Antibacterial, mildew-proof and anti-swelling degradable film for medical and health care and preparation method of antibacterial, mildew-proof and anti-swelling degradable film

Abstract

The invention relates to the technical field of medical films, in particular to a medical and sanitary antibacterial, mildew-proof and anti-swelling degradable film and a preparation method thereof. The antibacterial, mildew-proof and anti-swelling degradable film for medical and sanitary use is prepared from the following raw materials in parts by weight: 1-64 parts of strong acid and weak base metal salt, 20-28 parts of polyvinyl alcohol PVA, 1-4 parts of a cross-linking agent, 2-4 parts of a plasticizer and 160-240 parts of pure water. The cross-linking agent is an organic small molecule carrying at least one carboxyl or aldehyde functional group; the strong acid and weak base metal salt is dissolved in water to provide an acidic environment, and the dissociated Men < + > promotes hydroxyl on a side chain of polyvinyl alcohol PVA to react with carboxyl or aldehyde functional groups in a cross-linking agent to generate stable metal ion competitive coordination organic molecules. The PVA film provided by the invention has antibacterial, mildew-proof, swelling-resistant and antistatic effects, is used in the field of medical non-woven fabrics, and improves the safety of medical staff.

Description

Technical Field

[0001] The present invention relates to the technical field of medical films, and particularly to a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties and a preparation method thereof. Background Art

[0002] Due to its good high-temperature and low-temperature resistance, corrosion resistance, high tensile strength and flexibility, polyvinyl alcohol (PVA) film is applied in various fields, such as various plastic products, food packaging, disposable food containers, non-woven fabrics, industrial and household textiles. In addition, with the enhancement of people's environmental protection awareness, the degradable ability of PVA film itself has received extensive attention, making it a market with broad prospects.

[0003] Existing PVA films are troubled by consumers in terms of long-term water resistance. The reason is that PVA contains a large number of hydroxyl groups, which are easy to be hydrophilic and cause rapid swelling of itself, resulting in poor hydrolysis stability and limiting its application range. In addition, PVA films also have defects such as low antibacterial and mildew-proof properties, low tensile strength and no antistatic property, resulting in relatively single functions of PVA films and being unable to meet the performance requirements of medical films. There is an urgent need for a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties and a preparation method thereof. Summary of the Invention

[0004] In order to solve the technical defects of existing PVA films, such as poor hydrolysis stability, low antibacterial and mildew-proof properties, low tensile strength and no antistatic property, the present invention provides a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties and a preparation method thereof, which can meet the requirements of flame retardancy, antibacterial and mildew-proof, and anti-swelling of medical films.

[0005] The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties provided by the present invention is realized through the following technical solutions:

[0006] A degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made from the following raw materials in parts by weight: 1-64 parts of strong acid and weak base metal salts, 20-28 parts of polyvinyl alcohol (PVA), 1-4 parts of crosslinking agent, 2-4 parts of plasticizer, and 160-240 parts of pure water;

[0007] The crosslinking agent is an organic small molecule carrying at least one carboxyl or aldehyde functional group;

[0008] The strong acid and weak base metal salt dissociates Me n+ in an aqueous solution, and the Me n+ includes Fe 3+ , Fe 2+ , Cu 2+ , Cu + , Zn 2 + , Mn 2+ , Pb2+ 、 Ag + 、 Al 3+ 、 Au + at least one of

[0009] The strong acid and weak base metal salt is dissolved in water to provide an acidic environment, dissociating Me n+ to promote the reaction between the hydroxyl groups on the side chains of polyvinyl alcohol (PVA) and the carboxyl or aldehyde functional groups in the crosslinking agent to form stable metal ion-competing coordination organic molecules.

[0010] The PVA film in the present invention has antibacterial, mildew-proof, anti-swelling and antistatic effects, and is used in the field of medical non-woven fabrics to improve the safety of medical staff.

[0011] Preferably, the reaction equation of the metal ion-competing coordination organic molecule is as follows:

[0012]

[0013] The inorganic metal salt dissociates to produce metal ions Me n+ which exists in a coordinated form inside the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film, and can improve the antibacterial, mildew-proof, anti-swelling and antistatic effects of the PVA film.

