A medical adhesive tape and its preparation method

Abstract

This invention relates to the field of medical tape technology and discloses a medical tape and its preparation method, comprising the following steps: mixing polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water, stirring to obtain an antibacterial adhesive; coating the antibacterial adhesive onto the surface of a nonwoven fabric, drying to obtain an adhesive layer; and bonding a fabric substrate to the adhesive layer to obtain the medical tape. The antibacterial filler contains a composite antibacterial material with a multilayered antibacterial structure, exhibiting excellent antibacterial activity. Furthermore, the composite black phosphorus nanosheets are adhered between the layers, forming a composite layered material with high oxygen barrier properties, preventing black phosphorus from easily oxidizing upon contact with oxygen in the air, thus avoiding the loss of antibacterial activity of the medical tape. The formed composite layered material also possesses good mechanical properties, can weaken the stress in the tensile test of the medical tape, thereby distributing pressure, and has good flexibility.

Description

Technical Field

[0001] This invention relates to the field of medical tape technology, specifically to a medical tape and its preparation method. Background Technology

[0002] Medical tape is a product made by coating a substrate such as polyethylene film, thermoplastic polyurethane elastomer (TPU) film, or foam with adhesive through a coating process, and then rolling it into rolls or cutting it into sheets. Medical tape is inexpensive and widely used, serving purposes such as hemostasis, wound closure, surgical repair, and reconstruction of damaged or degenerated soft tissue, playing an indispensable role in the healthcare field. Adhesives are generally based on high-molecular-weight elastomers, combined with appropriate tackifying resins, softeners, antioxidants, fillers, crosslinking agents, and other additives through a molding process. Depending on the mixing method, different forms of adhesive products can be produced, such as solvent-based, water-emulsion, and solvent-free adhesives.

[0003] Medical tape has limited antibacterial activity, and bacteria can easily grow inside it or directly enter wounds through the tape, causing infection. Adding black phosphorus to medical tape can significantly improve its antibacterial activity and promote wound healing, but black phosphorus is easily oxidized in the air, causing the antibacterial activity of the medical tape to be lost. Adding organic antibacterial agents to medical tape and compounding them with inorganic material black phosphorus nanosheets greatly enhances the antibacterial activity of the medical tape, but during the stretching process, the organic antibacterial agents are prone to migrate and precipitate out of the adhesive layer of the medical tape, affecting the antibacterial activity. Summary of the Invention

[0004] This invention provides a medical tape and its preparation method, which solves the problems of insufficient antibacterial activity of existing medical tapes and the 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 method for preparing medical adhesive tape includes the following preparation steps:

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

[0008] S2. Apply antibacterial adhesive to the surface of non-woven fabric and dry it at 55-65℃ for 30-40 minutes to obtain an adhesive layer. Then, attach the fabric substrate to the surface of the adhesive layer to obtain medical tape.

[0009] The antibacterial filler is obtained by mixing and reacting composite antibacterial materials, carboxylated cellulose nanocrystals, crosslinking agents, tannic acid and chitosan;

[0010] The composite antibacterial material is obtained by mixing and reacting black phosphorus nanosheets loaded with metal-organic frameworks to adsorb organic antibacterial agents, and then with polydopamine-modified graphene oxide.

[0011] The black phosphorus nanosheets loaded with metal-organic frameworks are obtained by reacting black phosphorus nanosheets with glucose, followed by a reaction with zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole.

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

[0013] Furthermore, the thickness of the nonwoven fabric is 0.1-0.2mm.

[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 0.05-0.15mm.

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

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

[0019] A2. Add zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole to methanol, stir until homogeneous, add sodium formate and hydroxylated black phosphorus nanosheets, stir until homogeneous, purge with nitrogen, stir and react at 55-65℃ for 3-5h, centrifuge at 8000r / min to collect the product, wash the product, dry it to obtain black phosphorus nanosheets loaded with metal-organic framework;

[0020] A3. Add the organic antibacterial agent to ethanol and stir until completely dissolved. Add the black phosphorus nanosheets loaded with metal-organic framework and stir at a rate of 400-500 r / min for 20-30 min. Let stand for 1-2 h and place in a water bath at 40-50℃. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

[0021] A4. Add graphene oxide to deionized water, disperse it by sonication, add Tris-HCl buffer, sonicate it, add dopamine, disperse it by sonication again, centrifuge, wash and dry to obtain polydopamine-modified graphene oxide.

