Long-acting antibacterial self-cleaning hardening PET film and preparation method thereof

Abstract

The invention provides a long-acting antibacterial self-cleaning hardening PET film and a preparation method thereof. The method comprises the following steps: S1, preparing a copper deposition nano zinc oxide antibacterial material, S2, preparing an antibacterial-hardening composite material which is modified silicon dioxide or porous aluminum oxide, and S3, preparing a hydrophobic and oleophobic self-cleaning antibacterial-hardening composite material. According to the antibacterial material, through the synergistic effect of the antibacterial property of nano-zinc oxide and the antibacterial property of nano-copper elementary substance, the antibacterial effect of the PET film is remarkably improved, and the antibacterial effect is long-acting and lasting; the modified porous silicon dioxide or porous aluminum oxide is a high-hardness compound, the hardness and the wear resistance of the PET film can be obviously improved, and the antibacterial material is loaded in holes of the hardening material, so that the antibacterial-hardening composite material has the antibacterial property and does not affect the hardness of the hardening material at the same time; due to the preparation of the hydrophobic and oleophobic self-cleaning material, the composite material has self-cleaning, long-acting antibacterial and hardening effects, and can meet the application requirements of a highly-functionalized PET film.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional film materials, and relates to a PET film, specifically to a long-acting antibacterial self-cleaning and hardening PET film and a preparation method thereof. Background Art

[0002] Polyethylene terephthalate (PET) film is a very widely used film material due to its good physical and chemical properties. PET has the following characteristics: relatively high transparency, good optical properties, electrical insulation and chemical stability, and can resist the corrosion of most common chemicals. At the same time, PET also has excellent mechanical properties such as high strength, wear resistance, tensile resistance, tear resistance and good temperature resistance, so it is widely used in many fields such as printing labels, stickers, electronic displays, solar panels, glass, walls, etc. With the upgrading of market demand, the research and development of functional PET films has gradually become a hot spot to meet the needs of emerging fields such as electronics, electrical engineering, optoelectronics, photovoltaics, and construction. In recent years, there have been great improvements in the variety and quality of products in aspects such as optical film base films, release protective film base films for optoelectronics, solar cell backplane base films, window film base films, and colored films.

[0003] However, PET film materials still have the following limitations at present: (1) They do not have antibacterial properties, or the long-acting and safety of the antibacterial function are poor. At present, the antibacterial function of antibacterial PET film materials is prone to failure after long-term use in daily use environments, and some antibacterial PET film materials use silver nanoparticles as antibacterial materials, which have a risk of biological toxicity. (2) The existing PET film materials have insufficient hardness and poor wear resistance, which limits their applications. (3) The anti-pollution property is poor and they do not have self-cleaning function.

[0004] In view of this, it is necessary to further improve the existing PET film materials. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present invention is that the traditional PET film materials have poor long-acting antibacterial property, insufficient hardness and poor anti-pollution property, and thus a long-acting antibacterial self-cleaning and hardening PET film and a preparation method thereof are proposed.

[0006] To solve the above technical problems, the technical solution of the present invention is as follows:

[0007] The first aspect of the present invention provides a preparation method of a long-acting antibacterial self-cleaning and hardening PET film, which comprises the following steps:

[0008] S1. Prepare an antibacterial material: nano-zinc oxide photoreduces copper to obtain a copper-deposited nano-zinc oxide antibacterial material, wherein the mass of copper is 1-20% of the mass of nano-zinc oxide;

[0009] S2. Prepare the antibacterial and hardness-increasing composite material by loading the copper-deposited nano-zinc oxide antibacterial material obtained in step S1 onto the hardness-increasing material, where the hardness-increasing material is modified porous silica or porous alumina;

[0010] S3. Prepare the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material. Disperse the antibacterial and hardness-increasing composite material obtained in step S2 in a solvent, mix it evenly with ammonia water and deionized water, and then add tetraethyl orthosilicate, fluorosiloxane and water-based paint, and stir evenly;

[0011] S4. Coat the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material obtained in step S3 on the PET film, and obtain the long-lasting antibacterial self-cleaning hardness-increasing PET film after curing.

[0012] Preferably, step S1 includes:

[0013] S11. Add nano-zinc oxide to deionized water to obtain a premixed solution;

[0014] S12. Add CuSO4 solution and methanol to the premixed solution, mix evenly, and carry out photoreduction under light to obtain a photoreduction product;

[0015] S13. Filter the photoreduction product to obtain a filter residue, wash the filter residue, and dry it to obtain the elemental copper-deposited nano-zinc oxide antibacterial material.

[0016] Alternatively, preferably, when the hardness-increasing material is modified porous silica, step S2 includes:

[0017] S21. Prepare porous silica by dissolving a surfactant in water to obtain a surfactant solution;

[0018] S22. Add ammonia water with a concentration of 0.1 - 0.3 mol / L to the surfactant solution, stir evenly, and heat and stir at 60 - 80 °C for 1 - 2 h;

[0019] S23. Add tetraethyl silicate to the mixture obtained in step S22, continue to stir and react for 2 - 4 h, and remove the supernatant after the reaction to obtain a pre-product;

[0020] S24. Dry and calcine the pre-product to obtain porous spherical silica;

[0021] S25. Disperse the porous spherical silica in an organic solvent, add γ-aminopropyltriethoxysilane, heat and reflux at 80 - 90 °C for 18 - 20 h, wash and dry the product to obtain amino-modified silica;

[0022] S26. After dispersing the amino-modified silica in an organic solvent, maleic anhydride is added. The mass ratio of the amino-modified silica to maleic anhydride is 1 - 3:10 - 50. Heat reflux treatment is carried out at 60 - 90 °C for 18 - 30 hours. The reaction product is washed and dried to obtain carboxyl-modified silica;

[0023] S27. Disperse the copper-deposited nano-zinc oxide antibacterial material in water and continuously stir for 10 - 20 h to obtain an antibacterial material dispersion; Disperse the carboxyl-modified silica in water to obtain a modified silica dispersion. Drop the antibacterial material dispersion into the modified silica dispersion, add concentrated sulfuric acid, and carry out heat reflux treatment at 160 - 180 °C for 10 - 20 h. Among them, the mass ratio of the copper-deposited nano-zinc oxide antibacterial material to the carboxyl-modified silica is 4 - 6:2 - 5;

[0024] S28. After centrifuging the reflux product and removing the supernatant, wash the centrifuged product and dry it to obtain the antibacterial and hardening composite material.

