A method for preparing an antibacterial multifunctional optical film

Abstract

This case relates to a method for preparing an antibacterial multifunctional optical film, comprising: Step 1, mixing 100 parts by weight of PET chips, 7-15 parts by weight of antioxidant-modified excipients, and 1-4 parts by weight of compatibilizer, followed by melt extrusion and casting; Step 2, biaxially stretching the cast film to obtain a base film; Step 3, coating the base film with an antibacterial-enhancing multifunctional coating liquid, and UV curing to form an antibacterial-enhancing multifunctional coating layer, thereby obtaining an antibacterial multifunctional optical film. The antioxidant-modified excipients in the base film of this case, through the rich pore structure of mesoporous silica, load antioxidants, enabling the slow release of antioxidants, thus providing long-lasting antioxidant properties to the base film; by coating the base film with the antibacterial-enhancing multifunctional coating liquid to form an antibacterial-enhancing multifunctional coating, this case can endow the optical film with excellent antibacterial and self-healing properties, and also achieve a good anti-glare effect, thereby realizing the multifunctional enhancement and modification of the optical film.

Description

Technical Field

[0001] This invention relates to the field of membrane materials, and in particular to a method for preparing an antibacterial multifunctional optical film. Background Technology

[0002] Display screens, touch screens, and other devices typically require optical films for protection to reduce screen damage. PET films, due to their high light transmittance and chemical resistance, are widely used in the manufacture of optical films. For touch screens, antibacterial properties are an important function to inhibit bacterial transmission and protect user health. Adding antibacterial agents is a common method to impart antibacterial properties to optical films. Commonly used antibacterial agents include organic antibacterial agents (such as quaternary ammonium salts and quaternary phosphine salts) and inorganic antibacterial agents (such as nano-silver, silver ions, and zinc ions). For example, patent CN111909412B discloses an antibacterial optical film and its preparation method, which uses the addition of nano-sized silver ions to improve the antibacterial properties of the optical film. This approach has the following drawback: as usage time increases, the concentration of the antibacterial agent decreases due to consumption or loss, resulting in a significant decline in its antibacterial activity and thus insufficient antibacterial duration.

[0003] On the other hand, during transportation or use, the surface of the optical film is easily scratched or damaged by abrasions, which can affect its performance or shorten its lifespan. Imparting a certain degree of self-healing capability to the optical film can better address these issues. For example, patent CN120842654B discloses an optical film with self-healing function and its preparation method. Furthermore, when strong external light shines on the display surface, the resulting reflected glare reduces image visibility, leading to decreased contrast and visual fatigue. Therefore, anti-glare performance is also required for optical films.

[0004] In conclusion, providing multifunctional optical films with antibacterial properties, as well as self-healing and anti-glare characteristics, would significantly improve the performance of optical films and better meet market demands. However, reliable solutions are lacking in existing technologies. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing an antibacterial multifunctional optical film, addressing the shortcomings of the prior art.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method for preparing an antibacterial multifunctional optical film, comprising the following steps: Step 1: By weight, mix 100 parts PET chips, 7-15 parts antioxidant modified excipients, and 1-4 parts compatibilizer, then melt-extrude and cast into sheets. Step 2: Biaxially stretch the cast sheet to obtain the base film; Step 3: Apply an antibacterial and enhanced multifunctional coating liquid onto the base film, and UV cure to form an antibacterial and enhanced multifunctional coating, thereby obtaining the antibacterial multifunctional optical film; The antioxidant-modified excipients are prepared through the following steps: S1-1. Antioxidant-functionalized silica is prepared by loading antioxidants onto mesoporous silica: S1-2. Modified silica is obtained by using a silane coupling agent to modify the antioxidant-modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:3-8, stir evenly, melt and extrude, and granulate to obtain antioxidant modified auxiliary particles. The antibacterial enhanced multifunctional coating liquid comprises the following raw material components by weight: The composition includes: 60-90 parts polyurethane acrylate, 2-8 parts trifluoroethyl methacrylate, 4-15 parts glycidyl methacrylate, 3-12 parts diacetone acrylamide, 7-20 parts polyethylene glycol methacrylate thioctic acid, 4-10 parts zinc acrylate, 6-14 parts antibacterial reinforced multi-functional silica particles, 30-60 parts organic solvent, 1-5 parts photoinitiator, 1-4 parts emulsifier, and 0.5-5 parts additives. The antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Titanium-doped carbon dots are deposited on mesoporous silica to obtain loaded modified mesoporous silica; S2-2, Silver nanoparticles are loaded onto modified mesoporous silica to obtain antibacterial modified mesoporous silica; S2-3. Antibacterial modified mesoporous silica was modified using a silane coupling agent to obtain antibacterial enhanced multi-effect silica particles.

[0007] Preferably, the method for preparing the antibacterial multifunctional optical film includes the following steps: Step 1: By weight, mix 100 parts PET chips, 7-15 parts antioxidant modified excipients, and 1-4 parts compatibilizer evenly and then put them into a twin-screw extruder. Melt extrusion and casting are carried out at 240-265℃. Step 2: Longitudinally stretch the cast sheet at 90-100℃ with a stretching ratio of 2.5-3.5; then transversely stretch it at 105-115℃ with a stretching ratio of 3-5; cool to obtain the base film. Step 3: Apply an antibacterial and multifunctional coating solution to the base film, controlling the wet coating amount to 6-15 g / m². 2 An antibacterial and enhanced multifunctional coating is formed by UV curing under nitrogen protection, with the UV curing energy controlled at 500-700 mJ / cm². 2 The antibacterial multifunctional optical film was obtained.

[0008] Preferably, the antioxidant modified excipients are prepared through the following steps: S1-1. Add mesoporous silica to an antioxidant solution, stir, heat and vibrate, filter, wash, and dry to obtain antioxidant functionalized silica. S1-2. Add antioxidant functionalized silica to a mixed solution of deionized water and ethanol, stir, add silane coupling agent, heat and stir, filter, wash, and dry to obtain modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:3-8, stir evenly, melt extrude at 240-260℃, and granulate to obtain antioxidant modified granules.

[0009] Preferably, the antioxidant is selected from at least one of antioxidants 1010, 1076, 168, and B215; and the silane coupling agent is KH-570.

[0010] Preferably, the antioxidant modified excipients are prepared through the following steps: S1-1. Take 0.5-2g of mesoporous silica and add it to 50-160mL of acetone solution of antioxidant 1010 with a mass concentration of 3-10%. Stir for 0.5-2h, then shake at 50-65℃ for 6-24h, filter, wash with ethanol, and vacuum dry at 70-90℃ overnight to obtain antioxidant functionalized silica. S1-2. Add 1-4g of antioxidant functionalized silica to 80-300mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:1. Stir for 0.5-2h, then add 0.2-0.8g of silane coupling agent KH-570. Stir at 60-70℃ for 1.5-6h, filter, wash the solid product with ethanol and deionized water in sequence, and dry at 70-90℃ overnight to obtain modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 240-260℃, granulate, and dry to obtain antioxidant modified granules.