[0022] A5. Add polydopamine-modified graphene oxide to deionized water, stir evenly, add composite black phosphorus nanosheets, sonicate at 40-60KHz for 1-2 hours, filter, wash, and dry to obtain composite antibacterial material;

[0023] A6. Add chitosan to deionized water and stir at 35-40℃ for 20-30 minutes. Add crosslinking agent, composite antibacterial material, and carboxylated cellulose nanocrystals. Continue stirring for 1-2 hours. Remove the gel, wash it, and dry it at room temperature overnight to obtain the antibacterial filler.

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

[0025] Furthermore, during the A2 reaction process described above, the hydroxylated black phosphorus nanosheets combine with zinc ions in zinc nitrate hexahydrate, causing zinc ions to deposit on the surface of the hydroxylated black phosphorus nanosheets. 2-methylimidazole and 2-aminobenzothiazole serve 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, thus obtaining black phosphorus nanosheets loaded with a metal-organic framework.

[0026] Furthermore, in the A3 reaction process described above, the organic antibacterial agent is dissolved in ethanol, and the resulting solution is mixed with black phosphorus nanosheets loaded with a metal-organic framework. The porous structure on the surface of the black phosphorus nanosheets loaded with a metal-organic framework has excellent adsorption properties, which can adsorb the organic antibacterial agent solution onto the black phosphorus nanosheets loaded with a metal-organic framework. Moreover, the alcohols in the organic antibacterial agent can combine with the hydroxyl groups in the metal-organic framework. After drying and removing the ethanol, the organic antibacterial agent acts on the black phosphorus nanosheets loaded with a metal-organic framework, resulting in composite black phosphorus nanosheets.

[0027] Furthermore, during the A4 reaction described above, in the Tris-HCl buffer solution, dopamine can self-polymerize on the surface of graphene oxide to form polydopamine, thus forming polydopamine-modified graphene oxide. This gives the graphene oxide excellent adhesion properties, which is beneficial for adhering to the surface of composite black phosphorus nanosheets.

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

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

[0030] Further, in step A1, the 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] Further, in step A2, the 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 ratio of organic antibacterial agent, ethanol, and black phosphorus nanosheets loaded with metal-organic framework is (5-6)g:(45-55)mL:(2.6-2.8)g.

[0033] Further, in step A4, the ratio of graphene oxide, deionized water, Tris-HCl buffer, 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 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] Further, in step A6, the 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 black phosphorus nanosheets have a particle size of 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 framework. 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 would lead to oxidation of black phosphorus nanosheets and affect antibacterial activity and mechanical properties. In addition, the formation of an uneven structure on the black phosphorus nanosheets increases the contact area with bacteria and enhances antibacterial activity. Black phosphorus can generate reactive oxygen species under light or physiological conditions, which can destroy bacterial cell membranes and have a broad-spectrum bactericidal effect, which can improve the antibacterial activity of antibacterial tape.

[0043] (2) In the technical solution of the present invention, the organic antibacterial agent is adsorbed onto the black phosphorus nanosheets loaded with a metal-organic framework to obtain composite black phosphorus nanosheets. The black phosphorus nanosheets loaded with a metal-organic framework serve as a carrier structure for the organic antibacterial agent, which can load a large amount of organic antibacterial agent and has excellent adsorption performance, which increases the force on the organic antibacterial agent and prevents the organic antibacterial agent from migrating and precipitating. In addition, the organic antibacterial agent forms an organic antibacterial layer on the surface of the black phosphorus nanosheets. Combined with the inorganic material black phosphorus nanosheets, the organic-inorganic synergistic antibacterial effect is achieved, which greatly enhances the antibacterial activity of the medical tape.

[0044] (3) In the technical solution of the present invention, the polydopamine-modified graphene oxide surface contains a large number of phenolic hydroxyl groups, which have excellent adhesion properties and can be attached to the surface of composite black phosphorus nanosheets to obtain a composite layered material. On the one hand, the polydopamine-modified graphene oxide and composite black phosphorus nanosheets form an antibacterial multilayer structure, showing excellent antibacterial activity. Furthermore, the composite black phosphorus nanosheets are adhered between the layers, and the resulting composite layered material has high oxygen barrier properties, preventing black phosphorus from being easily oxidized by contact with oxygen in the air, which would cause the antibacterial activity of the medical tape to fail, and further improving the stability of the composite black phosphorus nanosheets. On the other hand, the resulting composite layered material has good mechanical properties, which can weaken the stress in the tensile test of the medical tape, thereby distributing the pressure. It has good softness, reduces the patient's pain, and helps to promote wound healing.