[0025] Preferably, when the hardening material is porous alumina, step S2 includes:

[0026] S21. Dissolve the surfactant in an organic solvent and stir evenly, then add concentrated nitric acid to obtain a premixed solution;

[0027] S22. Add aluminum isopropoxide to the premixed solution obtained in step S21. The mass ratio of aluminum isopropoxide to the surfactant is 10 - 20:4 - 6. Stir until the aluminum isopropoxide is dissolved, and age the obtained mixture at 60 - 80 °C for 48 - 72 h to obtain a gel product;

[0028] S23. Carry out calcination treatment on the gel product to obtain α-type porous alumina powder;

[0029] S24. Disperse the copper-deposited nano-zinc oxide antibacterial material in water, drop the obtained dispersion onto the α-type porous alumina powder obtained in step S23, impregnate for 24 - 48 h, then dry, and then calcine to obtain the antibacterial and hardening composite material. Among them, the mass ratio of the copper-deposited nano-zinc oxide antibacterial material to α-type porous alumina is 10 - 30%.

[0030] Preferably, step S3 includes:

[0031] Disperse the antibacterial and hardening composite material in an organic solvent, stir for 6 - 8 h, then add ammonia water and deionized water and stir evenly. Next, add tetraethyl orthosilicate, fluorosiloxane and waterborne paint, and continue to stir for 30 - 50 h to obtain a hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material. Among them, the volume ratio of ammonia water, deionized water, tetraethyl orthosilicate, fluorosiloxane and waterborne paint is: 5 - 10:8 - 15:0.3 - 2:0.2 - 1:10 - 20.

[0032] Preferably, the fluorosiloxane is one or more of perfluorodecyltriethoxysilane, perfluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane.

[0033] Preferably, in the long-acting antibacterial self-cleaning and hardening PET film, the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material is 20 - 200 nm.

[0034] Alternatively, preferably, in step S21, the surfactant is one or more of cetyltrimethylammonium bromide, octadecylammonium trimethyl chloride, octadecyltrimethylammonium bromide, hexadecylammonium trimethyl chloride, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromochloride; in step S24, the calcination includes heating the dried product at a heating rate of 1 - 2 °C / min to 500 - 600 °C, keeping it at a constant temperature for 4 - 6 h, and then cooling to room temperature; in steps S25 and S26, the organic solvent is toluene.

[0035] Preferably, in step S12, the photoreduction is: irradiating with a 12 Kw high-pressure mercury lamp for 30 min; in step S21, the surfactant is P123 and the organic solvent is absolute ethanol; in step S23, the calcination treatment includes: heating the gel product at a heating rate of 1 - 2 °C / min to 600 - 800 °C, calcining for 4 - 6 h, and then heating at a heating rate of 3 - 5 °C / min to 1000 - 1200 °C, calcining for 1 - 3 h; in step S24, the temperature of the calcination treatment is 400 - 600 °C and the time of the calcination treatment is 2 - 4 h.

[0036] The second aspect of the present invention provides a long-acting antibacterial self-cleaning and hardening PET film, which is prepared by the above preparation method.

[0037] The above technical solution of the present invention has the following advantages compared with the prior art:

[0038] The preparation method of the long-acting antibacterial self-cleaning hardening PET film provided by the present invention comprises the following steps: S1, preparing a copper-deposited nano zinc oxide antibacterial material, S2, loading the antibacterial material on a hardening material to obtain an antibacterial-hardening composite material, wherein the hardening material is modified silica or porous alumina, and S3, preparing a hydrophobic and oleophobic self-cleaning antibacterial-hardening composite material. Among them, the copper-deposited nano zinc oxide antibacterial material significantly improves the antibacterial effect of the PET film through the synergistic effect of the antibacterial property of nano zinc oxide itself and the antibacterial property of nano copper element, and the antibacterial effect is long-lasting; modified porous silica or porous alumina is a high-hardness compound, which can significantly improve the hardness and wear resistance of the PET film, and the antibacterial material is loaded in the pores of the hardening material, so that the antibacterial-hardening composite material has antibacterial property without affecting the hardness of the hardening material, and the preparation of the hydrophobic and oleophobic self-cleaning material enables the composite material to have both self-cleaning, long-acting antibacterial and hardening effects, and can meet the application requirements of highly functional PET films. DETAILED DESCRIPTION

[0039] In order to make the contents of the present invention more clearly understood, the present invention is further described in detail below based on specific embodiments of the present invention.

[0040] Example 1

[0041] This embodiment provides a method for preparing a long-lasting antibacterial self-cleaning hardening PET film, comprising the following steps:

[0042] S1. Preparation of antibacterial material: Nano zinc oxide photoreduction of copper to obtain copper-deposited nano zinc oxide antibacterial material, specifically comprising the following steps:

[0043] S11. Weigh 10 g of purchased needle-shaped nano zinc oxide and add it into a container containing 400 ml of deionized water to obtain a premixed solution.

[0044] S12. Add a solution containing 0.3 g of CuSO4 and 10 ml of methanol to the premixed solution, mix well, and then stir magnetically at a constant temperature. Then, irradiate with a high-pressure mercury lamp to perform photoreduction to obtain a photoreduction product.

[0045] S13, filtering the photoreduction product, and washing the obtained filter residue with deionized water for 4 times. After washing, drying at 60-80° C. to obtain a single copper-deposited nano zinc oxide antibacterial material. In this embodiment, the drying temperature is 60° C.

[0046] S2, preparing an antibacterial-hardening composite material, loading the copper-deposited nano zinc oxide antibacterial material obtained in step S1 on a hardening material, wherein the hardening material is modified porous silica, specifically comprising the following steps:

[0047] S21. Prepare porous silica. Weigh 1 g of cetyltrimethylammonium bromide (CTAB) and dissolve it in 150 ml of distilled water to obtain a surfactant solution.

[0048] S22. Add 30 ml of ammonia water with a concentration of 0.1 mol / L to the surfactant solution. After stirring evenly, transfer it to a 500-ml three-necked flask and heat and stir it for 1 h under the constant temperature condition of 60 °C.

