Medical adhesive tape and preparation method thereof

Abstract

The invention relates to the technical field of medical adhesive tapes, and discloses a medical adhesive tape and a preparation method thereof.The preparation method comprises the following preparation steps that polyvinyl pyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water are mixed and stirred, and an antibacterial adhesive is obtained; coating the antibacterial adhesive on the surface of a non-woven fabric material, drying to obtain an adhesive layer, and adhering a fabric base material to the surface of the adhesive layer to obtain the medical adhesive tape. The composite antibacterial material in the antibacterial filler contains an antibacterial multilayer structure and shows excellent antibacterial activity, and the composite black phosphorus nanosheet is adhered between layers, so that the formed composite layered material has relatively high barrier property to oxygen, and the situation that black phosphorus is in contact with oxygen in the air and is easy to oxidize, resulting in failure of the antibacterial activity of the medical adhesive tape, is avoided, and the service life of the medical adhesive tape is prolonged. The formed composite layered material has good mechanical properties, can weaken the stress of the medical adhesive tape in a tensile test so as to disperse the pressure, and has good flexibility.

Description

Technical Field

[0001] The present invention relates to the technical field of medical tapes, and specifically relates to a medical tape and a preparation method thereof. Background Art

[0002] Medical tapes are products formed by coating an adhesive on a base material such as a polyethylene film, a thermoplastic polyurethane elastomer (TPU) film, or a foam, and then curling them into rolls or cutting them into sheets. Medical tapes are inexpensive and widely used. They can be used for hemostasis, closing wounds, surgical repair, and reconstructing damaged or degenerated soft tissues, playing an important and indispensable role in the field of healthcare. Adhesives generally have a high-molecular elastomer as the main body, and are mixed with appropriate tackifying resins, softeners, anti-aging agents, fillers, cross-linking agents and other additives through a glue-making process. According to different mixing methods, different forms of adhesive products such as solvent-based, water-based emulsion, and solvent-free can be made.

[0003] The antibacterial activity of medical tapes is limited, and bacteria are likely to grow inside the medical tapes or directly penetrate through the tapes into the wounds, causing infections. Adding black phosphorus to medical tapes can significantly improve their antibacterial activity and promote wound healing. However, black phosphorus is easily oxidized in the air, resulting in the failure of the antibacterial activity of medical tapes. Adding organic antibacterial agents to medical tapes and compounding them with inorganic materials such as black phosphorus nanosheets can greatly enhance the antibacterial activity of medical tapes. However, during the stretching process of medical tapes, the organic antibacterial agents are likely to migrate and precipitate in the adhesive layer of the medical tapes, affecting the antibacterial activity. Summary of the Invention

[0004] The present invention provides a medical tape and a preparation method thereof, which solve the problems of insufficient antibacterial activity of existing medical tapes and easy migration and precipitation of organic antibacterial agents in the adhesive layer of medical tapes.

[0005] The technical solution of the present invention:

[0006] A preparation method of a medical tape includes the following preparation steps:

[0007] S1. Mix polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water, and stir at 70 - 80 °C for 20 - 30 min to obtain an antibacterial adhesive;

[0008] S2. Coat the antibacterial adhesive on the surface of a non-woven fabric material, and dry it at 55 - 65 °C for 30 - 40 min to obtain an adhesive layer. Then, attach a fabric base material to the surface of the adhesive layer to obtain a medical tape;

[0009] The antibacterial filler is obtained by mixing and reacting a composite antibacterial material, carboxylated cellulose nanocrystals, a cross-linking agent, tannic acid and chitosan;

[0010] The composite antibacterial material is obtained by adsorbing an organic antibacterial agent on black phosphorus nanosheets loaded with metal-organic frameworks, and then mixing and reacting with graphene oxide modified with polydopamine;

[0011] The black phosphorus nanosheets loaded with metal-organic frameworks are obtained by reacting black phosphorus nanosheets with glucose, and then mixing and reacting with zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole;

[0012] Furthermore, the mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water is (50-60):(15-25):(5-10):(15-20):(100-120).

[0013] Furthermore, the thickness of the non-woven fabric material is 0.1-0.2 mm.

[0014] Furthermore, the thickness of the adhesive layer is 0.2-0.3 mm.

[0015] Furthermore, the fabric substrate is selected from one of polyethylene film, TPU film and foam.

[0016] Furthermore, the thickness of the fabric substrate is 0.05-0.15 mm.

[0017] Furthermore, the antibacterial filler is specifically prepared by the following steps:

[0018] A1. Add black phosphorus nanosheets and glucose to N,N-dimethylformamide, stir evenly, remove oxygen by bubbling with argon, seal, place in a reaction kettle, react at 170-190 °C for 2-4 h, centrifuge and collect the crude product at a rate of 8000-10000 r / min, wash and dry the crude product to obtain hydroxylated black phosphorus nanosheets;