[0014] Preferably, a medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film is made from the following raw materials in parts by weight: 6 - 18 parts of strong acid and weak base metal salt, 20 - 28 parts of polyvinyl alcohol (PVA), 1 - 2 parts of crosslinking agent, 2 - 4 parts of plasticizer, and 180 - 200 parts of pure water.

[0015] Preferably, the inorganic metal salt is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, lead acetate, silver nitrate, and chloroauric acid.

[0016] Preferably, the crosslinking agent is one or a combination of salicylic acid, benzoic acid, p-hydroxybenzoic acid, and p-formylbenzoic acid.

[0017] More preferably, the crosslinking agent is benzoic acid with a lower cost.

[0018] Compared with several other crosslinking agents, benzoic acid has low cost, wide sources, easy hydrolysis and low polymerization degree, can reduce the overall production cost, and can ensure the mechanical properties and waterproof and breathable properties of the prepared medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film.

[0019] Preferably, the plasticizer is one or a combination of glycerol, ethylene glycol, propylene glycol, and butanediol.

[0020] Preferably, the degree of alcoholysis of the polyvinyl alcohol (PVA) is ≥79%, and the degree of polymerization is 300 - 2400. The polyvinyl alcohol (PVA) includes any one of PVA-2499, PVA-1788, PVA-1799, and PVA-2388.

[0021] More preferably, the medical and sanitary antibacterial, mildew-proof and anti-swelling degradable film mainly cross-links the hydroxyl groups inside the copper ion competitive coordination cross-linking agent and PVA-2499. And this metal ion coordination type degradable composite film is prepared by a sol-gel method in one step using anhydrous copper sulfate, benzoic acid, PVA-2499, and glycerol as raw materials.

[0022] The medical and sanitary antibacterial, mildew-proof and anti-swelling degradable film in the present invention has an antibacterial property against Candida albicans ≥99%, an antibacterial property against Escherichia coli >99%, an antibacterial property against Staphylococcus aureus >99%, a mildew-proof level of 0 - 1, a swelling rate <150%, a surface resistance of 10 6 ~10 9 Ω, a tensile strength >17N, a tear strength >0.5N, a water vapor transmission rate ≥550 g / m 2 / 24h, and a hydrostatic pressure ≥1500 mmH20.

[0023] A preparation method of a medical and sanitary antibacterial, mildew-proof and anti-swelling degradable film provided by the present invention is achieved through the following technical solutions:

[0024] A preparation method of a medical and sanitary antibacterial, mildew-proof and anti-swelling degradable film includes the following steps:

[0025] Step 1, preparation of a mixed gel solution: Mix accurately metered polyvinyl alcohol (PVA), cross-linking agent, plasticizer, and pure water evenly, heat to 80 - 95°C and stir for 1 - 4 hours, and then add an aqueous solution of a strong acid and weak base metal salt according to the ratio and stir for 1 - 4 hours to obtain a mixed gel solution.

[0026] Step 2, cool the mixed gel solution in Step 1 to 50 - 65°C and add it into a slot coater. Set the die head temperature to 60 - 120°C, the discharge thickness to 65 - 350 microns, the dry film thickness to 20 - 50 microns, the solution viscosity to 4000 - 6000 centipoise, and the solid content to 15 - 30%. Prepare a medical and sanitary degradable film with antibacterial, mildew-proof and anti-swelling properties through a one-step method.

[0027] Preferably, the specific preparation method of the mixed gel solution in the first step is as follows: Prepare an aqueous solution of a strong acid and weak base metal salt with a concentration of 50 - 320 g / L, add 20 - 28 parts of polyvinyl alcohol PVA, 1 - 5 parts of crosslinking agent, and 2 - 4 parts of plasticizer to 80 - 120 parts of pure water, heat from room temperature to 80 - 95 °C and stir for at least 2 hours, then add 80 - 120 parts of an anhydrous copper sulfate solution with a concentration of 50 - 320 g / L and stir for at least 2 hours to obtain the mixed gel solution.

[0028] The synthesis of the metal ion coordination type medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in the present invention has a relatively low difficulty, less synthesis pollution, is convenient for large-scale batch industrial production, and can further reduce the use cost of nano antibacterial agents, mildew-proof agents and anti-swelling agents, and enhance the market competitiveness of the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film.