[0049] S23. Add 10 ml of tetraethyl orthosilicate (TEOS) to the mixture obtained in step S22, continue stirring and reacting for 3 h. After the reaction ends, remove the supernatant to obtain a pre-product, and wash the pre-product with distilled water 3 times.

[0050] S24. Dry the washed pre-product at 50 - 70 °C for 10 - 12 h. In this example, the washed product is dried at 50 °C for 10 h. Then spread the dried product flat on a porcelain boat and place it in a tube furnace. Heat it to 500 °C at a heating rate of 1 °C / min, keep it at a constant temperature for 4 h, and then cool it evenly to room temperature to obtain porous spherical silica.

[0051] S25. Weigh 1 g of porous spherical silica and disperse it in 100 ml of toluene solution. Ultrasonically disperse it for 15 min, add 2 ml of γ-aminopropyltriethoxysilane to it, heat and reflux it at 80 °C for 18 h. After cooling, wash the product with deionized water and ethanol repeatedly 5 times, and dry it at 50 - 70 °C. In this example, the drying temperature is 50 °C to obtain amino-modified silica.

[0052] S26. Weigh 1 g of amino-modified silica and disperse it in 150 ml of toluene solution, add 15 g of maleic anhydride, heat and reflux it at 60 °C for 18 h. Wash the obtained reaction product with deionized water and ethanol repeatedly 5 times, and dry it at 50 - 70 °C to obtain carboxyl-modified silica. In this example, the drying temperature is 55 °C.

[0053] S27. Weigh 4 g of copper-deposited nano-zinc oxide antibacterial material and disperse it in 200 ml of water, continuously stir it for 10 h to obtain an antibacterial material dispersion; weigh 2 g of carboxyl-modified silica and disperse it in 200 ml of water to obtain a modified silica dispersion; drop the antibacterial material dispersion into the modified silica dispersion. After the dropping is completed, add 1 ml of concentrated sulfuric acid with a concentration of 75% to the mixed solution, and heat and reflux it at 170 °C for 10 h.

[0054] S28. After the reflux ends, perform centrifugation on the obtained mixed solution. After removing the supernatant, wash the product 5 times and then put the product into an oven and dry it at 60 °C for 15 h to obtain an antibacterial and hardness-increasing composite material.

[0055] S3. Prepare a hydrophobic and oleophobic self - cleaning antibacterial - hardening composite material. Weigh 2 g of the antibacterial - hardening composite material obtained in step S2, disperse and stir it in ethanol for 6 h, then add 5 ml of ammonia water and 8 ml of deionized water to it. After continuing to stir for 1 h until it is uniformly mixed, add 0.3 ml of tetraethyl orthosilicate, 0.2 ml of perfluorodecyltriethoxysilane, and 10 ml of SJ - 103 water - based paint, and magnetically stir for 30 h until it is uniformly stirred.

[0056] S4. Uniformly coat the hydrophobic and oleophobic self - cleaning antibacterial - hardening composite material obtained in step S3 on a PET film. After curing at room temperature for 20 - 72 h, a long - acting antibacterial self - cleaning hardening PET film is obtained. In this example, the curing time at room temperature is 40 h, and the thickness of the hydrophobic and oleophobic self - cleaning antibacterial - hardening composite material layer is 80 nm.

[0057] This example also provides a long - acting antibacterial self - cleaning hardening PET film, which is prepared by the above method.

[0058] The preparation method of the long - acting antibacterial self - cleaning hardening PET film provided in this example uses the method of in - situ deposition of nanometer zinc oxide by elemental copper. Through the synergistic effect of the antibacterial property of nanometer zinc oxide itself and the antibacterial property of nanometer copper, the antibacterial effect of the PET film is significantly improved, and the antibacterial effect is long - lasting. It solves the problem that the separation effect of photo - generated electrons and holes of zinc oxide by Cu doping in the traditional method is not obvious and the improvement effect on the antibacterial property of zinc oxide is not good. At the same time, by using modified porous silica or porous alumina as the hardening material, both of which are high - hardness compounds, the hardness and wear resistance of the PET film can be significantly improved. And by first preparing porous silica or alumina and loading the antibacterial material in the pore structure, it avoids the antibacterial material from affecting the surface structure of the hardening material, ensuring the hardness and wear resistance of the antibacterial - hardening material while also having a long - acting antibacterial effect. On the basis of the antibacterial - hardening material, a hydrophobic and oleophobic layer is formed in - situ by an in - situ method, which has a self - cleaning effect. The finally formed PET film has the effects of self - cleaning, long - acting antibacterial, and hardening at the same time, and can meet the application requirements of highly functional PET films. 2+ Doping has an insignificant separation effect on the photo - generated electrons and holes of zinc oxide and a poor improvement effect on the antibacterial property of zinc oxide. At the same time, by using modified porous silica or porous alumina as the hardening material, both of which are high - hardness compounds, the hardness and wear resistance of the PET film can be significantly improved. And by first preparing porous silica or alumina and loading the antibacterial material in the pore structure, it avoids the antibacterial material from affecting the surface structure of the hardening material, ensuring the hardness and wear resistance of the antibacterial - hardening material while also having a long - acting antibacterial effect. On the basis of the antibacterial - hardening material, a hydrophobic and oleophobic layer is formed in - situ by an in - situ method, which has a self - cleaning effect. The finally formed PET film has the effects of self - cleaning, long - acting antibacterial, and hardening at the same time, and can meet the application requirements of highly functional PET films.

[0059] Example 2

[0060] This example provides a preparation method of a long - acting antibacterial self - cleaning hardening PET film, which includes the following steps:

[0061] S1. Prepare an antibacterial material: Copper is photoreduced by nanometer zinc oxide to obtain a copper - deposited nanometer zinc oxide antibacterial material, which specifically includes the following steps:

[0062] S11. Weigh 20 g of commercially available needle - shaped nanometer zinc oxide and add it to a container containing 500 ml of deionized water to obtain a premixed solution.

[0063] S12. Add a solution containing 5 g of CuSO4 and 30 ml of methanol to the premixed solution. After mixing evenly, stir magnetically at a constant temperature, and then irradiate with a high-pressure mercury lamp for photoreduction to obtain a photoreduction product.

[0064] S13. Filter the photoreduction product by suction, and wash the obtained filter residue 4 times with deionized water. After washing, dry it at 60 - 80 °C to obtain a copper-deposited nano-zinc oxide antibacterial material. In this example, the drying temperature is 80 °C.

