Environment-friendly medicinal composite packaging film and preparation method thereof

Abstract

The invention relates to the field of medicinal packaging films, in particular to an environment-friendly medicinal composite packaging film and a preparation method thereof, which are used for solving the problems of poor mechanical property, antibacterial sanitary property and barrier property of the existing medicinal packaging film. The composite packaging film is composed of a polypropylene base film and a composite reinforcing layer, the existence of the composite reinforcing layer can improve the mechanical property of the polypropylene base film, effectively improve the impact and tear resistance of the polypropylene base film, effectively prevent permeation of moisture and gas, and avoid deliquescence and oxidation of drugs caused by moisture and oxygen to cause deterioration; the growth of microorganisms can be effectively inhibited, an excellent antibacterial function is endowed to the medicine, and the medicine can be effectively prevented from being polluted by the microorganisms in the storage and transportation processes; the preparation method is simple in process, convenient to operate and suitable for large-scale production, and the used raw materials are environment-friendly, so that the prepared composite packaging film has excellent environment-friendly performance.

Description

Technical Field

[0001] The present invention relates to the field of medicinal packaging films, and in particular to an environmentally friendly medicinal composite packaging film and a preparation method thereof. Background Art

[0002] Pharmaceutical packaging films play a crucial role in the storage, transportation, and distribution of pharmaceuticals, directly impacting their quality and safety. Polypropylene film, due to its lightweight, waterproof, corrosion-resistant, and excellent transparency, has been widely used in pharmaceutical packaging. However, single-use polypropylene film has limitations in mechanical properties, antibacterial hygiene, and barrier properties. It cannot effectively block the intrusion of oxygen, water vapor, and light. Furthermore, it is prone to microbial growth during storage and transportation, which can lead to drug deterioration and compromise quality. This makes it difficult to meet the packaging requirements of some demanding pharmaceuticals.

[0003] Therefore, the development of an environmentally friendly pharmaceutical composite packaging film and its preparation method is of great significance for improving the mechanical properties, antibacterial and hygienic properties, and barrier properties of the pharmaceutical packaging film. Summary of the Invention

[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide an environmentally friendly medicinal composite packaging film and a preparation method thereof, which solves the problems of poor mechanical properties, antibacterial and hygienic properties and barrier properties of existing medicinal packaging films.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An environmentally friendly medicinal composite packaging film, consisting of a polypropylene base film and composite reinforcement layers on both sides of the polypropylene base film;

[0007] Wherein, the composite reinforcement layer comprises the following components in parts by weight:

[0008] 12-16 parts of carnauba wax, 1-5 parts of composite enhancer, 0.3-0.5 parts of gum arabic, 0.8-1.2 parts of emulsifier, 2-3 parts of acetic acid and 100-110 parts of deionized water;

[0009] Wherein, the composite reinforcing agent is prepared by the following steps:

[0010] Step s1: Add hydroxyl carbon nanotubes, absolute ethanol, and deionized water into a three-necked flask equipped with a stirrer and a thermometer. Under the condition of ultrasonic treatment at an ultrasonic frequency of 30 - 40 kHz for 20 - 30 min, then add ammonia water solution and continue ultrasonic treatment for 8 - 10 min. Then, under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, stir and react for 10 - 20 min. Then, raise the temperature to 60 - 65 °C and continue stirring and reacting for 10 - 20 min. Then, add vinyltriethoxysilane and continue stirring and reacting for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Then, wash the precipitate with distilled water 3 - 5 times, and then place it in a vacuum drying oven and dry it at a temperature of 40 - 45 °C for 5 - 6 h to obtain alkenyl-grafted carbon nanotubes;

[0011] Step s2: Add chitosan, deionized water, and acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, stir and react for 20 - 30 min. Then, add maleic anhydride and continue stirring and reacting for 6 - 8 h. After the reaction is completed, cool the reaction product to room temperature, then add it to absolute acetone, then centrifuge. Then, place the precipitate in a vacuum drying oven and dry it at a temperature of 40 - 45 °C for 3 - 5 h to obtain alkenyl-grafted chitosan;

[0012] Step s3: Add alkenyl-grafted chitosan, deionized water, and acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, stir and react for 20 - 30 min. Then, add (3-acrylamidopropyl)trimethylammonium chloride and ammonium persulfate and continue stirring and reacting for 20 - 30 min. Then, raise the temperature to 60 - 65 °C and continue stirring and reacting for 2 - 3 h. Then, add alkenyl-grafted carbon nanotubes and continue stirring and reacting for 1 - 2 h. After the reaction is completed, cool the reaction product to room temperature, then freeze-dry to obtain a composite reinforcing agent.