[0011] Preferably, the antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Disperse mesoporous silica and titanium chloride in ethanol, then add salicylic acid, 2-mercaptoisobutyric acid and p-phenylenediamine, stir, and transfer the resulting mixture into a reaction vessel. React at 155-185℃ for 8-16 hours, filter, wash, and dry to obtain supported modified mesoporous silica. S2-2. The modified mesoporous silica was added to an ethanol solution of silver nitrate, ultrasonically dispersed, glucose was added, and ammonia was added dropwise under the dark to adjust the pH to alkaline. The mixture was heated and stirred to react. After the reaction was completed, the mixture was filtered, washed, and dried to obtain antibacterial modified mesoporous silica. S2-3. Take antibacterial modified mesoporous silica and deionized water, add them to ethanol, disperse them by ultrasonication, then add silane coupling agent KH-570, heat and stir to react, filter after the reaction is completed, wash and dry to obtain antibacterial enhanced multi-effect silica particles.

[0012] Preferably, the antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Take 0.75-3g of mesoporous silica and 0.25-1.1g of titanium chloride and add them to 100-400mL of ethanol. Disperse the mixture by ultrasonication for 30-120min. Then add 0.41-1.76g of salicylic acid, 0.3-1.2g of 2-mercaptoisobutyric acid and 0.11-0.44g of p-phenylenediamine. Stir for 15-60min. Transfer the resulting mixture to a reaction vessel lined with polytetrafluoroethylene. React at 155-185℃ for 8-16h. Filter the mixture. Wash the solid product with ethanol and dry it under vacuum at 80-100℃ for 12-48h to obtain the supported modified mesoporous silica. S2-2. Add 0.5-2g of loaded modified mesoporous silica to 30-120mL of ethanol solution of silver nitrate with a concentration of 0.005-0.05mol / L, and sonicate for 0.5-2h. Then add 0.1-0.36g of glucose, and adjust the pH to 9-10 by adding 5-15wt% ammonia water dropwise under the dark. Stir and react at 40-70℃ for 12-48h. After the reaction is completed, filter the solid product, wash it with deionized water, and vacuum dry it at 80-100℃ for 12-48h to obtain antibacterial modified mesoporous silica. S2-3. Take 1-4g of antibacterial modified mesoporous silica and 15-60mL of deionized water and add them to 60-240mL of ethanol. Disperse the mixture by ultrasonication for 0.5-2h. Then add 0.25-1g of silane coupling agent KH-570 and stir at 45-75℃ for 2.5-8h. Filter the mixture, wash the solid product with ethanol, and vacuum dry it at 80-100℃ for 12-48h to obtain antibacterial enhanced multi-effect silica particles.

[0013] Preferably, the antibacterial enhanced multifunctional coating solution is prepared through the following steps: S3-1. The organic solvent is divided into a first part solvent and a second part solvent. Polyurethane acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, diacetone acrylamide, polyethylene glycol methacrylate thioctic acid, zinc acrylate and emulsifier are added to the first part solvent and stirred for 0.5-2 hours to obtain mixture 1. S3-2. Add the antibacterial enhanced multi-effect silica particles to the second part of the solvent and ultrasonically disperse for 30-90 minutes. Add the resulting mixture 2 to mixture 1 under stirring, then add the photoinitiator and auxiliary agent, and stir for 5-30 minutes to obtain the antibacterial enhanced multi-functional coating liquid.

[0014] Preferably, the mesoporous silica has a particle size of 50-500 nm.

[0015] Preferably, the organic solvent is at least one of acetone and methyl ethyl ketone; the photoinitiator is at least one of photoinitiator TPO, photoinitiator TPO-L, photoinitiator 907, photoinitiator 1173, photoinitiator 184, and photoinitiator OXE-01; the emulsifier is at least one of emulsifier OP-13, emulsifier OP-10, sodium dodecylbenzene sulfonate, and polyoxyethylene stearate; and the additives include one or more of leveling agents, defoamers, and dispersants.

[0016] The beneficial effects of this invention are: This invention provides a method for preparing an antibacterial multifunctional optical film. The antioxidant-modified excipients in the base film of this invention load antioxidants through the rich pore structure of mesoporous silica, which can achieve the slow release of antioxidants, thereby providing the base film with long-lasting antioxidant performance.

[0017] This invention forms an antibacterial and multifunctional coating by coating an antibacterial and multifunctional coating liquid onto a base film, which can endow the optical film with excellent antibacterial and self-healing properties, and also achieve a good anti-glare effect, thereby realizing the multifunctional enhancement and modification of the optical film.

[0018] In the antibacterial enhanced multifunctional coating formulation of this invention, the combination of nano-silver and carbon dots can provide a dual antibacterial effect; the combination of polyethylene glycol methacrylate thiocate, carbon dots, and zinc acrylate can provide a triple self-healing effect based on three sources: disulfide bonds introduced by polyethylene glycol methacrylate thiocate, disulfide bonds formed by the thiol groups of carbon dots under light, and dynamic reversible metal coordination bonds formed by zinc acrylate, thereby enhancing the self-healing efficiency.

[0019] In this invention, the reactive oxygen species generated by carbon dots in the antibacterial enhanced multifunctional coating under light will inevitably diffuse into the base film. However, the antioxidants released by the antioxidant-modified excipients in the base film can efficiently remove the reactive oxygen species that have diffused into it, thereby preventing these reactive oxygen species from accelerating the aging of the PET substrate in the base film and reducing the negative impact of carbon dots in the system. Attached Figure Description

[0020] Figure 1 The antioxidant sustained-release performance test results are for the antioxidant modified excipients prepared in Example 1; Figure 2 The infrared absorption spectrum of the loaded modified mesoporous silica prepared in Example 1; Figure 3 XRD pattern of the antibacterial modified mesoporous silica prepared in Example 1; Figure 4 The test results show the singlet oxygen generation performance of the loaded modified mesoporous silica prepared in Example 1. Figure 5 The transmittance test results are for the optical films prepared in the examples and comparative examples; Figure 6 The haze test results are for the optical films prepared in the examples and comparative examples; Figure 7 The yellowing index test results of the optical films prepared for the examples and comparative examples; Figure 8 The antibacterial rate test results (before photoaging) of the optical films prepared for the examples and comparative examples. Figure 9 The antibacterial rate test results (after photoaging) of the optical films prepared for the examples and comparative examples. Figure 10 The self-healing efficiency test results of the optical films prepared for the examples and comparative examples are shown. Detailed Implementation

[0021] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0022] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0024] This invention provides a method for preparing an antibacterial multifunctional optical film, comprising the following steps: Step 1: By weight, mix 100 parts PET chips, 7-15 parts antioxidant modified excipients, and 1-4 parts compatibilizer evenly and then put them into a twin-screw extruder. Melt extrusion and casting are carried out at 240-265℃. Step 2: Longitudinally stretch the cast sheet at 90-100℃ with a stretching ratio of 2.5-3.5; then transversely stretch it at 105-115℃ with a stretching ratio of 3-5; cool to obtain the base film. Step 3: Apply an antibacterial and multifunctional coating solution to the base film, controlling the wet coating amount to 6-15 g / m². 2 UV curing under nitrogen protection forms an antibacterial and enhanced multifunctional coating, with the UV curing energy controlled at 500-700 mJ / cm². 2 The antibacterial multifunctional optical film was obtained.