[0065] S2. Prepare an antibacterial and hardening composite material by loading the copper-deposited nano-zinc oxide antibacterial material obtained in step S1 onto a hardening material, where the hardening material is modified porous silica. The specific steps are as follows:

[0066] S21. Prepare porous silica. Weigh 1.5 g of octadecylammonium trimethyl chloride and dissolve it in 150 ml of distilled water to obtain a surfactant solution.

[0067] S22. Add 40 ml of ammonia water with a concentration of 0.2 mol / L to the surfactant solution. After stirring evenly, transfer it to a 500 ml three-necked flask and heat and stir at a constant temperature of 70 °C for 1.5 h.

[0068] S23. Add 15 ml of tetraethyl orthosilicate (TEOS) to the mixture obtained in step S22, and continue stirring and reacting for 2 h. After the reaction, remove the supernatant to obtain a pre-product, and wash the pre-product 3 times with distilled water.

[0069] S24. Dry the washed pre-product at 50 - 70 °C for 10 - 12 h. In this example, the washed product is dried at 60 °C for 11 h, and then spread the dried product flat on a porcelain boat and place it in a tubular furnace. Heat it to 550 °C at a heating rate of 1.5 °C / min, keep it at a constant temperature for 5 h, and then cool it evenly to room temperature to obtain porous spherical silica.

[0070] S25. Weigh 1.5 g of porous spherical silica and disperse it in 150 ml of toluene solution. Ultrasonically disperse it for 18 min, add 3 ml of γ-aminopropyltriethoxysilane to it, heat and reflux at 85 °C for 19 h, cool it, and wash the product repeatedly 5 times with deionized water and ethanol, and dry it at 50 - 70 °C. In this example, the drying temperature is 60 °C to obtain amino-modified silica.

[0071] S26. Weigh 1.5 g of amino-modified silica and disperse it in 100 ml of toluene solution. Add 20 g of maleic anhydride and heat under reflux at 90 °C for 20 h. Wash the obtained reaction product repeatedly with deionized water and ethanol for 5 times, and dry it at 50 - 70 °C to obtain carboxyl-modified silica. In this example, the drying temperature is 60 °C.

[0072] S27. Weigh 5 g of copper-deposited nano-zinc oxide antibacterial material and disperse it in 250 ml of water, and continuously stir for 15 h to obtain an antibacterial material dispersion; weigh 4 g of carboxyl-modified silica and disperse it in 250 ml of water to obtain a modified silica dispersion; drop the antibacterial material dispersion into the modified silica dispersion. After the dropping is completed, add 1.5 ml of concentrated sulfuric acid with a concentration of 75% to the mixed solution and heat under reflux at 160 °C for 15 h.

[0073] S28. After the reflux is completed, centrifuge the obtained mixed solution. After removing the supernatant, wash the product 5 times and then put the product into an oven and dry it at 70 °C for 17 h to obtain an antibacterial and hardness-increasing composite material.

[0074] S3. Prepare a hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material. Weigh 2.5 g of the antibacterial and hardness-increasing composite material obtained in step S2, disperse it in ethanol and stir for 7 h, then add 10 ml of ammonia water and 9 ml of deionized water to it, continue to stir for 1.5 h until it is evenly mixed, then add 0.5 ml of tetraethyl orthosilicate, 1 ml of perfluorooctyltriethoxysilane and 15 ml of SJ-54A water-based paint, and magnetically stir for 40 h until it is evenly mixed.

[0075] S4. Uniformly coat the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material obtained in step S3 on a PET film. After curing at room temperature for 20 - 72 h, a long-lasting antibacterial self-cleaning and hardness-increasing PET film is obtained. In this example, the curing time at room temperature is 72 h, and the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material layer is 100 nm.

[0076] This example also provides a long-lasting antibacterial self-cleaning and hardness-increasing PET film, which is prepared by the above method.

[0077] Example 3

[0078] This example provides a preparation method of a long-lasting antibacterial self-cleaning and hardness-increasing PET film, including the following steps:

[0079] S1. Prepare an antibacterial material: nano-zinc oxide photoreduces copper to obtain a copper-deposited nano-zinc oxide antibacterial material, which specifically includes the following steps:

[0080] S11. Weigh 15 g of needle-shaped nano zinc oxide purchased externally and add it to a container containing 500 ml of deionized water to obtain a premixed solution.

[0081] S12. Add a solution containing 2 g of CuSO4 and 50 ml of methanol to the premixed solution. After mixing evenly, stir magnetically at a constant temperature, and then irradiate with a high-pressure mercury lamp for photoreduction to obtain a photoreduction product.

[0082] S13. Filter the photoreduction product by suction filtration, and wash the obtained filter residue 4 times with deionized water. After washing, dry it at 60 - 80 °C to obtain a copper-deposited nano zinc oxide antibacterial material. In this example, the drying temperature is 70 °C.

[0083] S2. Prepare an antibacterial and hardening composite material by loading the copper-deposited nano zinc oxide antibacterial material obtained in step S1 onto a hardening material, where the hardening material is modified porous silica. The specific steps are as follows:

[0084] S21. Prepare porous silica. Weigh 2.5 g of octadecyltrimethylammonium bromide and dissolve it in 150 ml of distilled water to obtain a surfactant solution.

[0085] S22. Add 40 ml of ammonia water with a concentration of 0.3 mol / L to the surfactant solution. After stirring evenly, transfer it to a 500 ml three-necked flask and heat and stir at a constant temperature of 80 °C for 2 h.

[0086] S23. Add 30 ml of tetraethyl orthosilicate (TEOS) to the mixture obtained in step S22, continue stirring and reacting for 4 h. After the reaction, remove the supernatant to obtain a pre-product, and wash the pre-product 3 times with distilled water.

[0087] S24. Dry the washed pre-product at 50 - 70 °C for 10 - 12 h. In this example, the washed product is dried at 70 °C for 12 h. Then spread the dried product flat on a porcelain boat and place it in a tubular furnace. Heat it to 600 °C at a heating rate of 2 °C / min, keep it at a constant temperature for 6 h, and then cool it evenly to room temperature to obtain porous spherical silica.

