Antibacterial medicinal aluminum foil and production method thereof

Abstract

The invention discloses an antibacterial medicinal aluminum foil and a production method thereof, and the production method comprises the following procedures: aluminum foil unwinding, traction, deviation correction, coating of a water-based antibacterial coating on the front surface of the aluminum foil, drying in a drying oven, traction, deviation correction and antibacterial medicinal aluminum foil winding. Comprising 40-60 parts of waterborne polyurethane resin, 30-40 parts of waterborne acrylic resin, 3-5 parts of a curing agent, 2-4 parts of a flatting agent, 1-3 parts of a dispersing agent, 1-3 parts of a defoaming agent, 1-3 parts of a coalescing agent, 3-8 parts of a thickening agent, 1-3 parts of an antibacterial agent and 20-30 parts of water. Compared with the prior art, the medical aluminum foil prepared by the preparation method disclosed by the invention has better antibacterial property, rupture strength and ultraviolet aging resistance.

Description

Technical Field

[0001] The invention relates to the technical field of pharmaceutical packaging materials, and in particular to an antibacterial medicinal aluminum foil and a production method thereof. Background Art

[0002] Medicinal aluminum foil is a special material designed for pharmaceutical packaging. It is an ideal choice for pharmaceutical packaging due to its excellent barrier, moisture resistance and light protection properties. In the pharmaceutical field, the application of medicinal aluminum foil is particularly strict. It usually needs to be compounded with paper, plastic and other materials to form a composite structure of at least three layers to meet the test requirements of sealing leakage performance, bursting pressure, rupture strength and so on. Medicinal aluminum foil is mainly used for blister packaging, such as aluminum-plastic blister packaging for tablets and capsules, and strip packaging. It is soft and can adapt to the packaging needs of various shapes of medicines. For drugs that require harder packaging to protect the drug form, the hardness and strength of medicinal aluminum foil also need to be adjusted accordingly to meet the requirements. Since drugs may be exposed to light, heat absorbed from the outside world or absorbed from external moisture during long-term storage, the drugs may undergo qualitative changes. The barrier, rupture strength and light resistance of general pharmaceutical packaging aluminum foil are poor, and the service life is short. Therefore, a new type of antibacterial medicinal aluminum foil is needed to meet the needs.

[0003] Prior art CN111549261A discloses a preparation method of a short-process cast-rolled billet to produce deep-drawn cold-formed medicinal aluminum foil, which sequentially undergoes the steps of smelting, cast-rolling, cold rolling, homogenization high-temperature treatment, intermediate rolling, longitudinal shearing, intermediate annealing, finishing rolling, foil rolling, coiling, rolling products, slitting, and furnace annealing. The raw materials of the invention are composed of an aluminum alloy and an Al-Fe intermediate alloy with a mass content of 20% or an additive containing an Fe mass content of 75%, wherein the proportions of each element in the aluminum alloy are Si=0.025-0.10%, Fe=1.25-1.65%, Cu=0.001-0.10%, Mn<0.05%, Mg<0.05%, Cr<0.05%, Zn<0.05%, Ti=0.01-0.04%, and the rest is Al. The medicinal aluminum foil provided by the invention has the advantages of high tearing strength, good barrier properties, and excellent deep-drawing and cold-forming performance, but its antibacterial performance is poor, which is not conducive to ensuring that the drug maintains its stability and effectiveness during the shelf life. Summary of the invention

[0004] In view of the above-mentioned defects of the prior art, the present invention provides an antibacterial medicinal aluminum foil and a production method thereof. The medicinal aluminum foil prepared by the present invention not only has excellent antibacterial properties, but also has good barrier properties, rupture strength and resistance to ultraviolet light aging.

[0005] To achieve the above-mentioned purpose, the present invention provides a method for producing an antibacterial medicinal aluminum foil, comprising the following steps: unwinding the aluminum foil - pulling - correcting the deviation - coating the front side of the aluminum foil with a water-based antibacterial coating - drying in an oven - pulling - correcting the deviation - winding the antibacterial medicinal aluminum foil.

[0006] Preferably, the aluminum foil has a width of 500-1000 mm and a thickness of 0.005-0.15 mm.

[0007] Preferably, the coating amount of the water-based antibacterial coating on the front side of the aluminum foil is 2-6 g / m 2 .

[0008] Preferably, the raw materials for preparing the water-based antibacterial coating include, by weight: 40-60 parts of water-based polyurethane resin, 30-40 parts of water-based acrylic resin, 3-5 parts of curing agent, 2-4 parts of leveling agent, 1-3 parts of dispersant, 1-3 parts of defoaming agent, 1-3 parts of film-forming aid, 3-8 parts of thickener, 1-3 parts of antibacterial agent, and 20-30 parts of water.