[0019] A2. Add zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole to methanol, stir evenly, add sodium formate and hydroxylated black phosphorus nanosheets, stir evenly, pass in nitrogen, stir and react at 55-65 °C for 3-5 h, centrifuge and collect the product at a speed of 8000 r / min, wash and dry the product to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0020] A3. Add the organic antibacterial agent to ethanol, stir until completely dissolved, add the black phosphorus nanosheets loaded with metal-organic frameworks, stir and mix at a rate of 400-500 r / min for 20-30 min, let stand for 1-2 h, place in a water bath at 40-50 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0021] A4. Graphene oxide is added to deionized water. After ultrasonic dispersion, Tris-HCl buffer solution is added. After ultrasonic treatment, dopamine is added, and then ultrasonic dispersion is carried out. After centrifugation, washing and drying, polydopamine-modified graphene oxide is obtained;

[0022] A5. The polydopamine-modified graphene oxide is added to deionized water and stirred evenly. Composite black phosphorus nanosheets are added, and ultrasonic treatment is carried out at 40 - 60 KHz for 1 - 2 h. After filtration, washing and drying, a composite antibacterial material is obtained;

[0023] A6. Chitosan is added to deionized water and stirred at 35 - 40 °C for 20 - 30 min. A crosslinking agent, the composite antibacterial material, and carboxylated cellulose nanocrystals are added, and stirring is continued for 1 - 2 h. The gel is taken out, and the gel is washed and dried at room temperature overnight to obtain an antibacterial filler.

[0024] Further, in the above A1 reaction process, in the organic solvent N,N-dimethylformamide, the temperature is raised to 170 - 190 °C, and the reaction is carried out for 2 - 4 h. The black phosphorus nanosheets react with glucose to form a large number of hydroxyl groups on the surface of the black phosphorus nanosheets, improving the surface activity of the black phosphorus nanosheets, and hydroxylated black phosphorus nanosheets are obtained.

[0025] Further, in the above A2 reaction process, the zinc ions in zinc nitrate hexahydrate combine with the hydroxylated black phosphorus nanosheets, causing the zinc ions to deposit on the surface of the hydroxylated black phosphorus nanosheets. 2-methylimidazole and 2-aminobenzothiazole are used as organic ligands, and the zinc ions react with the organic ligands to form a porous zinc-based metal-organic framework on the surface of the hydroxylated black phosphorus nanosheets, and black phosphorus nanosheets loaded with metal-organic frameworks are obtained.

[0026] Further, in the above A3 reaction process, the organic antibacterial agent is dissolved in ethanol, and the formed solution is mixed with the black phosphorus nanosheets loaded with metal-organic frameworks. The porous structure on the surface of the black phosphorus nanosheets loaded with metal-organic frameworks has excellent adsorption performance, and can adsorb the organic antibacterial agent solution onto the black phosphorus nanosheets loaded with metal-organic frameworks. Moreover, the alcohol substances in the organic antibacterial agent can combine with the hydroxyl groups in the metal-organic framework. After drying to remove ethanol, the organic antibacterial agent acts on the black phosphorus nanosheets loaded with metal-organic frameworks, and composite black phosphorus nanosheets are obtained.

[0027] Further, in the above A4 reaction process, in the Tris-HCl buffer solution, dopamine can self-polymerize on the surface of graphene oxide to form polydopamine, forming polydopamine-modified graphene oxide, making graphene oxide have excellent adhesion performance and being conducive to adhesion on the surface of the composite black phosphorus nanosheets.

[0028] Furthermore, during the above A5 reaction process, the surface of polydopamine-modified graphene oxide contains a large number of phenolic hydroxyl groups, which have excellent adhesion properties and can adhere to the surface of composite black phosphorus nanosheets to obtain a composite layered material.

[0029] Furthermore, during the above A6 reaction process, the oxygen-containing functional groups in the chitosan molecular chain can crosslink with silver ions in the crosslinking agent silver nitrate through hydrogen bonds to form a crosslinked network structure. Moreover, the oxygen-containing functional groups in the composite antibacterial material and carboxylated cellulose nanocrystals can also bind to silver ions in silver nitrate through hydrogen bonds, enabling the composite antibacterial material and carboxylated cellulose nanocrystals to be embedded in the crosslinked network structure to form a hydrogel structure, that is, an antibacterial filler.

[0030] Furthermore, in step A1, the dosage ratio of black phosphorus nanosheets, glucose, and N,N-dimethylformamide is (0.1 - 0.2) g : (0.1 - 0.3) g : (90 - 110) mL.

[0031] Furthermore, in step A2, the dosage ratio of zinc nitrate hexahydrate, 2-aminobenzothiazole, 2-methylimidazole, methanol, sodium formate, and hydroxylated black phosphorus nanosheets is (2.2 - 2.4) g : (1.6 - 2) g : (2.6 - 2.8) g : (90 - 110) mL : (1 - 2) g : (3 - 4) g.

[0032] Furthermore, in step A3, the dosage ratio of the organic antibacterial agent, ethanol, and black phosphorus nanosheets loaded with metal-organic frameworks is (5 - 6) g : (45 - 55) mL : (2.6 - 2.8) g.

[0033] Furthermore, in step A4, the dosage ratio of graphene oxide, deionized water, Tris-HCl buffer solution, and dopamine is (1.5 - 1.7) g : (150 - 160) mL : (0.5 - 1) g : (0.6 - 0.8) g.

[0034] Furthermore, in step A5, the dosage ratio of polydopamine-modified graphene oxide, deionized water, and composite black phosphorus nanosheets is (1 - 1.4) g : (90 - 110) mL : (0.8 - 1.2) g.

