Aging-resistant antibacterial film and preparation method thereof

Abstract

The application discloses an anti-aging and antibacterial film and a preparation method thereof, and relates to the technical field of film materials, and comprises the following raw materials: ethylene-vinyl alcohol copolymer, composite reinforcing agent, coupling agent, processing aid, anti-aging aid, 1-allyl-3-vinylimidazole chloride, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate, amino-functionalized metal organic framework material, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-bis(trifluoromethyl)diaminobiphenyl, carboxymethyl-beta-cyclodextrin, initiator and glutaraldehyde. The film has good anti-aging performance, remarkable antibacterial effect, sufficient performance stability, excellent mechanical and dynamic performance and long service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of thin film materials, and particularly relates to an anti-aging antibacterial thin film and a preparation method thereof. BACKGROUND

[0002] In many fields, such as food packaging, medical health, agricultural covering, etc., thin film materials play a crucial role. With the development of society and the improvement of people's living standards, the demand for thin film materials is increasing, and the performance requirements are increasingly stringent.

[0003] Traditional thin films are prone to oxidative degradation when exposed to light, heat and humidity for a long time, showing problems such as yellowing and embrittlement. After long-term storage, the strength, flexibility and other properties of the thin films decrease, affecting the use effect. Frequent replacement of thin films not only increases the economic burden, but also causes certain pollution to the environment. The existing technology often delays aging by adding a single anti-aging agent, but the existing single anti-aging agent cannot take into account the synergistic effect of ultraviolet shielding and thermal oxygen stability, resulting in a shorter service life of the thin film in outdoor or high temperature and humidity environments, and they are mostly small molecular compounds, which are easy to volatilize or migrate, and have insufficient long-term stability.

[0004] Antibacterial property is another important indicator for measuring the performance of thin film materials. Thin film materials with excellent antibacterial performance can effectively inhibit the growth of microorganisms and are safer to use. However, the antibacterial effect of traditional thin films is difficult to meet the demand. The widely used antibacterial thin films mostly use silver-based antibacterial agents (such as nano-silver) or organic antibacterial agents (such as quaternary ammonium salt). However, silver-based antibacterial agents are high in cost and have biological toxicity risk, and organic antibacterial agents have poor temperature resistance and are easy to migrate, resulting in a significant decrease in antibacterial performance with the use time. In addition, some inorganic antibacterial materials (such as nano-TiO2) have poor dispersibility, which easily leads to the deterioration of the mechanical properties of the thin films, limiting their application range.

[0005] In order to solve the above problems, the patent for invention with the publication number CN104151733B discloses a PVC film with antibacterial effect, which is made of the following raw materials in parts by weight: PVC film 100-200 parts, modified rosin resin 20-50 parts, antibacterial agent 2-10 parts, VAE emulsion 20-50 parts, and auxiliary agent 5-15 parts. The patent discloses a preparation method of the PVC film. The PVC film with antibacterial effect has the advantages of anti-tearing, anti-scratching, anti-adhesion, better flexibility, acid and alkali resistance, ultraviolet aging resistance, and strong antibacterial effect. However, the aging resistance and antibacterial stability still need to be further improved. Therefore, it is necessary to develop an aging-resistant antibacterial film with good aging resistance, significant antibacterial effect, sufficient performance stability, excellent mechanical properties, and long service life, which meets the market demand and has wide market value and application prospect, and has very important significance for promoting the development of the film material field. SUMMARY

[0006] Therefore, the purpose of the present application is to provide an aging-resistant antibacterial film with good aging resistance, significant antibacterial effect, sufficient performance stability, excellent mechanical properties, and long service life, and a preparation method thereof.

[0007] In order to achieve the above purpose, the present application provides the following technical solutions:

[0008] An aging-resistant antibacterial film is prepared from the following raw materials in parts by weight: ethylene-vinyl alcohol copolymer 50-70 parts, composite reinforcing agent 10-20 parts, coupling agent 1-3 parts, processing aid 0.5-1 part, anti-aging aid 3-6 parts, 1-allyl-3-vinylimidazole chloride 6-8 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 3-5 parts, amino-functionalized metal organic framework material 3-5 parts, 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 3-5 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1-2 parts, carboxymethyl-β-cyclodextrin 3-5 parts, initiator 0.8-1.2 parts, and glutaraldehyde 1-2 parts.

[0009] Preferably, the ethylene-vinyl alcohol copolymer is Soarnol DC3212B EVOH produced by Mitsubishi Chemical. TM .

[0010] Preferably, the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organic montmorillonite in a mass ratio of (1-2):1.

