Anti-aging antibacterial film and preparation method thereof

Abstract

The invention discloses an anti-aging antibacterial film and a preparation method thereof, and relates to the technical field of film materials. Comprising the following raw materials: an ethylene-vinyl alcohol copolymer, a composite reinforcement, a coupling agent, a processing aid, an anti-aging aid, 1-allyl-3-vinyl imidazole chloride salt, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl 2-methacrylate, an amino-functionalized metal organic framework material, 1, 2-propylene glycol, an antioxidant, a coupling agent, a coupling agent, a processing aid, an anti-aging aid, 1-allyl-3-vinyl imidazole chloride salt, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl 2-methacrylate, an antioxidant and a solvent. The preparation method comprises the following steps: adding 2, 3-bis (oxiranyl methyl)-5-(2-propenyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 2, 2 '-bis (trifluoromethyl) diaminobiphenyl, carboxymethyl-beta-cyclodextrin, an initiator and glutaraldehyde into a reaction kettle; the film is good in aging resistance, remarkable in antibacterial effect, sufficient in performance stability, excellent in mechanical property and long in service life.

Description

Technical Field

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

[0002] In many fields, such as food packaging, medical and 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 day by day, and the performance requirements for them are becoming increasingly stringent.

[0003] Traditional thin films are prone to oxidative degradation when exposed to light, humid and hot environments for a long time, manifested as problems such as yellowing and embrittlement. After long-term storage, their properties such as strength and flexibility decline, affecting the use effect. Frequent replacement of thin films not only increases the economic burden but also causes certain pollution to the environment. Existing technologies often delay aging by adding a single anti-aging agent, but the existing single anti-aging agents cannot take into account the synergistic effect of ultraviolet shielding and thermal oxygen stability, resulting in a short lifespan of the thin film in outdoor or high-temperature and high-humidity environments. Moreover, they are mostly small molecule compounds, easy to volatilize or migrate, and the long-term stability is insufficient.

[0004] Antibacterial property is another important indicator to measure the performance of thin film materials. Thin film materials with excellent antibacterial properties can effectively inhibit the growth of microorganisms and have higher use safety. However, the antibacterial effect of traditional thin films is difficult to meet the requirements. Currently, widely used antibacterial thin films mostly use silver-based antibacterial agents (such as nano-silver) or organic antibacterial agents (such as quaternary ammonium salts). However, silver-based antibacterial agents are costly and have the risk of biological toxicity, while organic antibacterial agents have poor heat resistance and are easy to migrate, resulting in a significant decline in antibacterial performance over time. In addition, some inorganic antibacterial materials (such as nano-TiO2) have poor dispersibility, which easily leads to deterioration of the mechanical properties of the thin film, limiting their application scope.

[0005] In order to solve the above problems, the invention patent with the authorization announcement number of CN104151733B discloses a PVC thin film with antibacterial effect. By weight, the thin film is made of the following raw materials: 100-200 parts of PVC film, 20-50 parts of modified rosin resin, 2-10 parts of antibacterial agent, 20-50 parts of VAE emulsion, and 5-15 parts of auxiliary agent. The invention discloses the preparation method of the PVC thin film. The PVC thin film with antibacterial effect described in the invention is not only tear-resistant, but also scratch-resistant and anti-adhesive. In addition, by adding VAE emulsion, the PVC thin film has better flexibility, acid and alkali resistance, ultraviolet aging resistance, etc. At the same time, the antibacterial agent coated on the surface also makes the PVC thin film have a strong antibacterial effect. However, its anti-aging performance and antibacterial stability still need to be further improved.

[0006] It can be seen that developing an anti-aging antibacterial film with good anti-aging performance, significant antibacterial effect, sufficient performance stability, excellent mechanical and mechanical properties, and long service life meets the market demand, has broad market value and application prospects, and is of great significance for promoting the development of the film material field. Summary of the Invention

[0007] In view of this, the purpose of the present invention is to provide an anti-aging antibacterial film with good anti-aging performance, significant antibacterial effect, sufficient performance stability, excellent mechanical and mechanical properties, and long service life, and a preparation method thereof.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] An anti-aging antibacterial film is made of the following raw materials by weight: 50-70 parts of ethylene-vinyl alcohol copolymer, 10-20 parts of composite reinforcing body, 1-3 parts of coupling agent, 0.5-1 part of processing aid, 3-6 parts of anti-aging aid, 6-8 parts of 1-allyl-3-vinylimidazolium chloride, 3-5 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, 3-5 parts of amino-functionalized metal-organic framework material, 3-5 parts of 1,3-bis(epoxyethylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1-2 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 3-5 parts of carboxymethyl-β-cyclodextrin, 0.8-1.2 parts of initiator, and 1-2 parts of glutaraldehyde.