[0035] Furthermore, in step A6, the dosage ratio of chitosan, deionized water, crosslinking agent, composite antibacterial material, and carboxylated cellulose nanocrystals is (6 - 6.4) g : (90 - 110) mL : (2.2 - 2.4) g : (1.1 - 1.3) g : (0.6 - 0.8) g.

[0036] Furthermore, the particle size of the black phosphorus nanosheets is 0.2 - 0.5 μm.

[0037] Furthermore, the organic antibacterial agent is tea tree oil extract powder.

[0038] Furthermore, the particle size of graphene oxide is 0.5 - 1 μm.

[0039] Furthermore, the crosslinking agent is silver nitrate.

[0040] Furthermore, the degree of deacetylation of chitosan is 90 - 92%, Shanghai Adamas Reagent Co., Ltd.

[0041] The present invention has the following beneficial effects:

[0042] (1) In the technical solution of the present invention, a zinc-based metal-organic framework with a network structure is formed on the surface of black phosphorus nanosheets to obtain black phosphorus nanosheets loaded with metal-organic frameworks. On the one hand, the synthesized metal-organic framework is a crystalline hybrid porous coordination material formed by the self-assembly of metal ions and organic ligands, which has excellent antibacterial activity. On the other hand, the porous structure of the metal-organic framework can adsorb air, avoiding direct contact between air and black phosphorus nanosheets, which may cause oxidation of black phosphorus nanosheets and affect antibacterial activity and mechanical properties. In addition, an uneven structure is formed on the black phosphorus nanosheets, increasing the contact area with bacteria and enhancing antibacterial activity; black phosphorus can generate reactive oxygen species under light or physiological conditions, which can damage the bacterial cell membrane, having a broad-spectrum bactericidal effect and being able to improve the antibacterial activity of the antibacterial tape.

[0043] (2) In the technical solution of the present invention, an organic antibacterial agent is adsorbed onto the black phosphorus nanosheets loaded with metal-organic frameworks to obtain composite black phosphorus nanosheets. The black phosphorus nanosheets loaded with metal-organic frameworks serve as the carrier structure of the organic antibacterial agent, which can load a relatively large amount of organic antibacterial agent and has excellent adsorption performance, increasing the interaction force with the organic antibacterial agent and avoiding the migration and precipitation of the organic antibacterial agent. In addition, the organic antibacterial agent forms an organic antibacterial layer on the surface of the black phosphorus nanosheets, compounding with the inorganic material black phosphorus nanosheets to complete the organic-inorganic synergistic antibacterial effect, greatly enhancing the antibacterial activity of the medical tape.

[0044] (3) In the technical solution of the present invention, the surface of polydopamine-modified graphene oxide contains a large number of phenolic hydroxyl groups, having excellent adhesion performance and being able to adhere to the surface of composite black phosphorus nanosheets to obtain a composite layered material. On the one hand, the polydopamine-modified graphene oxide and the composite black phosphorus nanosheets form an antibacterial multi-layer structure, showing excellent antibacterial activity, and adhering the composite black phosphorus nanosheets between the layers. The formed composite layered material has a high barrier performance to oxygen, avoiding the easy oxidation of black phosphorus when contacting with oxygen in the air, resulting in the failure of the antibacterial activity of the medical tape and further improving the stability of the composite black phosphorus nanosheets. On the other hand, the formed composite layered material has good mechanical properties, which can weaken the stress in the tensile test of the medical tape, and then disperse the pressure, having good flexibility, reducing the pain of patients and contributing to the promotion of wound healing.

[0045] (4) In the technical solution of the present invention, the composite antibacterial material and the carboxylated cellulose nanocrystals are embedded in the cross-linked network structure. On the one hand, chitosan and silver ions in the cross-linking agent silver nitrate are cross-linked through hydrogen bonds to form an antibacterial cross-linked network structure, further enhancing the antibacterial activity. Moreover, due to the excellent aspect ratio of the carboxylated cellulose nanocrystals, a dynamic cross-linked network structure capable of forming an absorption force can be formed during gel formation, enhancing the tensile properties of the medical tape. In addition, the composite antibacterial material is embedded in the antibacterial cross-linked network structure, enhancing the force on the antibacterial material. On the other hand, during the continuous stretching process of the medical tape, the substances migrated or volatilized from the organic antibacterial agent tea tree oil extract in the composite antibacterial material contain a large amount of alcohol substances. The alcohol hydroxyl group structure in the alcohol substances can combine with the composite antibacterial material and the carboxylated cellulose nanocrystals through hydrogen bonds, fixing the migrated or volatilized tea tree oil extract in the gel network structure, avoiding the reduction of antibacterial activity caused by the volatilization of the organic antibacterial agent, and further enhancing the cross-linking density and improving the mechanical properties of the medical tape. Detailed implementation mode

[0046] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0047] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0048] The organic antibacterial agent is tea tree oil extraction powder, batch number 20160922, Wuxi Chenfang Biotechnology Co., Ltd.

[0049] The degree of deacetylation of chitosan is 99%, Shanghai Adamas Reagent Co., Ltd.

[0050] Carboxylated cellulose nanocrystals, Qingdao Mingchuang Intelligent Technology Co., Ltd.