[0088] S25. Weigh 3 g of porous spherical silica and disperse it in 200 ml of toluene solution. Ultrasonically disperse it for 20 min, add 4 ml of γ-aminopropyltriethoxysilane to it, heat and reflux at 90 °C for 20 h. After cooling, wash the product 5 times repeatedly with deionized water and ethanol, and dry it at 50 - 70 °C. In this example, the drying temperature is 70 °C to obtain amino-modified silica.

[0089] S26. Weigh 3 g of the amino-modified silica and disperse it in 100 ml of toluene solution. Add 50 g of maleic anhydride and heat under reflux at 80 °C for 30 h. Wash the obtained reaction product repeatedly with deionized water and ethanol for 5 times, and dry it at 50 - 70 °C to obtain carboxyl-modified silica. In this example, the drying temperature is 70 °C.

[0090] S27. Weigh 6 g of the copper-deposited nano-zinc oxide antibacterial material and disperse it in 300 ml of water, and continuously stir for 20 h to obtain an antibacterial material dispersion; weigh 5 g of the carboxyl-modified silica and disperse it in 300 ml of water to obtain a modified silica dispersion; drop the antibacterial material dispersion into the modified silica dispersion. After the dropping is completed, add 3 ml of concentrated sulfuric acid with a concentration of 75% to the mixed solution, and heat under reflux at 180 °C for 20 h.

[0091] S28. After the reflux is completed, perform centrifugation on the obtained mixed solution. After removing the supernatant, wash the product 5 times and then put the product into an oven and dry it at 80 °C for 20 h to obtain an antibacterial and hardening composite material.

[0092] S3. Prepare a hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material. Weigh 3 g of the antibacterial and hardening composite material obtained in step S2, disperse it in ethanol and stir for 8 h, then add 8 ml of ammonia water and 15 ml of deionized water to it, continue to stir for 2 h until it is evenly mixed, and then add 2 ml of tetraethyl orthosilicate, 0.5 ml of trifluorooctyltrimethoxysilane and 20 ml of the water-based paint of the Three Tree brand, and magnetically stir for 50 h until it is evenly mixed.

[0093] S4. Uniformly coat the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material obtained in step S3 on a PET film, and cure it at room temperature for 20 - 72 h to obtain a long-lasting antibacterial self-cleaning and hardening PET film. In this example, the curing time at room temperature is 20 h, and the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material layer is 60 nm.

[0094] This example also provides a long-lasting antibacterial self-cleaning and hardening PET film, which is prepared by the above method.

[0095] Example 4

[0096] This example provides a preparation method of a long-lasting antibacterial self-cleaning and hardening PET film, including the following steps:

[0097] S1. Prepare an antibacterial material: Nano-zinc oxide photoreduces copper to obtain a copper-deposited nano-zinc oxide antibacterial material, which specifically includes the following steps:

[0098] S11. Weigh 10 g of the purchased needle-shaped nano-zinc oxide and add it to a container containing 400 ml of deionized water to obtain a premixed solution.

[0099] S12. Add a solution containing 0.3 g of CuSO4 and 10 ml of methanol to the premixed solution. After mixing evenly, stir magnetically at a constant temperature, and then irradiate with a high-pressure mercury lamp for photoreduction to obtain a photoreduction product.

[0100] S13. Filter the photoreduction product by suction filtration, and wash the obtained filter residue 4 times with deionized water. After washing, dry it at 60 - 80 °C to obtain a copper-deposited nano-zinc oxide antibacterial material. In this example, the drying temperature is 60 °C.

[0101] S2. Prepare an antibacterial and hardening composite material by loading the copper-deposited nano-zinc oxide antibacterial material obtained in step S1 onto a hardening material, where the hardening material is porous alumina. The specific steps are as follows:

[0102] S21. Weigh 4 g of surfactant P123, dissolve it in 100 ml of absolute ethanol, and stir evenly until completely dissolved. Then add 6 ml of concentrated nitric acid with a concentration of 65%.

[0103] S22. Add 10 g of aluminum isopropoxide to the premixed solution obtained in step S21, stir for 5 h until the aluminum isopropoxide is dissolved, and age the obtained mixture at 60 °C for 72 h to obtain a pale yellow xerogel product.

[0104] S23. Place the gel product in a muffle furnace for calcination treatment. Heat it to 800 °C at a heating rate of 1 °C / min and calcine for 4 h. Then heat it to 1000 °C at a heating rate of 3 °C / min and calcine for 1 h to obtain α-type porous alumina powder.

[0105] S24. Weigh 1 g of the copper-deposited nano-zinc oxide antibacterial material and disperse it in deionized water. Drop the obtained dispersion onto 10 g of the α-type porous alumina powder obtained in step S23. After impregnation for 48 h, place it in an oven and dry it overnight at 100 °C. Then calcine it at 400 °C for 3 h to obtain an antibacterial and hardening composite material.

[0106] S3. Prepare a hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material. Weigh 2 g of the antibacterial and hardening composite material obtained in step S2, disperse and stir it in ethanol for 6 h. Then add 5 ml of ammonia water and 8 ml of deionized water to it, continue to stir for 1 h until evenly mixed. Then add 0.3 ml of tetraethyl orthosilicate, 0.2 ml of perfluorodecyltriethoxysilane, and 10 ml of SJ-103 water-based paint, and stir magnetically for 30 h until evenly mixed.

[0107] S4. Uniformly coat the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material obtained in step S3 on the PET film, and cure it at room temperature for 20 - 72 h to obtain the long-lasting antibacterial self-cleaning hardening PET film. In this example, the curing time at room temperature is 40 h, and the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material layer is 80 nm.

[0108] This example also provides a long-lasting antibacterial self-cleaning hardening PET film, which is prepared by the above method.

[0109] Example 5

[0110] This example provides a preparation method of a long-lasting antibacterial self-cleaning hardening PET film, including the following steps:

[0111] S1. Prepare the antibacterial material: nano-zinc oxide photoreduces copper to obtain copper-deposited nano-zinc oxide antibacterial material, specifically including the following steps:

[0112] S11. Weigh 20 g of commercially available needle-shaped nano-zinc oxide and add it to a container containing 500 ml of deionized water to obtain a premixed solution.

[0113] S12. Add a solution containing 5 g of CuSO4 and 30 ml of methanol to the premixed solution, mix evenly, stir magnetically at a constant temperature, and then irradiate with a high-pressure mercury lamp for photoreduction to obtain a photoreduction product.