[0045] (4) In the technical solution of the present invention, the composite antibacterial material and 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, which further enhances the antibacterial activity. Moreover, the excellent aspect ratio of carboxylated cellulose nanocrystals enables the gel to form a dynamic cross-linked network structure that can absorb attraction, thereby enhancing the tensile properties of the medical tape. In addition, the composite antibacterial material is embedded in the antibacterial cross-linked network structure, which enhances the force of the antibacterial material. On the other hand, during the continuous stretching process of the medical tape, the organic antibacterial agent tea tree oil extract in the composite antibacterial material migrates or volatilizes, containing a large amount of alcohol. The hydroxyl structure in the alcohol can be combined with the composite antibacterial material and carboxylated cellulose nanocrystals through hydrogen bonds, fixing the migrated or volatilized tea tree oil extract in the gel network structure, avoiding the volatilization of organic antibacterial agents that leads to a decrease in antibacterial activity, and further enhancing the cross-linking density and improving the mechanical properties of the medical tape. Detailed Implementation

[0046] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0047] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

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

[0049] Chitosan has a degree of deacetylation of 99%, manufactured by 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 black phosphorus nanosheets have a particle size of 0.5 μm.

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

[0054] Black phosphorus nanosheets are prepared by the following steps:

[0055] 0.5 g of black phosphorus crystals were added to 200 mL of N-methylpyrrolidone and sonicated at 23 kHz for 6 h. The mixture was then centrifuged at 7000 r / min for 15 min, and the supernatant was collected. The mixture was then centrifuged at 12000 r / min for 15 min, and the precipitate was collected. The precipitate was washed three times with isopropanol and dried in an oven at 45 ℃ for 24 h to obtain black phosphorus nanosheets.

[0056] Example 1: The antibacterial filler was prepared by the following steps:

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

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

[0059] A3. Add 5.5g of tea tree oil extract powder to 50mL of ethanol and stir until completely dissolved. Add 2.7g of black phosphorus nanosheets loaded with a metal-organic framework and stir at 450r / min for 25min. Let stand for 1.5h and place in a 45℃ water bath. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

[0060] A4. 1.6 g of graphene oxide was added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 0.8 g of Tris-HCl buffer solution with pH 8.5 was added and ultrasonically dispersed for 20 min at 25 °C and 2000 r / min. 0.7 g of dopamine was added and ultrasonically dispersed for 2 h at 30 °C and 2000 r / min. The mixture was centrifuged at 10000 r / min for 60 min. The product was collected, washed twice with ethanol, and dried in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide.

[0061] A5. Add 1.2g of polydopamine-modified graphene oxide to 100mL of deionized water, stir well, add 1g of composite black phosphorus nanosheets, sonicate at 50KHz for 1.5h, filter, wash 3 times with deionized water, and dry overnight in an oven at 50℃ to obtain composite antibacterial material.

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

[0063] Comparative Example 1 differs from Example 1 in that the black phosphorus nanosheets loaded with metal-organic frameworks are replaced with hydroxylated black phosphorus nanosheets, while the remaining steps and raw materials are the same as in Example 1.

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

[0065] A1. Add 0.15g of black phosphorus nanosheets and 0.2g of glucose to 100mL of N,N-dimethylformamide, stir well, bubble with argon for 30min to remove oxygen, seal, place in a reaction vessel, react at 180℃ for 3h, collect crude product by centrifugation at 9000r / min, wash crude product 3 times with N,N-dimethylformamide, wash 3 times with isopropanol, dry in 70℃ oven for 10min to obtain hydroxylated black phosphorus nanosheets;

[0066] A2. Add 5.5g of tea tree oil extract powder to 50mL of ethanol and stir until completely dissolved. Add 2.7g of hydroxylated black phosphorus nanosheets and stir at 450r / min for 25min. Let stand for 1.5h and place in a 45℃ water bath. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

[0067] A3. 1.6 g of graphene oxide was added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 0.8 g of Tris-HCl buffer solution with pH 8.5 was added and ultrasonically dispersed for 20 min at 25 °C and 2000 r / min. 0.7 g of dopamine was added and ultrasonically dispersed for 2 h at 30 °C and 2000 r / min. The mixture was centrifuged at 10000 r / min for 60 min. The product was collected, washed twice with ethanol, and dried in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide.