[0010] Preferably, the ethylene-vinyl alcohol copolymer is Soarnol TM DC3212B EVOH produced by Mitsubishi Chemical.

[0011] Preferably, the composite reinforcing body is a mixture of nano-zinc oxide and polymer-grade nano-organophilic montmorillonite in a mass ratio of (1-2):1.

[0012] Preferably, the average particle size of the nano-zinc oxide is 10-80nm.

[0013] Preferably, the polymer-grade nano-organophilic montmorillonite is NANOLC-NP301 polymer-grade organophilic montmorillonite provided by Zhejiang Fenghong New Materials Co., Ltd.

[0014] Preferably, the coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0015] Preferably, the processing aid is calcium stearate.

[0016] 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).

[0017] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0018] Preferably, the hindered amine light stabilizer is hindered amine light stabilizer HS-944.

[0019] Preferably, there is no special requirement for the source of the amino-functionalized metal-organic framework material. In one embodiment of the present invention, the amino-functionalized metal-organic framework material is prepared by the method of Example 1 of the invention patent with the application publication number CN119591889A.

[0020] Preferably, the initiator is at least one of benzoyl peroxide and azobisisobutyronitrile.

[0021] Another object of the present invention is to provide a method for preparing the anti-aging and antibacterial film, comprising the following steps:

[0022] Step S1: Mix other raw materials except carboxymethyl-β-cyclodextrin evenly by weight to obtain a mixed material. Add the mixed material to N,N-dimethylformamide, stir evenly, then cast it onto the surface of a smooth mold, and dry it in a forced-air drying oven at 65 - 85 °C for 8 - 10 h to preliminarily form a film. Then place the formed film in a steam environment containing glutaraldehyde and react at a certain temperature of 40 - 50 °C for 2 - 3 hours;

[0023] Step S2: Immerse the film prepared in Step S1 in an aqueous solution of carboxymethyl-β-cyclodextrin at 50 - 60 °C for 30 - 40 h. Then take out the film and put it into deionized water, soak it at room temperature for 8 - 10 h, and change the deionized water every 2 hours. Finally, place the film in a vacuum drying oven and dry it at 80 - 90 °C for 10 - 15 h to obtain the anti-aging and antibacterial film.

[0024] Preferably, the mass ratio of the mixed material to N,N-dimethylformamide is 1:(4 - 7).

[0025] Preferably, the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0026] The beneficial effects of adopting the above technical solutions are as follows:

[0027] (1) The method for preparing the anti-aging and antibacterial film provided by the present invention has a simple process, convenient operation control, low dependence on equipment, high preparation efficiency and high finished product qualification rate, is suitable for large-scale industrial production, and has high popularization and application value.

[0028] (2) The anti-aging antibacterial film provided by the present invention is made of the following raw materials by weight: 50-70 parts of ethylene-vinyl alcohol copolymer, 10-20 parts of composite reinforcing agent, 1-3 parts of coupling agent, 0.5-1 part of processing aid, 3-6 parts of anti-aging aid, 6-8 parts of 1-allyl-3-vinylimidazolium chloride, 3-5 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate, 3-5 parts of amino-functionalized metal-organic framework material, 3-5 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1-2 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 3-5 parts of carboxymethyl-β-cyclodextrin, 0.8-1.2 parts of initiator, and 1-2 parts of glutaraldehyde. Through the mutual cooperation and joint action of the raw materials, the prepared anti-aging antibacterial film has good anti-aging performance, significant antibacterial effect, sufficient performance stability, excellent mechanical properties, and long service life.