[0029] In summary, the present invention has the following advantages:

[0030] 1. The PVA film in the present invention has antibacterial, mildew-proof, anti-swelling and antistatic effects, and is used in the field of medical non-woven fabrics to improve the safety of medical staff.

[0031] 2. The synthesis technology of the metal ion coordination type medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in the present invention has a relatively low difficulty, less pollution, is convenient for large-scale batch industrial production, and can further reduce the use cost of nano antibacterial agents, mildew-proof agents and anti-swelling agents, and enhance the market competitiveness of the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film.

[0032] 3. The medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in the present invention has an antibacterial performance against Candida albicans ≥ 99%, an antibacterial performance against Escherichia coli > 99%, an antibacterial performance against Staphylococcus aureus > 99%, a mildew-proof level of 0 - 1, a swelling rate < 120%, a surface resistance of 10 6 ~10 9 Ω, a tensile strength > 17 N, a tear strength > 0.5 N, a water vapor transmission rate ≥ 550 g / m2 / 24 h, and a hydrostatic pressure ≥ 1500 mmH20. Specific Embodiments

[0033] In order to further understand the creativity and technological progress of the present invention, the preferred implementation schemes of the present invention will be discussed in detail below in combination with examples and comparative examples.

[0034] Example: A medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film is made from the following raw materials in parts by weight: 1 - 64 parts of strong acid and weak base metal salt, 20 - 28 parts of polyvinyl alcohol PVA, 1 - 4 parts of crosslinking agent, 2 - 4 parts of plasticizer, and 160 - 240 parts of pure water.

[0035] Preferably, a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made from the following raw materials in parts by weight: 6-18 parts of strong-acid weak-base metal salts, 20-28 parts of polyvinyl alcohol (PVA), 1-2 parts of cross-linking agent, 2-4 parts of plasticizer, and 180-200 parts of pure water.

[0036] The degree of alcoholysis of the polyvinyl alcohol (PVA) is ≥79%, and the degree of polymerization is 300-2400. Specifically, the polyvinyl alcohol (PVA) is any one of PVA-2499, PVA-1788, PVA-1799, and PVA-2388. Further preferably, the polyvinyl alcohol (PVA) is PVA-2499.

[0037] The cross-linking agent is an organic small molecule carrying at least one carboxyl or aldehyde functional group, specifically one or a combination of salicylic acid, benzoic acid, p-hydroxybenzoic acid, and p-formylbenzoic acid. Further preferably, the cross-linking agent is benzoic acid with a lower cost. Compared with other cross-linking agents, benzoic acid has low cost, wide sources, easy hydrolysis, and low degree of polymerization, which can reduce the overall production cost and ensure the mechanical properties and waterproof and breathable properties of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties.

[0038] The plasticizer is one or a combination of glycerol, ethylene glycol, propylene glycol, and butanediol.

[0039] The strong-acid weak-base metal salt dissociates Me n+ ,Me n+ including Fe 3+ ,Fe 2+ ,Cu 2+ ,Cu + ,Zn 2+ ,Mn 2+ ,Pb 2+ ,Ag + ,Al 3+ ,Au + and at least one of them. Specifically, the strong-acid weak-base metal salt is at least one of copper sulfate, copper chloride, copper nitrate, manganese sulfate, manganese chloride, manganese nitrate, zinc sulfate, zinc chloride, zinc nitrate, iron chloride, iron nitrate, aluminum sulfate, lead chloride, lead nitrate, lead acetate, silver nitrate, and chloroauric acid. Further preferably, the strong-acid weak-base metal salt is copper sulfate.

[0040] The strong-acid weak-base metal salt dissolves in water to provide an acidic environment and dissociates Me n+ to promote the reaction between the hydroxyl groups on the side chain of polyvinyl alcohol (PVA) and the carboxyl or aldehyde functional groups in the cross-linking agent to form a stable metal ion competitive coordination organic molecule. The inorganic metal salt dissociates the metal ion Me n+ which exists in the form of coordination inside the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties, and can improve the antibacterial, mildew-proof, anti-swelling and antistatic effects of the PVA film.