[0051] The fabric substrate is selected from polyethylene film.

[0052] The particle size of black phosphorus nanosheets is 0.5 μm.

[0053] The particle size of graphene oxide is 0.8 μm, Zhongke Leiming (Beijing) Technology Co., Ltd.

[0054] The black phosphorus nanosheets are specifically prepared by the following steps:

[0055] Add 0.5 g of black phosphorus crystals to 200 mL of N-methylpyrrolidone, ultrasonically treat for 6 h at a frequency of 23 kHz, centrifuge at a rate of 7000 r / min for 15 min, collect the supernatant and then centrifuge at a rate of 12000 r / min for 15 min, collect the precipitate, wash the precipitate with isopropanol 3 times, and dry in an oven at 45 °C for 24 h to obtain black phosphorus nanosheets.

[0056] The antibacterial filler of Example 1 is specifically prepared by the following steps:

[0057] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge to collect the crude product at a rate of 9000 r / min, wash the crude product with N,N-dimethylformamide 3 times and isopropanol 3 times, and dry in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0058] A2. Add 2.3 g of zinc nitrate hexahydrate, 1.8 g of 2-aminobenzothiazole and 2.7 g of 2-methylimidazole to 100 mL of methanol, stir evenly, add 1.5 g of sodium formate and 3.5 g of hydroxylated black phosphorus nanosheets, stir evenly, introduce nitrogen, stir and react at 60 °C for 3 - 5 h, centrifuge to collect the product at a speed of 8000 r / min, wash the product with methanol 3 times and deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0059] A3. Add 5.5 g of tea tree oil extraction powder to 50 mL of ethanol, stir until completely dissolved, add 2.7 g of black phosphorus nanosheets loaded with metal-organic frameworks, stir and mix at a rate of 450 r / min for 25 min, let stand for 1.5 h, place in a water bath at 45 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0060] A4. Add 1.6 g of graphene oxide to 150 mL of deionized water, ultrasonically disperse for 1 h, add 0.8 g of Tris-HCl buffer solution with a pH of 8.5, ultrasonically disperse at 25 °C and 2000 r / min for 20 min, add 0.7 g of dopamine, ultrasonically disperse at 30 °C and 2000 r / min for 2 h, centrifuge and separate at a rotation speed of 10000 r / min for 60 min, collect the product, wash with ethanol 2 times, and dry in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide;

[0061] A5. Add 1.2 g of polydopamine-modified graphene oxide to 100 mL of deionized water, stir evenly, add 1 g of composite black phosphorus nanosheets, sonicate for 1.5 h at 50 KHz, filter, wash with deionized water three times, and dry overnight in an oven at 50 °C to obtain a composite antibacterial material;

[0062] A6. Add 6.2 g of chitosan to 100 mL of deionized water, stir at 38 °C for 25 min, add 2.3 g of silver nitrate, 1.2 g of the composite antibacterial material, and 0.7 g of carboxylated cellulose nanocrystals, continue to stir for 1.5 h, take out the gel, wash the gel three times with deionized water, and dry overnight at room temperature to obtain an antibacterial filler.

[0063] Comparative Example 1 The difference between this comparative example and Example 1 is that the black phosphorus nanosheets loaded with metal-organic frameworks are replaced by hydroxylated black phosphorus nanosheets, and the remaining steps and raw materials are the same as those in Example 1.

[0064] The antibacterial filler is specifically prepared by the following steps:

[0065] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge and collect the crude product at a rate of 9000 r / min, wash the crude product three times with N,N-dimethylformamide and three times with isopropanol, and dry in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0066] A2. Add 5.5 g of tea tree oil extract powder to 50 mL of ethanol, stir until completely dissolved, add 2.7 g of hydroxylated black phosphorus nanosheets, stir and mix at a rate of 450 r / min for 25 min, let stand for 1.5 h, place in a water bath at 45 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0067] A3. Add 1.6 g of graphene oxide to 150 mL of deionized water, ultrasonically disperse for 1 h, add 0.8 g of Tris-HCl buffer solution with a pH of 8.5, ultrasonically disperse at 25 °C and 2000 r / min for 20 min, add 0.7 g of dopamine, ultrasonically disperse at 30 °C and 2000 r / min for 2 h, centrifuge and separate at a speed of 10000 r / min for 60 min, wash the collected product twice with ethanol, and dry in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide;

[0068] A4. Add 1.2 g of polydopamine-modified graphene oxide to 100 mL of deionized water, stir evenly, add 1 g of composite black phosphorus nanosheets, sonicate for 1.5 h at 50 KHz, filter, wash with deionized water three times, and dry overnight in an oven at 50 °C to obtain a composite antibacterial material;

[0069] A5. Add 6.2 g of chitosan to 100 mL of deionized water, stir at 38 °C for 25 min, add 2.3 g of silver nitrate, 1.2 g of the composite antibacterial material, and 0.7 g of carboxylated cellulose nanocrystals, continue to stir for 1.5 h, take out the gel, wash the gel three times with deionized water, and dry overnight at room temperature to obtain an antibacterial filler.