[0025] The antioxidant-modified excipients are prepared through the following steps: S1-1. Antioxidant-functionalized silica is prepared by loading antioxidants onto mesoporous silica: Take 0.5-2g of mesoporous silica and add it to 50-160mL of acetone solution of antioxidant 1010 with a mass concentration of 3-10%. Stir for 0.5-2h, then shake at 50-65℃ for 6-24h, filter, wash with ethanol, and vacuum dry at 70-90℃ overnight to obtain antioxidant functionalized silica. S1-2. Modified silica is obtained by using a silane coupling agent to modify the antioxidant-modified silica: Add 1-4g of antioxidant functionalized silica to 80-300mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:1. Stir for 0.5-2h, then add 0.2-0.8g of silane coupling agent KH-570. Stir at 60-70℃ for 1.5-6h, filter, wash the solid product with ethanol and deionized water in sequence, and dry at 70-90℃ overnight to obtain modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 240-260℃, granulate, and dry to obtain antioxidant modified granules.

[0026] The antibacterial enhanced multifunctional coating liquid comprises the following raw material components by weight: The composition includes: 60-90 parts polyurethane acrylate, 2-8 parts trifluoroethyl methacrylate, 4-15 parts glycidyl methacrylate, 3-12 parts diacetone acrylamide, 7-20 parts polyethylene glycol methacrylate thioctic acid, 4-10 parts zinc acrylate, 6-14 parts antibacterial reinforced multi-functional silica particles, 30-60 parts organic solvent, 1-5 parts photoinitiator, 1-4 parts emulsifier, and 0.5-5 parts additives. This antibacterial enhanced multifunctional coating solution was prepared through the following steps: S3-1. The organic solvent is divided into a first part solvent and a second part solvent. Polyurethane acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, diacetone acrylamide, polyethylene glycol methacrylate thioctic acid, zinc acrylate and emulsifier are added to the first part solvent and stirred for 0.5-2 hours to obtain mixture 1. S3-2. Add the antibacterial enhanced multi-effect silica particles to the second part of the solvent and ultrasonically disperse for 30-90 minutes. Add the resulting mixture 2 to mixture 1 under stirring, then add the photoinitiator and auxiliary agent, and stir for 5-30 minutes to obtain the antibacterial enhanced multi-functional coating liquid.

[0027] The antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Deposit titanium-doped carbon dots on mesoporous silica to obtain supported modified mesoporous silica: Take 0.75-3g of mesoporous silica and 0.25-1.1g of titanium chloride and add them to 100-400mL of ethanol. Disperse the mixture by ultrasonication for 30-120min. Then add 0.41-1.76g of salicylic acid, 0.3-1.2g of 2-mercaptoisobutyric acid and 0.11-0.44g of p-phenylenediamine. Stir for 15-60min. Transfer the resulting mixture to a reaction vessel lined with polytetrafluoroethylene. React at 155-185℃ for 8-16h. Filter the mixture. Wash the solid product with ethanol and dry it under vacuum at 80-100℃ for 12-48h to obtain the supported modified mesoporous silica. S2-2, Loading silver nanoparticles onto modified mesoporous silica yields antibacterial modified mesoporous silica: Add 0.5-2g of loaded modified mesoporous silica to 30-120mL of ethanol solution of silver nitrate with a concentration of 0.005-0.05mol / L, and sonicate for 0.5-2h. Then add 0.1-0.36g of glucose, and adjust the pH to 9-10 by adding 5-15wt% ammonia water dropwise under the dark. Stir and react at 40-70℃ for 12-48h. After the reaction is completed, filter, wash the solid product with deionized water, and vacuum dry at 80-100℃ for 12-48h to obtain antibacterial modified mesoporous silica. S2-3. Antibacterial modified mesoporous silica was modified using a silane coupling agent to obtain antibacterial enhanced multi-functional silica particles: Take 1-4g of antibacterial modified mesoporous silica and 15-60mL of deionized water and add them to 60-240mL of ethanol. Disperse the mixture by ultrasonication for 0.5-2h, then add 0.25-1g of silane coupling agent KH-570. Stir at 45-75℃ for 2.5-8h, filter, wash the solid product with ethanol, and vacuum dry at 80-100℃ for 12-48h to obtain antibacterial enhanced multi-effect silica particles.

[0028] Invention Mechanism This invention utilizes mesoporous silica to load antioxidants, which are then blended with PET chips and melt-extruded to prepare antioxidant-modified excipients, which are then added to the base film raw material. The abundant pores of the mesoporous silica load the antioxidants, enabling slow-release and providing long-lasting antioxidant properties to the base film. Simultaneously, the addition of mesoporous silica also improves the hardness and film resistance of the base film, enhances its barrier properties against oxygen and moisture, and strengthens its stability and weather resistance.

[0029] This invention forms an antibacterial and multifunctional coating by coating an antibacterial and multifunctional coating liquid onto a base film. This coating endows the optical film with excellent antibacterial and self-healing properties, and also provides a good anti-glare effect, thereby achieving multifunctional enhancement and modification of the optical film. The mechanism of the antibacterial and multifunctional coating liquid is explained in detail below.

[0030] 1. In the antibacterial and enhanced multifunctional coating, polyurethane acrylate is used as the main polymer monomer. The introduction of the polyurethane component, through its urethane bonds (-NHCOO-) and hydrogen bonds, can improve the density and mechanical strength of the base coating, enhance its barrier properties, slow down the penetration of oxidizing substances, and improve its antioxidant capacity. Trifluoroethyl methacrylate introduces high-energy CF bonds, which helps improve the density of the formed antibacterial and enhanced multifunctional coating, improving its barrier capacity, UV resistance, and weather resistance. Diacetone acrylamide introduces amide bonds that can form hydrogen bonds, enhancing intermolecular forces and improving thermal stability and antioxidant capacity. Glycidyl methacrylate can increase the polymer's crosslinking density, thermal stability, and anti-aging properties, thereby indirectly improving its antioxidant resistance.

[0031] 2. The lipoic acid polyethylene glycol methacrylate added to the antibacterial enhanced multifunctional coating is a polyethylene glycol derivative containing both lipoic acid (LA) and methacrylate (MAC) groups. Its molecular structure uses polyethylene glycol (PEG) chains as connecting bridges, with lipoic acid covalently bonded to one end and methacrylate groups attached to the other. Lipoic acid contains disulfide bonds, which can form a dynamic disulfide bond cross-linking network in the anti-glare self-healing layer. These disulfide bonds can be activated at room temperature, under heating, or with light / free radical initiators, achieving reversible breakage and recombination through exchange reactions, thus providing self-healing properties for the formed antibacterial enhanced multifunctional coating. Hydrogen bonds formed by components such as diacetone and acrylamide in the system can further enhance the self-healing properties.

