Puncture-resistant medical packaging film and preparation method thereof

Abstract

The invention relates to the technical field of medical supplies, and discloses an anti-puncture medical packaging film and a preparation method thereof. Comprising the following raw materials in parts by weight: an ethylene copolymer, modified aramid fibers, a reinforcing agent, an auxiliary agent, an antioxidant and an antistatic agent. The preparation method of the anti-puncture medical packaging film comprises the following steps: raw material blending, tape casting, film blank drying, stretching and shaping, and rolling. According to the technology, the modified aramid fibers are fully dispersed in the packaging film with the ethylene copolymer as the matrix, so that the puncture resistance of the packaging film is greatly improved, sharp objects are effectively prevented from penetrating through the packaging film, medical products are better protected, the damage risk of the products in the transportation and storage process is reduced, meanwhile, through modification, the service life of the packaging film is prolonged, and the service life of the packaging film is prolonged. The antibacterial performance is improved, and the medical material is more suitable for protection application of medical equipment.

Description

Technical Field

[0001] The present invention relates to the technical field of medical supplies, in particular to a puncture-resistant medical packaging film and a preparation method thereof. Background Art

[0002] Medical packaging films serve as a crucial protective barrier for medical devices and consumables, and their performance directly impacts the safety and effectiveness of these products. In the practical application of medical packaging, packaging films must withstand various external forces during storage, transportation, and use to prevent damage to the packaging, which could lead to contamination of the medical devices or consumables within, potentially posing a medical risk. However, traditional medical packaging films are typically based on common polymer materials such as polyethylene and polypropylene. While these materials possess certain flexibility and barrier properties, they lack puncture resistance. They are easily punctured by impact or compression from sharp objects, disrupting the sterile environment within the packaging and increasing the risk of contamination of medical devices and consumables. To address this issue, existing approaches have attempted to improve puncture resistance by increasing film thickness or modifying film structure. However, these methods often result in reduced film flexibility, increased costs, and potentially compromise other film properties, such as air permeability and transparency, making them difficult to meet the comprehensive performance requirements for medical packaging. Therefore, developing medical packaging films with excellent puncture resistance and comprehensive performance is of great practical significance. Summary of the Invention

[0003] (1) Technical problems solved In view of the deficiencies in the prior art, the present invention provides a puncture-resistant medical packaging film and a preparation method thereof.

[0004] (2) Technical solution To achieve the above object, the present invention provides the following technical solution: a puncture-resistant medical packaging film, comprising the following raw materials in parts by weight: 60-80 parts of ethylene copolymer, 10-30 parts of modified aramid fiber, 2-5 parts of reinforcing agent, 2-5 parts of auxiliary agent, 1-3 parts of antioxidant, and 1-3 parts of antistatic agent.

[0005] Furthermore, the ethylene copolymer is one of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.

[0006] Furthermore, the preparation method of the modified aramid fiber comprises the following steps: 10-20 parts of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea and 0.5-2 parts of initiator potassium persulfate are dissolved in a solvent to prepare a grafting monomer solution with a mass fraction of 5-10% and a potassium persulfate solution with a mass fraction of 0.5-2%. The two solutions are mixed and stirred evenly; 10-30 parts of aramid fiber are washed with deionized water, dried in a drying oven at 60-80°C for 1-2 hours, then immersed in the mixed solution and reacted in a constant temperature water bath at 60-80°C for 2-4 hours with continuous stirring during the reaction. After the reaction is completed, the fiber is removed, repeatedly washed with deionized water, and dried in a drying oven at 60-80°C to constant weight.

[0007] Furthermore, the solvent is one of methanol, ethanol and water.