[0011] Preferably, the average particle size of the nano zinc oxide is 10-80 nm.

[0012] Preferably, the polymer-grade nano organic montmorillonite is NANOLC-NP301 polymer-grade organic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.

[0013] Preferably, the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0014] Preferably, the processing aid is calcium stearate.

[0015] Preferably, the anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:(0.8-1.2).

[0016] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0017] Preferably, the hindered amine light stabilizer is hindered amine light stabilizer HS-944.

[0018] Preferably, the source of the amino-functionalized metal-organic framework material has no special requirements. In an embodiment of the present application, the amino-functionalized metal-organic framework material is prepared according to the method of Example 1 of the invention patent with the application publication number CN119591889A.

[0019] Preferably, the initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.

[0020] Another object of the present application is to provide a preparation method of the anti-aging antibacterial film, comprising the following steps:

[0021] Step S1, mix other raw materials except carboxymethyl-β-cyclodextrin uniformly according to weight parts to obtain a mixture, add the mixture into N,N-dimethylformamide, stir uniformly, then pour into a smooth mold surface, dry in a forced air drying oven at 65-85℃ for 8-10h to preliminarily form a film; then place the formed film in a steam environment containing glutaraldehyde, react at a certain temperature of 40-50℃ for 2-3h;

[0022] Step S2, soak the film prepared in step S1 in a carboxymethyl-β-cyclodextrin aqueous solution at 50-60℃ for 30-40h, then take out the film and put it into deionized water, soak at room temperature for 8-10h, replace the deionized water every 2h; finally, place the film in a vacuum drying oven at 80-90℃ and dry for 10-15h to obtain an anti-aging antibacterial film.

[0023] Preferably, the mass ratio of the mixture and N,N-dimethylformamide is 1:(4-7).

[0024] Preferably, the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0025] The technical scheme has the beneficial effects that:

[0026] (1) The preparation method of the anti-aging antibacterial film has simple process, convenient operation control, low dependence on equipment, high preparation efficiency and product qualification rate, is suitable for industrial large-scale production, and has high popularization and application value.

[0027] (2) The anti-aging antibacterial film comprises the following raw materials in parts by weight: ethylene-vinyl alcohol copolymer 50-70 parts, composite reinforcing agent 10-20 parts, coupling agent 1-3 parts, processing aid 0.5-1 part, anti-aging aid 3-6 parts, 1-allyl-3-vinylimidazole chloride salt 6-8 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 3-5 parts, amino-functionalized metal organic framework material 3-5 parts, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 3-5 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1-2 parts, carboxymethyl-β-cyclodextrin 3-5 parts, initiator 0.8-1.2 parts, and glutaraldehyde 1-2 parts. Through the mutual cooperation of the raw materials, the prepared anti-aging antibacterial film has good anti-aging performance, remarkable antibacterial effect, sufficient performance stability, excellent mechanical mechanical performance, and long service life.

[0028] (3) The anti-aging antibacterial film provided by the application takes ethylene-vinyl alcohol copolymer (EVOH) as a base material, EVOH has excellent gas barrier properties, and the hydroxyl groups in the molecular structure of EVOH can participate in subsequent reactions, laying a foundation for constructing an interpenetrating network structure; the introduction of composite reinforcing agents can improve the antibacterial effect and mechanical properties; coupling agents can improve the dispersion uniformity of the composite reinforcing agents and the compatibility between the composite reinforcing agents and other raw materials, and the triazinone introduced on the coupling agents can also help to improve the anti-aging performance; the combination of 1-allyl-3-vinylimidazole chloride, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate and 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione can introduce imidazole salt, benzotriazole and triazinone structures into the molecular structure of the film at the same time, and these structures can work together under the multiple effects of electronic effect, steric effect and conjugation effect with fluorine-containing biphenyl and cyclodextrin structures, further improving the anti-aging performance, antibacterial effect, performance stability and mechanical properties of the film; carboxymethyl-β-cyclodextrin can undergo ion exchange reaction with 1-allyl-3-vinylimidazole chloride to form an ion crosslinking structure, and the epoxy group on 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione can also undergo epoxy ring-opening reaction with the amino group on 2,2'-bis(trifluoromethyl)diaminobiphenyl and amino-functionalized metal organic framework material to form a multiple interpenetrating network structure, effectively improving the anti-aging performance and mechanical properties of the film; glutaraldehyde can improve the crosslinking degree of the film, and further improve the above-mentioned properties.