[0032] 3. The antibacterial enhanced multi-functional silica particles added to the antibacterial enhanced multi-functional coating are obtained by depositing titanium-doped carbon dots on mesoporous silica, then loading nano-silver particles, and finally modifying the surface with a silane coupling agent. The modification with the silane coupling agent can introduce double bonds on the surface of the mesoporous silica. These double bonds can participate in the polymerization of monomers in the antibacterial enhanced multi-functional coating, thereby promoting the uniform and stable dispersion of the antibacterial enhanced multi-functional silica particles in the system.

[0033] Titanium-doped carbon dots deposited on mesoporous silica were prepared using salicylic acid, 2-mercaptoisobutyric acid, p-phenylenediamine, and titanium chloride via a one-pot hydrothermal method. These carbon dots possess abundant functional groups, including carboxyl, amino, hydroxyl, and thiol groups. The functions of these carbon dots include: (1) Carbon dots can efficiently generate reactive oxygen species (such as hydroxyl radicals ·OH and singlet oxygen) under light. 1 Reactive oxygen species (ROS, etc.) can provide excellent antibacterial activity with good long-lasting properties. By loading mesoporous silica, the dispersibility and stability of carbon dots can be improved, thereby enhancing the long-lasting antibacterial effect through the action of carbon dots. Titanium doping in carbon dots can further improve the reactive oxygen generation efficiency of carbon dots under illumination by introducing new energy levels into the band gap of the carbon dots, promoting the separation of photogenerated electron-hole pairs, and improving ultraviolet light absorption efficiency.

[0034] (2) 2-Mercaptoisobutyric acid introduces abundant thiol groups. The free radicals generated by the carbon dots under light can promote the oxidation of thiol groups to disulfide bonds. The dynamic reversibility of disulfide bonds can provide self-healing properties (Li Yayu. Preparation and performance regulation of self-healing materials based on multiple hydrogen bonds [D]. Jiangnan University, 2020.), thereby further enhancing the self-healing ability of the anti-glare self-healing layer. Therefore, the optical film of the present invention is particularly suitable for use in scenarios where light can be received, such as outdoor scenarios, so that its antibacterial properties can be better utilized.

[0035] (3) Nanoscale mesoporous silica can form a micro-rough structure in the coating, causing diffuse reflection of incident light rather than specular reflection, thereby reducing glare; while the carbon dots deposited on the surface of mesoporous silica can form more nano-protrusion structures, which can increase the surface roughness of mesoporous silica, thereby further improving the anti-glare performance.

[0036] (4) Silver nanoparticles loaded on mesoporous silica exhibit broad antibacterial activity, further enhancing antibacterial performance. They also provide antibacterial effects even without light, thus compensating for the light-dependent antibacterial properties of carbon dots. Loading through the porous structure of mesoporous silica provides a sustained-release effect and improves the dispersibility of silver nanoparticles, thereby prolonging the antibacterial duration. However, inevitably, with prolonged use, silver nanoparticles are gradually consumed or lost, leading to a decrease in antibacterial ability. The enhanced antibacterial performance of carbon dots is provided by reactive oxygen species generated under light, resulting in a better antibacterial duration and compensating for the shortcomings of silver nanoparticles in this regard. Therefore, the combination of carbon dots and silver nanoparticles can achieve a synergistic enhancement in antibacterial performance.

[0037] 4. The zinc acrylate added to the antibacterial and enhanced multifunctional coating solution can further improve the self-healing performance of the prepared coating by forming dynamic and reversible metal coordination bonds between zinc ions and carboxyl groups and amino groups in the system. The bond energy of the metal coordination bonds can reach as high as 87-332 KJ / mol, which can provide good self-healing ability (Sheng Yeming. Preparation and performance study of environmentally friendly self-healing coatings [D]. South China University of Technology, 2021.).

[0038] Therefore, in the antibacterial enhanced multifunctional coating formulation of the present invention, the combination of nano-silver and carbon dots can provide a dual antibacterial effect; the combination of thioctic acid polyethylene glycol methacrylate, carbon dots, and zinc acrylate can provide a triple self-healing effect based on three sources: disulfide bonds introduced by thioctic acid polyethylene glycol methacrylate, disulfide bonds formed by the thiol groups of carbon dots under light, and dynamic reversible metal coordination bonds formed by zinc acrylate, thereby enhancing the self-healing efficiency.

[0039] In this invention, the reactive oxygen species generated by carbon dots in the antibacterial enhanced multifunctional coating under light will inevitably diffuse into the base film. However, the antioxidants released by the antioxidant-modified excipients in the base film can efficiently remove the reactive oxygen species that have diffused into it, thereby preventing these reactive oxygen species from accelerating the aging of the PET substrate in the base film and reducing the negative impact of carbon dots in the system.

[0040] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0041] The main sources of raw materials in the examples and comparative examples are described below: PET chips, brand: Shanghai Yuanfang, grade CB602, purchased from Ningbo Dihong Plastics Co., Ltd. Compatibilizer AX 8900, brand Arkema, purchased from Guangzhou Yongzheng Chemical Co., Ltd.; Mesoporous silica, with an average particle size of 200 nm and a pore size of 5-20 nm, was purchased from Beijing Zhongke Keyou Nanotechnology Co., Ltd. Antioxidant 1010, brand: BASF, purchased from Shanghai Decheng Chemical Co., Ltd.; Silane coupling agent KH-570 was purchased from Nanjing Rong'an Chemical Technology Co., Ltd. Polyurethane acrylate, model HY-7902, purchased from Shanghai Huiyan New Materials Co., Ltd. Trifluoroethyl methacrylate, glycidyl methacrylate, and diacetone acrylamide were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Zinc acrylate, purchased from Nantong Runfeng Petrochemical Co., Ltd. Polyethylene glycol methacrylate (LA-PEG-MAC), molecular weight 2K (MW), product number P027005, was purchased from Shanghai Tuoyang Biotechnology Co., Ltd. Photoinitiator TPO-L was purchased from Nanjing Milan Chemical Co., Ltd. Emulsifier OP-13 was purchased from Haian Petrochemical Plant in Jiangsu Province. Salicylic acid and p-phenylenediamine were purchased from Nanjing Chemical Reagent Co., Ltd. 2-Mercaptoisobutyric acid, CAS No. 4695-31-2, was purchased from Hubei Watson Chemical Technology Co., Ltd.

[0042] Example 1: A method for preparing an antibacterial multifunctional optical film, comprising the following steps: Step 1: By weight, mix 100 parts of PET masterbatch (pre-dried at 100℃ for 12h), 11 parts of antioxidant modified auxiliary particles, and 2 parts of compatibilizer (compatibilizer AX 8900) evenly and put them into a twin-screw extruder. Melt extrusion and casting are carried out at 255℃. Step 2: The cast sheet is longitudinally stretched at 95℃ with a stretching ratio of 3.2; then it is transversely stretched at 110℃ with a stretching ratio of 4; cooled to obtain the base film; Step 3: Apply an antibacterial and multifunctional coating solution to the base film, controlling the wet coating amount to 12 g / m². 2 UV curing under nitrogen protection forms an antibacterial and enhanced multifunctional coating, with the UV curing energy controlled at 600 mJ / cm². 2 The antibacterial multifunctional optical film was obtained.