[0041] The reaction equation of metal ions competing for coordination with organic molecules is as follows:

[0042]

[0043] A preparation method of a degradable film for medical and health use with antibacterial, antifungal and anti-swelling properties includes the following steps:

[0044] Step 1: Prepare an aqueous solution of a strong acid and weak base metal salt with a concentration of 50 - 320 g / L. Add 20 - 28 parts of polyvinyl alcohol PVA, 1 - 5 parts of cross-linking agent, and 2 - 4 parts of plasticizer to 80 - 120 parts of pure water. Heat from room temperature to 80 - 95 °C and stir for at least 2 hours, then add 80 - 120 parts of an anhydrous copper sulfate solution with a concentration of 50 - 320 g / L and stir for at least 2 hours to obtain a mixed gel solution.

[0045] Step 2: Cool the mixed gel solution in Step 1 to 50 - 65 °C and add it into a slot coater. Set the die head temperature to 60 - 120 °C, the discharge thickness to 65 - 350 microns, the dry film thickness to 20 - 50 microns, the solution viscosity to 4000 - 6000 centipoise, and the solid content to 15 - 30%. Prepare a medical and health use degradable film with antibacterial, antifungal and anti-swelling properties through a one-step method.

[0046] Example 1: A degradable film for medical and health use with antibacterial, antifungal and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 1 g of benzoic acid, 4 g of glycerol and 200 g of pure water.

[0047] The degree of polymerization of polyvinyl alcohol PVA-2499 is 2400, the degree of alcoholysis is ≥99%, the purity is >98.5%, Anhui Wanwei High-Tech Materials Co., Ltd.

[0048] A preparation method of a degradable film for medical and health use with antibacterial, antifungal and anti-swelling properties includes the following steps:

[0049] Step 1: Preparation of the mixed gel solution: First, prepare an anhydrous copper sulfate solution: Mix 8 g of anhydrous copper sulfate with 100 mL of pure water evenly to obtain the finished copper sulfate solution; then add 24 g of PVA-2499, 4 g of glycerol, and 1 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C and stir at 200 r / min for 2 hours, and finally add the above-prepared finished copper sulfate solution, and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain a mixed gel solution;

[0050] Step 2: Cool the mixed gel solution in Step 1 to 60°C and add it into the slot coater. Set the die head temperature to 120°C, the coating thickness to 250 microns, the dry film thickness to 50 microns, the solution viscosity to 5000 centipoise, and the solid content to 18.5%. Finally, prepare a degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties by a one-step method.

[0051] The difference between Example 2 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol, and 200 g of pure water.

[0052] The difference between Example 3 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 1 g of salicylic acid, 4 g of glycerol, and 200 g of pure water.

[0053] The difference between Example 4 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of salicylic acid, 4 g of glycerol, and 200 g of pure water.

[0054] The difference between Example 5 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 1 g of p-hydroxybenzoic acid, 4 g of glycerol, and 200 g of pure water.

[0055] The difference between Example 6 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of p-hydroxybenzoic acid, 4 g of glycerol, and 200 g of pure water.

[0056] The difference between Example 7 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 1 g of p-formylbenzoic acid, 4 g of glycerol, and 200 g of pure water.

[0057] The difference between Example 8 and Example 1 is that the degradable film for medical and health use with antibacterial, antifungal, and anti-swelling properties is made of 8 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of p-formylbenzoic acid, 4 g of glycerol, and 200 g of pure water.