[0009] Preferably, the preparation method of the water-based antibacterial coating comprises the following steps: Mix water-based polyurethane resin, water-based acrylic resin, curing agent, leveling agent, dispersant, defoaming agent, film-forming aid and water, and disperse at high speed at 650-850 rpm for 3-8 minutes to obtain a mixed solution; then add the antibacterial agent and thickener to the mixed solution, and disperse at high speed at 900-1200 rpm for 15-20 minutes to obtain a water-based coating.

[0010] Preferably, the curing agent is an isocyanate curing agent.

[0011] Preferably, the leveling agent is selected from one of German BYK-345, BYK-333 and BYK-330.

[0012] Preferably, the dispersant is selected from BYK-156, BYK-151, BYK-153, TEGO® Dispers 750W, and TEGO® Dispers 655 of German BYK.

[0013] Preferably, the defoaming agent is one or more of polydimethylsiloxane, German BYK-093, BYK-025, BYK-028, BYK-092.

[0014] Preferably, the film-forming aid is selected from one of dipropylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether and ethylene glycol tert-butyl ether.

[0015] Preferably, the thickener is selected from palygorskite and modified palygorskite.

[0016] Preferably, the preparation method of the modified palygorskite comprises the following steps, calculated by weight: 10-15 parts of palygorskite and 5-8 parts of modifier are added to 100-140 parts of ethylene glycol, ultrasonically dispersed for 20-40 minutes, and then mixed and stirred at 75-85°C for 5-8 hours; then; centrifuged, the precipitate was collected, washed with ethanol 2-3 times, and vacuum dried at 35-45°C for 22-25 hours to obtain modified palygorskite.

[0017] Further preferably, the modifier is selected from one of cardanol, eugenol and catechol.

[0018] In the coating preparation process, palygorskite is directly mixed with waterborne polyurethane resin and waterborne acrylic resin and is easy to agglomerate in the polymer matrix, resulting in a decrease in the physical and mechanical properties of the coating. In view of this, the present inventors modify palygorskite by using cardanol, eugenol, and catechol as modifiers. The phenolic hydroxyl group in the modifier structure can form hydrogen bonding forces with the exposed -OH and Si-OH of palygorskite, and is grafted on palygorskite to obtain modified palygorskite. The benzene ring in the modifier structure can increase the steric hindrance between molecules, slowing down the agglomeration phenomenon between palygorskite particles. The modification of the modifier can not only improve the problem of uneven dispersion of palygorskite in the polymer substrate, but also help to improve the antibacterial and anti-ultraviolet properties of palygorskite. Compared with eugenol and catechol, the carbon 15 straight chain containing unsaturated double bonds in the meta position of the benzene ring of cardanol can not only wrap palygorskite, so that it has better dispersibility in the polymer substrate, but also provide good toughness, excellent hydrophobicity and low permeability for the water-based coating system.

[0019] Preferably, the preparation method of the antibacterial agent comprises the following steps, calculated by weight: S1, dissolving 0.5-2 parts of hexadecyltrimethylammonium bromide in 8-20 parts of water, then adjusting the pH of the solution to 10.5-11.5, adding 1-4 parts of ethyl orthosilicate dropwise thereto for reaction for 3-6 hours, then subjecting the obtained mixed system to a hydrothermal reaction at 125-140° C. for 20-25 hours, washing, and drying to obtain mesoporous silica; S2, adding 0.9-1.1 parts of maleic anhydride and 2.9-3.1 parts of quercetin to 45-55 parts of dimethyl sulfoxide solution, and then stirring at 35-45°C overnight to obtain a mixed solution A; adding 1.8-2 parts of 1-ethyl-3-(3-dimethyl)aminopropyl-carbodiimide and 1.6-1.8 parts of N-hydroxysuccinimide to 10 parts by weight of dimethyl sulfoxide to obtain a mixed solution B; adding the mixed solution B dropwise to the mixed solution A at room temperature and stirring for 25-35 minutes to obtain a mixed solution C; adding 8-12 parts of an aqueous solution containing 2-8 mg / mL of ε-polylysine to the mixed solution C, stirring at 28-32°C for 22-25 hours to obtain a mixture; the mixture is dialyzed with distilled water for 2-3 days, and then concentrated and dried with a rotary evaporator to obtain a solid, i.e., a polylysine-quercetin complex; S3. Mix 2-5 parts of polylysine-quercetin complex and 0.5-2 parts of mesoporous silica, then add 40-60 parts of anhydrous ethanol and mix evenly to form a suspension, then stir the suspension at 24-26°C, 600-800rpm, 0.04-0.06MPa for 3-5h, return to atmospheric pressure, centrifuge, and dry to obtain mesoporous silica microcapsules loaded with polylysine-quercetin complex, i.e., antibacterial agent.