[0043] In this embodiment, the antioxidant-modified excipients are prepared through the following steps: S1-1. Antioxidant-functionalized silica is prepared by loading antioxidants onto mesoporous silica: 1 g of mesoporous silica was added to 80 mL of acetone solution containing 6% antioxidant 1010, stirred for 1 h, then shaken at 60 °C for 12 h, filtered, washed with ethanol, and vacuum dried at 80 °C overnight to obtain antioxidant functionalized silica. S1-2. Modified silica is obtained by using a coupling agent to modify the antioxidant-resistant silica. Add 2g of antioxidant functionalized silica to 150mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:1. Stir for 1h, then add 0.4g of silane coupling agent KH-570. Stir at 65℃ for 3h, filter, wash the solid product with ethanol and deionized water in sequence, and dry at 80℃ overnight to obtain modified silica.

[0044] S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 250℃, granulate, and dry to obtain antioxidant modified granules.

[0045] In this embodiment, the antibacterial enhanced multifunctional coating liquid comprises the following raw material components by weight: 70 parts polyurethane acrylate, 5 parts trifluoroethyl methacrylate, 9 parts glycidyl methacrylate, 6 parts diacetone acrylamide, 10 parts thioctic acid polyethylene glycol methacrylate, 7 parts zinc acrylate, 8.5 parts antibacterial reinforced multi-effect silica particles, 45 parts organic solvent, 3 parts photoinitiator, 2 parts emulsifier, and 1.5 parts additives.

[0046] The antibacterial enhanced multifunctional coating solution is prepared through the following steps: S3-1. The organic solvent is divided into a first part solvent and a second part solvent according to a volume ratio of 5:1. Polyurethane acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, diacetone acrylamide, thioctic acid polyethylene glycol methacrylate, zinc acrylate and emulsifier are added to the first part solvent and stirred for 1 hour to obtain mixture 1. S3-2. Add the antibacterial enhanced multi-effect silica particles to the second part of the solvent and ultrasonically disperse for 45 minutes. Add the resulting mixture 2 to mixture 1 under stirring, then add the photoinitiator and auxiliary agent, and stir for 15 minutes to obtain the antibacterial enhanced multi-functional coating liquid.

[0047] The organic solvent is acetone, the photoinitiator is photoinitiator TPO, the emulsifier is emulsifier OP-13, and the additives include 1 part by weight of leveling agent (BYK-361N from BYK GmbH, Germany) and 0.5 parts by weight of defoamer (EFKA2527 from Efka GmbH, Netherlands).

[0048] In this embodiment, the antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Titanium-doped carbon dots are deposited on mesoporous silica to obtain loaded modified mesoporous silica; 1.5 g of mesoporous silica and 0.57 g of titanium chloride were added to 200 mL of ethanol and ultrasonically dispersed for 60 min. Then, 0.83 g of salicylic acid, 0.6 g of 2-mercaptoisobutyric acid and 0.22 g of p-phenylenediamine were added and stirred for 30 min. The resulting mixture was transferred to a polytetrafluoroethylene-lined reactor and reacted at 170 °C for 12 h. The mixture was filtered, the solid product was washed with ethanol, and vacuum dried overnight at 90 °C to obtain the supported modified mesoporous silica. S2-2, Loaded silver nanoparticles: 1 g of modified mesoporous silica was added to 60 mL of 0.02 mol / L silver nitrate ethanol solution and ultrasonically dispersed for 1 h. Then, 0.18 g of glucose was added, and 10 wt% ammonia was added dropwise under light to adjust the pH to 9. The mixture was stirred at 60 °C for 24 h. After the reaction was completed, the mixture was filtered, the solid product was washed with deionized water, and vacuum dried at 70 °C for 24 h to obtain antibacterial modified mesoporous silica. S2-3, Coupling agent modification: Take 2g of antibacterial modified mesoporous silica and 30mL of deionized water and add them to 120mL of ethanol. Disperse the mixture by ultrasonication for 1h, then add 0.5g of silane coupling agent KH-570. Stir at 60℃ for 5h, filter, wash the solid product with ethanol, and dry it overnight at 80℃ to obtain antibacterial enhanced multi-effect silica particles.

[0049] Example 2: A method for preparing an antibacterial multifunctional optical film, comprising the following steps: Step 1: By weight, mix 100 parts of PET masterbatch (pre-dried at 100℃ for 12h), 11 parts of antioxidant modified auxiliary particles, and 2 parts of compatibilizer (compatibilizer AX 8900) evenly and put them into a twin-screw extruder. Melt extrusion and casting are carried out at 260℃. Step 2: The cast sheet is longitudinally stretched at 90℃ with a stretching ratio of 3.2; then it is transversely stretched at 105℃ with a stretching ratio of 4; cooled to obtain the base film; Step 3: Apply an antibacterial and multifunctional coating solution to the base film, controlling the wet coating amount to 12 g / m². 2 UV curing under nitrogen protection forms an antibacterial and enhanced multifunctional coating, with the UV curing energy controlled at 600 mJ / cm². 2 The antibacterial multifunctional optical film was obtained.

[0050] In this embodiment, the antioxidant-modified excipients are prepared through the following steps: S1-1. Antioxidant-functionalized silica is prepared by loading antioxidants onto mesoporous silica: 1 g of mesoporous silica was added to 80 mL of acetone solution containing 6% antioxidant 1010, stirred for 1 h, then shaken at 55 °C for 12 h, filtered, washed with ethanol, and vacuum dried at 80 °C overnight to obtain antioxidant functionalized silica. S1-2. Modified silica is obtained by using a coupling agent to modify the antioxidant-resistant silica. Add 2g of antioxidant functionalized silica to 150mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:1. Stir for 1h, then add 0.4g of silane coupling agent KH-570. Stir at 65℃ for 3h, filter, wash the solid product with ethanol and deionized water in sequence, and dry at 80℃ overnight to obtain modified silica.

[0051] S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 255℃, granulate, and dry to obtain antioxidant modified granules.

[0052] In this embodiment, the antibacterial enhanced multifunctional coating liquid comprises the following raw material components by weight: 70 parts polyurethane acrylate, 6 parts trifluoroethyl methacrylate, 8.5 parts glycidyl methacrylate, 6.5 parts diacetone acrylamide, 10 parts thioctic acid polyethylene glycol methacrylate, 7 parts zinc acrylate, 8.5 parts antibacterial reinforced multi-functional silica particles, 45 parts organic solvent, 3 parts photoinitiator, 2 parts emulsifier, and 1.5 parts additives.

[0053] The preparation method of the antibacterial enhanced multifunctional coating liquid is the same as in Example 1.