[0029] (3) The anti-aging antibacterial film provided by the present invention uses ethylene-vinyl alcohol copolymer (EVOH) as the base material. EVOH has excellent gas barrier properties, and the hydroxyl groups in its molecular structure can participate in subsequent reactions, laying a foundation for constructing an interpenetrating network structure; the introduction of the composite reinforcing agent can improve the antibacterial effect and mechanical properties; the coupling agent can improve the dispersion uniformity of the composite reinforcing agent and the compatibility with other raw materials, and the introduced triazinone on it can also be beneficial to improving the anti-aging performance; the combined use of 1-allyl-3-vinylimidazolium chloride, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate, and 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione simultaneously introduces imidazolium salt, benzotriazole, and triazinone structures into the molecular structure of the film. These structures, under the multiple effects of electronic effect, steric effect, and conjugation effect, etc., cooperate with each other to further improve the anti-aging performance, antibacterial effect, performance stability, and mechanical properties of the film; carboxymethyl-β-cyclodextrin can undergo an ion exchange reaction with 1-allyl-3-vinylimidazolium chloride to form an ionic cross-linked structure. At the same time, the epoxy groups on 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione can also undergo an epoxy ring-opening reaction with the amino groups on 2,2'-bis(trifluoromethyl)diaminobiphenyl and the 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 increase the cross-linking degree of the film, and further improve the above properties.

[0030] (4) The anti-aging and antibacterial film provided by the present invention, with the addition of amino-functionalized metal-organic framework materials and the cooperation with other raw materials, can effectively improve the antibacterial performance and the overall structural stability; through the reasonable selection of the preparation process parameters, the prepared film has better anti-aging performance, more significant antibacterial effect, higher performance stability, more excellent mechanical properties, and longer service life. Detailed implementation manners

[0031] To enable those skilled in the art to better understand the technical solutions of the present invention and to make the above-mentioned features, objectives, and advantages of the present invention clearer and more understandable, the present invention will be further described below in conjunction with embodiments. The embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0032] Example 1

[0033] An anti-aging and antibacterial film is made from the following raw materials by weight: 70 parts of ethylene-vinyl alcohol copolymer, 10 parts of composite reinforcing agent, 1 part of coupling agent, 0.5 part of processing aid, 3 parts of anti-aging aid, 6 parts of 1-allyl-3-vinylimidazolium chloride, 3 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, 3 parts of amino-functionalized metal-organic framework material, 3 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1 part of 2,2'-bis(trifluoromethyl)benzidine, 3 parts of carboxymethyl-β-cyclodextrin, 0.8 part of initiator, and 1 part of glutaraldehyde.

[0034] The ethylene-vinyl alcohol copolymer is Soarnol TM DC3212B EVOH produced by Mitsubishi Chemical; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organophilic montmorillonite in a mass ratio of 1:1; the average particle size of the nano-zinc oxide is 10 nm; the polymer-grade nano-organophilic montmorillonite is NANOLC-NP301 polymer-grade organophilic 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 antioxidant and 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 by the method of Example 1 of the invention with the application publication number CN119591889A; the initiator is dibenzoyl peroxide.

[0035] A preparation method of the anti-aging antibacterial film comprises the following steps:

[0036] Step S1: After mixing other raw materials except carboxymethyl-β-cyclodextrin evenly by weight, a mixed material is obtained. The mixed material is added to N,N-dimethylformamide, stirred evenly, and then cast onto the surface of a smooth mold, and dried in a forced air drying oven at 65 °C for 8 h 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 h. The mass ratio of the mixed material to N,N-dimethylformamide is 1:4.

[0037] Step S2: The film prepared in Step S1 is soaked in an aqueous solution of carboxymethyl-β-cyclodextrin at 50 °C for 30 h, then the film is taken out and put into deionized water, soaked at room temperature for 8 h, and the deionized water is changed every 2 h. Finally, the film is dried in a vacuum drying oven at 80 °C for 10 h to obtain the anti-aging antibacterial film. The mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0038] Example 2

[0039] An anti-aging antibacterial film is made of the following raw materials by weight: 65 parts of ethylene-vinyl alcohol copolymer, 13 parts of composite reinforcing body, 1.5 parts of coupling agent, 0.6 part of processing aid, 4 parts of anti-aging aid, 6.5 parts of 1-allyl-3-vinylimidazolium chloride, 3.5 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, 3.5 parts of amino-functionalized metal-organic framework material, 3.5 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1.2 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 3.5 parts of carboxymethyl-β-cyclodextrin, 0.9 part of initiator, and 1.2 parts of glutaraldehyde.