[0020] Preferably, the step S3 may also be, by weight: 2-5 parts of polylysine-quercetin complex and 0.5-2 parts of mesoporous silica are mixed, and then 40-60 parts of anhydrous ethanol are added and mixed evenly to form a suspension, and then the suspension is placed at 24-26°C, 600-800rpm, -0.1 to -0.5MPa vacuum and stirred for 3-5h, restored to atmospheric pressure, centrifuged, and dried to obtain mesoporous silica microcapsules with internal loading of polylysine-quercetin complex; 0.5-3 parts of mesoporous silica microcapsules with internal loading of polylysine-quercetin complex are mixed with 10-20 parts of 0.01-0.05mol / L tris(hydroxymethylaminomethane)-hydrochloric acid buffer with a pH of 8.5-9.5, and then 1-3 parts of dopamine hydrochloride are added, and the mixture is reacted at 35-37°C for 15-18h to obtain a mixture; thereafter, the mixture is washed and dried to obtain modified mesoporous silica microcapsules, i.e., an antibacterial agent.

[0021] The invention comprises the following steps: maleic anhydride and quercetin are mixed for reaction, during which the anhydride ring of the maleic anhydride opens and forms an ester bond with a hydroxyl group of the quercetin to form an intermediate product; then 1-ethyl-3-(3-dimethyl)aminopropyl-carbodiimide and N-hydroxysuccinimide are introduced and mixed with the intermediate product to activate the carboxyl group in the structure thereof; then, epsilon-polylysine is introduced, so that the amino group in the epsilon-polylysine reacts with the active carboxyl group in the intermediate product to form a stable amide bond, thereby grafting the polylysine onto the quercetin to form a polylysine-quercetin complex. The present invention finds that although the polylysine-quercetin complex formed by grafting quercetin with polylysine can show stronger antibacterial activity and antioxidant performance than quercetin or polylysine alone, it may show poor stability in aqueous media due to its molecular structure and charge distribution characteristics. When it is directly mixed with water-based polyurethane resin, water-based acrylic resin and other raw materials to prepare water-based coatings, it may not only cause its antibacterial and antioxidant activities to be significantly reduced, but also may cause precipitation in the coating, resulting in phase separation, which makes it impossible to be evenly distributed during the coating film formation process, resulting in a decrease in the adhesion of the coating film. At the same time, it may also cause the coating to have problems such as poor leveling and uneven drying during the construction process, affecting the usability and construction performance of the coating.

[0022] In view of the problems existing in the above-mentioned polylysine-quercetin complex, the present invention prepares mesoporous silica, and the polylysine-quercetin complex is loaded in the mesoporous silica to form a mesoporous silica microcapsule, and the mesoporous silica has a high specific surface area and an ordered pore structure and has good chemical stability, which can not only provide more adsorption sites for the polylysine-quercetin complex, increase its load, and improve the stability of the polylysine-quercetin complex, but also contribute to the uniform dispersion of the polylysine-quercetin complex, reduce agglomeration and precipitation, and help the polylysine-quercetin complex to play an antibacterial and antioxidant effect in the coating. In addition, the present invention also mixes the mesoporous silica microcapsule with dopamine hydrochloride under alkaline conditions, and the dopamine molecules are oxidatively polymerized to form the adsorption and chemical bonding of polydopamine on the surface of the mesoporous silica, so that the polydopamine is firmly fixed on the surface of the mesoporous silica to obtain a modified mesoporous silica microcapsule. Polydopamine is grafted on the surface of mesoporous silica microcapsules to form a polydopamine layer. The polydopamine layer can absorb ultraviolet rays and has good corrosion resistance, which is beneficial to improving the photostability and chemical stability of the mesoporous silica microcapsules. The polydopamine layer has rich functional groups and good biocompatibility, which is beneficial to the dispersion and compatibility of the mesoporous silica microcapsules loaded with polysaccharide-quercetin complexes in the coating, thereby improving the mechanical and chemical properties of the coating.

[0023] The present invention also provides an antibacterial medicinal aluminum foil produced by the above method.

[0024] Beneficial effects of the present invention: 1. Compared with the prior art, an antibacterial medicinal aluminum foil is prepared by coating a water-based antibacterial coating during the production process of the medicinal aluminum foil. The water-based antibacterial coating prepared by the present invention has excellent adhesion to the aluminum foil and can form a smooth and uniform antibacterial coating when coated on the aluminum foil, thereby giving the medicinal aluminum foil excellent antibacterial properties, barrier properties and resistance to ultraviolet light aging, thereby ensuring the service life and stability of the medicinal aluminum foil. When used in pharmaceutical packaging, it can provide moisture-proof, oxygen-proof and shielding protection for the pharmaceuticals, ensuring that the pharmaceuticals maintain their stability and effectiveness during the shelf life.

[0025] 2. Compared with the prior art, the present invention introduces modified mesoporous silica microcapsules loaded with polylysine-quercetin complexes and modified palygorskite modified with cardanol, which are used in conjunction with water-based polyurethane resin and water-based acrylic resin to prepare water-based coatings. During the coating preparation process, the two can improve the barrier properties, antibacterial properties and UV aging resistance of the water-based coating through chemical crosslinking and physical effects, and at the same time give it better aluminum foil adhesion, so that it can adhere tightly to medicinal aluminum foil, which is beneficial to the application of medicinal aluminum foil in the field of pharmaceutical packaging. DETAILED DESCRIPTION

[0026] Parameters for specific chemical substances used, sources.