[0054] The preparation method of the antibacterial enhanced multi-effect silica particles is the same as in Example 1.

[0055] Example 3 The only difference between this example and Example 1 is that the amount of antioxidant modified excipients added to the raw material of the base film is 10 parts by weight.

[0056] Example 4 The only difference between this example and Example 1 is that the amount of antibacterial enhanced multifunctional silica particles added to the antibacterial enhanced multifunctional coating liquid is 8 parts by weight.

[0057] Comparative Example 1: The only difference between this example and Example 1 is that no antioxidant modified excipients are added to the raw materials of the base film.

[0058] Comparative Example 2: The only difference between this example and Example 1 is that: Step one in this example is as follows: by weight, 100 parts of PET masterbatch (pre-dried at 100℃ for 12h), 9 parts of modified auxiliary particles, 2 parts of antioxidant 1010, and 2 parts of compatibilizer (compatibilizer AX 8900) are mixed evenly and then fed into a twin-screw extruder, melt-extruded at 255℃, and cast into sheets. The modified excipients are prepared through the following steps: S1-1. Modified silica is obtained by using a coupling agent to modify mesoporous silica. 2g of mesoporous silica was added to 150mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:1. After stirring for 1h, 0.4g of silane coupling agent KH-570 was added. The mixture was stirred at 65℃ for 3h, filtered, and the solid product was washed with ethanol and deionized water in sequence. It was then dried at 80℃ overnight to obtain modified silica.

[0059] S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 250℃, granulate, and dry to obtain modified auxiliary granules.

[0060] Comparative Example 3: The only difference between this example and Example 1 is that: Antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1, Loading silver nanoparticles onto mesoporous silica: 1 g of mesoporous silica was added to 60 mL of 0.02 mol / L silver nitrate ethanol solution and ultrasonically dispersed for 1 h. Then, 0.18 g of glucose was added, and 10 wt% ammonia was added dropwise under the dark to adjust the pH to 9. The mixture was stirred at 60 °C for 24 h. After the reaction was completed, the mixture was filtered, the solid product was washed with deionized water, and vacuum dried at 70 °C for 24 h to obtain antibacterial modified mesoporous silica. S2-2, Coupling agent modification: Take 2g of antibacterial modified mesoporous silica and 30mL of deionized water and add them to 120mL of ethanol. Disperse the mixture by ultrasonication for 1h, then add 0.5g of silane coupling agent KH-570. Stir at 60℃ for 5h, filter, wash the solid product with ethanol, and dry it overnight at 80℃ to obtain antibacterial enhanced multi-effect silica particles.

[0061] The only difference between Comparative Example 4 and Example 1 is that titanium chloride is not added in step S2-1 of the preparation of antibacterial enhanced multi-effect silica particles.

[0062] The only difference between Comparative Example 5 and Example 1 is that 2-mercaptoisobutyric acid is not added in step S2-1 of the preparation of antibacterial enhanced multi-effect silica particles, and the amount of salicylic acid added is changed to 1.43g.

[0063] Comparative Example 6: The only difference between this example and Example 1 is that: Antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Deposit titanium-doped carbon dots on mesoporous silica to obtain loaded modified mesoporous silica; the specific steps are the same as in Example 1. S2-2, Coupling agent modification: Take 2g of loaded modified mesoporous silica and 30mL of deionized water and add them to 120mL of ethanol. Disperse the mixture by ultrasonication for 1h, then add 0.5g of silane coupling agent KH-570. Stir at 60℃ for 5h, filter, wash the solid product with ethanol, and dry at 80℃ overnight to obtain antibacterial enhanced multi-effect silica particles.

[0064] Comparative Example 7: The only difference between this example and Example 1 is that the antibacterial enhanced multifunctional coating does not contain polyethylene glycol methacrylate thioctic acid.

[0065] The only difference between Comparative Example 8 and Example 1 is that the antibacterial enhanced multifunctional coating liquid does not contain antibacterial enhanced multi-effect silica particles, and the antibacterial enhanced multifunctional coating liquid is prepared through the following steps: S3-1. Polyurethane acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, diacetone acrylamide, polyethylene glycol methacrylate thioctic acid, zinc acrylate and emulsifier are added to an organic solvent and stirred for 1 hour to obtain mixture 1. S3-2. Add photoinitiator and additives to mixture 1, stir for 15 minutes to obtain antibacterial enhanced multifunctional coating liquid.

[0066] Performance Test 1: The following tests and characterizations were performed on the antioxidant-modified excipients, supported modified mesoporous silica, and antibacterial modified mesoporous silica prepared in Example 1: 1. Antioxidant sustained-release performance of antioxidant modified excipients Weigh 10g of the antioxidant-modified excipients prepared in Example 1 and add them to 500mL of acetone. Disperse the mixture ultrasonically for 30min to obtain a sample mixture. Maintain stirring at 400rpm and immersion at 60℃. Start timing and detect the concentration of antioxidant 1010 in the sample mixture every 10 hours (using high-performance liquid chromatography). Calculate the cumulative release of antioxidant 1010 at different immersion times and plot a sustained-release curve. From the test results (… Figure 1 As can be seen, antioxidant-modified excipients can achieve the sustained release of antioxidants.

[0067] 2. Figure 2 The infrared absorption spectrum of the loaded modified mesoporous silica prepared in Example 1 shows that titanium-doped carbon dots were successfully loaded onto the mesoporous silica.

[0068] 3. Figure 3 The image shows the XRD pattern of the antibacterial modified mesoporous silica prepared in Example 1, which demonstrates the successful synthesis of elemental silver on the supported modified mesoporous silica.

[0069] 4. Singlet oxygen generation performance test of loaded modified mesoporous silica The modified mesoporous silica prepared in Example 1 was added to deionized water and ultrasonically dispersed for 60 min to obtain a series of dispersions with different concentrations (0, 0.2 mg / mL, 0.4 mg / mL, 0.6 mg / mL, 0.8 mg / mL, and 1 mg / mL). Simultaneously, the mesoporous silica used in Example 1 was ultrasonically dispersed in deionized water to prepare a dispersion with a concentration of 1 mg / mL as control group 1. The modified mesoporous silica prepared in Comparative Example 4 was ultrasonically dispersed in deionized water to prepare a dispersion with a concentration of 1 mg / mL as control group 2. All dispersions were placed in air and irradiated with a fluorescent lamp (irradiation energy 1 W / cm²). 2 After 5 min, the fluorescence intensity of each dispersion at 525 nm under 504 nm excitation light was detected using the SOSG singlet oxygen fluorescent probe (Dalian Meilun Biotechnology Co., Ltd.) to determine the singlet oxygen content: the stronger the fluorescence intensity, the higher the singlet oxygen content.

[0070] Test results are as follows Figure 4 As shown, the fluorescence intensity gradually increases with the increase of the composite particle concentration, indicating that the composite particles can efficiently generate singlet oxygen. Combined with the results of control group 1, this demonstrates that singlet oxygen is generated by titanium-doped carbon dots loaded on mesoporous silica. Combined with the results of control group 2, this indicates that titanium doping in the carbon dots can improve their singlet oxygen generation efficiency.