[0114] S13. Filter the photoreduction product by suction filtration, wash the obtained filter residue 4 times with deionized water, and dry it at 60 - 80 °C after washing to obtain the elemental copper-deposited nano-zinc oxide antibacterial material. In this example, the drying temperature is 80 °C.

[0115] S2. Prepare the antibacterial and hardening composite material by loading the copper-deposited nano-zinc oxide antibacterial material obtained in step S1 onto the hardening material, and the hardening material is porous alumina, specifically including the following steps:

[0116] S21. Weigh 5 g of surfactant P123, dissolve it in 200 ml of absolute ethanol, stir evenly until completely dissolved, and then add 7 ml of concentrated nitric acid with a concentration of 65%.

[0117] S22. Add 15 g of aluminum isopropoxide to the premixed solution obtained in step S21, stir for 6 h until the aluminum isopropoxide is dissolved, and age the obtained mixture at 70 °C for 60 h to obtain a pale yellow xerogel product.

[0118] S23. Place the gel product in a muffle furnace for calcination treatment, heat it to 600 °C at a heating rate of 1.5 °C / min, calcine for 5 h, and then heat it to 1200 °C at a heating rate of 4 °C / min and calcine for 2 h to obtain α-type porous alumina powder.

[0119] S24. Weigh 3 g of the copper-deposited nano-zinc oxide antibacterial material and disperse it in deionized water. Drop the obtained dispersion onto 15 g of the α-type porous alumina powder obtained in step S23. After impregnation for 36 h, place it in an oven and dry it overnight at 100 °C, and then calcine it at 500 °C for 2 h to obtain an antibacterial and hardness-increasing composite material.

[0120] S3. Prepare a hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material. Weigh 2.5 g of the antibacterial and hardness-increasing composite material obtained in step S2, disperse and stir it in ethanol for 7 h. Then add 10 ml of ammonia water and 9 ml of deionized water to it, continue to stir for 1.5 h until it is uniformly mixed, and then add 0.5 ml of tetraethyl orthosilicate, 1 ml of perfluorooctyltriethoxysilane and 15 ml of SJ-54A water-based paint, and magnetically stir for 40 h until it is uniformly mixed.

[0121] S4. Uniformly coat the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material obtained in step S3 on a PET film. After curing at room temperature for 20 - 72 h, a long-acting antibacterial self-cleaning and hardness-increasing PET film is obtained. In this example, the curing time at room temperature is 72 h, and the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardness-increasing composite material layer is 100 nm.

[0122] This example also provides a long-acting antibacterial self-cleaning and hardness-increasing PET film, which is prepared by the above method.

[0123] Example 6

[0124] This example provides a preparation method of a long-acting antibacterial self-cleaning and hardness-increasing PET film, including the following steps:

[0125] S1. Prepare an antibacterial material: nano-zinc oxide photoreduces copper to obtain a copper-deposited nano-zinc oxide antibacterial material, which specifically includes the following steps:

[0126] S11. Weigh 15 g of commercially available needle-shaped nano-zinc oxide and add it to a container containing 500 ml of deionized water to obtain a premixed solution.

[0127] S12. Add a solution containing 2 g of CuSO4 and 50 ml of methanol to the premixed solution. After mixing evenly, perform constant-temperature magnetic stirring, and then irradiate it with a high-pressure mercury lamp for photoreduction to obtain a photoreduction product.

[0128] S13. Filter the photoreduction product by suction filtration, and wash the obtained filter residue 4 times with deionized water. After washing, dry it at 60 - 80 °C to obtain a single copper-deposited nano-zinc oxide antibacterial material. In this example, the drying temperature is 70 °C.

[0129] S2. Prepare an antibacterial and hardness - increasing composite material by loading the copper - deposited nano - zinc oxide antibacterial material obtained in step S1 onto a hardness - increasing material, where the hardness - increasing material is porous alumina. The specific steps are as follows:

[0130] S21. Weigh 6 g of surfactant P123, dissolve it in 300 ml of absolute ethanol, stir evenly until completely dissolved, and then add 10 ml of concentrated nitric acid with a concentration of 65%.

[0131] S22. Add 20 g of aluminum isopropoxide to the premixed solution obtained in step S21, stir for 7 h until the aluminum isopropoxide is dissolved, and age the resulting mixture at 80 °C for 48 h to obtain a pale - yellow xerogel product.

[0132] S23. Place the xerogel product in a muffle furnace for calcination. Heat it to 700 °C at a heating rate of 2 °C / min and calcine for 6 h, then heat it to 1100 °C at a heating rate of 5 °C / min and calcine for 3 h to obtain α - type porous alumina powder.

[0133] S24. Weigh 10 g of the copper - deposited nano - zinc oxide antibacterial material and disperse it in deionized water. Drop the resulting dispersion onto 65 g of the α - type porous alumina powder obtained in step S23, impregnate for 48 h, then place it in an oven and dry overnight at 100 °C, and then calcine at 600 °C for 4 h to obtain the antibacterial and hardness - increasing composite material.

[0134] S3. Prepare a hydrophobic and oleophobic self - cleaning antibacterial and hardness - increasing composite material. Weigh 3 g of the antibacterial and hardness - increasing composite material obtained in step S2, disperse and stir it in ethanol for 8 h, then add 8 ml of ammonia water, 15 ml of deionized water, continue to stir for 2 h until evenly mixed, then add 2 ml of tetraethyl orthosilicate, 0.5 ml of 1,1,1,3,3,3 - hexafluoro - 2 - (trifluoromethoxy) propyltrimethoxysilane, and 20 ml of the water - based paint of Three Trees brand, and magnetically stir for 50 h until evenly mixed.

[0135] S4. Uniformly coat the hydrophobic and oleophobic self - cleaning antibacterial and hardness - increasing composite material obtained in step S3 on a PET film. After curing at room temperature for 20 - 72 h, a long - acting antibacterial self - cleaning hardness - increasing PET film is obtained. In this example, the curing time at room temperature is 20 h, and the thickness of the hydrophobic and oleophobic self - cleaning antibacterial and hardness - increasing composite material layer is 60 nm.

[0136] This example also provides a long - acting antibacterial self - cleaning hardness - increasing PET film, which is prepared by the above - mentioned method.