[0008] Furthermore, the preparation method of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea comprises the following steps: A1. Mix 20-40 parts of hydroxyethyl methacrylate and 30-50 parts of epichlorohydrin, stir evenly, add 0.1-0.3% by mass of p-diphenol as a polymerization inhibitor, raise the temperature to 50-60°C, slowly add sodium hydroxide in batches, maintain the temperature at 60-80°C, and react with vigorous stirring for 4-6 hours. After the reaction, cool to room temperature, slowly add 10% by mass dilute hydrochloric acid dropwise until the pH reaches 7, transfer to a separatory funnel, add ethyl acetate to extract the organic phase, discard the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter, and remove the solvent by distillation under reduced pressure to obtain hydroxyethyl methacrylate glycidyl ether; A2. Add 10-20 parts of hydroxyethyl methacrylate glycidyl ether to 100-120 parts of acetone and stir to dissolve it completely. Dissolve 10-15 parts of trimethylamine in 30-60 parts of deionized water to prepare a trimethylamine acetone solution. A3. Place the hydroxyethyl methacrylate glycidyl ether acetone solution in an ice-water bath and start an electric stirrer at a stirring speed of 200-300 r / min. Slowly add the trimethylamine acetone solution dropwise to the hydroxyethyl methacrylate glycidyl ether solution. After the addition is complete, heat the mixture to 40-50°C and continue the reaction at this temperature for 4-6 hours while stirring. A4. After the reaction is completed, the acetone solution is removed by distillation under reduced pressure, and the residue is recrystallized from a mixed solvent of ethyl acetate / diethyl ether in a volume ratio of 1:3. The solid product is collected by filtration to obtain a crude product; A5. Dissolve the crude product in deionized water, add excess sodium carbonate solid to a pH of 9-10, and extract three times with dichloromethane. Combine the organic phases, dry over anhydrous sodium sulfate, and then distill under reduced pressure to remove the solvent. Dry the aqueous phase under vacuum to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A6. Dissolve 10-20 parts of hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride in 100-120 parts of anhydrous tetrahydrofuran and cool to 0°C in an ice-water bath. Dissolve 40-80 parts of diethylenetriamine in 150-200 parts of anhydrous tetrahydrofuran and slowly add dropwise to the above solution, controlling the temperature not to exceed 10°C. After the addition is complete, react at room temperature for 2-4 hours. After the reaction is complete, remove the solvent by distillation under reduced pressure, and recrystallize the residue from a mixed solvent of ethanol / ether in a volume ratio of 1:4 to obtain amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A7. Dissolve 10-15 parts of toluene diisocyanate in 100-200 parts of anhydrous tetrahydrofuran, cool in an ice-water bath at 0-5°C, slowly dropwise add a mixed solution of 10-15 parts of 2-hydroxypropionitrile and 50 parts of tetrahydrofuran while passing nitrogen. After the addition is complete, heat to 25-30°C and react for 2-3 hours to generate a mono-protected toluene diisocyanate intermediate. Add 10-20 parts of amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride to 100-120 parts of tetrahydrofuran, pass nitrogen, stir to dissolve, slowly dropwise add the mono-protected toluene diisocyanate intermediate solution, control the temperature at 25-30°C, react for 3-4 hours, and after the reaction is complete, add an excess of 10% aqueous hydrochloric acid solution to the reaction system and stir at room temperature for 1-2 minutes. h was deprotected, the pH was adjusted to 7-8 with sodium carbonate solid, the solvent was removed by distillation under reduced pressure, the residue was extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea.

[0009] Furthermore, the reinforcing agent is one of polyvinyl alcohol, polyacrylamide, and nanocellulose.

[0010] Furthermore, the auxiliary agent is one of polyvinyl pyrrolidone, polydimethylsiloxane and polyethylene glycol.

[0011] Furthermore, the antioxidant is one of 1010, 1076, and 1135.

[0012] Furthermore, the antistatic agent is one of sodium dodecylbenzenesulfonate, sodium stearate, and triethanolamine.

[0013] Furthermore, a method for preparing a puncture-resistant medical packaging film comprises the following steps: S1. Raw material blending: slowly add ethylene copolymer to toluene solvent, stir and dissolve in a water bath at 60-80°C to prepare an ethylene copolymer solution with a mass fraction of 10-30%. Cut the modified aramid fiber into 3-5 mm short fibers, add the fibers to the ethylene copolymer solution, and then add a reinforcing agent, an auxiliary agent, an antioxidant, and an antistatic agent. Use a high-speed disperser to disperse the fibers at a speed of 2000-5000 r / min for 30-60 minutes, and place the fibers in a vacuum degassing machine at a vacuum degree of -0.06-0.08 MPa for 30-60 minutes. S2. Tape casting: Pour the degassed mixed solution into the hopper of the tape casting machine, and use a scraper to evenly coat the solution on a stainless steel cooling roller at a temperature of 60-80°C to form a film with uniform thickness. The gap between the scraper and the cooling roller is set to 0.1 mm, and the casting speed is 5 m / min. S3, film blank drying: the film blank after tape casting is sent to the hot air drying oven for solvent volatilization. The temperature of the drying oven is controlled in stages. The temperature is set at 60~80℃ in the first stage and maintained for 30~60 minutes. In the second stage, the temperature is raised to 100~120℃ and maintained for 10~20 minutes. S4. Stretching and shaping: The dried film is sent to a stretching machine for biaxial stretching and shaping. First, it is stretched in the longitudinal direction at a stretching ratio of 1.5 times, and the stretching temperature is 80-90°C; then it is stretched in the transverse direction at a stretching ratio of 2 times, and the stretching temperature is 90-95°C. The mechanical properties and dimensional stability of the film are improved by biaxial stretching. After stretching, the film is heat-set at 100-120°C for 10-30 minutes; S5. Winding: Use a winding device to roll the stretched and shaped packaging film into a roll at a speed of 8 m / min. During the winding process, the winding tension is controlled at 10 N to obtain a finished medical packaging film.

[0014] (3) Beneficial technical effects A puncture-resistant medical packaging film comprises the following raw materials in parts by weight: ethylene copolymer, modified aramid fiber, reinforcing agent, auxiliary agent, antioxidant and antistatic agent.