[0071] II. The following describes the performance testing of the optical films prepared in the examples and comparative examples: 1. Light transmittance and haze were tested according to standard GB / T 2410-2008. The test results are shown in Table 1 below. Figure 5 , Figure 6 As shown: Table 1 The test results show that the optical films prepared in Examples 1-4 have good optical properties.

[0072] 2. Photoaging resistance The optical film sample was aged under a xenon lamp for 360 hours with an irradiation intensity of 1 W / m². 2 The temperature was controlled at 50℃ and the humidity at 50%RH. After aging, the yellowing index of the test samples was calculated according to GB / T7975-2005 standard. The test results are shown in Table 2 and... Figure 7As shown: Table 2 The test results show that Examples 1-4 have good resistance to light aging; the base film of Comparative Example 1 did not have antioxidant modified particles added, so it could not effectively remove active oxygen diffused from the antibacterial enhanced multifunctional coating, which led to the aggravation of yellowing of the base film; the results of Comparative Example 2 show that mesoporous silica loaded with antioxidants is beneficial to improving its antioxidant performance.

[0073] In Comparative Example 3, the carbon dots were not loaded. Analysis of the carbon dots' characteristics revealed a dual effect during photoaging: firstly, carbon dots absorb ultraviolet light, thus improving photoaging resistance; secondly, carbon dots generate reactive oxygen species under light, which accelerates aging and leads to yellowing. Therefore, the final effect on the yellowing index is the result of the interaction of these two effects. In this invention, because the base film can release antioxidants to scavenge reactive oxygen species, the effect of reactive oxygen species in accelerating yellowing is inhibited, i.e., effect two is suppressed, thereby reducing the negative effects of carbon dots. The results of Comparative Example 3 also show that, regarding photoaging performance, the comprehensive effect of carbon dots in this invention can improve the photoaging resistance of the optical film to a certain extent.

[0074] The results of Comparative Example 8 show that antibacterial enhanced multi-effect silica particles can improve the photoaging resistance of optical films as a whole.

[0075] 3. Antibacterial properties: The antibacterial rate was tested according to standard GB / T31402-2015; the strain used was Staphylococcus aureus ATCC6538P. The antibacterial rate was tested under natural light and dark conditions, and the antibacterial rate was also tested after photoaging according to the method in section 2.

[0076] The test results are shown in Table 3 below. Figure 8 , Figure 9 As shown: Table 3 The test results show that the optical films of Examples 1-4 and Comparative Examples 1-2 all have excellent antibacterial properties. The antibacterial properties under light are stronger than those under dark conditions, which is attributed to the fact that the carbon dots in the antibacterial enhanced multi-effect silica particles can efficiently generate active oxygen with antibacterial effects under light. Moreover, after aging, the antibacterial rate under light remains basically unchanged, but the antibacterial rate under dark conditions decreases significantly, which is attributed to the fact that the antibacterial effect provided by carbon dots has a longer duration than the antibacterial effect provided by nano-silver.

[0077] In Comparative Example 3, no carbon dots were deposited in the antibacterial enhanced multi-effect silica particles, resulting in the lack of antibacterial effect brought by the photoactive oxygen of carbon dots and a significant decrease in the antibacterial rate. The results of Comparative Example 4 are attributed to the fact that doping titanium in carbon dots is beneficial to improving the ability to generate active oxygen. The results of Comparative Example 5 show that doping S in carbon dots can improve the ability to generate active oxygen.

[0078] The antibacterial enhanced multi-effect silica particles in Comparative Example 6 were not loaded with silver nanoparticles, which significantly reduced their antibacterial performance, especially their antibacterial ability under dark conditions.

[0079] The antibacterial rate of Comparative Example 7 remained basically unchanged, while Comparative Example 8 did not add antibacterial enhanced multi-effect silica particles, which significantly reduced the antibacterial rate.

[0080] 4. Self-healing performance The test was conducted according to the test method in the standard "HG / T 5675-2020 Self-Healing Curing Film for Optical Functional Films". Specifically, a copper brush was used to repeatedly stroke the surface of the optical film sample under a force of 1 kg and a temperature of 2.5 °C for 10 strokes. After that, the sample was placed on a black substrate, and the repair time of the film surface was observed under illumination. The repair time was taken as the test result of the self-healing efficiency. The test results are shown in Table 4 and... Figure 10 As shown: Table 4 The test results show that the optical films of Examples 1-4 have good self-healing properties. The carbon dot raw material of Comparative Example 5 did not contain 2-mercaptoisobutyric acid, which can introduce thiol groups, resulting in a decrease in self-healing properties. The antibacterial enhanced multifunctional coating liquid of Comparative Example 7 did not contain polyethylene glycol methacrylate thioctic acid, resulting in a significant decrease in self-healing properties. The antibacterial enhanced multifunctional coating liquid of Comparative Example 8 did not contain antibacterial enhanced multi-effect silica particles, resulting in a significant reduction in self-healing ability.

[0081] 5. Anti-glare performance, tested according to the method in patent CN107200860B: The back of the optical film sample was adhered to a black acrylic plate using commercially available OCA adhesive (20μm thickness) to create a test piece with no back reflection. The optical film sample was placed horizontally with its front side facing up under normal sunlight. The sample was then visually observed at a 30° angle to the horizontal to determine its anti-glare performance. Specific standards are as follows: (1) White blur: (A) There is basically no white blur, and the visibility is good; (B) There is slight white blur, which does not affect the clarity; (C) White blur, which slightly affects the clarity; (D) White blur, which affects the observation effect.

[0082] (2) Image reflection: (A) There is basically no image reflection; (B) There is image reflection, which does not affect the observation effect; (C) There is image reflection, which slightly affects the observation effect; (D) There is image reflection, which affects the observation effect.

[0083] The test results are shown in Table 5: Table 5 The test results show that the optical films of Examples 1-4 have better anti-glare performance, while the anti-glare performance of Comparative Examples 3 and 8 is significantly reduced.

[0084] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A method for preparing an antibacterial multifunctional optical film, characterized in that, Includes the following steps: Step 1: By weight, mix 100 parts PET chips, 7-15 parts antioxidant modified excipients, and 1-4 parts compatibilizer, then melt-extrude and cast into sheets. Step 2: Biaxially stretch the cast sheet to obtain the base film; Step 3: Apply an antibacterial and enhanced multifunctional coating liquid onto the base film, and UV cure to form an antibacterial and enhanced multifunctional coating, thereby obtaining the antibacterial multifunctional optical film; The antioxidant-modified excipients are prepared through the following steps: S1-1. Antioxidant-functionalized silica is prepared by loading antioxidants onto mesoporous silica: S1-2. Modified silica is obtained by using a silane coupling agent to modify the antioxidant-modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:3-8, stir evenly, melt and extrude, and granulate to obtain antioxidant modified auxiliary particles. The antibacterial enhanced multifunctional coating liquid comprises the following raw material components by weight: The composition includes: 60-90 parts polyurethane acrylate, 2-8 parts trifluoroethyl methacrylate, 4-15 parts glycidyl methacrylate, 3-12 parts diacetone acrylamide, 7-20 parts polyethylene glycol methacrylate thioctic acid, 4-10 parts zinc acrylate, 6-14 parts antibacterial reinforced multi-functional silica particles, 30-60 parts organic solvent, 1-5 parts photoinitiator, 1-4 parts emulsifier, and 0.5-5 parts additives. The antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Titanium-doped carbon dots are deposited on mesoporous silica to obtain loaded modified mesoporous silica; S2-2, Silver nanoparticles are loaded onto modified mesoporous silica to obtain antibacterial modified mesoporous silica; S2-3. Antibacterial modified mesoporous silica was modified using a silane coupling agent to obtain antibacterial enhanced multi-effect silica particles.