[0013] As a further scheme of the present invention: The dosage ratio of the hydroxyl carbon nanotubes, absolute ethanol, deionized water, ammonia water, and vinyltriethoxysilane in step s1 is 2 g : 30 - 35 mL : 2 - 3 mL : 10 - 15 mL : 7 - 13 mL.

[0014] As a further scheme of the present invention: The hydroxyl carbon nanotubes in step s1 are TNSMH1 short high-purity multi-walled carbon nanotubes; the mass fraction of the ammonia water is 20 - 22%.

[0015] As a further solution of the present invention: the dosage ratio of the chitosan, deionized water, acetic acid and maleic anhydride in step s2 is 5 g: 50 - 55 mL: 0.5 - 0.9 mL: 1.1 - 2.3 g.

[0016] As a further solution of the present invention: the chitosan in step s2 is chitosan with a deacetylation degree ≥ 95% and a viscosity of 100 - 200 mPa·s.

[0017] As a further solution of the present invention: the dosage ratio of the alkenyl-grafted chitosan, deionized water, acetic acid, (3-acrylamidopropyl) trimethyl ammonium chloride, ammonium persulfate and alkenyl-grafted carbon nanotubes in step s3 is 10 g: 80 - 90 mL: 2 - 4 mL: 0.8 - 2.2 g: 0.2 - 0.4 g: 0.5 - 1.5 g.

[0018] As a further solution of the present invention: a preparation method of an environmentally friendly pharmaceutical composite packaging film includes the following steps:

[0019] Step 1: Weigh 12 - 16 parts of carnauba wax, 1 - 5 parts of composite reinforcing agent, 0.3 - 0.5 parts of gum arabic, 0.8 - 1.2 parts of emulsifier, 2 - 3 parts of acetic acid and 100 - 110 parts of deionized water according to weight, and set aside;

[0020] Step 2: Add the composite reinforcing agent, acetic acid and deionized water into a mixer, stir and mix at a temperature of 25 - 30 °C and a stirring rate of 800 - 1000 r / min for 30 - 50 min, then add carnauba wax, gum arabic and emulsifier and continue to stir and mix for 10 - 15 min, then raise the temperature to 80 - 85 °C and continue to stir and mix for 2 - 3 h, and then cool to room temperature to obtain a film-forming solution;

[0021] Step 3: Cast polypropylene resin into a film through a casting machine to obtain a polypropylene base film;

[0022] Step 4: Coat the film-forming solution on the inner and outer surfaces of the polypropylene base film, then place it in a vacuum drying oven, dry it at a temperature of 60 - 65 °C for 20 - 30 min, then raise the temperature to 80 - 90 °C and continue to dry for 10 - 15 min to cure the film and form a composite reinforcing layer to obtain the environmentally friendly pharmaceutical composite packaging film.

[0023] As a further solution of the present invention: the carnauba wax is carnauba wax T1.

[0024] As a further solution of the present invention: the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio.

[0025] As a further solution of the present invention: the polypropylene resin is LG PP R3450.

[0026] Advantages of the present invention:

[0027] An environmentally friendly pharmaceutical composite packaging film and a preparation method thereof according to the present invention, by stirring and mixing a composite enhancer, acetic acid and deionized water, and then adding carnauba wax, gum arabic and an emulsifier and continuing to stir and mix to obtain a film-forming solution, and then casting the polypropylene resin into a film by a casting machine to obtain a polypropylene base film, and then coating the film-forming solution on the inner and outer surfaces of the polypropylene base film and curing to form a film to form a composite reinforcement layer, thereby obtaining an environmentally friendly pharmaceutical composite packaging film; the composite packaging film is composed of a polypropylene base film and composite reinforcement layers on both sides of the polypropylene base film, and the presence of the composite reinforcement layer can improve the mechanical properties of the polypropylene base film, effectively improve the ability of the polypropylene base film to resist impact and tearing, and can effectively prevent the penetration of moisture and gas, avoid the deliquescence and oxidation of drugs caused by moisture and oxygen, and thus lead to deterioration, and can also effectively inhibit the growth of microorganisms, endowing it with excellent antibacterial function, and can effectively prevent the contamination of drugs by microorganisms during storage and transportation; the preparation method has simple process and convenient operation, is suitable for large-scale production, and the raw materials used are environmentally friendly, so that the prepared composite packaging film has excellent environmental protection performance. Among them, the carnauba wax molecule structure contains a long hydrocarbon chain, with excellent hydrophobicity and low gas permeability. During the film-forming process, its molecules are closely arranged to form a continuous and dense wax layer, which, like a physical barrier, significantly reduces the diffusion rate of gas and moisture, and can effectively hinder the penetration of small molecules such as oxygen and water vapor, thereby greatly improving the barrier properties of the packaging film to oxygen and water vapor.

[0028] In the process of preparing the composite packaging film, a composite reinforcing agent was first prepared. First, vinyltriethoxysilane was used for modification. After the siloxane on vinyltriethoxysilane was hydrolyzed into silanol, it was grafted onto the surface of hydroxyl carbon nanotubes, improving the dispersibility of hydroxyl carbon nanotubes and avoiding their agglomeration. At the same time, a large number of alkenyl groups were introduced to obtain alkenyl-grafted carbon nanotubes. Then, chitosan and maleic anhydride reacted. The molecular structure of chitosan contains a large number of amino and hydroxyl groups, which can react with maleic anhydride. A large number of alkenyl groups were introduced into the chitosan molecular structure to obtain alkenyl-grafted chitosan. Finally, (3-acrylamidopropyl) trimethylammonium chloride and alkenyl-grafted carbon nanotubes were used to modify alkenyl-grafted chitosan. Under the initiation of ammonium persulfate, the three substances polymerized using alkenyl groups, thereby grafting quaternary ammonium groups and carbon nanotubes onto the molecular structure of chitosan to obtain a composite reinforcing agent. The chitosan in this composite reinforcing agent has biocompatibility, degradability, excellent environmental protection performance, and certain antibacterial properties. After introducing quaternary ammonium groups, its antibacterial performance can be further significantly improved. The carbon nanotubes in this composite reinforcing agent have a unique nanostructure, can fill the tiny pores in the composite reinforcing layer, further improve the barrier performance of the composite packaging film, and the carbon nanotubes have extremely high strength and modulus, and can significantly improve the mechanical properties of the composite packaging film as a nano-reinforcing phase. Detailed implementation mode

[0029] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0030] Example 1:

[0031] This example is a preparation method of an environmentally friendly medicinal composite packaging film, including the following steps:

[0032] Step S1: Add 2 g of hydroxyl carbon nanotubes TNSMH1, 30 mL of absolute ethanol, and 2 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Under the condition of an ultrasonic frequency of 30 kHz, perform ultrasonic treatment for 20 min. Then add 10 mL of an ammonia water solution with a mass fraction of 20% and continue ultrasonic treatment for 8 min. Then, under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, stir and react for 10 min. Then raise the temperature to 60 °C and continue stirring and reacting for 10 min. Then add 7 mL of vinyltriethoxysilane and continue stirring and reacting for 4 h. After the reaction ends, cool the reaction product to room temperature, then centrifuge. Then wash the precipitate with distilled water 3 times, and then place it in a vacuum drying oven and dry it at a temperature of 40 °C for 5 h to obtain alkenyl-grafted carbon nanotubes;

[0033] [[ID=३]]Step S2: Add 5 g of chitosan with a deacetylation degree ≥ ९५% and a viscosity of १०० - २०० mPa·s, ५० mL of deionized water, and ०.५ mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of २५ °C and a stirring rate of २०० r / min, stir and react for २० min. Then add १.१ g of maleic anhydride and continue stirring and reacting for ६ h. After the reaction ends, cool the reaction product to room temperature, then add it to anhydrous acetone, then centrifuge. Then place the precipitate in a vacuum drying oven and dry it at a temperature of ४० °C for ३ h to obtain alkenyl-grafted chitosan;