[0040] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TMDC3212B EVOH; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organophilic montmorillonite in a mass ratio of 1.3:1; the average particle size of the nano-zinc oxide is 30 nm; the polymer-grade nano-organophilic montmorillonite is NANOLC-NP301 polymer-grade organophilic 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 antioxidant and 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 by the method of Example 1 of the invention with the application publication number CN119591889A; the initiator is azobisisobutyronitrile.

[0041] A preparation method of the anti-aging and antibacterial film comprises the following steps:

[0042] Step S1: After mixing other raw materials except carboxymethyl-β-cyclodextrin evenly by weight, a mixed material is obtained. The mixed material is added to N,N-dimethylformamide, stirred evenly, and then cast on the surface of a smooth mold and dried in a forced-air drying oven at 70 °C for 8.5 h to preliminarily form a film. Then the formed film is placed in a steam environment containing glutaraldehyde and reacted at a certain temperature of 43 °C for 2.3 hours; the mass ratio of the mixed material to N,N-dimethylformamide is 1:5.

[0043] Step S2: The film prepared in Step S1 is soaked in an aqueous solution of carboxymethyl-β-cyclodextrin at 53 °C for 33 h, then the film is taken out and put into deionized water and soaked at room temperature for 8.5 h, and the deionized water is changed every 2 hours. Finally, the film is dried in a vacuum drying oven at 83 °C for 12 h to obtain the anti-aging and antibacterial film; the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0044] Example 3

[0045] An anti-aging antibacterial film is made from the following raw materials by weight: 60 parts of ethylene-vinyl alcohol copolymer, 15 parts of composite reinforcing agent, 2 parts of coupling agent, 0.7 part of processing aid, 4.5 parts of anti-aging aid, 7 parts of 1-allyl-3-vinylimidazolium chloride, 4 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate, 4 parts of amino-functionalized metal-organic framework material, 4 parts of 1,3-bis(epoxyethylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1.5 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4 parts of carboxymethyl-β-cyclodextrin, 1 part of initiator, and 1.5 parts of glutaraldehyde.

[0046] 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-organophilic 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-organophilic montmorillonite is NANOLC-NP301 polymer-grade organophilic 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 antioxidant and 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 by the method of Example 1 of the invention with the application publication number CN119591889A; the initiator is dibenzoyl peroxide.

[0047] A preparation method of the anti-aging antibacterial film includes the following steps:

[0048] Step S1: Mix the other raw materials except carboxymethyl-β-cyclodextrin evenly by weight to obtain a mixed material. Add the mixed material to N,N-dimethylformamide, stir evenly, and cast it onto the surface of a smooth mold. Dry it in a forced-air drying oven at 75 °C for 9 h to preliminarily form a film. Then place the formed film in a steam environment containing glutaraldehyde and react at a certain temperature of 45 °C for 2.5 hours; the mass ratio of the mixed material to N,N-dimethylformamide is 1:5.5.

[0049] Step S2, soaking the film prepared in step S1 in an aqueous solution of carboxymethyl-β-cyclodextrin at 55°C for 35 hours, then taking out the film and placing it in deionized water, soaking it at room temperature for 9 hours, and replacing the deionized water every 2 hours; finally, placing the film in a vacuum drying oven at 85°C for 13 hours to obtain an aging-resistant antibacterial film; the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0050] Example 4

[0051] An aging-resistant antibacterial film is made of the following raw materials in parts by weight: 55 parts of ethylene-vinyl alcohol copolymer, 18 parts of composite reinforcement, 2.5 parts of coupling agent, 0.9 parts of processing aid, 5.5 parts of anti-aging aid, 7.5 parts of 1-allyl-3-vinyl imidazole chloride, 4.5 parts of 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, 4.5 parts of amino-functionalized metal organic framework material, 4.5 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1.8 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4.5 parts of carboxymethyl-β-cyclodextrin, 1.1 parts of initiator and 1.8 parts of glutaraldehyde.

[0052] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TM DC3212B EVOH; the composite reinforcement 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 70nm; 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 stearic acid calcium acid; 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 prepared according to the method of embodiment 1 of the invention patent with application publication number CN119591889A; the initiator is a mixture of dibenzoyl peroxide and azobisisobutyronitrile in a mass ratio of 3:5.