[0015] Modified aramid fiber is modified with N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea. N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea is formed by reacting hydroxyethyl methacrylate with epichlorohydrin to form hydroxyethyl methacrylate glycidyl ether, which is then reacted with trimethylamine hydrochloride and grafted with quaternary ammonium groups to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. The amino group is then terminated and protected with one of the diisocyanates of 2-hydroxypropionitrile p-toluene diisocyanate to form a carbamate bond. The resulting product is then reacted with amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride and deprotected. The isocyanate reacts with the amino and hydroxyl groups on the surface of the aramid fiber to form urea or carbamate bonds, forming covalent crosslinks and enhancing the strength of the aramid fiber.

[0016] The process of the present invention significantly improves the puncture resistance of the packaging film by fully dispersing the modified aramid fiber in the packaging film based on ethylene copolymer, effectively preventing sharp objects from penetrating the packaging film, better protecting medical products, and reducing the risk of damage to products during transportation and storage. At the same time, after modification, the antibacterial performance is improved, making it more suitable for the protection of medical equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a performance test data diagram of the present invention.

[0018] Figure 2 It is a graph of the antibacterial performance test data of the present invention. DETAILED DESCRIPTION

[0019] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0020] Reference Figure 1 and Figure 2 As shown: the formula components of the puncture-resistant medical packaging film of the present invention are commercially available unless otherwise specified; The parts used in the present invention are by mass.

[0021] Example 1, a puncture-resistant medical packaging film, characterized by comprising the following raw materials in parts by weight: 60 parts of ethylene copolymer, 10 parts of modified aramid fiber, 2 parts of reinforcing agent, 2 parts of auxiliary agent, 1 part of antioxidant, and 1 part of antistatic agent.

[0022] The ethylene copolymer is ethylene-vinyl acetate copolymer.

[0023] The reinforcing agent is polyvinyl alcohol.

[0024] The auxiliary agent is polyvinyl pyrrolidone.

[0025] The antioxidant is 1010.

[0026] The antistatic agent is sodium dodecylbenzenesulfonate.

[0027] The preparation method of modified aramid fiber comprises the following steps: 10 parts of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea and 0.5 parts of initiator potassium persulfate were dissolved in solvent methanol to prepare a 5% by mass grafting monomer solution and a 0.5% by mass potassium persulfate solution. The two solutions were mixed and stirred evenly. 10 parts of aramid fiber were washed with deionized water, dried in a 60°C drying oven for 1 h, then immersed in the mixed solution and reacted in a constant temperature water bath at 60°C for 2 h with continuous stirring during the reaction. After the reaction, the fiber was removed, repeatedly washed with deionized water, and dried in a 60°C drying oven to constant weight.

[0028] The preparation method of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea comprises the following steps: A1. Mix 20 parts of hydroxyethyl methacrylate and 30 parts of epichlorohydrin, stir evenly, add 0.1% by mass of a polymerization inhibitor, p-diphenol, raise the temperature to 50°C, slowly add sodium hydroxide in batches, maintain the temperature at 60°C, and react with vigorous stirring for 4 hours. After the reaction, cool to room temperature, slowly add 10% by mass dilute hydrochloric acid dropwise until the pH reaches 7, transfer to a separatory funnel, add ethyl acetate to extract the organic phase, discard the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter, and remove the solvent by distillation under reduced pressure to obtain hydroxyethyl methacrylate glycidyl ether; A2, 10 parts of hydroxyethyl methacrylate glycidyl ether were added to 100 parts of acetone, stirred to dissolve completely, 10 parts of trimethylamine were dissolved in 30 parts of deionized water to prepare a trimethylamine acetone solution; A3. Place the hydroxyethyl methacrylate glycidyl ether acetone solution in an ice-water bath, start an electric stirrer at a stirring speed of 200 r / min, and slowly add the trimethylamine acetone solution dropwise to the hydroxyethyl methacrylate glycidyl ether solution. After the addition is complete, heat the mixture to 40°C and continue the reaction at this temperature for 4 hours while stirring. A4. After the reaction is completed, the acetone solution is removed by distillation under reduced pressure, and the residue is recrystallized from a mixed solvent of ethyl acetate / diethyl ether in a volume ratio of 1:3. The solid product is collected by filtration to obtain a crude product; A5. The crude product was dissolved in deionized water, and excess sodium carbonate solid was added to pH 9. The mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and then the solvent was removed by distillation under reduced pressure. The aqueous phase was dried under vacuum to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride; A6. Dissolve 10 parts of hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride in 100 parts of anhydrous tetrahydrofuran and cool to 0°C in an ice-water bath. Dissolve 40 parts of diethylenetriamine in 150 parts of anhydrous tetrahydrofuran and slowly add the solution dropwise, controlling the temperature not to exceed 10°C. After the addition is complete, react at room temperature for 2 hours. After the reaction is complete, remove the solvent by distillation under reduced pressure, and recrystallize the residue from a mixed solvent of ethanol / ether in a volume ratio of 1:4 to obtain amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A7. Dissolve 10 parts of toluene diisocyanate in 100 parts of anhydrous tetrahydrofuran, cool to 0°C in an ice-water bath, and slowly dropwise add a mixed solution of 10 parts of 2-hydroxypropionitrile and 50 parts of tetrahydrofuran while purging with nitrogen. After the addition is complete, heat to 25°C and react for 2 h to produce a mono-protected toluene diisocyanate intermediate. Add 10 parts of amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride to 100 parts of tetrahydrofuran, purge with nitrogen, stir to dissolve, and slowly dropwise add the mono-protected toluene diisocyanate intermediate solution. Control the temperature at 25°C and react for 3 h. After the reaction is completed, add an excess of 10% aqueous hydrochloric acid to the reaction system, stir at room temperature for 1 h for deprotection, adjust the pH to 7 with sodium carbonate solid, and remove the solvent by distillation under reduced pressure. Extract the residue three times with dichloromethane. Combine the organic phases, dry over anhydrous sodium sulfate, and distill under reduced pressure to produce N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea.

