤度为：2.5dtex，干态断裂强度为2.8cN/dtex。可以在8天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
实施例6
本例提供一种海藻酸盐医用纤维的制备方法，及采用该方法制成的海藻酸盐医用纤维。
该海藻酸盐医用纤维的制备方法包括如下步骤：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维。
其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将脱乙酰度为99％的壳聚糖溶解于1wt％的酸醋水溶液中得到；其中，壳聚糖溶液中，壳聚糖的含量为3wt％，壳聚糖的重均分子量为1.8×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.05mol/L；
含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为3wt％，采用的海藻酸钠的重均分子量为6×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.3mol/L；
含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为20∶100；
第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.1mol/L，锌离子的浓度为0.1mol/L，第一凝固浴的凝固温度为30℃，停留时间为 3s；
第二凝固浴为通过将氯化钙溶解于50wt％的乙醇水溶液中得到，且控制钙离子浓度为0.3mol/L，第二凝固浴的凝固温度为50℃，停留时间为2s；
洗涤浴为80wt％的乙醇水溶液。
所述的海藻酸盐医用纤维，纺丝速率为20m/s，拉伸倍数为3倍，得到纤维的纤度为：2.4dtex，干态断裂强度为2.8cN/dtex。可以在7天内持续释放银离子、钙离子、铜离子和锌离子；并且对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
应用试验：系列实验包括了本专利制备的海藻酸盐医用纤维安全性与有效性评价。其中安全性评价按照GB/T 16886医疗器械的生物学评价的要求进行。有效性评价包括抗菌性能、水蒸气透过性能与动物学评价。
生物相容性测试：
参照GB/T 16886医疗器械的生物学评价，分别对本专利制备的海藻酸盐医用纤维(按实施例1)进行细胞毒性、豚鼠迟发接触性致敏、皮肤刺激等评价。
细胞内毒性试验按照GB/T 16886-5《医疗器械生物学评价第5部分：体外细胞毒性试验》进行测试；豚鼠迟发型接触致敏试验按照GB/T 16886-10《医疗器械生物学评价第10部分：刺激与迟发型超敏反应试验》进行测试，采用最大限度试验Magnusson和Kligman法。皮肤刺激试验按照GB/T 16886-10《医疗器械生物学评价第10部分：刺激与迟发型超敏反应试验》进行测试。
结果表明：本发明上述实施例1制备获得的海藻酸盐医用纤维细胞毒性小于2级，无皮肤致敏反应，无皮内刺激反应，具有良好的生物安全性。
抗菌性能测试
将实施例1的海藻酸盐医用纤维样品，采用AATCC-100对抗菌性能进行测试，抗菌率为99％；连续使用10天后，采用AATCC-100对抗菌性能进行测试，抗菌率为99％。
离子释放性能测试：
采用上述实施例1中的海藻酸盐医用纤维作为短纤维，制备得到医用敷料。将敷料产品浸泡在模拟体液PBS中，用原子吸收光谱仪测试模拟体液中释放的银离子、 锌离子、铜离子与钙离子含量，测试持续6天。测试时间点分别为3h、6h、9h、12h、24h、48h、72h、96h、120h、144h。离子释放率＝不同时间点模拟体液中的离子含量/医用敷料中的离子总含量，测试结果参见图1所示，在使用过程中，银离子与钙离子会在较短的时间内快速释放大部分(后续银离子保持较少量的持续释放以确保持续抗菌效果等，钙离子在释放一段时间内基本达到了峰值)，锌离子在前中期保持较快释放速度而中后期释放相对较慢但仍然保持一定的释放速度并几乎在较后段达到峰值，铜离子的释放基本保持一个较稳定的频率，并几乎一直持续到峰值。这一过程与伤口愈合所需要的微量元素刚好相吻合，银离子对于治疗感染伤口有非常好的抗菌效果，能够加快伤口的愈合，贯穿伤口愈合的整个过程，因此，在前期需要较快速地释放，在中后期释放速度可以较慢但又能够在中后期保持持续释放的能力；在伤口愈合的早期阶段，钙离子(Ca 2+)被认为可以帮助伤口止血、促进再上皮化，其次钙离子还可以在伤口愈合中后期，起到稳定生物膜的作用，因此，要求钙离子在最初始的阶段迅速达到较大的释放程度以满足伤口止血促进再上皮化的目的，同时在中后期也有一定的释放，进而起到稳定生物膜的作用等；伤口愈合中后期(增殖和成熟过程阶段)，锌离子(Zn 2+)作为维持蛋白质结构完整性和调节基因表达的酶的一个必要组分，参与免疫、细胞生长和迁移的调节，在伤口愈合中发挥关键作用，因此，其要求锌离子能够贯穿整个伤口愈合过程，并满足前期较大量的释放并在中后期也具有较好地持续释放能力。在伤口愈合中后期的增殖和重塑阶段，铜离子(Cu 2+)可诱导血管内皮生长因子的表达，促进血管生成，维持胶原的稳定性，因此，要求铜离子自始至终都保持一个较稳定地释放频次，尤其是在中后期需要保持较佳的释放速度进而以满足伤口的增殖与重塑等，由图1的测试结果表明本发明制成的海藻酸盐医用纤维完全能够满足上述伤口各个阶段的愈合过程，其离子有效释放量以及频率符合伤口愈合的各个阶段所需。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (14)