[0027] Waterborne polyurethane resin, brand: U9900, from Oubaodi Resin Co., Ltd.; Water-based acrylic resin, brand: AC3660, from Oubaodi Resin Co., Ltd.; Palygorskite, mesh number: 325 mesh; Cardanol, model: NX-2021, viscosity 45-75cps, Cardolite Corporation; Isocyanate curing agent, brand: Bayhydur XP 2655, brand: Bayer; ε-Poly-lysine, molecular weight: 4000.

[0028] Example 1 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0029] The preparation method of the antibacterial agent comprises the following steps: S1, dissolving 1 part by weight of hexadecyltrimethylammonium bromide in 10 parts by weight of water, then adjusting the pH of the solution to 11, adding 3 parts by weight of ethyl orthosilicate dropwise thereto and reacting for 4 hours, then subjecting the resulting mixed system to a hydrothermal reaction at 130° C. for 22 hours, washing, and drying to obtain mesoporous silica; S2, adding 1 part by weight of maleic anhydride and 3 parts by weight of quercetin to 50 parts by weight of dimethyl sulfoxide solution, and then stirring at 40°C overnight to obtain a mixed solution A; adding 1.9 parts by weight of 1-ethyl-3-(3-dimethyl)aminopropyl-carbodiimide and 1.7 parts by weight of N-hydroxysuccinimide to 10 parts by weight of dimethyl sulfoxide to obtain a mixed solution B; adding the mixed solution B dropwise to the mixed solution A at room temperature and stirring for 30 minutes to obtain a mixed solution C; adding 10 parts by weight of an aqueous solution containing 5 mg / mL of ε-polylysine to the mixed solution C, stirring at 30°C for 24 hours to obtain a mixture; the mixture was dialyzed with distilled water (MWCO 14000) for 3 days, and then concentrated and dried with a rotary evaporator to obtain a solid, i.e., a polylysine-quercetin complex; S3. Mix 4 parts by weight of the polylysine-quercetin complex and 1 part by weight of mesoporous silica, then add 50 parts by weight of anhydrous ethanol and mix evenly to form a suspension, then stir the suspension at 25°C, 700 rpm, and 0.05 MPa for 4 hours, return to atmospheric pressure, centrifuge, and dry to obtain mesoporous silica microcapsules loaded with the polylysine-quercetin complex, i.e., an antibacterial agent.

[0030] Example 2 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0031] The preparation method of the antibacterial agent comprises the following steps: S1, dissolving 1 part by weight of hexadecyltrimethylammonium bromide in 10 parts by weight of water, then adjusting the pH of the solution to 11, adding 3 parts by weight of ethyl orthosilicate dropwise thereto and reacting for 4 hours, then subjecting the resulting mixed system to a hydrothermal reaction at 130° C. for 22 hours, washing, and drying to obtain mesoporous silica; S2, adding 1 part by weight of maleic anhydride and 3 parts by weight of quercetin to 50 parts by weight of dimethyl sulfoxide solution, and then stirring at 40°C overnight to obtain a mixed solution A; adding 1.9 parts by weight of 1-ethyl-3-(3-dimethyl)aminopropyl-carbodiimide and 1.7 parts by weight of N-hydroxysuccinimide to 10 parts by weight of dimethyl sulfoxide to obtain a mixed solution B; adding the mixed solution B dropwise to the mixed solution A at room temperature and stirring for 30 minutes to obtain a mixed solution C; adding 10 parts by weight of an aqueous solution containing 5 mg / mL of ε-polylysine to the mixed solution C, stirring at 30°C for 24 hours to obtain a mixture; the mixture was dialyzed with distilled water (MWCO 14000) for 3 days, and then concentrated and dried with a rotary evaporator to obtain a solid, i.e., a polylysine-quercetin complex; S3. Mix 4 parts by weight of a polylysine-quercetin complex and 1 part by weight of mesoporous silica, then add 50 parts by weight of anhydrous ethanol and mix evenly to form a suspension, then stir the suspension at 25°C, 700rpm, and 0.05MPa for 4 hours, return to atmospheric pressure, centrifuge, and dry to obtain mesoporous silica microcapsules loaded with polylysine-quercetin complexes; mix 1 part by weight of mesoporous silica microcapsules loaded with polylysine-quercetin complexes with 15 parts by weight of 0.05 mol / L tris(hydroxymethylaminomethane)-hydrochloric acid buffer at a pH of 9, then add 2 parts by weight of dopamine hydrochloride, and react at 36°C for 17 hours to obtain a mixture; then wash and dry the mixture to obtain modified mesoporous silica microcapsules, i.e., an antibacterial agent.

[0032] Example 3 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0033] The preparation method of the antibacterial agent is consistent with that of Example 2.