[0034] Step S3: Add 10 g of alkenyl-grafted chitosan, 80 mL of deionized water, and 2 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, stir and react for 20 min. Then add 0.8 g of (3-acrylamidopropyl) trimethylammonium chloride and 0.2 g of ammonium persulfate and continue stirring and reacting for 20 min. Then raise the temperature to 60 °C and continue stirring and reacting for 2 h. Then add 0.5 g of alkenyl-grafted carbon nanotubes and continue stirring and reacting for 1 h. After the reaction ends, cool the reaction product to room temperature, then freeze-dry to obtain a composite reinforcing agent;

[0035] Step S4: Weigh 12 parts of carnauba wax, 1 part of composite reinforcing agent, 0.3 part of gum arabic, 0.8 part of emulsifier, 2 parts of acetic acid, and 100 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0036] Step S5: Add the composite enhancer, acetic acid, and deionized water into a mixer, stir and mix for 30 min under the conditions of a temperature of 25°C and a stirring rate of 800 r / min. Then add carnauba wax, gum arabic, and an emulsifier and continue to stir and mix for 10 min. Then raise the temperature to 80°C and continue to stir and mix for 2 h. Then cool to room temperature to obtain a film-forming solution.

[0037] Step S6: Cast the polypropylene resin into a film through a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450.

[0038] Step S7: Coat the film-forming solution on the inner and outer surfaces of the polypropylene-based film, then place it in a vacuum drying oven, dry for 20 min under the condition of a temperature of 60°C, then raise the temperature to 80°C and continue to dry for 10 min to cure into a film, forming a composite reinforcing layer with a thickness of 5 μm to obtain an environmentally friendly pharmaceutical composite packaging film.

[0039] Example 2:

[0040] The present embodiment is a preparation method of an environmentally friendly pharmaceutical composite packaging film, including the following steps:

[0041] Step S1: Add 2 g of hydroxyl carbon nanotube TNSMH1, 32 mL of absolute ethanol, and 2.5 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer, perform ultrasonic treatment for 25 min under the condition of an ultrasonic frequency of 35 kHz, then add 12 mL of an ammonia water solution with a mass fraction of 21% and continue ultrasonic treatment for 9 min. Then stir and react for 15 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min. Then raise the temperature to 62°C and continue to stir and react for 15 min. Then add 10 mL of vinyltriethoxysilane and continue to stir and react for 4.5 h. After the reaction ends, cool the reaction product to room temperature, then centrifuge, then wash the precipitate with distilled water for 4 times, and then place it in a vacuum drying oven and dry for 5.5 h under the condition of a temperature of 42°C to obtain alkenyl-grafted carbon nanotubes.

[0042] Step S2: Add 5 g of chitosan with a deacetylation degree ≥95% and a viscosity of 100 - 200 mPa·s, 52 mL of deionized water, and 0.7 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 25 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min. Then add 1.7 g of maleic anhydride and continue to stir and react for 7 h. After the reaction ends, cool the reaction product to room temperature, then add it to anhydrous acetone, then centrifuge, and then place the precipitate in a vacuum drying oven and dry for 4 h under the condition of a temperature of 42°C to obtain alkenyl-grafted chitosan.

[0043] Step S3: Add 10 g of vinyl-grafted chitosan, 85 mL of deionized water, and 3 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 25 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min. Then add 1.5 g of (3-acrylamidopropyl) trimethylammonium chloride and 0.3 g of ammonium persulfate, and continue to stir and react for 25 min. Then raise the temperature to 62°C and continue to stir and react for 2.5 h. Then add 1 g of vinyl-grafted carbon nanotubes and continue to stir and react for 1.5 h. After the reaction is completed, cool the reaction product to room temperature, and then freeze-dry to obtain a composite reinforcing agent;

[0044] Step S4: Weigh 14 parts of carnauba wax, 3 parts of the composite reinforcing agent, 0.4 part of gum arabic, 1 part of emulsifier, 2.5 parts of acetic acid, and 105 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0045] Step S6: Add the composite reinforcing agent, acetic acid, and deionized water into a mixer, stir and mix for 40 min under the conditions of a temperature of 28°C and a stirring rate of 900 r / min. Then add carnauba wax, gum arabic, and emulsifier, and continue to stir and mix for 12 min. Then raise the temperature to 82°C and continue to stir and mix for 2.5 h. Then cool to room temperature to obtain a film-forming solution;