[0070] Comparative Example 2 The difference between this comparative example and Example 1 is that the composite black phosphorus nanosheets are replaced with black phosphorus nanosheets loaded with metal-organic frameworks, and the remaining steps and raw materials are the same as those in Example 1.

[0071] The antibacterial filler is specifically prepared by the following steps:

[0072] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge to collect the crude product at a rate of 9000 r / min, wash the crude product three times with N,N-dimethylformamide and three times with isopropanol, and dry in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0073] A2. Add 2.3 g of zinc nitrate hexahydrate, 1.8 g of 2-aminobenzothiazole, and 2.7 g of 2-methylimidazole to 100 mL of methanol, stir evenly, add 1.5 g of sodium formate and 3.5 g of hydroxylated black phosphorus nanosheets, stir evenly, introduce nitrogen, stir and react at 60 °C for 3 - 5 h, centrifuge to collect the product at a speed of 8000 r / min, wash the product three times with methanol and three times with deionized water, and dry in an oven at 60 °C for 10 min to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0074] A3. Add 1.6 g of graphene oxide to 150 mL of deionized water, ultrasonically disperse for 1 h, add 0.8 g of Tris-HCl buffer solution with a pH of 8.5, ultrasonically disperse at 25 °C and 2000 r / min for 20 min, add 0.7 g of dopamine, ultrasonically disperse at 30 °C and 2000 r / min for 2 h, centrifuge and separate at a rotation speed of 10000 r / min for 60 min, collect the product, wash it twice with ethanol, and dry in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide;

[0075] A4. Add 1.2 g of polydopamine-modified graphene oxide to 100 mL of deionized water, stir evenly, add 1 g of black phosphorus nanosheets loaded with metal-organic frameworks, ultrasonically treat for 1.5 h at 50 KHz, filter, wash with deionized water 3 times, and dry overnight in an oven at 50 °C to obtain a composite antibacterial material;

[0076] A5. Add 6.2 g of chitosan to 100 mL of deionized water, stir at 38 °C for 25 min, add 2.3 g of silver nitrate, 1.2 g of the composite antibacterial material, and 0.7 g of carboxylated cellulose nanocrystals, continue to stir for 1.5 h, take out the gel, wash the gel with deionized water 3 times, and dry overnight at room temperature to obtain an antibacterial filler.

[0077] Comparative Example 3 The difference between this comparative example and Example 1 is that polydopamine-modified graphene oxide is not added, and the remaining steps and raw materials are the same as those in Example 1.

[0078] The antibacterial filler is specifically prepared by the following steps:

[0079] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge to collect the crude product at a rate of 9000 r / min, wash the crude product with N,N-dimethylformamide 3 times and isopropanol 3 times, and dry in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0080] A2. Add 2.3 g of zinc nitrate hexahydrate, 1.8 g of 2-aminobenzothiazole, and 2.7 g of 2-methylimidazole to 100 mL of methanol, stir evenly, add 1.5 g of sodium formate and 3.5 g of hydroxylated black phosphorus nanosheets, stir evenly, introduce nitrogen, stir and react at 60 °C for 3 - 5 h, centrifuge to collect the product at a speed of 8000 r / min, wash the product with methanol 3 times and deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0081] A3. Add 5.5 g of tea tree oil extraction powder to 50 mL of ethanol, stir until completely dissolved, add 2.7 g of black phosphorus nanosheets loaded with metal-organic frameworks, stir and mix at a rate of 450 r / min for 25 min, let stand for 1.5 h, place in a water bath at 45 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0082] A4. Add 6.2 g of chitosan to 100 mL of deionized water, stir at 38 °C for 25 min, add 2.3 g of silver nitrate, 1.2 g of composite black phosphorus nanosheets, and 0.7 g of carboxylated cellulose nanocrystals, continue to stir for 1.5 h, take out the gel, wash the gel 3 times with deionized water, and dry it overnight at room temperature to obtain the antibacterial filler.

[0083] Comparative Example 4 The difference between this comparative example and Example 1 is that carboxylated cellulose nanocrystals were not added, and the remaining steps and raw materials were the same as those in Example 1.

[0084] The antibacterial filler is specifically prepared by the following steps:

[0085] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge and collect the crude product at a speed of 9000 r / min, wash the crude product 3 times with N,N-dimethylformamide and 3 times with isopropanol, and dry it in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0086] A2. Add 2.3 g of zinc nitrate hexahydrate, 1.8 g of 2-aminobenzothiazole, and 2.7 g of 2-methylimidazole to 100 mL of methanol, stir evenly, add 1.5 g of sodium formate and 3.5 g of hydroxylated black phosphorus nanosheets, stir evenly, introduce nitrogen, stir and react at 60 °C for 3 - 5 h, centrifuge and collect the product at a speed of 8000 r / min, wash the product 3 times with methanol and 3 times with deionized water, and dry it in an oven at 60 °C for 10 min to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0087] A3. Add 5.5 g of tea tree oil extraction powder to 50 mL of ethanol, stir until completely dissolved, add 2.7 g of black phosphorus nanosheets loaded with metal-organic frameworks, stir and mix at a speed of 450 r / min for 25 min, let stand for 1.5 h, place in a water bath at 45 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0088] A4. Add 1.6 g of graphene oxide to 150 mL of deionized water, ultrasonically disperse for 1 h, add 0.8 g of Tris-HCl buffer solution with a pH of 8.5, ultrasonically disperse at 25 °C and 2000 r / min for 20 min, add 0.7 g of dopamine, ultrasonically disperse at 30 °C and 2000 r / min for 2 h, centrifuge and separate at a speed of 10000 r / min for 60 min, wash the collected product 2 times with ethanol, and dry it in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide;