[0068] A4. Add 1.2g of polydopamine-modified graphene oxide to 100mL of deionized water, stir well, add 1g of composite black phosphorus nanosheets, sonicate at 50KHz for 1.5h, filter, wash 3 times with deionized water, and dry overnight in an oven at 50℃ to obtain composite antibacterial material.

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

[0070] Comparative Example 2 differs from Example 1 in that the composite black phosphorus nanosheets are replaced with black phosphorus nanosheets loaded with a metal-organic framework, while the remaining steps and raw materials are the same as in Example 1.

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

[0072] A1. Add 0.15g of black phosphorus nanosheets and 0.2g of glucose to 100mL of N,N-dimethylformamide, stir well, bubble with argon for 30min to remove oxygen, seal, place in a reaction vessel, react at 180℃ for 3h, collect crude product by centrifugation at 9000r / min, wash crude product 3 times with N,N-dimethylformamide, wash 3 times with isopropanol, dry in 70℃ oven for 10min to obtain hydroxylated black phosphorus nanosheets;

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

[0074] A3. 1.6 g of graphene oxide was added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 0.8 g of Tris-HCl buffer solution with pH 8.5 was added and ultrasonically dispersed for 20 min at 25 °C and 2000 r / min. 0.7 g of dopamine was added and ultrasonically dispersed for 2 h at 30 °C and 2000 r / min. The mixture was centrifuged at 10000 r / min for 60 min. The product was collected, washed twice with ethanol, and dried in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide.

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

[0076] A5. Add 6.2g of chitosan to 100mL of deionized water and stir at 38℃ for 25min. Add 2.3g of silver nitrate, 1.2g of composite antibacterial material, and 0.7g of carboxylated cellulose nanocrystals. Continue stirring for 1.5h. Take out the gel, wash the gel three times with deionized water, and dry it at room temperature overnight to obtain the antibacterial filler.

[0077] The difference between Comparative Example 3 and Example 1 is that no polydopamine-modified graphene oxide was added, while the remaining steps and raw materials were the same as in Example 1.

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

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

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

[0081] A3. Add 5.5g of tea tree oil extract powder to 50mL of ethanol and stir until completely dissolved. Add 2.7g of black phosphorus nanosheets loaded with a metal-organic framework and stir at 450r / min for 25min. Let stand for 1.5h and place in a 45℃ water bath. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

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

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

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

[0085] A1. Add 0.15g of black phosphorus nanosheets and 0.2g of glucose to 100mL of N,N-dimethylformamide, stir well, bubble with argon for 30min to remove oxygen, seal, place in a reaction vessel, react at 180℃ for 3h, collect crude product by centrifugation at 9000r / min, wash crude product 3 times with N,N-dimethylformamide, wash 3 times with isopropanol, dry in 70℃ oven for 10min to obtain hydroxylated black phosphorus nanosheets;

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

[0087] A3. Add 5.5g of tea tree oil extract powder to 50mL of ethanol and stir until completely dissolved. Add 2.7g of black phosphorus nanosheets loaded with a metal-organic framework and stir at 450r / min for 25min. Let stand for 1.5h and place in a 45℃ water bath. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

[0088] A4. 1.6 g of graphene oxide was added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 0.8 g of Tris-HCl buffer solution with pH 8.5 was added and ultrasonically dispersed for 20 min at 25 °C and 2000 r / min. 0.7 g of dopamine was added and ultrasonically dispersed for 2 h at 30 °C and 2000 r / min. The mixture was centrifuged at 10000 r / min for 60 min. The product was collected, washed twice with ethanol, and dried in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide.

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

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

[0091] The difference between Comparative Example 5 and Example 1 is that chitosan and silver nitrate were not added, while the remaining steps and raw materials were the same as in Example 1.

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

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

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

[0095] A3. Add 5.5g of tea tree oil extract powder to 50mL of ethanol and stir until completely dissolved. Add 2.7g of black phosphorus nanosheets loaded with a metal-organic framework and stir at 450r / min for 25min. Let stand for 1.5h and place in a 45℃ water bath. Heat until the ethanol evaporates and remove to obtain composite black phosphorus nanosheets.