[0029] A method for preparing a puncture-resistant medical packaging film comprises the following steps: S1. Raw material blending: Slowly add ethylene copolymer to toluene solvent, stir and dissolve in a 60°C water bath to prepare a 10% by mass ethylene copolymer solution. Cut the modified aramid fiber into 3 mm short fibers, add the fibers to the ethylene copolymer solution, and then add reinforcing agent, auxiliary agent, antioxidant, and antistatic agent. Use a high-speed disperser to disperse the fibers at a speed of 2000 r / min for 30 minutes, and place them in a vacuum degassing machine for treatment at a vacuum degree of -0.06 MPa for 30 minutes. S2. Tape casting: Pour the degassed mixed solution into the hopper of the tape casting machine, and use a scraper to evenly coat the solution on a stainless steel cooling roller at a temperature of 60°C to form a film with uniform thickness. The gap between the scraper and the cooling roller is set to 0.1 mm, and the casting speed is 5 m / min. S3, film blank drying: the film blank after tape casting is sent to a hot air drying oven for solvent volatilization. The temperature of the drying oven is controlled in stages. The temperature is set at 60°C in the first stage and maintained for 30 minutes. The temperature is raised to 100°C in the second stage and maintained for 10 minutes. S4. Stretching and shaping: The dried film is sent to a stretching machine for biaxial stretching and shaping. It is first stretched in the longitudinal direction at a stretching ratio of 1.5 times and the stretching temperature is 80°C; then stretched in the transverse direction at a stretching ratio of 2 times and the stretching temperature is 90°C. The mechanical properties and dimensional stability of the film are improved by biaxial stretching. After stretching, the film is heat-set at 100°C for 10 minutes. S5. Winding: Use a winding device to roll the stretched and shaped packaging film into a roll at a speed of 8 m / min. During the winding process, the winding tension is controlled at 10 N to obtain a finished medical packaging film.

[0030] Example 2, a puncture-resistant medical packaging film, characterized by comprising the following raw materials in parts by weight: 70 parts of ethylene copolymer, 20 parts of modified aramid fiber, 3 parts of reinforcing agent, 4 parts of auxiliary agent, 2 parts of antioxidant, and 2 parts of antistatic agent.

[0031] The ethylene copolymer is ethylene-ethyl acrylate copolymer.

[0032] The enhancer is polyacrylamide.

[0033] The auxiliary agent is polydimethylsiloxane.

[0034] The antioxidant is 1076.

[0035] The antistatic agent is sodium stearate.

[0036] The preparation method of modified aramid fiber comprises the following steps: 15 parts of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea and 1 part of initiator potassium persulfate were dissolved in solvent ethanol to prepare a 6% by mass grafting monomer solution and a 1% by mass potassium persulfate solution. The two solutions were mixed and stirred evenly. 20 parts of aramid fiber were washed with deionized water, dried in a 70°C drying oven for 1.5 h, then immersed in the mixed solution and reacted in a constant temperature water bath at 70°C for 3 h with continuous stirring during the reaction. After the reaction, the fiber was removed, repeatedly washed with deionized water, and dried in a 70°C drying oven to constant weight.