[0034] The steps of preparing the modified palygorskite are as follows: 14 parts by weight of palygorskite and 7 parts by weight of cardanol were added to 130 parts by weight of ethylene glycol, ultrasonically dispersed for 35 minutes, and then mixed and stirred at 82°C for 7 hours; then, centrifuged, the precipitate was collected, washed with ethanol 3 times, and vacuum dried at 42°C for 24 hours to obtain modified palygorskite.

[0035] Example 4 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0036] The preparation method of the antibacterial agent is consistent with that of Example 2.

[0037] The steps of preparing the modified palygorskite are as follows: 14 parts by weight of palygorskite and 7 parts by weight of catechol were added to 130 parts by weight of ethylene glycol, ultrasonically dispersed for 35 minutes, and then mixed and stirred at 82°C for 7 hours; then, centrifuged, the precipitate was collected, washed with ethanol three times, and vacuum dried at 42°C for 24 hours to obtain modified palygorskite.

[0038] Example 5 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0039] The preparation method of the antibacterial agent is consistent with that of Example 2.

[0040] The steps of preparing the modified palygorskite are as follows: 14 parts by weight of palygorskite and 7 parts by weight of eugenol were added to 130 parts by weight of ethylene glycol, ultrasonically dispersed for 35 minutes, and then mixed and stirred at 82°C for 7 hours; then, centrifuged, the precipitate was collected, washed with ethanol 3 times, and vacuum dried at 42°C for 24 hours to obtain modified palygorskite.

[0041] Comparative Example 1 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of modified mesoporous silica microcapsules and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0042] The steps of preparing the modified mesoporous silica microcapsules are as follows: S1, dissolving 1 part by weight of hexadecyltrimethylammonium bromide in 10 parts by weight of water, then adjusting the pH of the solution to 11, adding 3 parts by weight of ethyl orthosilicate dropwise thereto and reacting for 4 hours, then subjecting the resulting mixed system to a hydrothermal reaction at 130° C. for 22 hours, washing, and drying to obtain mesoporous silica; S2. Mix 1 part by weight of mesoporous silica microcapsules with 15 parts by weight of 0.05 mol / L tris(hydroxymethyl)aminomethane-hydrochloric acid buffer solution with a pH of 9, then add 2 parts by weight of dopamine hydrochloride, and react at 36° C. for 17 hours to obtain a mixture; then wash and dry the mixture to obtain modified mesoporous silica microcapsules.

[0043] The preparation method of the modified palygorskite is consistent with that of Example 3.

[0044] Comparative Example 2 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0045] The preparation method of the antibacterial agent comprises the following steps: S1, dissolving 1 part by weight of hexadecyltrimethylammonium bromide in 10 parts by weight of water, then adjusting the pH of the solution to 11, adding 3 parts by weight of ethyl orthosilicate dropwise thereto and reacting for 4 hours, then subjecting the resulting mixed system to a hydrothermal reaction at 130° C. for 22 hours, washing, and drying to obtain mesoporous silica; S2. Mix 4 parts by weight of ε-polylysine and 1 part by weight of mesoporous silica, then add 50 parts by weight of anhydrous ethanol and mix evenly to form a suspension, then place the suspension under the conditions of 25°C, 700rpm, and 0.05MPa and stir for 4 hours, return to atmospheric pressure, centrifuge, and dry to obtain mesoporous silica microcapsules with polylysine loaded internally; mix 1 part by weight of mesoporous silica microcapsules with polylysine loaded internally with 15 parts by weight of 0.05 mol / L tris(hydroxymethylaminomethane)-hydrochloric acid buffer with a pH of 9, then add 2 parts by weight of dopamine hydrochloride, and react at 36°C for 17 hours to obtain a mixture; then wash and dry the mixture to obtain modified mesoporous silica microcapsules, i.e., an antibacterial agent.

[0046] The preparation method of the modified palygorskite is consistent with that of Example 3.

[0047] Comparative Example 3 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0048] The preparation method of the antibacterial agent comprises the following steps: S1, dissolving 1 part by weight of hexadecyltrimethylammonium bromide in 10 parts by weight of water, then adjusting the pH of the solution to 11, adding 3 parts by weight of ethyl orthosilicate dropwise thereto and reacting for 4 hours, then subjecting the resulting mixed system to a hydrothermal reaction at 130° C. for 22 hours, washing, and drying to obtain mesoporous silica; S2. Mix 4 parts by weight of quercetin and 1 part by weight of mesoporous silica, then add 50 parts by weight of anhydrous ethanol and mix evenly to form a suspension, then place the suspension under the conditions of 25°C, 700rpm, and 0.05MPa and stir for 4 hours, return to atmospheric pressure, centrifuge, and dry to obtain mesoporous silica microcapsules loaded with quercetin; mix 1 part by weight of mesoporous silica microcapsules loaded with quercetin and 15 parts by weight of 0.05 mol / L tris(hydroxymethylaminomethane)-hydrochloric acid buffer solution with a pH of 9, then add 2 parts by weight of dopamine hydrochloride, and react at 36°C for 17 hours to obtain a mixture; then wash and dry the mixture to obtain modified mesoporous silica microcapsules, i.e., an antibacterial agent.