  1. 一种海藻酸盐医用纤维的制备方法，其特征在于，所述制备方法包括：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥，卷绕，得到海藻酸盐医用纤维；
    其中，该含有铜离子的壳聚糖溶液通过将硝酸铜溶于壳聚糖溶液中制得，壳聚糖溶液通过将大于95％的壳聚糖溶解于1-6wt％的酸醋水溶液中得到；壳聚糖溶液中，壳聚糖的含量为3-10wt％，壳聚糖的重均分子量为1.0×10 6-2.2×10 6g/mol；含有铜离子的壳聚糖溶液中，铜离子的含量为0.05-0.2mol/L；
    含有银离子的海藻酸钠溶液通过将硝酸银溶于海藻酸钠溶液中制得，海藻酸钠溶液通过将海藻酸纳溶解在去离子水中得到，其中海藻酸钠含量为3-8wt％，采用的海藻酸钠的重均分子量为3.0×10 5-6×10 5g/mol；含有银离子的海藻酸钠溶液中，银离子含量为0.1-0.5mol/L；
    含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液的体积比为5-20∶100；
    第一凝固浴为通过将氯化钙与氯化锌按比例溶解在水中得到，且控制钙离子浓度为0.1-0.3mol/L，锌离子的浓度为0.1-0.5mol/L，第一凝固浴的凝固温度为30-40℃，停留时间为3-6s；
    第二凝固浴为通过将氯化钙溶解于50-70wt％的乙醇水溶液中得到，且控制钙离子浓度为0.3-0.5mol/L，第二凝固浴的凝固温度为40-50℃，停留时间为2-4s；
    洗涤浴为80-90wt％的乙醇水溶液。
  2. 一种海藻酸盐医用纤维的制备方法，其特征在于，所述制备方法包括：将含有铜离子的壳聚糖溶液与含有银离子的海藻酸钠溶液混合，得到共混纺丝液，然后经湿法纺丝，再分别经过第一凝固浴、第二凝固浴中处理，洗涤浴洗涤，牵伸，干燥；其中，所述含有铜离子的壳聚糖溶液中，铜离子的含量为0.05-0.2mol/L；所述含有银离子的海藻酸钠溶液中，银离子含量为0.1-0.5mol/L；所述第一凝固浴为含有钙离子与锌离子的水溶液，所述第二凝固浴为含有钙离子的乙醇水溶液。
  3. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述含有铜离子的壳聚糖溶液与所述含有银离子的海藻酸钠溶液的体积比为5-20∶100。
  4. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述含有 铜离子的壳聚糖溶液中，采用的壳聚糖的重均分子量为1.0×10 6-2.2×10 6g/mol。
  5. 根据权利要求2-4中任一项所述的海藻酸盐医用纤维的制备方法，其特征在于，所述含有铜离子的壳聚糖溶液通过将硝酸铜、硫酸铜或醋酸铜溶于壳聚糖溶液中制得，所述壳聚糖溶液通过将脱乙酰度大于95％的壳聚糖溶解于1-6wt％的酸醋水溶液中得到；其中，所述壳聚糖溶液中，壳聚糖的含量为3-10wt％。
  6. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述含有银离子的海藻酸钠溶液中，采用的海藻酸钠的重均分子量为3.0×10 5-6×10 5g/mol。
  7. 根据权利要求2或3或6所述的海藻酸盐医用纤维的制备方法，其特征在于，所述含有银离子的海藻酸钠溶液通过将硝酸银、硫酸银、磷酸银或过氯酸银溶于海藻酸钠溶液中制得，所述海藻酸钠溶液通过将海藻酸纳溶解在水中得到，其中海藻酸钠含量为3-8wt％。
  8. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述第一凝固浴中，钙离子浓度为0.1-0.3mol/L，锌离子的浓度为0.1-0.5mol/L，第一凝固浴的凝固温度为30-40℃，停留时间为3-6s。
  9. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述第二凝固浴中，钙离子浓度为0.3-0.5mol/L，第二凝固浴的凝固温度为40-50℃，停留时间为2-4s。
  10. 根据权利要求2所述的海藻酸盐医用纤维的制备方法，其特征在于，所述湿法纺丝中，纺丝速率为10-20m/s，拉伸倍数为2-5倍。
  11. 一种权利要求2-10中任一项所述的制备方法制成的海藻酸盐医用纤维。
  12. 根据权利要求11所述的海藻酸盐医用纤维，其特征在于，钙离子、锌离子、铜离子和阴离子分别位于所述海藻酸盐医用纤维的纤维基体中。
  13. 一种权利要求11或12所述的海藻酸盐医用纤维作为短纤维用于制备非织造医用敷料的用途，其中，海藻酸盐医用纤维的纤维长度为35-150mm，纤度为：2.0-5dtex，干态断裂强度为2.5-3.5cN/dtex。
  14. 根据权利要求13所述的用途，其特征在于，所述非织造医用敷料在7-10天内能够分别持续释放银离子、钙离子、铜离子和锌离子，对对大肠杆菌、金黄色葡萄球菌、白色念珠菌、铜绿假单胞菌的杀菌率均在98％以上。
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