[0037] The preparation method of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea comprises the following steps: A1. Mix 30 parts of hydroxyethyl methacrylate and 40 parts of epichlorohydrin, stir evenly, add 0.2% by mass of p-diphenol as a polymerization inhibitor, raise the temperature to 55°C, slowly add sodium hydroxide in batches, maintain the temperature at 70°C, and react with vigorous stirring for 5 hours. After the reaction, cool to room temperature, slowly add 10% by mass dilute hydrochloric acid dropwise until the pH is 7, transfer to a separatory funnel, add ethyl acetate to extract the organic phase, discard the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter, and distill under reduced pressure to remove the solvent to obtain hydroxyethyl methacrylate glycidyl ether; A2, 15 parts of hydroxyethyl methacrylate glycidyl ether were added to 110 parts of acetone, stirred to dissolve completely, 12 parts of trimethylamine were dissolved in 45 parts of deionized water to prepare a trimethylamine acetone solution; A3. Place the hydroxyethyl methacrylate glycidyl ether acetone solution in an ice-water bath, start an electric stirrer at a stirring speed of 250 r / min, and slowly add the trimethylamine acetone solution dropwise to the hydroxyethyl methacrylate glycidyl ether solution. After the addition is complete, heat the mixture to 45°C and continue the reaction at this temperature for 5 h while stirring. A4. After the reaction is completed, the acetone solution is removed by distillation under reduced pressure, and the residue is recrystallized from a mixed solvent of ethyl acetate / diethyl ether in a volume ratio of 1:3. The solid product is collected by filtration to obtain a crude product; A5. The crude product was dissolved in deionized water, and excess sodium carbonate solid was added to pH 9. The mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and then the solvent was removed by distillation under reduced pressure. The aqueous phase was dried under vacuum to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride; A6. Dissolve 15 parts of hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride in 110 parts of anhydrous tetrahydrofuran and cool to 0°C in an ice-water bath. Dissolve 60 parts of diethylenetriamine in 180 parts of anhydrous tetrahydrofuran and slowly add the mixture dropwise to the above solution, controlling the temperature not to exceed 10°C. After the addition is complete, react at room temperature for 3 hours. After the reaction is complete, remove the solvent by distillation under reduced pressure, and recrystallize the residue from a mixed solvent of ethanol / ether in a volume ratio of 1:4 to obtain amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A7. Dissolve 12 parts of toluene diisocyanate in 150 parts of anhydrous tetrahydrofuran, cool in an ice-water bath to 3°C, slowly dropwise add a mixed solution of 12 parts of 2-hydroxypropionitrile and 50 parts of tetrahydrofuran, while passing nitrogen protection. After the addition is complete, heat to 25°C and react for 2.5 hours to generate a mono-protected toluene diisocyanate intermediate; add 15 parts of amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride to 110 parts of tetrahydrofuran, pass nitrogen, stir to dissolve, slowly dropwise add the mono-protected toluene diisocyanate intermediate solution, control the temperature at 25°C, react for 3.5 hours, and after the reaction is complete, add an excess of 10% hydrochloric acid aqueous solution to the reaction system and stir at room temperature for 1.2 hours. h deprotection, the pH was adjusted to 7 with sodium carbonate solid, the solvent was removed by distillation under reduced pressure, the residue was extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea.

[0038] A method for preparing a puncture-resistant medical packaging film comprises the following steps: S1. Raw material blending: Slowly add ethylene copolymer to toluene solvent, stir and dissolve in a 70°C water bath to prepare a 20% by mass ethylene copolymer solution. Cut the modified aramid fiber into 4 mm short fibers, add the fibers to the ethylene copolymer solution, and then add a reinforcing agent, an auxiliary agent, an antioxidant, and an antistatic agent. Use a high-speed disperser to disperse the fibers at a speed of 3000 r / min for 45 minutes, and place them in a vacuum degassing machine for 45 minutes at a vacuum degree of -0.07 MPa. S2. Tape casting: Pour the degassed mixed solution into the hopper of the tape casting machine and evenly coat the solution on a stainless steel cooling roller at a temperature of 70°C using a scraper to form a film with uniform thickness. The gap between the scraper and the cooling roller is set to 0.1 mm and the casting speed is 5 m / min. S3, film drying: the film after casting is sent to the hot air drying oven for solvent volatilization. The temperature of the drying oven is controlled in stages. The temperature is set at 70℃ in the first stage and maintained for 45 minutes. The temperature is raised to 110℃ in the second stage and maintained for 15 minutes. S4. Stretching and shaping: The dried film is sent to a stretching machine for biaxial stretching and shaping. It is first stretched in the longitudinal direction at a stretching ratio of 1.5 times and a stretching temperature of 85°C; then stretched in the transverse direction at a stretching ratio of 2 times and a stretching temperature of 90°C. The mechanical properties and dimensional stability of the film are improved by biaxial stretching. After stretching, the film is heat-set at 110°C for 20 minutes. S5. Winding: Use a winding device to roll the stretched and shaped packaging film into a roll at a speed of 8 m / min. During the winding process, the winding tension is controlled at 10 N to obtain a finished medical packaging film.

[0039] Example 3, a puncture-resistant medical packaging film, characterized by comprising the following raw materials in parts by weight: 80 parts of ethylene copolymer, 30 parts of modified aramid fiber, 5 parts of reinforcing agent, 5 parts of auxiliary agent, 3 parts of antioxidant, and 3 parts of antistatic agent.

[0040] The ethylene copolymer is ethylene-butyl acrylate copolymer.

[0041] The reinforcing agent is nanocellulose.

[0042] The auxiliary agent is polyethylene glycol.

[0043] The antioxidant is 1135.

[0044] The antistatic agent is triethanolamine.

[0045] The preparation method of modified aramid fiber comprises the following steps: 20 parts of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea and 2 parts of initiator potassium persulfate were dissolved in solvent water to prepare a 10% by mass grafting monomer solution and a 2% by mass potassium persulfate solution. The two solutions were mixed and stirred evenly. 30 parts of aramid fiber were washed with deionized water, dried in an 80°C drying oven for 2 h, then immersed in the mixed solution and reacted in a constant temperature water bath at 80°C for 4 h with continuous stirring during the reaction. After the reaction, the fiber was removed, repeatedly washed with deionized water, and dried in an 80°C drying oven to constant weight.