[0053] A method for preparing the aging-resistant antibacterial film comprises the following steps:

[0054] Step S1: Mix other raw materials except carboxymethyl-β-cyclodextrin evenly by weight to obtain a mixed material. Add the mixed material into N,N-dimethylformamide, stir evenly, then cast it onto the surface of a smooth mold, and dry it in a forced-air drying oven at 80 °C for 9.5 h to preliminarily form a film. Then place the formed film in a steam environment containing glutaraldehyde and react at a certain temperature of 48 °C for 2.8 hours; the mass ratio of the mixed material to N,N-dimethylformamide is 1:6.5.

[0055] Step S2: Immerse the film prepared in Step S1 in an aqueous solution of carboxymethyl-β-cyclodextrin at 58 °C for 38 h, then take out the film and put it into deionized water, soak it at room temperature for 9.5 h, and change the deionized water every 2 hours. Finally, place the film in a vacuum drying oven and dry it at 88 °C for 14 h to obtain an aging-resistant antibacterial film; the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0056] Example 5

[0057] An aging-resistant antibacterial film is made from the following raw materials by weight: 50 parts of ethylene-vinyl alcohol copolymer, 20 parts of composite reinforcing agent, 3 parts of coupling agent, 1 part of processing aid, 6 parts of anti-aging aid, 8 parts of 1-allyl-3-vinylimidazolium chloride, 5 parts of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, 5 parts of amino-functionalized metal-organic framework material, 5 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 5 parts of carboxymethyl-β-cyclodextrin, 1.2 parts of initiator, and 2 parts of glutaraldehyde.

[0058] The ethylene-vinyl alcohol copolymer is Soarnol produced by Mitsubishi Chemical TMDC3212B EVOH; the composite reinforcing agent is a mixture of nano-zinc oxide and polymer-grade nano-organophilic montmorillonite in a mass ratio of 2:1; the average particle size of the nano-zinc oxide is 80 nm; the polymer-grade nano-organophilic montmorillonite is NANOLC-NP301 polymer-grade organophilic 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 antioxidant and hindered amine light stabilizer in a mass ratio of 1:1.2; 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 by the method of Example 1 of the invention with the application publication number CN119591889A; the initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.

[0059] A preparation method of the anti-aging and antibacterial film comprises the following steps:

[0060] Step S1: After mixing other raw materials except carboxymethyl-β-cyclodextrin evenly by weight to obtain a mixed material, adding the mixed material into N,N-dimethylformamide, stirring evenly, casting onto the surface of a smooth mold, and drying in a blast drying oven at 85 °C for 10 h to preliminarily form a film; then placing the formed film in a steam environment containing glutaraldehyde and reacting at a certain temperature of 50 °C for 3 hours; the mass ratio of the mixed material to N,N-dimethylformamide is 1:7;

[0061] Step S2: Immersing the film prepared in Step S1 in an aqueous solution of carboxymethyl-β-cyclodextrin at 60 °C for 40 h, then taking out the film and putting it into deionized water, soaking at room temperature for 10 h, and changing the deionized water every 2 hours; finally, drying the film in a vacuum drying oven at 90 °C for 15 h to obtain the anti-aging and antibacterial film; the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.

[0062] Comparative Example 1

[0063] An anti-aging and antibacterial film and its preparation method are basically the same as those of Example 1, except that 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate and amino-functionalized metal-organic framework material are not added.

[0064] Comparative Example 2

[0065] An anti-aging antibacterial film and its preparation method, which is basically the same as Example 1, except that 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and carboxymethyl-β-cyclodextrin are not added.