[0049] The preparation method of the modified palygorskite is consistent with that of Example 3.

[0050] Comparative Example 4 A method for producing an antibacterial medicinal aluminum foil comprises the following steps: selecting an aluminum foil with a width of 600 mm and a thickness of 0.008 mm for unwinding, pulling, correcting deviation, and coating the front side of the aluminum foil with a water-based antibacterial coating in an amount of 4.5 g / m 2 - oven drying - traction - deviation correction - antibacterial medicinal aluminum foil rolling; the preparation method of the water-based antibacterial coating has the following steps: 50 parts by weight of an aqueous polyurethane resin, 35 parts by weight of an aqueous acrylic resin, 4 parts by weight of an isocyanate curing agent, 3 parts by weight of BYK-333, 2 parts by weight of BYK-153, 2 parts by weight of BYK-093, 2 parts by weight of dipropylene glycol butyl ether and 22 parts by weight of water were mixed, and the mixture was dispersed at a high speed of 800 rpm for 5 minutes to obtain a mixed solution; 2 parts by weight of an antibacterial agent and 6 parts by weight of modified palygorskite were added to the mixed solution, and the mixture was dispersed at a high speed of 1000 rpm for 18 minutes to obtain a water-based coating.

[0051] The preparation method of the antibacterial agent comprises the following steps: 1 part by weight of maleic anhydride and 3 parts by weight of quercetin are added to 50 parts by weight of dimethyl sulfoxide solution, and then stirred at 40°C overnight to obtain a mixed solution A; 1.9 parts by weight of 1-ethyl-3-(3-dimethyl)aminopropyl-carbodiimide and 1.7 parts by weight of N-hydroxysuccinimide are added to 10 parts by weight of dimethyl sulfoxide to obtain a mixed solution B; the mixed solution B is added dropwise to the mixed solution A at room temperature and stirred for 30 minutes to obtain a mixed solution C; 10 parts by weight of an aqueous solution containing 5 mg / mL of ε-polylysine is added to the mixed solution C, and stirred at 30°C for 24 hours to obtain a mixture; the mixture is dialyzed with distilled water (MWCO 14000) for 3 days, and then concentrated and dried with a rotary evaporator to obtain a solid, i.e., a polylysine-quercetin complex, i.e., an antibacterial agent.

[0052] The preparation method of the modified palygorskite is consistent with that of Example 3.

[0053] Test Example 1 Antibacterial performance test The medicinal aluminum foils prepared in Examples 1-5 of the present invention and Comparative Examples 1-4 were respectively taken as test samples for performance testing, and the antibacterial properties of the test samples of each embodiment and comparative example were tested with reference to the test method provided in the standard "Determination of antibacterial activity on the surface of plastics and other non-porous materials"; experimental bacteria: Escherichia coli (commercially available, ATCC8739), Staphylococcus aureus (commercially available, ATCC6538); Barrier properties The medicinal aluminum foils prepared in Examples 1-5 and Comparative Examples 1-4 of the present invention were respectively taken as test samples for performance testing. The oxygen permeability (cm2) of the test samples of the embodiments and comparative examples was tested according to the test method provided in the standard "YBB00082003-2015 Gas Permeability Determination Method". 3 / (m 2 •24h•0.1MPa)); refer to the test method provided in the standard "YBB00092003-2015 Water Vapor Transmission Rate Determination Method" to test the water vapor transmission rate (g / (m 2 •24h)); not more than 0.5g / (m 2 •24h)); Bursting Strength The medicinal aluminum foils prepared in Examples 1-5 and Comparative Examples 1-4 of the present invention were respectively taken as test samples for performance testing, and the bursting strength (KPa) of the test samples of each embodiment and comparative example was tested with reference to the test method provided in the standard "YBB00152002-2015 Aluminum Foil for Pharmaceutical Packaging"; then the test samples of each embodiment and comparative example were placed in a test box of model DL-0207 (wavelength of 330nm, irradiance of 5W / m 2 ) for 7 days, and then test the light aging resistance of the sample by referring to the standard test sample's rupture strength after light aging; The specific data of the test results are shown in Table 1: Table 1 As can be seen from Table 1, in terms of antibacterial performance, by comparing Examples 1-5 with Comparative Examples 1-4, it is found that Example 1 in which mesoporous silica microcapsules with internally loaded polylysine-quercetin complexes are added as antibacterial agents and Examples 2-5 in which modified mesoporous silica microcapsules with internally loaded polylysine-quercetin complexes are added as antibacterial agents have higher antibacterial rates against Escherichia coli and Staphylococcus aureus than Comparative Example 1 in which modified mesoporous silica microcapsules without internal loads are added as antibacterial agents and Comparative Examples 2-3 in which modified mesoporous silica microcapsules with internally loaded polylysine or quercetin are added as antibacterial agents, and Comparative Example 4 in which polylysine-quercetin complexes are added as antibacterial agents, indicating that modified mesoporous silica microcapsules with internally loaded polylysine-quercetin complexes as antibacterial agents are beneficial to significantly improve the antibacterial effect of aluminum foil; By comparing Examples 1-5, it is found that adding both internally loaded polylysine- The antibacterial rates of Examples 3-5 of modified mesoporous silica microcapsules and modified palygorskite of quercetin complex against Escherichia coli and Staphylococcus aureus are higher than those of Example 1 of simultaneously adding mesoporous silica microcapsules and palygorskite with internally loaded polylysine-quercetin complex and Example 2 of simultaneously adding modified mesoporous silica microcapsules and palygorskite with internally loaded polylysine-quercetin complex. Among them, Example 3 of simultaneously adding modified mesoporous silica microcapsules with internally loaded polylysine-quercetin complex and modified palygorskite modified with cardanol has the best antibacterial effect, with the antibacterial rates against Escherichia coli and Staphylococcus aureus reaching 99.5% and 99.2%, respectively. The analysis shows that the reason may be that the polylysine-quercetin complex has stronger antibacterial and antioxidant properties, and loading it in mesoporous silica microcapsules is beneficial to improving the stability of the polylysine-quercetin complex, and can achieve long-term antibacterial effect. In addition, the use of polydopamine to modify the surface of mesoporous silica microcapsules is more conducive to increasing the dispersibility and compatibility of mesoporous silica microcapsules in the polymer system, making the distribution uniform, which is conducive to improving the antibacterial performance. At the same time, the present invention uses cardanol-modified palygorskite in conjunction with polydopamine-modified mesoporous silica microcapsules loaded with polysaccharide-quercetin complexes. During the coating preparation process, the hydroxyl groups on the surface of the modified palygorskite can interact with the hydroxyl groups in the polydopamine or polylysine-quercetin complex on the surface of the modified mesoporous silica microcapsules to form hydrogen bonds, or the aromatic rings of cardanol and polydopamine may enhance the interaction through π-π stacking, thereby improving the stability and synergistic effect of the two in the coating, thereby further improving the antibacterial performance.