[0046] Step S9: Cast the polypropylene resin into a film through a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0047] Step S7: Coat the film-forming solution on the inner and outer surfaces of the polypropylene-based film, then place it in a vacuum drying oven, dry for 25 min under the condition of a temperature of 62°C, then raise the temperature to 85°C and continue to dry for 12 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, obtaining an environmentally friendly pharmaceutical composite packaging film.

[0048] Example 3:

[0049] This example is a preparation method of an environmentally friendly pharmaceutical composite packaging film, including the following steps:

[0050] Step S1: Add 2 g of hydroxyl carbon nanotubes TNSMH1, 35 mL of absolute ethanol, and 3 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically treat for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then add 15 mL of ammonia water with a mass fraction of 22% and continue ultrasonic treatment for 10 min. Then stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then raise the temperature to 65 °C and continue stirring and reacting for 20 min. Then add 13 mL of vinyltriethoxysilane and continue stirring and reacting for 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Then wash the precipitate with distilled water 3 - 5 times. Then place it in a vacuum drying oven and dry at a temperature of 45 °C for 6 h to obtain alkenyl-grafted carbon nanotubes;

[0051] Step S2: Add 5 g of chitosan with a deacetylation degree ≥ 95% and a viscosity of 100 - 200 mPa·s, 55 mL of deionized water, and 0.9 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then add 2.3 g of maleic anhydride and continue stirring and reacting for 8 h. After the reaction is completed, cool the reaction product to room temperature. Then add it to anhydrous acetone. Then centrifuge. Then place the precipitate in a vacuum drying oven and dry at a temperature of 45 °C for 5 h to obtain alkenyl-grafted chitosan;

[0052] Step S3: Add 10 g of alkenyl-grafted chitosan, 90 mL of deionized water, and 4 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then add 2.2 g of (3-acrylamidopropyl)trimethylammonium chloride and 0.4 g of ammonium persulfate and continue stirring and reacting for 3 min. Then raise the temperature to 65 °C and continue stirring and reacting for 3 h. Then add 1.5 g of alkenyl-grafted carbon nanotubes and continue stirring and reacting for 2 h. After the reaction is completed, cool the reaction product to room temperature. Then freeze-dry to obtain a composite reinforcing agent;

[0053] Step S4: Weigh 16 parts of carnauba wax, 5 parts of composite reinforcing agent, 0.5 part of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0054] Step S5: Add the composite enhancer, acetic acid, and deionized water into a mixer, stir and mix them at a temperature of 30°C and a stirring rate of 1000 r / min for 50 min. Then add carnauba wax, gum arabic, and emulsifier and continue to stir and mix for 15 min. Then raise the temperature to 85°C and continue to stir and mix for 3 h. Then cool to room temperature to obtain the film-forming liquid;

[0055] Step S6: Cast the polypropylene resin into a film by a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0056] Step S7: Coat the film-forming liquid on the inner and outer surfaces of the polypropylene-based film, then place it in a vacuum drying oven, dry it at a temperature of 65°C for 30 min, then raise the temperature to 90°C and continue to dry for 15 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, obtaining the environmentally friendly medicinal composite packaging film.

[0057] Comparative Example 1:

[0058] This comparative example is a preparation method of an environmentally friendly medicinal composite packaging film, including the following steps:

[0059] Step S1: Weigh 0.5 parts of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water by weight and set aside; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0060] Step S2: Add acetic acid and deionized water into a mixer, stir and mix them at a temperature of 30°C and a stirring rate of 1000 r / min for 50 min. Then add gum arabic and emulsifier and continue to stir and mix for 15 min. Then raise the temperature to 85°C and continue to stir and mix for 3 h. Then cool to room temperature to obtain the film-forming liquid;

[0061] Step S3: Cast the polypropylene resin into a film by a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0062] Step S4: Coat the film-forming liquid on the inner and outer surfaces of the polypropylene-based film, then place it in a vacuum drying oven, dry it at a temperature of 65°C for 30 min, then raise the temperature to 90°C and continue to dry for 15 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, obtaining the environmentally friendly medicinal composite packaging film.