[0066] To further illustrate the unexpected positive technical effects achieved by the products of each embodiment of the present invention, relevant performance tests were carried out on the anti-aging antibacterial films prepared in each example. The test results are shown in Table 1, and the test methods are as follows: The antibacterial performance was carried out according to QB / T2591-2003A, and the test strain was Staphylococcus aureus ATCC6538; the tensile strength was tested according to GB / T13022-1991, the test speed was 10±2 mm / min, the test temperature was 23°C, the relative humidity was 50%, the test sample was a type II dumbbell-shaped specimen, and an i-Strentek 1510 electronic universal testing machine was used for testing; for anti-aging, the products of each example were respectively placed in a fluorescent ultraviolet lamp aging test chamber, and the test conditions were set as: irradiance 0.89 W / m 2 (340 nm), blackboard temperature 60°C, test duration 168 hours. After taking out, it was cooled to room temperature, and the tensile strength after aging was measured. It was measured by the retention rate of tensile strength. The larger the value, the better the anti-aging property. The retention rate of tensile strength = tensile strength after aging / tensile strength before aging × 100%, where the tests of tensile strength after aging and tensile strength before aging were both carried out according to GB / T13022-1991.

[0067] Table 1 Performance test results of anti-aging antibacterial films

[0068] Project Tensile strength (MPa) Antibacterial rate (%) Aging resistance (%) Example 1 49.3 99.7 99.3 Example 2 50.1 99.7 99.5 Example 3 50.6 99.9 99.6 Example 4 51.8 99.9 99.8 Example 5 52.7 99.9 99.9 Comparative Example 1 44.5 97.5 98.2 Comparative Example 2 42.2 98.8 97.6

[0069] As can be seen from Table 1, the anti-aging antibacterial films disclosed in each embodiment of the present invention have better mechanical properties, more excellent antibacterial properties and anti-aging properties than the products of the comparative examples. The combined use of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, amino-functionalized metal-organic framework materials, 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.

[0070] The foregoing has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification is only the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. An anti-aging antibacterial film, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of ethylene-vinyl alcohol copolymer, 10-20 parts of composite reinforcement, 1-3 parts of coupling agent, 0.5-1 parts of processing aid, 3-6 parts of anti-aging aid, 6-8 parts of 1-allyl-3-vinyl imidazole chloride, 3-5 parts of 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, 3-5 parts of amino-functionalized metal organic framework material, 3-5 parts of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1-2 parts of 2,2'-bis(trifluoromethyl)diaminobiphenyl, 3-5 parts of carboxymethyl-β-cyclodextrin, 0.8-1.2 parts of initiator and 1-2 parts of glutaraldehyde.

2. The anti-aging antibacterial film according to claim 1, characterized in that: The ethylene-vinyl alcohol copolymer is Soarnol TM DC3212B EVOH.

3. The anti-aging antibacterial film according to claim 1, characterized in that: The composite reinforcement is prepared by mixing nano zinc oxide and polymer-grade nano organic montmorillonite in a mass ratio of (1-2):

1.

4. The anti-aging antibacterial film according to claim 3, characterized in that: The average particle size of the nano zinc oxide is 10-80nm.

5. The anti-aging antibacterial film according to claim 3, characterized in that: The polymer-grade nano-organic montmorillonite is NANOLC-NP301 polymer-grade organic montmorillonite.

6. The anti-aging antibacterial film according to claim 1, characterized in that: The coupling agent is 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; and the processing aid is calcium stearate.

7. The anti-aging antibacterial film according to claim 1, characterized in that: 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; and the hindered amine light stabilizer is hindered amine light stabilizer HS-944.

8. The anti-aging antibacterial film according to claim 1, characterized in that: The initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.

9. A method for preparing the aging-resistant antibacterial film according to any one of claims 1 to 8, characterized in that: The steps include: Step S1, after mixing the other raw materials except carboxymethyl-β-cyclodextrin uniformly by weight, a mixed material is obtained, the mixed material is added into N,N-dimethylformamide, stirred uniformly, cast onto a smooth mold surface, and dried in a blast drying oven at 65-85° C. for 8-10 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 40-50° C. for 2-3 hours; Step S2, soaking the film prepared in step S1 in an aqueous solution of carboxymethyl-β-cyclodextrin at 50-60° C. for 30-40 hours, then taking out the film and placing it in deionized water, soaking it at room temperature for 8-10 hours, and replacing the deionized water every 2 hours; finally, placing the film in a vacuum drying oven at 80-90° C. and drying it for 10-15 hours to obtain an aging-resistant antibacterial film.

10. The method for preparing the aging-resistant antibacterial film according to claim 9, characterized in that: The mass ratio of the mixed material to N,N-dimethylformamide is 1:(4-7); the mass percentage concentration of the aqueous solution of carboxymethyl-β-cyclodextrin is 5%.