[0054] As can be seen from Table 1, in terms of barrier performance, by comparing Examples 1-5 with Comparative Examples 1-4, it is found that the oxygen permeability and water vapor permeability of Examples 3-5 and Comparative Examples 1-3 are lower than those of Examples 1-2 and Comparative Example 4; by comparing Examples 3-5 with Comparative Examples 1-3, it is found that the oxygen permeability and water vapor permeability of Examples 3 and Comparative Examples 1-3 are lower than those of Examples 4-5, among which Example 3 has the lowest oxygen permeability and water vapor permeability and the best barrier performance; this indicates that the simultaneous addition of modified mesoporous silica microcapsules loaded with polylysine-quercetin composites and modified palygorskite modified with cardanol is beneficial to improving the barrier performance. The reason may be that the modified mesoporous silica microcapsules loaded with polylysine-quercetin complex and the modified palygorskite modified with cardanol are uniformly dispersed in the coating, the high specific surface area and porous structure of mesoporous silica can form an effective barrier, and the long chain structure of cardanol can also enhance the density of the coating. The two can be used together to form a dense network structure, which can effectively block the permeation of oxygen and water vapor and reduce the oxygen permeability and water vapor permeability. At the same time, the functional groups on the surface of modified palygorskite and modified mesoporous silica microcapsules loaded with polylysine-quercetin complex may chemically cross-link with the functional groups in waterborne polyurethane resin and waterborne acrylic resin, enhancing the overall structure of the coating, which is conducive to further reducing the oxygen permeability and water vapor permeability and increasing the barrier performance.

[0055] As can be seen from Table 1, in terms of rupture strength, before and after UV aging, by comparing Examples 1-5 and Comparative Examples 1-4, it is found that the rupture strength of Examples 3-5 and Comparative Examples 1-3 is higher than that of Examples 1-2 and Comparative Example 4, and the decrease in rupture strength is less than that of Examples 1-2 and Comparative Example 4; by comparing Examples 3-5 and Comparative Examples 1-3, it is found that the rupture strength of Examples 3 and Comparative Examples 1-3 is higher than that of Examples 4-5, and the decrease in rupture strength is less than that of Examples 4-5, among which Example 3 has the highest rupture strength, the smallest decrease in rupture strength after UV aging, and the best rupture strength and UV aging resistance; it indicates that the simultaneous addition of modified mesoporous silica microcapsules with internally loaded polylysine-quercetin complexes and modified palygorskite modified with cardanol is beneficial to improving the rupture strength and UV aging resistance. The reason may be that the modified mesoporous silica microcapsules loaded with polylysine-quercetin complex and modified palygorskite modified with cardanol are used in synergy during the preparation of the coating. The two can form a physical cross-linked network in the coating, increasing the cohesion and mechanical stability of the coating. At the same time, the functional groups on the surface of the modified mesoporous silica microcapsules loaded with polylysine-quercetin complex and modified palygorskite modified with cardanol may form hydrogen bonds or covalent bonds with the hydroxyl and carboxyl functional groups in the waterborne polyurethane resin and waterborne acrylic resin, enhancing the interfacial bonding force and further enhancing the stability of the cross-linked network, improving the adhesion of the coating to the aluminum foil, thereby enhancing the rupture strength of the aluminum foil. In addition, the addition of modified palygorskite and modified mesoporous silica microcapsules loaded with polylysine-quercetin complex improves the light stability of the coating. The two can form a physical barrier in the coating to absorb and scatter ultraviolet light. When aluminum foil is irradiated with ultraviolet light, the cardanol grafted on the modified palygorskite and the polydopamine layer on the modified mesoporous silica microcapsule can absorb ultraviolet light, reduce the damage of ultraviolet light to the aluminum foil coating, improve the light aging resistance of the aluminum foil coating, and extend the service life of the aluminum foil. At the same time, polydopamine and polylysine-quercetin complex have antioxidant properties, which can scavenge free radicals triggered by ultraviolet light and reduce the damage of free radicals to polymer chains in the coating, thereby reducing the damage of ultraviolet light to the rupture strength of the aluminum foil.