[0096] A4. 1.6 g of graphene oxide was added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 0.8 g of Tris-HCl buffer solution with pH 8.5 was added and ultrasonically dispersed for 20 min at 25 °C and 2000 r / min. 0.7 g of dopamine was added and ultrasonically dispersed for 2 h at 30 °C and 2000 r / min. The mixture was centrifuged at 10000 r / min for 60 min. The product was collected, washed twice with ethanol, and dried in an oven at 70 °C for 8 h to obtain polydopamine-modified graphene oxide.

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

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

[0099] Example 2: A method for preparing medical adhesive tape, comprising the following preparation steps:

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

[0101] S2. Apply the antibacterial adhesive to the surface of the non-woven fabric using a coating machine, dry it at 55°C for 30 minutes to obtain an adhesive layer, and then bond the fabric substrate to the surface of the adhesive layer to obtain medical tape.

[0102] The mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water is 50:15:5:15:100.

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

[0104] The adhesive layer thickness is 0.2 mm.

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

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

[0107] Example 3: A method for preparing medical adhesive tape, comprising the following preparation steps:

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

[0109] S2. Apply antibacterial adhesive to the surface of non-woven fabric and dry it at 60°C for 35 minutes to obtain an adhesive layer. Then, attach the fabric substrate to the surface of the adhesive layer to obtain medical tape.

[0110] The mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water is 55:20:8:18:110.

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

[0112] The adhesive layer thickness is 0.1 mm.

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

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

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

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

[0117] S2. Apply the antibacterial adhesive to the surface of the non-woven fabric using a coating machine, and dry it at 65°C for 40 minutes to obtain an adhesive layer. Then, bond the fabric substrate to the surface of the adhesive layer to obtain medical tape.

[0118] The mass ratio of polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water is 60:25:10:20:120.

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

[0120] The adhesive layer thickness is 0.3 mm.

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

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

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

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

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

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

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

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

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

[0130] Elongation at break performance test: The elongation at break of the above-prepared medical tape was tested according to GB / T 30776-2014 "Test methods for tensile strength and elongation at break of adhesive tape".

[0131] Antibacterial performance test: Take 0.1g of the medical tape prepared above and 10mL of 1×10 7 A mixture of CFU / mL *E. coli* and *Staphylococcus aureus* bacterial suspensions was placed in a test tube and incubated on a shaker at 37°C and 120 rpm for 4 hours. This was used as the experimental group. The control group consisted of a suspension without the prepared medical tape. The bacterial suspensions from both the experimental and control groups were diluted to 1×10⁻⁶. 5 CFU / mL, take 100μL of bacterial suspension and spread it onto the surface of an agar plate. Incubate in a 37℃ shaking incubator for 24h. Calculate the antibacterial rate by plate colony counting method. Antibacterial rate = (b1-b2) / b1×100%, where b1 is the colony count of the blank group and b2 is the colony count of the experimental group.

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

[0133] Table 1

[0134]

[0135]

[0136] In Comparative Example 6, the antibacterial filler prepared by replacing the black phosphorus nanosheets loaded with a metal-organic framework with hydroxylated black phosphorus nanosheets and adding it to medical tape resulted in a decrease in its antibacterial and mechanical properties. This demonstrates that the metal-organic framework formed on the surface of black phosphorus nanosheets can serve as a carrier structure for organic antibacterial agents, increasing the force on the organic antibacterial agents and preventing their migration and precipitation. Furthermore, the porous structure of the metal-organic framework can adsorb air, preventing direct contact between air and black phosphorus nanosheets, which would lead to oxidation of the black phosphorus nanosheets and affect their antibacterial activity and mechanical properties. It can also form an uneven structure on the black phosphorus nanosheets, increasing the contact area with bacteria and enhancing antibacterial activity. In contrast, Comparative Example 6 lacked a metal-organic framework, resulting in a decrease in its antibacterial and mechanical properties.

[0137] In Comparative Example 7, the antibacterial filler prepared by replacing the composite black phosphorus nanosheets with black phosphorus nanosheets loaded with a metal-organic framework was added to the medical tape, and its antibacterial performance decreased. This proves that when the organic antibacterial agent is adsorbed onto the black phosphorus nanosheets loaded with a metal-organic framework, the organic antibacterial agent forms an organic antibacterial layer on the surface of the black phosphorus nanosheets. Combined with the inorganic material black phosphorus nanosheets, the organic-inorganic synergistic antibacterial effect is achieved, which greatly enhances the antibacterial activity of the medical tape. However, in Comparative Example 7, the lack of organic antibacterial agent resulted in a decrease in its antibacterial performance.