[0137] Comparative Example 1

[0138] This comparative example provides a preparation method of a PET film. This method is basically the same as that of Example 1, with the difference being the preparation of the antibacterial material. In this comparative example, the antibacterial material is prepared by the following method of copper - doped nano - zinc oxide:

[0139] Weigh 10 g of purchased needle-shaped nano zinc oxide, add it to a container containing 400 ml of deionized water to obtain a nano zinc oxide solution. Then, dropwise add an aqueous solution containing 0.3 g of CuSO4 into the nano zinc oxide solution. After the addition, magnetically stir at a constant temperature for 3 - 4 h. After that, perform suction filtration and wash the filter residue with deionized water 4 times. After the washing is completed, place the product in an oven and dry it at 60 °C to obtain the antibacterial material. The remaining steps are the same as those in Example 1.

[0140] Comparative Example 2

[0141] This comparative example provides a method for preparing a PET film. The difference between this method and that of Example 1 is that it does not contain the step of loading the copper-deposited nano zinc oxide antibacterial material onto the hardening material. Instead, directly disperse the copper-deposited nano zinc oxide antibacterial material in ethanol, and then prepare a PET film with a hydrophobic and oleophobic layer.

[0142] Comparative Example 3

[0143] This comparative example provides a method for preparing a PET film. The difference between this method and those of Example 1 and Example 4 is that silica or alumina is coated on the outside of the copper-deposited nano zinc oxide antibacterial material. The specific steps are as follows: Stir 600 ml of 30% copper-deposited zinc oxide aqueous dispersion for 30 min. Dissolve 30 g of sodium silicate in water and dropwise add it to the copper-deposited zinc oxide dispersion under magnetic stirring. After the addition, continue stirring for 1 h. Adjust the pH value to 9, then age for 2 h, and then obtain the copper-deposited nano zinc oxide coated with silica through filtration, washing, and drying.

[0144] The specific preparation steps of the copper-deposited zinc oxide coated with alumina are as follows: Weigh 10 g of copper-deposited zinc oxide, disperse it in water and stir, then add a 13% concentration of NaHCO3 solution, and then add an Al2(SO4)3 solution, controlling the proportion of Al2O3 to be 5%. React at 50 °C for 30 min to obtain a precipitate. Filter the precipitate, wash it with deionized water, dry it at 120 °C, and then calcine it for 1 h to obtain the copper-deposited nano zinc oxide coated with alumina. The remaining steps are the same as those in Example 1.

[0145] Comparative Example 4

[0146] This comparative example provides a method for preparing a PET film. The difference between this method and that of Example 1 is that the silica or alumina loaded with the antibacterial material is redispersed in water and then added to SJ-103 water wash paint, and then coated on the PET film. After curing at room temperature, a PET film is obtained.

[0147] Experimental Example

[0148] 1. Antibacterial Experiment

[0149] Referring to the antibacterial performance test method of GB / T 31402-2015, the same film thickness was coated on the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite PET film prepared by the methods provided in Examples 1-3 and Comparative Examples 1-4. Then, the prepared PET film was cut into the same size, the surface was wiped clean, rinsed with sterile water, and dried at 60 °C for 2 h. Escherichia coli and Staphylococcus aureus were inoculated on the surface of the dried film, and irradiated under a 30W fluorescent lamp for 24 h, and the antibacterial rate was observed and detected. The antibacterial performance test results are shown in Table 1 below.

[0150] Table 1

[0151] Sample Antibacterial rate against Escherichia coli Antibacterial rate against Staphylococcus aureus Example 1 99.99％ 99.96％ Example 2 99.98％ 99.98％ Example 3 99.97％ 99.95％ Comparative example 1 69.87％ 59.75％ Comparative example 2 99.95％ 99.98％ Comparative example 3 99.52％ 99.48％ Comparative example 4 99.95％ 99.97％

[0152] It can be seen from the above test results that the antibacterial effect of the PET film with the antibacterial material prepared by the copper-doped nano-zinc oxide method is worse than that of the PET film prepared by the method provided in Example 1; the antibacterial effect of the PET film prepared by the antibacterial and hardening material obtained by copper deposition on the outer surface of nano-zinc oxide coated with silica or alumina is also slightly worse, indicating that the antibacterial effect is affected after doping with copper and coating with silica or alumina.

[0153] 2. Contact angle test

[0154] The PET films prepared by the methods provided in Examples 1-3 and Comparative Examples 1-4 were cut into the same size, and a pipette was used to vertically drop water, oil, and n-hexadecane onto the surface of the film, and a contact angle measuring instrument was used to measure the contact angle on the surface of the film. The average value of the five measurements was used as the contact angle measurement result, and the test results are shown in Table 2:

[0155] Table 2

[0156]

[0157]

[0158] It can be seen from the above test results that the PET films prepared by the methods provided in Examples 1-3 of the present application have good hydrophobic and oleophobic properties, making the film have a self-cleaning effect.

[0159] 3. Abrasion resistance test

[0160] The PET films prepared by the methods provided in Examples 1-3 and Comparative Examples 1-4 were cut into the same size, and the wear resistance of the test samples was tested at 25 °C using 1000-mesh steel wool under a pressure of 500 g. The test results are shown in Table 3:

[0161] Table 3

[0162] Sample Coating abrasion resistance test Example 1 No scratches after 2000 times Example 2 No scratches after 2000 times Example 3 No scratches after 2000 times Comparative example 1 Scratches and abrasions appeared after 1650 times Comparative example 2 Scratches and abrasions appeared after 480 times Comparative example 3 No scratches after 2000 times Comparative example 4 No scratches after 2000 times

[0163] As can be seen from the above test results, the PET film prepared by the method provided in Embodiments 1-3 of the present application has good wear resistance.

[0164] 4. Hardness test

[0165] The PET films prepared by the methods provided in Embodiments 1-3 and Comparative Examples 1-4 were cut into the same size. A set of pencils with hardness ranging from 9B to 9H was prepared. The test coating sample was fixed with the front side facing up to ensure that the test surface was flat and free of impurities. Scratches were made at an angle of 45° between the pencil and the coating surface. Starting from the hardest pencil, the tests were carried out one by one in order from hard to soft. The test results are shown in Table 4 below:

[0166] Table 4

[0167]

[0168]

[0169] As can be seen from the above test results, the PET film prepared by the method provided in Embodiments 1-3 of the present application has higher hardness.