[0029] (4) The anti-aging antibacterial film provided by the application, by the reasonable selection of the preparation process parameters, has better anti-aging performance, more significant antibacterial effect, more sufficient performance stability, more excellent mechanical properties and longer service life. DETAILED DESCRIPTION

[0030] In order to enable the person skilled in the art to better understand the technical solutions of the present application, and to make the above-mentioned features, objects and advantages of the present application more clear and easy to understand, the present application will be further described below in combination with examples. The examples are only used to illustrate the present application and not to limit the scope of the present application.

[0031] Example 1

[0032] An anti-aging antibacterial film, comprising the following raw materials in parts by weight: ethylene-vinyl alcohol copolymer 70 parts, composite reinforcing agent 10 parts, coupling agent 1 part, processing aid 0.5 part, anti-aging aid 3 parts, 1-allyl-3-vinylimidazole chloride 6 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 3 parts, amino-functionalized metal organic framework material 3 parts, 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 3 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1 part, carboxymethyl-β-cyclodextrin 3 parts, initiator 0.8 part, glutaraldehyde 1 part.

[0033] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TM DC3212B EVOH; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organic montmorillonite in a mass ratio of 1:1; the average particle size of the nano-zinc oxide is 10 nm; the polymer-grade nano-organic montmorillonite is NANOLC-NP301 polymer-grade organic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.; the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; the processing aid is calcium stearate; the anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:0.8; the antioxidant is antioxidant 1010; the hindered amine light stabilizer is hindered amine light stabilizer HS-944; the amino-functionalized metal organic framework material is prepared according to the method of Example 1 of the invention patent with the application publication number CN119591889A; and the initiator is dibenzoyl peroxide.

[0034] A preparation method of the anti-aging antibacterial film, comprising the following steps:

[0035] In step S1, the raw materials except for carboxymethyl-β-cyclodextrin are mixed uniformly in parts by weight to obtain a mixture, the mixture is added to N,N-dimethylformamide, stirred uniformly, and then cast onto a smooth mold surface, and dried at 65°C in a forced air drying oven for 8 hours to preliminarily form a film; then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 40°C for 2 hours; the mass ratio of the mixture to N,N-dimethylformamide is 1:4;

[0036] Step S2, the film prepared in step S1 is soaked in a carboxymethyl-β-cyclodextrin aqueous solution at 50℃ for 30h, then the film is taken out and placed in deionized water, soaked at room temperature for 8h, and the deionized water is replaced every 2h; finally, the film is placed in a vacuum drying oven at 80℃ and dried for 10h to obtain an anti-aging antibacterial film; the mass percentage concentration of the carboxymethyl-β-cyclodextrin aqueous solution is 5%.

[0037] Example 2

[0038] An anti-aging antibacterial film is prepared from the following raw materials in parts by weight: ethylene-vinyl alcohol copolymer 65 parts, composite reinforcing agent 13 parts, coupling agent 1.5 parts, processing aid 0.6 parts, anti-aging aid 4 parts, 1-allyl-3-vinylimidazole chloride 6.5 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 3.5 parts, amino-functionalized metal-organic framework material 3.5 parts, 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 3.5 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1.2 parts, carboxymethyl-β-cyclodextrin 3.5 parts, initiator 0.9 parts, glutaraldehyde 1.2 parts.

[0039] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TM DC3212B EVOH; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organic montmorillonite in a mass ratio of 1.3:1; the average particle size of the nano-zinc oxide is 30nm; the polymer-grade nano-organic montmorillonite is NANOLC-NP301 polymer-grade organic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.; the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; the processing aid is calcium stearate; the anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:0.9; the antioxidant is antioxidant 1076; the hindered amine light stabilizer is hindered amine light stabilizer HS-944; the amino-functionalized metal-organic framework material is prepared according to the method of Example 1 of the invention patent with publication number CN119591889A; the initiator is azobisisobutyronitrile.

[0040] A method for preparing the anti-aging antibacterial film, comprising the following steps:

[0041] Step S1, other raw materials except carboxymethyl-β-cyclodextrin are mixed uniformly by weight parts to obtain a mixture, the mixture is added to N,N-dimethylformamide, stirred uniformly, then cast on a smooth mold surface, dried in a blast drying oven at 70℃ for 8.5h to make the film preliminary formed; then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 43℃ for 2.3h; the mass ratio of the mixture and N,N-dimethylformamide is 1:5;

[0042] Step S2, the film prepared in step S1 is soaked in a carboxymethyl-β-cyclodextrin aqueous solution at 53℃ for 33h, then the film is taken out and placed in deionized water, soaked at room temperature for 8.5h, and the deionized water is replaced every 2h; finally, the film is placed in a vacuum drying oven at 83℃ for 12h to obtain an anti-aging antibacterial film; the mass percentage concentration of the carboxymethyl-β-cyclodextrin aqueous solution is 5%.