[0046] The preparation method of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea comprises the following steps: A1. Mix 40 parts of hydroxyethyl methacrylate and 50 parts of epichlorohydrin, stir evenly, add 0.3% by mass of p-diphenol as a polymerization inhibitor, raise the temperature to 60°C, slowly add sodium hydroxide in batches, maintain the temperature at 80°C, and react with vigorous stirring for 6 hours. After the reaction, cool to room temperature, slowly add 10% by mass dilute hydrochloric acid dropwise until the pH is 7, transfer to a separatory funnel, add ethyl acetate to extract the organic phase, discard the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter, and remove the solvent by distillation under reduced pressure to obtain hydroxyethyl methacrylate glycidyl ether; A2, 20 parts of hydroxyethyl methacrylate glycidyl ether were added to 120 parts of acetone, stirred to dissolve completely, 15 parts of trimethylamine were dissolved in 60 parts of deionized water to prepare a trimethylamine acetone solution; A3. Place the hydroxyethyl methacrylate glycidyl ether acetone solution in an ice-water bath. Turn on an electric stirrer at a stirring speed of 300 r / min. Slowly add the trimethylamine acetone solution dropwise to the hydroxyethyl methacrylate glycidyl ether solution. After the addition is complete, heat the mixture to 50°C and continue the reaction at this temperature for 4-6 hours while stirring. A4. After the reaction is completed, the acetone solution is removed by distillation under reduced pressure, and the residue is recrystallized from a mixed solvent of ethyl acetate / diethyl ether in a volume ratio of 1:3. The solid product is collected by filtration to obtain a crude product; A5. The crude product was dissolved in deionized water, and excess sodium carbonate solid was added to pH 10. The mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and then the solvent was removed by distillation under reduced pressure. The aqueous phase was dried under vacuum to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride; A6. Dissolve 20 parts of hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride in 120 parts of anhydrous tetrahydrofuran and cool to 0°C in an ice-water bath. Dissolve 80 parts of diethylenetriamine in 200 parts of anhydrous tetrahydrofuran and slowly add the mixture dropwise to the above solution, controlling the temperature not to exceed 10°C. After the addition is complete, react at room temperature for 4 hours. After the reaction is complete, remove the solvent by distillation under reduced pressure, and recrystallize the residue from a mixed solvent of ethanol / diethyl ether in a volume ratio of 1:4 to obtain amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A7. Dissolve 15 parts of toluene diisocyanate in 200 parts of anhydrous tetrahydrofuran, cool to 5°C in an ice-water bath, and slowly dropwise add a mixed solution of 15 parts of 2-hydroxypropionitrile and 50 parts of tetrahydrofuran while purging with nitrogen. After the dropwise addition is complete, heat to 30°C and react for 3 hours to produce a mono-protected toluene diisocyanate intermediate. Add 20 parts of amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride to 120 parts of tetrahydrofuran, purge with nitrogen, stir to dissolve, and slowly dropwise add the mono-protected toluene diisocyanate intermediate solution. Control the temperature at 30°C and react for 4 hours. After the reaction is completed, add an excess of 10% aqueous hydrochloric acid to the reaction system, stir at room temperature for 2 hours for deprotection, adjust the pH to 8 with sodium carbonate solid, and remove the solvent by distillation under reduced pressure. Extract the residue three times with dichloromethane. Combine the organic phases, dry over anhydrous sodium sulfate, and distill under reduced pressure to produce N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea.

[0047] A method for preparing a puncture-resistant medical packaging film comprises the following steps: S1. Raw material blending: slowly add ethylene copolymer to toluene solvent, stir and dissolve in a water bath at 80°C to prepare a 30% by mass ethylene copolymer solution, cut the modified aramid fiber into 5 mm short fibers, add the fibers to the ethylene copolymer solution, and then add reinforcing agent, auxiliary agent, antioxidant, and antistatic agent. Use a high-speed disperser to disperse the fibers at a speed of 5000 r / min for 60 min, and place them in a vacuum degassing machine and treat at a vacuum degree of -0.08 MPa for 60 min. S2. Tape casting: Pour the degassed mixed solution into the hopper of the tape casting machine, and use a scraper to evenly coat the solution on a stainless steel cooling roller at a temperature of 80°C to form a film with uniform thickness. The gap between the scraper and the cooling roller is set to 0.1 mm, and the casting speed is 5 m / min. S3, film drying: the film after casting is sent to the hot air drying oven for solvent volatilization. The temperature of the drying oven is controlled in stages. The temperature is set at 80℃ in the first stage and maintained for 60 minutes. The temperature is raised to 120℃ in the second stage and maintained for 20 minutes. S4. Stretching and shaping: The dried film is sent to a stretching machine for biaxial stretching and shaping. It is first stretched in the longitudinal direction at a stretching ratio of 1.5 times and a stretching temperature of 90°C; then stretched in the transverse direction at a stretching ratio of 2 times and a stretching temperature of 95°C. The mechanical properties and dimensional stability of the film are improved by biaxial stretching. After stretching, the film is heat-set at 120°C for 30 minutes. S5. Winding: Use a winding device to roll the stretched and shaped packaging film into a roll at a speed of 8 m / min. During the winding process, the winding tension is controlled at 10 N to obtain a finished medical packaging film.