[0170] Obviously, the above embodiments are only examples for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A preparation method of a long-acting antibacterial self-cleaning and hardening PET film, characterized in that, The steps are as follows: S1. Prepare the antibacterial material: Copper is deposited on nano-zinc oxide by photoreduction to obtain a copper-deposited nano-zinc oxide antibacterial material, where the mass of copper is 1-20% of the mass of nano-zinc oxide. S2. Prepare the antibacterial and hardening composite material. Load the copper-deposited nano-zinc oxide antibacterial material obtained in step S1 onto the hardening material, and the hardening material is modified porous silica or porous alumina. S3. Prepare the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material. Disperse the antibacterial and hardening composite material obtained in step S2 in a solvent, mix it evenly with ammonia water and deionized water, and then add tetraethyl orthosilicate, fluorosiloxane and water-based paint, and stir evenly. S4. Coat the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material obtained in step S3 on the PET film, and cure it to obtain a long-lasting antibacterial self-cleaning hardening PET film.

2. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 1, wherein, The step S1 includes: S11. Add nano-zinc oxide to deionized water to obtain a premixed solution. S12. Add CuSO4 solution and methanol to the premixed solution, mix evenly, and carry out photoreduction under light to obtain a photoreduction product. S13. Filter the photoreduction product to obtain a filter residue, wash the filter residue, and dry it to obtain a single copper-deposited nano-zinc oxide antibacterial material.

3. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 2, characterized in that, When the hardening material is modified porous silica, the step S2 includes: S21. Prepare porous silica. Dissolve the surfactant in water to obtain a surfactant solution. S22. Add ammonia water with a concentration of 0.1-0.3 mol / L to the surfactant solution, stir evenly, and heat and stir at 60-80 °C for 1-2 h. S23. Add tetraethyl silicate to the mixture obtained in step S22, continue to stir and react for 2-4 h, and remove the supernatant after the reaction ends to obtain a pre-product. S24. Dry and calcine the pre-product to obtain porous spherical silica. S25. Disperse the porous spherical silica in an organic solvent, add γ-aminopropyltriethoxysilane, and heat and reflux at 80-90 °C for 18-20 h. Wash and dry the product to obtain amino-modified silica. S26. Disperse the amino-modified silica in an organic solvent, add maleic anhydride, and the mass ratio of the amino-modified silica to maleic anhydride is 1-3:10-50. Heat and reflux at 60-90 °C for 18-30, wash and dry the reaction product to obtain carboxyl-modified silica. S27. Disperse the copper-deposited nano-zinc oxide antibacterial material in water and continuously stir for 10-20 h to obtain an antibacterial material dispersion. Disperse the carboxyl-modified silica in water to obtain a modified silica dispersion. Drop the antibacterial material dispersion into the modified silica dispersion, add concentrated sulfuric acid, and heat and reflux at 160-180 °C for 10-20 h, where the mass ratio of the copper-deposited nano-zinc oxide antibacterial material to the carboxyl-modified silica is 4-6:2-5. S28. Centrifuge the reflux product and remove the supernatant, wash the centrifuged product and dry it to obtain the antibacterial and hardening composite material.

4. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 2, characterized in that, When the hardening material is porous alumina, step S2 includes: S21. Dissolve a surfactant in an organic solvent and stir evenly, then add concentrated nitric acid to obtain a premixed solution; S22. Add aluminum isopropoxide to the premixed solution obtained in step S21. The mass ratio of aluminum isopropoxide to the surfactant is 10 - 20:4 - 6. Stir until the aluminum isopropoxide dissolves, and age the obtained mixture at 60 - 80 °C for 48 - 72 h to obtain a gel product; S23. Calcinate the gel product to obtain α-type porous alumina powder; S24. Disperse the copper-deposited nano-zinc oxide antibacterial material in water, drop the obtained dispersion liquid onto the α-type porous alumina powder obtained in step S23, impregnate for 24 - 48 h, then dry and calcinate to obtain an antibacterial and hardening composite material, wherein the mass ratio of the copper-deposited nano-zinc oxide antibacterial material to α-type porous alumina is 10 - 30%.

5. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 3 or 4, characterized in that Step S3 includes: Disperse the antibacterial and hardening composite material in an organic solvent, stir for 6 - 8 h, then add ammonia water and deionized water and stir evenly, and then add tetraethyl orthosilicate, fluorosiloxane and water-based paint, and continue to stir for 30 - 50 h to obtain a hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material, wherein the volume ratio of ammonia water, deionized water, tetraethyl orthosilicate, fluorosiloxane and water-based paint is: 5 - 10:8 - 15:0.3 - 2:0.2 - 1:10 - 20.

6. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 5, characterized in that, The fluorosiloxane is one or more of perfluorodecyltriethoxysilane, perfluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane.

7. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 6, characterized in that, In the long-acting antibacterial self-cleaning hardening PET film, the thickness of the hydrophobic and oleophobic self-cleaning antibacterial and hardening composite material is 20 - 200 nm.

8. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 3, characterized in that, In step S21, the surfactant is one or more of cetyltrimethylammonium bromide, octadecylaminotrimethylammonium chloride, octadecyltrimethylammonium bromide, hexadecylaminotrimethylammonium chloride, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromochloride; in step S24, the calcination includes heating the dried product at a heating rate of 1 - 2 °C / min to 500 - 600 °C, keeping it at a constant temperature for 4 - 6 h and then cooling to room temperature; in step S25 and step S26, the organic solvent is toluene.

9. The preparation method of the long-acting antibacterial self-cleaning and hardening PET film according to claim 4, characterized in that, In step S12, the photoreduction is: irradiating with a 12 Kw high-pressure mercury lamp for 30 min; in step S21, the surfactant is P123 and the organic solvent is absolute ethanol; In step S23, the calcination treatment includes: heating the gel product at a heating rate of 1 - 2 °C / min to 600 - 800 °C, calcining for 4 - 6 h, and then heating at a heating rate of 3 - 5 °C / min to 1000 - 1200 °C and calcining for 1 - 3 h; in step S24, the temperature of the calcination treatment is 400 - 600 °C and the time of the calcination treatment is 2 - 4 h.

10. A long-acting antibacterial self-cleaning and hardening PET film, characterized in that, The long-acting antibacterial self-cleaning and hardening PET film is prepared by the preparation method described in any one of claims 1-9.

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