[0138] In Comparative Example 8, the antibacterial filler prepared without polydopamine-modified graphene oxide was added to medical tape, resulting in a decrease in its antibacterial and mechanical properties. This demonstrates that polydopamine-modified graphene oxide adheres to the surface of the composite black phosphorus nanosheets, forming an antibacterial multilayer structure that exhibits excellent antibacterial activity. Furthermore, the composite black phosphorus nanosheets are adhered between the layers, forming a composite layered material with high oxygen barrier properties, further improving the stability of the composite black phosphorus nanosheets. The resulting composite layered material also has good mechanical properties, which can reduce the stress in the tensile test of the medical tape and thus distribute the pressure. In contrast, Comparative Example 8 lacks an antibacterial multilayer structure, resulting in a decrease in its antibacterial and mechanical properties.

[0139] When the antibacterial filler prepared without carboxylated cellulose nanocrystals in Comparative Example 9 was added to medical tape, its mechanical strength and antibacterial properties decreased. This demonstrates that the migrating or volatile substances of the organic antibacterial agent tea tree oil extract can bind with carboxylated cellulose nanocrystals through hydrogen bonds, fixing the migrating or volatile tea tree oil extract in the gel network structure. This prevents the antibacterial activity from decreasing due to the volatilization of the organic antibacterial agent and further enhances the cross-linking density, thereby improving the mechanical properties of the medical tape. In addition, carboxylated cellulose nanocrystals can form a dynamic cross-linked network structure that absorbs attraction, enhancing the tensile properties of the medical tape. However, Comparative Example 9, lacking carboxylated cellulose nanocrystals, showed a decrease in its mechanical strength and antibacterial properties.

[0140] When the antibacterial filler prepared without chitosan and silver nitrate in Comparative Example 10 was added to medical tape, its mechanical strength and antibacterial properties decreased. This proves that chitosan and silver ions in the crosslinking agent silver nitrate are crosslinked through hydrogen bonds to form an antibacterial crosslinked network structure, which has good antibacterial activity and mechanical properties. Furthermore, embedding the composite antibacterial material into the antibacterial crosslinked network structure enhances the effect of the antibacterial material and prevents the migration and precipitation of the antibacterial material. In contrast, the gel structure formed by the lack of chitosan and silver nitrate in Comparative Example 10 resulted in a decrease in its antibacterial and mechanical properties.

[0141] The data in Table 1 show that the medical tapes prepared in Examples 2-4 met the performance requirements, while the medical tapes prepared in Comparative Examples 6-10 did not meet the performance requirements. This indicates that the medical tapes prepared in this invention have excellent antibacterial and tensile properties.

[0142] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0143] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing medical adhesive tape, characterized in that, The preparation steps include the following: S1. Mix polyvinylpyrrolidone, polyvinyl alcohol, antibacterial filler, glycerin and deionized water, and stir at 70-80℃ for 20-30 minutes to obtain an antibacterial adhesive; S2. Apply antibacterial adhesive to the surface of non-woven fabric and dry it at 55-65℃ for 30-40 minutes to obtain an adhesive layer. Then, attach the fabric substrate to the surface of the adhesive layer to obtain medical tape. The antibacterial filler is obtained by mixing and reacting composite antibacterial materials, carboxylated cellulose nanocrystals, crosslinking agents, tannic acid and chitosan; The composite antibacterial material is obtained by mixing and reacting black phosphorus nanosheets loaded with metal-organic frameworks to adsorb organic antibacterial agents, and then with polydopamine-modified graphene oxide. The black phosphorus nanosheets loaded with metal-organic frameworks are obtained by reacting black phosphorus nanosheets with glucose, followed by a reaction with zinc nitrate hexahydrate, 2-aminobenzothiazole and 2-methylimidazole. The organic antibacterial agent is tea tree oil extract powder; The crosslinking agent is silver nitrate.

2. The method for preparing a medical adhesive tape according to claim 1, characterized in that, The black phosphorus nanosheets have a particle size of 0.2-0.5 μm.

3. The method for preparing a medical adhesive tape according to claim 1, characterized in that, The graphene oxide has a particle size of 0.5-1 μm.

4. The method for preparing a medical adhesive tape according to claim 1, characterized in that, The degree of deacetylation of the chitosan is 90-92%.

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

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

7. The method for preparing a medical adhesive 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 0.05-0.15mm.

8. A medical tape prepared by the method of any one of claims 1-7.

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