[0048] Comparative Example 1: The aramid fiber was not modified, and the rest of the process was the same as in Example 1.

[0049] Comparative Example 2: Aramid fiber was modified with hydroxyethyl methacrylate glycidyl ether, and the remaining processes were the same as those in Example 1.

[0050] Comparative Example 3: A melt blending-twin-screw extrusion process was adopted, with the screw speed set to 150 r / min, the temperature of zone 1 to 160°C, the temperature of zone 2 to 170°C, the temperature of zone 3 to 180°C, the temperature of zone 4 to 190°C, the temperature of zone 5 to 200°C, and the die head temperature to 200°C. After extrusion, the product was water-cooled for shaping and then hauled and wound. The remaining processes were the same as in Example 1.

[0051] Performance testing: 1. Mechanical strength test: The test objects are the medical packaging films prepared in Examples 1 to 3 and Comparative Examples 1 to 3. The puncture resistance is tested according to ASTM F1306, the tensile strength and elongation at break are tested according to GB / T 1040.3-2006, and the tear strength is tested according to GB / T 16578.1-2008. The results are shown in the appendix of the manual. Figure 1 ; Attached to the instruction manual Figure 1 It can be seen that the comparative example has lower puncture resistance, tensile strength, elongation at break, and tear strength than the example, indicating that the process of the example can produce a medical packaging film with higher mechanical strength.

[0052] 2. Antibacterial performance test: According to YY / T 0853-2011 "Evaluation of performance of antibacterial materials for medical devices", the antibacterial performance of Examples 1 to 3 and Comparative Examples 1 to 3 was tested, and Escherichia coli was selected as the test strain to test the antibacterial rate. The results are shown in the appendix of the specification. Figure 2 ; Attached to the instruction manual Figure 2 It can be seen that the antibacterial rates of Comparative Examples 1 and 2 are lower than those of the embodiment, indicating that the modification of the aramid fiber can improve the antibacterial properties of the medical packaging bag.

[0053] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A puncture-resistant medical packaging film, characterized in that: It includes the following raw materials in parts by weight: 60-80 parts of ethylene copolymer, 10-30 parts of modified aramid fiber, 2-5 parts of reinforcing agent, 2-5 parts of auxiliary agent, 1-3 parts of antioxidant, 1-3 parts of antistatic agent; The preparation method of modified aramid fiber comprises the following steps: 10-20 parts of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea and 0.5-2 parts of initiator potassium persulfate are dissolved in a solvent to prepare a grafting monomer solution with a mass fraction of 5-10% and a potassium persulfate solution with a mass fraction of 0.5-2%. The two solutions are mixed and stirred evenly; 10-30 parts of aramid fiber are washed with deionized water, dried in a drying oven at 60-80°C for 1-2 hours, then immersed in the mixed solution and reacted in a constant temperature water bath at 60-80°C for 2-4 hours with continuous stirring during the reaction. After the reaction, the fiber is removed, repeatedly washed with deionized water, and dried in a drying oven at 60-80°C to constant weight.

2. The puncture-resistant medical packaging film according to claim 1, characterized in that: The ethylene copolymer is one of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and ethylene-butyl acrylate copolymer.

3. The puncture-resistant medical packaging film according to claim 1, characterized in that: The solvent is one of methanol, ethanol and water.

4. The puncture-resistant medical packaging film according to claim 1, characterized in that: The preparation method of N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl) urea comprises the following steps: A1. Mix 20-40 parts of hydroxyethyl methacrylate and 30-50 parts of epichlorohydrin, stir evenly, add 0.1-0.3% by mass of p-diphenol as a polymerization inhibitor, raise the temperature to 50-60°C, slowly add sodium hydroxide in batches, maintain the temperature at 60-80°C, and react with vigorous stirring for 4-6 hours. After the reaction, cool to room temperature, slowly add 10% by mass dilute hydrochloric acid dropwise until the pH reaches 7, transfer to a separatory funnel, add ethyl acetate to extract the organic phase, discard the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter, and remove the solvent by distillation under reduced pressure to obtain hydroxyethyl methacrylate glycidyl ether; A2. Add 10-20 parts of hydroxyethyl methacrylate glycidyl ether to 100-120 parts of acetone and stir to dissolve it completely. Dissolve 10-15 parts of trimethylamine in 30-60 parts of deionized water to prepare a trimethylamine acetone solution. A3. Place the hydroxyethyl methacrylate glycidyl ether acetone solution in an ice-water bath and start an electric stirrer at a stirring speed of 200-300 r / min. Slowly add the trimethylamine acetone solution dropwise to the hydroxyethyl methacrylate glycidyl ether solution. After the addition is complete, heat the mixture to 40-50°C and continue the reaction at this temperature for 4-6 hours while stirring. A4. After the reaction is completed, the acetone solution is removed by distillation under reduced pressure, and the residue is recrystallized from a mixed solvent of ethyl acetate / diethyl ether in a volume ratio of 1:

3. The solid product is collected by filtration to obtain a crude product; A5. Dissolve the crude product in deionized water, add excess sodium carbonate solid to a pH of 9-10, and extract three times with dichloromethane. Combine the organic phases, dry over anhydrous sodium sulfate, and then distill under reduced pressure to remove the solvent. Dry the aqueous phase under vacuum to obtain hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A6. Dissolve 10-20 parts of hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride in 100-120 parts of anhydrous tetrahydrofuran and cool to 0°C in an ice-water bath. Dissolve 40-80 parts of diethylenetriamine in 150-200 parts of anhydrous tetrahydrofuran and slowly add dropwise to the above solution, controlling the temperature not to exceed 10°C. After the addition is complete, react at room temperature for 2-4 hours. After the reaction is complete, remove the solvent by distillation under reduced pressure, and recrystallize the residue from a mixed solvent of ethanol / ether in a volume ratio of 1:4 to obtain amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride. A7. Dissolve 10-15 parts of toluene diisocyanate in 100-200 parts of anhydrous tetrahydrofuran, cool in an ice-water bath at 0-5°C, slowly dropwise add a mixed solution of 10-15 parts of 2-hydroxypropionitrile and 50 parts of tetrahydrofuran while passing nitrogen. After the addition is complete, heat to 25-30°C and react for 2-3 hours to generate a mono-protected toluene diisocyanate intermediate. Add 10-20 parts of amino-terminated hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride to 100-120 parts of tetrahydrofuran, pass nitrogen, stir to dissolve, slowly dropwise add the mono-protected toluene diisocyanate intermediate solution, control the temperature at 25-30°C, react for 3-4 hours, and after the reaction is complete, add an excess of 10% aqueous hydrochloric acid solution to the reaction system and stir at room temperature for 1-2 minutes. h was deprotected, the pH was adjusted to 7-8 with sodium carbonate solid, the solvent was removed by distillation under reduced pressure, the residue was extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain N-(hydroxyethyl methacrylate glycidyl ether trimethylammonium chloride)-N'-(tolyl)urea.

5. The puncture-resistant medical packaging film according to claim 1, characterized in that: The reinforcing agent is one of polyvinyl alcohol, polyacrylamide and nanocellulose.

6. The puncture-resistant medical packaging film according to claim 1, characterized in that: The auxiliary agent is one of polyvinyl pyrrolidone, polydimethylsiloxane and polyethylene glycol.

7. The puncture-resistant medical packaging film according to claim 1, characterized in that: The antioxidant is one of 1010, 1076, and 1135.

8. The puncture-resistant medical packaging film according to claim 1, characterized in that: The antistatic agent is one of sodium dodecylbenzene sulfonate, sodium stearate and triethanolamine.

9. The method for preparing a puncture-resistant medical packaging film according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Raw material blending: slowly add ethylene copolymer to toluene solvent, stir and dissolve in a water bath at 60-80°C to prepare an ethylene copolymer solution with a mass fraction of 10-30%. Cut the modified aramid fiber into 3-5 mm short fibers, add the fibers to the ethylene copolymer solution, and then add a reinforcing agent, auxiliary agent, antioxidant, and antistatic agent. Use a high-speed disperser to disperse the fibers at a speed of 2000-5000 rpm for 30-60 minutes. Place the fibers in a vacuum degassing machine and treat at a vacuum degree of -0.06-0.08 MPa for 30-60 minutes. S2. Tape casting: Pour the degassed mixed solution into the hopper of the tape casting machine, and use a scraper to evenly coat the solution on a stainless steel cooling roller at a temperature of 60-80°C to form a film with uniform thickness. The gap between the scraper and the cooling roller is set to 0.1 mm, and the casting speed is 5 m / min. S3, film blank drying: the film blank after tape casting is sent to the hot air drying oven for solvent volatilization. The temperature of the drying oven is controlled in stages. The temperature is set at 60~80℃ in the first stage and maintained for 30~60 minutes. In the second stage, the temperature is raised to 100~120℃ and maintained for 10~20 minutes. S4. Stretching and shaping: The dried film is sent to a stretching machine for biaxial stretching and shaping. First, it is stretched in the longitudinal direction at a stretching ratio of 1.5 times, and the stretching temperature is 80-90°C; then it is stretched in the transverse direction at a stretching ratio of 2 times, and the stretching temperature is 90-95°C. The mechanical properties and dimensional stability of the film are improved by biaxial stretching. After stretching, the film is heat-set at 100-120°C for 10-30 minutes; S5. Winding: Use a winding device to roll the stretched and shaped packaging film into a roll at a speed of 8 m / min. During the winding process, control the winding tension to 10 N to obtain a finished medical packaging film.

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