[0043] Example 3

[0044] An anti-aging antibacterial film is prepared from the following raw materials by weight parts: ethylene-vinyl alcohol copolymer 60 parts, composite reinforcing agent 15 parts, coupling agent 2 parts, processing aid 0.7 parts, anti-aging aid 4.5 parts, 1-allyl-3-vinylimidazole chloride salt 7 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 4 parts, amino-functionalized metal-organic framework material 4 parts, 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 4 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1.5 parts, carboxymethyl-β-cyclodextrin 4 parts, initiator 1 part, glutaraldehyde 1.5 parts.

[0045] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TMDC3212B EVOH; the composite reinforcing body is a mixture of nano zinc oxide and polymer grade nano organic montmorillonite in a mass ratio of 1.5:1; the average particle size of the nano zinc oxide is 50 nm; the polymer grade nano organic montmorillonite is NANOLC-NP301 polymer grade organic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.; the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; the processing aid is calcium stearate; the anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:1; the antioxidant is antioxidant 168; the hindered amine light stabilizer is hindered amine light stabilizer HS-944; the amino-functionalized metal-organic framework material is prepared according to the method of Example 1 of the invention patent with the application publication number CN119591889A; and the initiator is dibenzoyl peroxide.

[0046] A preparation method of the anti-aging antibacterial film, comprising the following steps:

[0047] In step S1, other raw materials except carboxymethyl-β-cyclodextrin are uniformly mixed by weight parts to obtain a mixture, the mixture is added to N,N-dimethylformamide, stirred uniformly, and then cast on a smooth mold surface, and dried at 75°C in a blowing drying oven for 9h to preliminarily form a film; then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 45°C for 2.5 hours; the mass ratio of the mixture to N,N-dimethylformamide is 1:5.5;

[0048] In step S2, the film prepared in step S1 is soaked in a carboxymethyl-β-cyclodextrin aqueous solution at 55°C for 35h, then the film is taken out and placed in deionized water, soaked at room temperature for 9h, and the deionized water is replaced every 2 hours; finally, the film is placed in a vacuum drying oven at 85°C for 13h to obtain an anti-aging antibacterial film; the mass percentage concentration of the carboxymethyl-β-cyclodextrin aqueous solution is 5%.

[0049] Example 4

[0050] An anti-aging antibacterial film, comprising the following raw materials made by weight parts: ethylene-vinyl alcohol copolymer 55 parts, composite reinforcing agent 18 parts, coupling agent 2.5 parts, processing aid 0.9 parts, anti-aging aid 5.5 parts, 1-allyl-3-vinylimidazole chloride salt 7.5 parts, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate 4.5 parts, amino-functionalized metal organic framework material 4.5 parts, 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 4.5 parts, 2,2'-bis(trifluoromethyl)diaminobiphenyl 1.8 parts, carboxymethyl-β-cyclodextrin 4.5 parts, initiator 1.1 parts, glutaraldehyde 1.8 parts.

[0051] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TM DC3212B EVOH; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organic montmorillonite in a mass ratio of 1.8:1; the average particle size of the nano-zinc oxide is 70 nm; the polymer-grade nano-organic montmorillonite is NANOLC-NP301 polymer-grade organic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.; the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; the processing aid is calcium stearate; the anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:1.1; the antioxidant is a mixture of antioxidant 1010, antioxidant 1076 and antioxidant 168 in a mass ratio of 1:2:1; the hindered amine light stabilizer is hindered amine light stabilizer HS-944; the amino-functionalized metal organic framework material is made according to the method of Example 1 of the invention patent with the application publication number CN119591889A; the initiator is a mixture of dibenzoyl peroxide and azobisisobutyronitrile in a mass ratio of 3:5.

[0052] A preparation method of the anti-aging antibacterial film, comprising the following steps:

[0053] In step S1, the other raw materials except carboxymethyl-β-cyclodextrin are mixed uniformly by weight parts to obtain a mixture, the mixture is added to N,N-dimethylformamide, stirred uniformly, and then cast onto a smooth mold surface, and dried at 80°C in a forced air drying oven for 9.5 hours to preliminarily form a film; then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 48°C for 2.8 hours; the mass ratio of the mixture to N,N-dimethylformamide is 1:6.5;

[0054] Step S2, the film prepared in step S1 is soaked in a carboxymethyl-β-cyclodextrin aqueous solution at 58°C for 38h, then the film is taken out and placed in deionized water, soaked at room temperature for 9.5h, and the deionized water is replaced every 2h; finally, the film is placed in a vacuum drying oven at 88°C for 14h to obtain an anti-aging antibacterial film; the mass percentage concentration of the carboxymethyl-β-cyclodextrin aqueous solution is 5%.