[0089] A5. Add 1.2 g of polydopamine-modified graphene oxide to 100 mL of deionized water, stir evenly, add 1 g of composite black phosphorus nanosheets, ultrasonically treat for 1.5 h at 50 KHz, filter, wash with deionized water 3 times, and dry overnight in an oven at 50 °C to obtain a composite antibacterial material;

[0090] A6. Add 6.2 g of chitosan to 100 mL of deionized water, stir at 38 °C for 25 min, add 2.3 g of silver nitrate and 1.2 g of the composite antibacterial material, continue to stir for 1.5 h, take out the gel, wash the gel with deionized water 3 times, and dry overnight at room temperature to obtain an antibacterial filler.

[0091] Comparative Example 5 The difference between this comparative example and Example 1 is that no chitosan and silver nitrate are added, and the remaining steps and raw materials are the same as those in Example 1.

[0092] The antibacterial filler is specifically prepared by the following steps:

[0093] A1. Add 0.15 g of black phosphorus nanosheets and 0.2 g of glucose to 100 mL of N,N-dimethylformamide, stir evenly, bubble with argon for 30 min to remove oxygen, then seal, place in a reaction kettle, react at 180 °C for 3 h, centrifuge to collect the crude product at a rate of 9000 r / min, wash the crude product with N,N-dimethylformamide 3 times and isopropanol 3 times, and dry in an oven at 70 °C for 10 min to obtain hydroxylated black phosphorus nanosheets;

[0094] A2. Add 2.3 g of zinc nitrate hexahydrate, 1.8 g of 2-aminobenzothiazole, and 2.7 g of 2-methylimidazole to 100 mL of methanol, stir evenly, add 1.5 g of sodium formate and 3.5 g of hydroxylated black phosphorus nanosheets, stir evenly, pass in nitrogen, stir and react at 60 °C for 3 - 5 h, centrifuge to collect the product at a speed of 8000 r / min, wash the product with methanol 3 times and deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain black phosphorus nanosheets loaded with metal-organic frameworks;

[0095] A3. Add 5.5 g of tea tree oil extraction powder to 50 mL of ethanol, stir until completely dissolved, add 2.7 g of black phosphorus nanosheets loaded with metal-organic frameworks, stir and mix at a rate of 450 r / min for 25 min, let stand for 1.5 h, place in a water bath at 45 °C, heat until the ethanol evaporates, take out to obtain composite black phosphorus nanosheets;

[0096] A4. Add 1.6 g of graphene oxide to 150 mL of deionized water, ultrasonically disperse for 1 h, add 0.8 g of Tris-HCl buffer with a pH of 8.5, ultrasonically disperse for 20 min at 25 °C and 2000 r / min, add 0.7 g of dopamine, ultrasonically disperse for 2 h at 30 °C and 2000 r / min, centrifuge at a speed of 10000 r / min for 60 min, collect the product, wash it twice with ethanol, and dry it in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide;

[0097] A5. Add 1.2 g of polydopamine-modified graphene oxide to 100 mL of deionized water, stir evenly, add 1 g of composite black phosphorus nanosheets, ultrasonically treat at 50 KHz for 1.5 h, filter, wash with deionized water three times, and dry overnight in an oven at 50 °C to obtain a composite antibacterial material.

[0098] A6. Mix 1.2 g of the composite antibacterial material and 0.7 g of carboxylated cellulose nanocrystals to obtain an antibacterial filler.

[0099] Example 2 A preparation method of a medical tape, comprising the following preparation steps:

[0100] S1. Mix polyvinylpyrrolidone, polyvinyl alcohol, the antibacterial filler prepared in Example 1, glycerol and deionized water, and stir at 70 °C for 20 min to obtain an antibacterial adhesive;

[0101] S2. Coating the antibacterial adhesive on the surface of the non-woven fabric by a coating machine, drying at 55 °C for 30 min to obtain an adhesive layer, and laminating a fabric substrate on the surface of the adhesive layer to obtain a medical tape;

[0102] Among them, the mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water is 50:15:5:15:100;

[0103] The thickness of the non-woven fabric is 0.1 mm.

[0104] The thickness of the adhesive layer is 0.2 mm.

[0105] The fabric substrate is selected from a polyethylene film.

[0106] The thickness of the fabric substrate is 0.05 mm.

[0107] Example 3 A preparation method of a medical tape, comprising the following preparation steps:

[0108] S1. Mix polyvinylpyrrolidone, polyvinyl alcohol, the antibacterial filler prepared in Example 1, glycerol and deionized water, and stir at 75 °C for 25 min to obtain an antibacterial adhesive;

[0109] S2. Coating the antibacterial adhesive on the surface of the non-woven fabric material, drying it at 60 °C for 35 min to obtain the adhesive layer, and laminating the fabric substrate on the surface of the adhesive layer to obtain the medical tape;

[0110] Among them, the mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water is 55:20:8:18:110;

[0111] The thickness of the non-woven fabric material is 0.15 mm.