Claims

1. A method for producing an antibacterial medicinal aluminum foil, characterized in that: The method comprises the following steps: unwinding of aluminum foil - pulling - deviation correction - coating of the front side of the aluminum foil with water-based antibacterial coating - oven drying - pulling - deviation correction - winding of the antibacterial medicinal aluminum foil.

2. The method for producing the antibacterial medicinal aluminum foil according to claim 1, characterized in that: The width of the aluminum foil is 500-1000mm and the thickness is 0.005-0.15mm.

3. The method for producing the antibacterial medicinal aluminum foil according to claim 1, characterized in that: The coating amount of water-based antibacterial coating on the front of aluminum foil is 2-6g / m 2 .

4. The method for producing the antibacterial medicinal aluminum foil according to claim 1, characterized in that: The raw materials for preparing the water-based antibacterial coating include, by weight: 40-60 parts of water-based polyurethane resin, 30-40 parts of water-based acrylic resin, 3-5 parts of curing agent, 2-4 parts of leveling agent, 1-3 parts of dispersant, 1-3 parts of defoaming agent, 1-3 parts of film-forming aid, 3-8 parts of thickener, 1-3 parts of antibacterial agent and 20-30 parts of water.

5. The method for producing the antibacterial medicinal aluminum foil according to claim 4, characterized in that: The preparation method of the water-based antibacterial coating comprises the following steps: A waterborne polyurethane resin, a waterborne acrylic resin, a curing agent, a leveling agent, a dispersant, a defoaming agent, a film-forming aid and water are mixed, and dispersed at a high speed of 650-850 rpm for 3-8 minutes to obtain a mixed solution; an antibacterial agent and a thickener are added to the mixed solution, and dispersed at a high speed of 900-1200 rpm for 15-20 minutes to obtain a waterborne antibacterial coating.

6. The method for producing the antibacterial medicinal aluminum foil according to claim 4 or 5, characterized in that: The curing agent is an isocyanate curing agent; the leveling agent is selected from one of BYK-345, BYK-333, and BYK-330 of German BYK; the dispersant is selected from one of BYK-156, BYK-151, BYK-153, TEGO®Dispers750W, and TEGO®Dispers655 of German BYK.

7. The method for producing the antibacterial medicinal aluminum foil according to claim 4 or 5, characterized in that: The defoaming agent is one or more of polydimethylsiloxane, German BYK-093, BYK-025, BYK-028, BYK-092; the film-forming aid is one of dipropylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, and ethylene glycol tert-butyl ether.

8. The method for producing the antibacterial medicinal aluminum foil according to claim 4 or 5, characterized in that: The thickener is selected from one of palygorskite and modified palygorskite; The steps of the preparation method of the modified palygorskite are as follows, calculated by weight: 10-15 parts of palygorskite and 5-8 parts of modifier are added to 100-140 parts of ethylene glycol, and ultrasonically dispersed for 20-40 minutes, and then mixed and stirred at 75-85°C for 5-8 hours; then, centrifuged, the precipitate was collected, washed with ethanol 2-3 times, and vacuum dried at 35-45°C for 22-25 hours to obtain modified palygorskite; The modifier is selected from one of cardanol, eugenol and catechol.

9. The method for producing the antibacterial medicinal aluminum foil according to claim 4 or 5, characterized in that: The preparation method of the antibacterial agent comprises synthesizing mesoporous silica, preparing a polylysine-quercetin complex, and then combining the two to form a mesoporous silica microcapsule with an internally loaded complex. The mesoporous silica microcapsule with an internally loaded complex can also be mixed with dopamine hydrochloride under alkaline conditions to obtain a modified mesoporous silica microcapsule. 10.An antibacterial medicinal aluminum foil, characterized in that: Produced by the method described in any one of claims 1 to 9.

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