[0055] Comparative Example 1

[0056] An anti-aging antibacterial film and a preparation method thereof, which are basically the same as those of Example 1, except that 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methyl acrylate and amino-functionalized metal-organic framework material are not added.

[0057] Comparative Example 2

[0058] An anti-aging antibacterial film and a preparation method thereof, which are basically the same as those of Example 1, except that 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and carboxymethyl-β-cyclodextrin are not added.

[0059] In order to further illustrate the unexpected positive technical effects achieved by the products of the embodiments of the present application, the anti-aging antibacterial films prepared in each example were tested for relevant performance, and the test results are shown in Table 1, and the test methods are as follows: the antibacterial performance was tested according to QB / T 2591-2003A, and the test strain was Staphylococcus aureus ATCC6538; the tensile strength was tested according to GB / T 13022-1991, the test speed was 10±2mm / min, the test temperature was 23°C, the relative humidity was 50%, the test sample was a type II dumbbell-shaped sample, and an i-Strentek 1510 electronic universal testing machine was used for testing; the anti-aging property was tested by placing each product in a fluorescent ultraviolet light aging test box, and the test conditions were set as follows: irradiance 0.89W / m²(340nm), blackboard temperature 60°C, test duration 168 hours, and after cooling to room temperature, the tensile strength after aging was measured, and the retention rate of the tensile strength was used as a measure, the greater the value, the better the anti-aging property, the retention rate of the tensile strength = tensile strength after aging / tensile strength before aging x 100%, and the test of the tensile strength before and after aging was performed according to GB / T 13022-1991.

[0060] Table 1 Performance test results of anti-aging antibacterial films

[0061]

[0062] As can be seen from Table 1, the anti-aging antibacterial film disclosed by each embodiment of the present application has better mechanical properties, more excellent antibacterial properties and aging resistance than the comparative product, and the combination of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl 2-methyl acrylate, amino-functionalized metal organic framework material, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and carboxymethyl-β-cyclodextrin is beneficial to improving the above properties. The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited by the above embodiments, and the above embodiments and descriptions are only the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection required by the present application is defined by the appended claims and their equivalents.

Claims

1. An anti-aging antibacterial film, characterized by, The preparation method of the anti-aging antibacterial film comprises the following steps: Step S1, other raw materials except carboxymethyl-beta-cyclodextrin are mixed uniformly according to weight parts to obtain a mixture, the mixture is added into N,N-dimethylformamide, stirred uniformly, then cast on a smooth mold surface, dried at 65-85 DEG C in a blast drying oven for 8-10h to preliminarily form the film; then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 40-50 DEG C for 2-3h; Step S2, the film prepared in step S1 is soaked in a carboxymethyl-beta-cyclodextrin aqueous solution at 50-60 DEG C for 30-40h, then the film is taken out and placed in deionized water, soaked at room temperature for 8-10h, and the deionized water is replaced every 2h; finally, the film is dried in a vacuum drying oven at 80-90 DEG C for 10-15h to obtain the anti-aging antibacterial film. The average particle size of the nano zinc oxide is 10-80nm.

2. The anti-microbial film according to claim 1, wherein The ethylene-vinyl alcohol copolymer is Soarnol TM DC3212B EVOH.

3. The anti-microbial film according to claim 1, wherein The polymer grade nano organic montmorillonite is NANOLC-NP301 polymer grade organic montmorillonite.

4. The anti-microbial film according to claim 1, wherein The processing aid is calcium stearate.

5. The aging-resistant antibacterial film according to claim 1, wherein The anti-aging aid is a mixture of an antioxidant and a hindered amine light stabilizer in a mass ratio of 1:(0.8-1.2); the antioxidant is at least one of antioxidant 1010, antioxidant 1076 and antioxidant 168; the hindered amine light stabilizer is hindered amine light stabilizer HS-944.

6. The aging-resistant antibacterial film according to claim 1, wherein The initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.

7. The aging-resistant antibacterial film according to claim 1, wherein The mass ratio of the mixture to N,N-dimethylformamide is 1:(4-7); the mass percentage concentration of the carboxymethyl-beta-cyclodextrin aqueous solution is 5%.

8. The aging-resistant antibacterial film according to claim 1, wherein ​

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