[0112] The thickness of the adhesive layer is 0.1 mm.

[0113] The fabric substrate is selected from polyethylene films.

[0114] The thickness of the fabric substrate is 0.1 mm.

[0115] Example 4 A method for preparing a medical tape, comprising the following preparation steps:

[0116] S1. Mixing polyvinylpyrrolidone, polyvinyl alcohol, the antibacterial filler prepared in Example 1, glycerol and deionized water, and stirring at 80 °C for 30 min to obtain the antibacterial adhesive;

[0117] S2. Coating the antibacterial adhesive on the surface of the non-woven fabric material through a coating machine, drying it at 65 °C for 40 min to obtain the adhesive layer, and laminating the fabric substrate on the surface of the adhesive layer to obtain the medical tape;

[0118] Among them, the mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water is 60:25:10:20:120;

[0119] The thickness of the non-woven fabric material is 0.2 mm.

[0120] The thickness of the adhesive layer is 0.3 mm.

[0121] The fabric substrate is selected from polyethylene films.

[0122] The thickness of the fabric substrate is 0.15 mm.

[0123] Comparative Example 6 The difference between this comparative example and Example 3 is that the antibacterial filler prepared in Example 1 is replaced with the substance prepared in Comparative Example 1, and the remaining steps are the same as those in Example 3.

[0124] Comparative Example 7 The difference between this comparative example and Example 3 is that the antibacterial filler prepared in Example 1 is replaced with the substance prepared in Comparative Example 2, and the remaining steps are the same as those in Example 3.

[0125] Comparative Example 8 The difference between this comparative example and Example 3 is that the antibacterial filler prepared in Example 1 is replaced with the substance prepared in Comparative Example 3, and the remaining steps are the same as those in Example 3.

[0126] Comparative Example 9 The difference between this comparative example and Example 3 is that the antibacterial filler prepared in Example 1 is replaced with the substance prepared in Comparative Example 4, and the remaining steps are the same as those in Example 3.

[0127] Comparative Example 10 The difference between this comparative example and Example 3 is that the antibacterial filler prepared in Example 1 is replaced with the substance prepared in Comparative Example 5, and the remaining steps are the same as those in Example 3.

[0128] Now, the performance of the medical tapes prepared in Examples 2 - 4 and Comparative Examples 6 - 10 was tested.

[0129] Tensile property test: The medical tape samples prepared above were cut into strip-shaped specimens with a size of 6 cm × 1 cm, and tested on an ELF-3200 type biomaterial testing machine at a tensile speed of 50 mm / min.

[0130] Elongation at break property test: According to the standard of GB / T 30776-2014 "Test Method for Tensile Strength and Elongation at Break of Adhesive Tape", the elongation at break of the medical tapes prepared above was tested.

[0131] Antibacterial property test: Take 0.1 g of the medical tape prepared above and mix it with 10 mL of 1×10 7 CFU / mL Escherichia coli suspension / Staphylococcus aureus suspension and put them into a test tube, place it on a constant temperature shaking incubator and culture at 37 °C at a rotation speed of 120 r / min for 4 h. This is used as the experimental group, and the one without mixing the medical tape prepared above is used as the blank group. Take out the bacterial suspensions of the experimental group and the blank group, dilute them to 1×10 5 CFU / mL respectively, take 100 μL of each bacterial suspension and coat it on the surface of the agar plate, put it into a 37 °C shaking incubator and incubate for 24 h. Calculate the antibacterial rate by the plate colony counting method. Antibacterial rate = (b1 - b2) / b1 × 100%, where b1 is the number of colonies in the blank group and b2 is the number of colonies in the experimental group.

[0132] The measured data are shown in Table 1 below:

[0133] Table 1

[0134]

[0135]

[0136] In Comparative Example 6, the antibacterial filler prepared by replacing the metal-organic framework-loaded black phosphorus nanosheets with hydroxylated black phosphorus nanosheets was added to the medical tape, and its antibacterial performance and mechanical properties decreased. This proved that forming a metal-organic framework on the surface of black phosphorus nanosheets could serve as a carrier structure for organic antibacterial agents, increase the interaction force with organic antibacterial agents, avoid the migration and precipitation of organic antibacterial agents, and the porous structure of the metal-organic framework could adsorb air, preventing direct contact between air and black phosphorus nanosheets, which would cause the oxidation of black phosphorus nanosheets, affecting antibacterial activity and mechanical properties. Additionally, it could form a concave-convex structure on the black phosphorus nanosheets, increasing the contact area with bacteria and enhancing antibacterial activity. In Comparative Example 6, the lack of a metal-organic framework led to a decrease in antibacterial performance and mechanical properties.

[0137] In Comparative Example 7, the antibacterial filler prepared by replacing the composite black phosphorus nanosheets with metal-organic framework-loaded black phosphorus nanosheets was added to the medical tape, and its antibacterial performance decreased. This proved that adsorbing organic antibacterial agents onto metal-organic framework-loaded black phosphorus nanosheets formed an organic antibacterial layer on the surface of black phosphorus nanosheets, and the inorganic material black phosphorus nanosheets were compounded to achieve an organic-inorganic synergistic antibacterial effect, greatly enhancing the antibacterial activity of the medical tape. In Comparative Example 7, the lack of organic antibacterial agents led to a decrease in antibacterial performance.