[0063] Comparative Example 2:

[0064] This comparative example is a preparation method of an environmentally friendly medicinal composite packaging film, including the following steps:

[0065] Step S1: Weigh 16 parts of carnauba wax, 0.5 part of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0066] Step S2: Add acetic acid and deionized water into a mixer, stir and mix at a temperature of 30 °C and a stirring rate of 1000 r / min for 50 min, then add carnauba wax, gum arabic, and emulsifier and continue to stir and mix for 15 min, then raise the temperature to 85 °C and continue to stir and mix for 3 h, and then cool to room temperature to obtain a film-forming solution;

[0067] Step S3: Cast and form a film from polypropylene resin through a casting machine to obtain a polypropylene base film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0068] Step S4: Coat the film-forming solution on the inner and outer surfaces of the polypropylene base film, then place it in a vacuum drying oven, dry it at a temperature of 65 °C for 30 min, then raise the temperature to 90 °C and continue to dry for 15 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, obtaining an environmentally friendly pharmaceutical composite packaging film.

[0069] Comparative Example 3:

[0070] The preparation method of an environmentally friendly pharmaceutical composite packaging film in this comparative example includes the following steps:

[0071] Step S1: Weigh 16 parts of carnauba wax, 5 parts of chitosan, 0.5 part of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0072] Step S2: Add chitosan, acetic acid, and deionized water into a mixer, stir and mix at a temperature of 30 °C and a stirring rate of 1000 r / min for 50 min, then add carnauba wax, gum arabic, and emulsifier and continue to stir and mix for 15 min, then raise the temperature to 85 °C and continue to stir and mix for 3 h, and then cool to room temperature to obtain a film-forming solution;

[0073] Step S3: Cast and form a film from polypropylene resin through a casting machine to obtain a polypropylene base film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0074] Step S4: Coat the inner and outer surfaces of the polypropylene base film with the film-forming solution, then place it in a vacuum drying oven and dry it at 65 °C for 30 min, then raise the temperature to 90 °C and continue drying for 15 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, obtaining an environmentally friendly pharmaceutical composite packaging film.

[0075] Comparative Example 4:

[0076] This comparative example is a preparation method of an environmentally friendly pharmaceutical composite packaging film, including the following steps:

[0077] Step S1: Add 5 g of chitosan with a deacetylation degree of ≥95% and a viscosity of 100 - 200 mPa·s, 55 mL of deionized water, and 0.9 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer, stir and react at 30 °C and a stirring rate of 300 r / min for 30 min, then add 2.3 g of maleic anhydride and continue stirring and reacting for 8 h. After the reaction ends, cool the reaction product to room temperature, then add it to anhydrous acetone, then centrifuge, and then place the precipitate in a vacuum drying oven and dry it at 45 °C for 5 h to obtain vinyl-grafted chitosan;

[0078] Step S2: Add 10 g of vinyl-grafted chitosan, 90 mL of deionized water, and 4 mL of acetic acid into a three-necked flask equipped with a stirrer and a thermometer, stir and react at 30 °C and a stirring rate of 300 r / min for 30 min, then add 2.2 g of (3-acrylamidopropyl) trimethylammonium chloride and 0.4 g of ammonium persulfate and continue stirring and reacting for 30 min, then raise the temperature to 65 °C and continue stirring and reacting for 3 h. After the reaction ends, cool the reaction product to room temperature, then freeze-dry to obtain a composite reinforcing agent;

[0079] Step S3: Weigh 16 parts of carnauba wax, 5 parts of composite reinforcing agent, 0.5 part of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water by weight for standby; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0080] Step S4: Add the composite reinforcing agent, acetic acid, and deionized water into a mixer, stir and mix at 30 °C and a stirring rate of 1000 r / min for 50 min, then add carnauba wax, gum arabic, and emulsifier and continue stirring and mixing for 15 min, then raise the temperature to 85 °C and continue stirring and mixing for 3 h, then cool to room temperature to obtain a film-forming solution;

[0081] Step S5: Cast the polypropylene resin into a film through a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0082] Step S6: Coat the film-forming solution on the inner and outer surfaces of the polypropylene-based film, then place it in a vacuum drying oven and dry it at a temperature of 65 °C for 30 min, then raise the temperature to 90 °C and continue drying for 15 min to cure the film and form a composite reinforcing layer with a thickness of 5 μm, thus obtaining an environmentally friendly pharmaceutical composite packaging film.