[0058] Example 9 is different from Example 2 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 2 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 2 g of anhydrous copper sulfate with 100 mL of pure water evenly to obtain the finished copper sulfate solution. Then, add 24 g of PVA-2499, 4 g of glycerol and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C and stir at 200 r / min for 2 hours. Finally, add the above-prepared finished copper sulfate solution and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0059] Example 10 is different from Example 2 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 10 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 10 g of anhydrous copper sulfate with 100 mL of pure water evenly to obtain the finished copper sulfate solution. Then, add 24 g of PVA-2499, 4 g of glycerol and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C and stir at 200 r / min for 2 hours. Finally, add the above-prepared finished copper sulfate solution and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0060] Example 11 is different from Example 2 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 16 g of anhydrous copper sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 16 g of anhydrous copper sulfate with 100 mL of pure water evenly to obtain the finished copper sulfate solution. Then, add 24 g of PVA-2499, 4 g of glycerol and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C and stir at 200 r / min for 2 hours. Finally, add the above-prepared finished copper sulfate solution and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0061] Example 12 is different from Example 1 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 8 g of manganese sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 8 g of manganese sulfate with 100 mL of pure water evenly to obtain the finished manganese sulfate solution; then add 24 g of PVA-2499, 4 g of glycerol, and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C, stir at 200 r / min for 2 hours, and finally add the above-prepared finished manganese sulfate solution, and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0062] Example 13 is different from Example 1 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 8 g of zinc sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 8 g of zinc sulfate with 100 mL of pure water evenly to obtain the finished zinc sulfate solution; then add 24 g of PVA-2499, 4 g of glycerol, and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C, stir at 200 r / min for 2 hours, and finally add the above-prepared finished zinc sulfate solution, and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0063] Example 14 is different from Example 1 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 8 g of iron sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is as follows: Step 1, preparation of the mixed gel solution: First, prepare the anhydrous copper sulfate solution: Mix 8 g of iron sulfate with 100 mL of pure water evenly to obtain the finished iron sulfate solution; then add 24 g of PVA-2499, 4 g of glycerol, and 2 g of benzoic acid to 100 mL of pure water, heat from room temperature to 90 °C, stir at 200 r / min for 2 hours, and finally add the above-prepared finished iron sulfate solution, and maintain stirring at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0064] Example 15 is different from Example 1 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 8 g of silver sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties lies in: Step 1, preparation of the mixed gel solution: first prepare a copper sulfate anhydrous solution: 8 g of silver sulfate is mixed evenly with 100 mL of pure water to obtain the finished silver sulfate solution; then 24 g of PVA-2499, 4 g of glycerol and 2 g of benzoic acid are added to 100 mL of pure water, heated from room temperature to 90 °C and stirred at 200 r / min for 2 hours, and finally the above-prepared finished silver sulfate solution is added, and stirring is continued at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0065] Example 16 is different from Example 1 in that: the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is made of 8 g of lead sulfate, 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties lies in: Step 1, preparation of the mixed gel solution: first prepare a copper sulfate anhydrous solution: 8 g of lead sulfate is mixed evenly with 100 mL of pure water to obtain the finished lead sulfate solution; then 24 g of PVA-2499, 4 g of glycerol and 2 g of benzoic acid are added to 100 mL of pure water, heated from room temperature to 90 °C and stirred at 200 r / min for 2 hours, and finally the above-prepared finished lead sulfate solution is added, and stirring is continued at 200 r / min at 90 °C for 2 hours to obtain the mixed gel solution.

[0066] Comparative Example 1: The degradable film is made of 24 g of PVA-2499, 4 g of glycerol and 196 g of pure water.

[0067] The preparation method of the degradable film includes the following steps:

[0068] Step 1, preparation of the mixed gel solution: 24 g of PVA-2499 and 4 g of glycerol are added to 200 g of pure water, heated from 25 °C to 90 °C and stirred for 4 hours to obtain the mixed gel solution;

[0069] Step 2, cooling the mixed gel solution in Step 1 to 60 °C and adding it into the slot coater. The die head temperature is set to 120 °C, the discharge thickness is set to 250 microns, the dry film thickness is set to 50 microns, the solution viscosity is set to 5000 centipoise, and the solid content is set to 18%. Finally, a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties is prepared by a one-step method.

[0070] The difference between Comparative Example 2 and Comparative Example 1 is that the degradable film is made of 24 g of PVA-2499, 8 g of anhydrous copper sulfate, 4 g of glycerol and 196 g of pure water.

[0071] The difference in the preparation method of the degradable film is as follows: Step 1, preparation of the mixed gel solution: 24 g of PVA-2499, 8 g of anhydrous copper sulfate, and 4 g of glycerol are added to 200 g of pure water, and the mixture is heated from 25 °C to 90 °C and stirred for 4 hours to obtain the mixed gel solution.

[0072] The difference between Comparative Example 3 and Example 1 is that the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film is made of 24 g of polyvinyl alcohol PVA-2499, 2 g of benzoic acid, 4 g of glycerol and 200 g of pure water. The difference in the preparation method of the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film is as follows: Step 1, preparation of the mixed gel solution: 24 g of PVA-2499, 4 g of glycerol, and 2 g of benzoic acid are added to 100 mL of pure water, and the mixture is heated from room temperature to 90 °C and stirred at 200 r / min for 4 hours to obtain the mixed gel solution.