[0138] In Comparative Example 8, the antibacterial filler without adding polydopamine-modified graphene oxide was added to the medical tape, and its antibacterial performance and mechanical properties decreased. This proved that polydopamine-modified graphene oxide adhered to the surface of composite black phosphorus nanosheets to form an antibacterial multilayer structure, showing excellent antibacterial activity, and adhered the composite black phosphorus nanosheets between layers. The formed composite layered material had a high barrier property to oxygen, further improving the stability of composite black phosphorus nanosheets, and the formed composite layered material had good mechanical properties, which could weaken the stress of the tensile test of the medical tape and thus disperse the pressure. In Comparative Example 8, the lack of an antibacterial multilayer structure led to a decrease in antibacterial performance and mechanical properties.

[0139] In Comparative Example 9, the antibacterial filler without adding carboxylated cellulose nanocrystals was added to the medical tape, and its mechanical strength and antibacterial performance decreased. This proved that the migrated or volatilized substances of the organic antibacterial agent tea tree oil extract could bind to carboxylated cellulose nanocrystals through hydrogen bonds, fixing the migrated or volatilized tea tree oil extract in the gel network structure, avoiding the reduction of antibacterial activity caused by the volatilization of the organic antibacterial agent, and further enhancing the crosslinking density and improving the mechanical properties of the medical tape. In addition, carboxylated cellulose nanocrystals could form a dynamic crosslinked network structure that absorbed gravity, enhancing the tensile properties of the medical tape. In Comparative Example 9, the lack of carboxylated cellulose nanocrystals led to a decrease in mechanical strength and antibacterial performance.

[0140] The antibacterial filler prepared without adding chitosan and silver nitrate in Comparative Example 10 was added to the medical tape, and its mechanical strength and antibacterial performance decreased. This proved that the silver ions in chitosan and the cross-linking agent silver nitrate were cross-linked by hydrogen bonds to form an antibacterial network structure, which had good antibacterial activity and mechanical properties. Moreover, embedding the composite antibacterial material into the antibacterial network structure enhanced the force on the antibacterial material and avoided the migration and precipitation of the antibacterial material. However, the gel structure formed by chitosan and silver nitrate was lacking in Comparative Example 10, resulting in a decrease in its antibacterial performance and mechanical properties.

[0141] The data in Table 1 show that the medical tapes prepared in Examples 2-4 meet the requirements of the test performance, while the medical tapes prepared in Comparative Examples 6-10 do not meet the performance requirements standards, indicating that the medical tapes prepared by the present invention have excellent antibacterial performance and tensile properties.

[0142] In the description of the specification, the description of reference terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0143] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the invention or exceed the scope defined by the claims of this patent, they should fall within the protection scope of the present invention.

Claims

1. A method for preparing a medical tape, characterized in that: The method comprises the following preparation steps: S1. Mix polyvinyl pyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water, and stir at 70-80° C. for 20-30 min to obtain an antibacterial adhesive; S2. The antibacterial adhesive is applied to the surface of the non-woven fabric, and dried at 55-65°C for 30-40 min to obtain an adhesive layer, and a fabric substrate is attached to the surface of the adhesive layer to obtain a medical tape; The antibacterial filler is obtained by a mixed reaction of a composite antibacterial material, carboxylated cellulose nanocrystals, a cross-linking agent, tannic acid and chitosan; The composite antibacterial material is obtained by mixing and reacting the black phosphorus nanosheets loaded with metal organic frameworks with the organic antibacterial agent and then with the graphene oxide modified with polydopamine. The metal organic framework-loaded black phosphorus nanosheets are obtained by reacting the black phosphorus nanosheets with glucose and then mixing and reacting with zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole.

2. The method for preparing a medical tape according to claim 1, characterized in that: The particle size of the black phosphorus nanosheet is 0.2-0.5 μm.

3. The method for preparing a medical tape according to claim 1, characterized in that: The organic antibacterial agent is tea tree oil extract powder.

4. The method for preparing a medical tape according to claim 1, characterized in that: The graphene oxide particle size is 0.5-1 μm.

5. The method for preparing a medical tape according to claim 1, characterized in that: The cross-linking agent is silver nitrate.

6. The method for preparing a medical tape according to claim 1, characterized in that: The chitosan has a deacetylation degree of 90-92%.

7. The method for preparing a medical tape according to claim 1, characterized in that: The mass ratio of polyvinyl pyrrolidone, polyvinyl alcohol, antibacterial filler, glycerol and deionized water is (50-60):(15-25):(5-10):(15-20):(100-120).

8. The method for preparing a medical tape according to claim 1, characterized in that: The thickness of the non-woven fabric is 0.1-0.2 mm; the thickness of the adhesive layer is 0.2-0.3 mm.

9. The method for preparing a medical tape according to claim 1, characterized in that: The fabric substrate is selected from one of PE film, TPU film and foam; the thickness of the fabric substrate is 0.05-0.15 mm.

10. A medical tape prepared by the method for preparing a medical tape according to any one of claims 1 to 9.

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