[0083] Comparative Example 5:

[0084] This comparative example is a method for preparing an environmentally friendly pharmaceutical composite packaging film, including the following steps:

[0085] Step S1: Add 2 g of hydroxycarbon nanotube TNSMH1, 35 mL of absolute ethanol, and 3 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer, ultrasonically treat it for 30 min under the condition of an ultrasonic frequency of 40 kHz, then add 15 mL of ammonia water with a mass fraction of 22% and continue ultrasonically treat it for 10 min, then stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then raise the temperature to 65 °C and continue stirring and reacting for 20 min, then add 13 mL of vinyltriethoxysilane and continue stirring and reacting for 5 h. After the reaction ends, cool the reaction product to room temperature, then centrifuge, then wash the precipitate with distilled water 3 - 5 times, and then place it in a vacuum drying oven and dry it at a temperature of 45 °C for 6 h to obtain alkenyl-grafted carbon nanotubes;

[0086] Step S2: Weigh 16 parts of carnauba wax, 5 parts of alkenyl-grafted carbon nanotubes, 0.5 part of gum arabic, 1.2 parts of emulsifier, 3 parts of acetic acid, and 110 parts of deionized water according to weight, and set aside; the carnauba wax is carnauba wax T1; the emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio;

[0087] Step S3: Add the alkenyl-grafted carbon nanotubes, acetic acid, and deionized water into a mixer, stir and mix them for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 1000 r / min, then add the carnauba wax, gum arabic, and emulsifier and continue stirring and mixing for 15 min, then raise the temperature to 85 °C and continue stirring and mixing for 3 h, and then cool to room temperature to obtain a film-forming solution;

[0088] Step S4: Cast the polypropylene resin into a film through a casting machine to obtain a polypropylene-based film with a thickness of 50 μm; the polypropylene resin is LG PP R3450;

[0089] Step S5: Coat the inner and outer surfaces of the polypropylene base film with the film-forming solution, then place it in a vacuum drying oven and dry it at a temperature of 65°C for 30 minutes, then raise the temperature to 90°C and continue drying for 15 minutes to cure and form a film, forming a composite reinforcement layer with a thickness of 5 μm, and obtaining an environmentally friendly pharmaceutical composite packaging film.

[0090] Test the tensile strength of the environmentally friendly pharmaceutical composite packaging films of Examples 1-3 and Comparative Examples 1-5 in accordance with GB / T 1040.3-2006, test the antibacterial rate against Escherichia coli in accordance with WS / T 650-2019, test the water contact angle using a DSA 30 contact angle analyzer, and test the water vapor transmission rate in accordance with GB 1037-1988. The test results are shown in the following table:

[0091]

[0092] Referring to the data in the above table, from the comparison between Examples 1-3 and Comparative Examples 1-5, it can be known that the environmentally friendly pharmaceutical composite packaging film of the present application has excellent mechanical properties, antibacterial and hygienic properties, and barrier properties.

[0093] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0094] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by this application, they should all fall within the protection scope of the present invention.

Claims

1. An environmentally friendly pharmaceutical composite packaging film, characterized in that, It is composed of a polypropylene base film and composite reinforcing layers on both sides of the polypropylene base film; Among them, the composite reinforcing layer includes the following components in parts by weight: 12 - 16 parts of carnauba wax, 1 - 5 parts of composite reinforcing agent, 0.3 - 0.5 parts of arabic gum, 0.8 - 1.2 parts of emulsifier, 2 - 3 parts of acetic acid, and 100 - 110 parts of deionized water; Among them, the composite reinforcing agent is prepared by the following steps: Step s1: Ultrasonically treat hydroxyl carbon nanotubes, absolute ethanol, and deionized water, then add ammonia water solution and continue ultrasonic treatment, then add vinyltriethoxysilane and stir for reaction. After the reaction ends, cool the reaction product, then centrifuge, and then wash and dry the precipitate to obtain alkenyl-grafted carbon nanotubes; Step s2: Stir and react chitosan, deionized water, and acetic acid, then add maleic anhydride and continue stirring for reaction. After the reaction ends, cool the reaction product, then add it to anhydrous acetone, then centrifuge, and then dry the precipitate to obtain alkenyl-grafted chitosan; Step s3: Stir and react alkenyl-grafted chitosan, deionized water, and acetic acid, then add (3-acrylamidopropyl)trimethylammonium chloride, ammonium persulfate, and alkenyl-grafted carbon nanotubes and continue stirring for reaction. After the reaction ends, cool the reaction product, then freeze-dry to obtain the composite reinforcing agent.