[0073] Performance detection test:

[0074] 1. Test method for antibacterial activity value: Determined according to ISO 18184.

[0075] 2. Test method for antibacterial rate: Determined according to GB / T 20944.2-2007. The sample sterilization method is autoclaving. The contact culture time between the sample and the bacterial solution is 18 h. The control sample is a common PE breathable film. The colony concentrations are Staphylococcus aureus ATCC 6538: 2.0×10 5 CFU / mL; Escherichia coli 8099: 1.9×10 5 CFU / mL; Candida albicans ATCC 10231: 1.6×10 5 CFU / mL; The judgment criterion is that when the antibacterial value ≥ 2 or the antibacterial rate ≥ 99%, it is proved that it has antibacterial effect) determination.

[0076] 3. Test method for antistatic grade: Use a double-electrode four-probe surface resistance resistivity tester to test the surface resistance of the film material. If the surface resistance of the tested film material < 10 9 ohms, it is considered to have antistatic performance and is OK. If the surface resistance of the tested film material > 10 9 ohms, it is considered that it does not have antistatic performance and is NG.

[0077] 4. Test method for water vapor transmission rate: Determined according to GB / T 19082-2023. When the water vapor transmission rate ≥ 550 g / m 2 / 24 h, it is recorded as Pass, otherwise it is recorded as NG.

[0078] 5. Test method for tensile strength: Determined in accordance with FZ / T 60005.

[0079] 6. Test method for hydrostatic pressure: Determined in accordance with GB / T 19082-2023. Hydrostatic pressure ≥ 1500 mmH2O is recorded as Pass, otherwise recorded as NG.

[0080] 7. Test method for anti-swelling performance: Determine the swelling degree of the film material by the gravimetric method.

[0081] 8. Test method for mildew prevention: Determined in accordance with GB / T 24346-2009.

[0082] 9. Test method for tear strength: Determined in accordance with GB / T 3917.2.

[0083] Table 1: Test parameter table of antibacterial and mildew-proof properties of PVA films in Examples 1-16 and Comparative Examples 1-3

[0084]

[0085]

[0086] Table 2: Test parameter table of physical and chemical properties of PVA films in Examples 1-16 and Comparative Examples 1-3

[0087]

[0088] Combining Examples 1-16 and Comparative Examples 1-3 and Tables 1-2, it can be seen that the copper ion coordination type medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in the present invention has antibacterial, mildew-proof, anti-swelling and antistatic effects, and is used in the field of medical non-woven fabrics to reduce the bacterial infection and static electricity risks of medical staff.

[0089] Combining Examples 1-16 and Comparative Examples 1-3 and Tables 1-2, it can be seen that considering the comprehensive production cost and physical and chemical properties, the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in Example 2 is an industrial mass production plan. Only from the perspective of physical and chemical properties, the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in Example 4 is relatively excellent, but the price of salicylic acid in its raw materials is more than three times that of benzoic acid, and the overall cost is relatively high.

[0090] In summary, the medical and hygienic antibacterial, mildew-proof and anti-swelling degradable film in the present invention has antibacterial performance against Candida albicans ≥ 99%, antibacterial performance against Escherichia coli > 99%, antibacterial performance against Staphylococcus aureus > 99%, mildew prevention level of 0-1, swelling rate < 120%, and surface resistance of 10 6 ~10 9Ω, tensile strength > 17 N, tear strength > 0.5 N, water vapor transmission rate ≥ 550 g / m 2 / 24 h, hydrostatic pressure ≥ 1500 mmH20.

[0091] It should be noted that: This specific embodiment is only an explanatory illustration of the technical solution of the present invention, and it is not a limitation of the present invention. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of the present invention, it is protected by the patent law.