2. The environmentally friendly medicinal composite packaging film according to claim 1, characterized in that, The dosage ratio of the hydroxyl carbon nanotubes, absolute ethanol, deionized water, ammonia water, and vinyltriethoxysilane in step s1 is 2g:30 - 35mL:2 - 3mL:10 - 15mL:7 - 13mL.

3. An environmentally friendly pharmaceutical composite packaging film according to claim 1, characterized in that, The hydroxyl carbon nanotubes in step s1 are TNSMH1 short high-purity multi-walled carbon nanotubes; the mass fraction of the ammonia water is 20 - 22%.

4. An environmentally friendly medicinal composite packaging film according to claim 1, characterized in that, The dosage ratio of the chitosan, deionized water, acetic acid, and maleic anhydride in step s2 is 5g:50 - 55mL:0.5 - 0.9mL:1.1 - 2.3g.

5. The environmentally friendly pharmaceutical composite packaging film according to claim 1, wherein The chitosan in step s2 is chitosan with a deacetylation degree ≥95% and a viscosity of 100 - 200mPa·s.

6. The environmentally friendly pharmaceutical composite packaging film according to claim 1, wherein, The dosage ratio of the alkenyl-grafted chitosan, deionized water, acetic acid, (3-acrylamidopropyl)trimethylammonium chloride, ammonium persulfate, and alkenyl-grafted carbon nanotubes in step s3 is 10g:80 - 90mL:2 - 4mL:0.8 - 2.2g:0.2 - 0.4g:0.5 - 1.5g.

7. A preparation method of an environmentally friendly pharmaceutical composite packaging film, characterized in that, It includes the following steps: Step one: Weigh 12 - 16 parts of carnauba wax, 1 - 5 parts of composite reinforcing agent, 0.3 - 0.5 parts of arabic gum, 0.8 - 1.2 parts of emulsifier, 2 - 3 parts of acetic acid, and 100 - 110 parts of deionized water according to parts by weight and set aside; Step two: Add the composite reinforcing agent, acetic acid, and deionized water to a mixer, stir and mix at a temperature of 25 - 30°C and a stirring rate of 800 - 1000r / min for 30 - 50min, then add carnauba wax, arabic gum, and emulsifier and continue stirring and mixing for 10 - 15min, then raise the temperature to 80 - 85°C and continue stirring and mixing for 2 - 3h, and then cool to room temperature to obtain a film-forming solution; Step 3: Cast the polypropylene resin into a film through a casting machine to obtain a polypropylene-based film; Step 4: Coat the inner and outer surfaces of the polypropylene-based film with the film-forming solution, then place it in a vacuum drying oven and dry it for 20 - 30 min under the condition of a temperature of 60 - 65 °C, and then raise the temperature to 80 - 90 °C and continue to dry it for 10 - 15 min to cure the film and form a composite reinforcement layer, thereby obtaining an environmentally friendly pharmaceutical composite packaging film.

8. The preparation method of an environmentally friendly pharmaceutical composite packaging film according to claim 7, characterized in that The carnauba wax is carnauba wax T1.

9. The preparation method of an environmentally friendly pharmaceutical composite packaging film according to claim 7, characterized in that, The emulsifier is a mixture of span-80 emulsifier and tween-80 emulsifier in an equal mass ratio.

10. The preparation method of an environmentally friendly pharmaceutical composite packaging film according to claim 7, characterized in that, The polypropylene resin is LG PP R3450.

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