Claims

1. A degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties, characterized in that: It is made from the following raw materials in parts by weight: 1-64 parts of strong acid and weak base metal salts, 20-28 parts of polyvinyl alcohol PVA, 1-4 parts of crosslinking agent, 2-4 parts of plasticizer, and 160-240 parts of pure water; The crosslinking agent is an organic small molecule carrying at least one carboxyl or aldehyde functional group; The strong acid-weak base metal salt dissociates into Me in an aqueous solution n+ , where the Me n+ includes at least one of Fe 3+ , Fe 2+ , Cu 2+ , Cu + , Zn 2+ , Mn 2 + , Pb 2+ , Ag + , Al 3+ , Au + ; The strong acid and weak base metal salt dissolves in water to provide an acidic environment and dissociate Me n+ It promotes the reaction between the hydroxyl groups on the side chain of polyvinyl alcohol (PVA) and the carboxyl or aldehyde functional groups in the crosslinking agent to form stable metal ion-competing coordination organic molecules.

2. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 1, characterized in that: The reaction equation for the metal ions to competitively coordinate with organic molecules is as follows:

3. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 2, wherein: It is made from the following raw materials in parts by weight: 6-18 parts of strong acid and weak base metal salts, 20-28 parts of polyvinyl alcohol PVA, 1-2 parts of crosslinking agent, 2-4 parts of plasticizer, and 180-200 parts of pure water.

4. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 3, characterized in that: The strong acid and weak base metal salts are at least one of copper sulfate, copper chloride, copper nitrate, manganese sulfate, manganese chloride, manganese nitrate, zinc sulfate, zinc chloride, zinc nitrate, iron chloride, iron nitrate, aluminum sulfate, lead chloride, lead nitrate, lead acetate, silver nitrate, chloroauric acid.

5. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 3, characterized in that: The crosslinking agent is one or a combination of salicylic acid, benzoic acid, p-hydroxybenzoic acid, p-formylbenzoic acid.

6. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 3, characterized in that: The plasticizer is one or a combination of glycerol, ethylene glycol, propylene glycol, butylene glycol.

7. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 3, characterized in that: The degree of alcoholysis of the polyvinyl alcohol PVA is ≥79%, and the degree of polymerization is 300-2400. The polyvinyl alcohol PVA includes any one of PVA-2499, PVA-1788, PVA-1799, and PVA-2388.

8. The degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 3, wherein: The antibacterial, mildew-proof and anti-swelling degradable film for medical and health use has antibacterial properties against Candida albicans > 99%, antibacterial properties against Escherichia coli > 99%, antibacterial properties against Staphylococcus aureus > 99%, mildew-proof level of 0-1, swelling rate tested by weight method ≤ 120%, surface resistance of 10 6 ~10 9 Ω, tensile strength > 17 N, tear strength > 0.5 N, water vapor transmission rate ≥ 550 g / m 2 / 24 h, hydrostatic pressure ≥ 1500 mmH20.

9. A method for preparing a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to any one of claims 1-8, characterized in that: It includes the following steps: Step 1, preparation of the mixed gel solution: Mix accurately measured polyvinyl alcohol PVA, crosslinking agent, plasticizer, and pure water evenly, heat up to 80-95°C and stir for 1-4 hours, then add the strong acid and weak base metal salt aqueous solution according to the ratio and stir for 1-4 hours to obtain the mixed gel solution. Step 2, cool the mixed gel solution in Step 1 to 50-65°C and add it into the slot coater. Set the die head temperature to 60-120°C, the discharge thickness to 65-350 microns, the dry film thickness to 20-50 microns, the solution viscosity to 4000-6000 centipoise, and the solid content to 15-30%. Prepare a medical and hygienic degradable film with antibacterial, antifungal, and anti-swelling properties by a one-step method.

10. The preparation method of a degradable film for medical and health use with antibacterial, mildew-proof and anti-swelling properties according to claim 9, characterized in that: The specific preparation method of the mixed gel solution in Step 1 is as follows: Prepare a strong acid and weak base metal salt aqueous solution with a concentration of 50-320 g / L. Add 20-28 parts of polyvinyl alcohol PVA, 1-5 parts of crosslinking agent, and 2-4 parts of plasticizer to 80-120 parts of pure water. Heat from room temperature to 80-95°C and stir for at least 2 hours, then add 80-120 parts of an anhydrous copper sulfate solution with a concentration of 50-320 g / L and stir for at least 2 hours to obtain the mixed gel solution.

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