2. The method for preparing the antibacterial multifunctional optical film according to claim 1, characterized in that, Includes the following steps: Step 1: By weight, mix 100 parts PET chips, 7-15 parts antioxidant modified excipients, and 1-4 parts compatibilizer evenly and then put them into a twin-screw extruder. Melt extrusion and casting are carried out at 240-265℃. Step 2: Longitudinally stretch the cast sheet at 90-100℃ with a stretching ratio of 2.5-3.5; then transversely stretch it at 105-115℃ with a stretching ratio of 3-5; cool to obtain the base film. Step 3: Apply an antibacterial and multifunctional coating solution to the base film, controlling the wet coating amount to 6-15 g / m². 2 An antibacterial and enhanced multifunctional coating is formed by UV curing under nitrogen protection, with the UV curing energy controlled at 500-700 mJ / cm². 2 The antibacterial multifunctional optical film was obtained.

3. The method for preparing the antibacterial multifunctional optical film according to claim 1, characterized in that, The antioxidant-modified excipients are prepared through the following steps: S1-1. Add mesoporous silica to an antioxidant solution, stir, heat and vibrate, filter, wash, and dry to obtain antioxidant functionalized silica. S1-2. Add antioxidant functionalized silica to a mixed solution of deionized water and ethanol, stir, add silane coupling agent, heat and stir, filter, wash, and dry to obtain modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:3-8, stir evenly, melt extrude at 240-260℃, and granulate to obtain antioxidant modified granules.

4. The method for preparing the antibacterial multifunctional optical film according to claim 3, characterized in that, in, The antioxidant is selected from at least one of antioxidants 1010, 1076, 168, and B215; the silane coupling agent is KH-570.

5. The method for preparing the antibacterial multifunctional optical film according to claim 4, characterized in that, The antioxidant-modified excipients are prepared through the following steps: S1-1. Take 0.5-2g of mesoporous silica and add it to 50-160mL of acetone solution of antioxidant 1010 with a mass concentration of 3-10%. Stir for 0.5-2h, then shake at 50-65℃ for 6-24h, filter, wash with ethanol, and vacuum dry at 70-90℃ overnight to obtain antioxidant functionalized silica. S1-2. Add 1-4g of antioxidant functionalized silica to 80-300mL of a mixed solution of deionized water and ethanol in a volume ratio of 1:

1. Stir for 0.5-2h, then add 0.2-0.8g of silane coupling agent KH-570. Stir at 60-70℃ for 1.5-6h, filter, wash the solid product with ethanol and deionized water in sequence, and dry at 70-90℃ overnight to obtain modified silica. S1-3. Mix modified silica and PET chips at a mass ratio of 1:4, stir evenly, add to a twin-screw extruder, melt extrude at 240-260℃, granulate, and dry to obtain antioxidant modified granules.

6. The method for preparing the antibacterial multifunctional optical film according to claim 1, characterized in that, The antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Disperse mesoporous silica and titanium chloride in ethanol, then add salicylic acid, 2-mercaptoisobutyric acid and p-phenylenediamine, stir, and transfer the resulting mixture into a reaction vessel. React at 155-185℃ for 8-16 hours, filter, wash, and dry to obtain supported modified mesoporous silica. S2-2. The modified mesoporous silica was added to an ethanol solution of silver nitrate, ultrasonically dispersed, glucose was added, and ammonia was added dropwise under the dark to adjust the pH to alkaline. The mixture was heated and stirred to react. After the reaction was completed, the mixture was filtered, washed, and dried to obtain antibacterial modified mesoporous silica. S2-3. Take antibacterial modified mesoporous silica and deionized water, add them to ethanol, disperse them by ultrasonication, then add silane coupling agent KH-570, heat and stir to react, filter after the reaction is completed, wash and dry to obtain antibacterial enhanced multi-effect silica particles.

7. The method for preparing the antibacterial multifunctional optical film according to claim 6, characterized in that, The antibacterial enhanced multi-effect silica particles are prepared through the following steps: S2-1. Take 0.75-3g of mesoporous silica and 0.25-1.1g of titanium chloride and add them to 100-400mL of ethanol. Disperse the mixture by ultrasonication for 30-120min. Then add 0.41-1.76g of salicylic acid, 0.3-1.2g of 2-mercaptoisobutyric acid and 0.11-0.44g of p-phenylenediamine. Stir for 15-60min. Transfer the resulting mixture to a reaction vessel lined with polytetrafluoroethylene. React at 155-185℃ for 8-16h. Filter the mixture. Wash the solid product with ethanol and dry it under vacuum at 80-100℃ for 12-48h to obtain the supported modified mesoporous silica. S2-2. Add 0.5-2g of loaded modified mesoporous silica to 30-120mL of ethanol solution of silver nitrate with a concentration of 0.005-0.05mol / L, and sonicate for 0.5-2h. Then add 0.1-0.36g of glucose, and adjust the pH to 9-10 by adding 5-15wt% ammonia water dropwise under the dark. Stir and react at 40-70℃ for 12-48h. After the reaction is completed, filter the solid product, wash it with deionized water, and vacuum dry it at 80-100℃ for 12-48h to obtain antibacterial modified mesoporous silica. S2-3. Take 1-4g of antibacterial modified mesoporous silica and 15-60mL of deionized water and add them to 60-240mL of ethanol. Disperse the mixture by ultrasonication for 0.5-2h. Then add 0.25-1g of silane coupling agent KH-570 and stir at 45-75℃ for 2.5-8h. Filter the mixture, wash the solid product with ethanol, and vacuum dry it at 80-100℃ for 12-48h to obtain antibacterial enhanced multi-effect silica particles.

8. The method for preparing the antibacterial multifunctional optical film according to claim 1, characterized in that, The antibacterial enhanced multifunctional coating solution is prepared through the following steps: S3-1. The organic solvent is divided into a first part solvent and a second part solvent. Polyurethane acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, diacetone acrylamide, polyethylene glycol methacrylate thioctic acid, zinc acrylate and emulsifier are added to the first part solvent and stirred for 0.5-2 hours to obtain mixture 1. S3-2. Add the antibacterial enhanced multi-effect silica particles to the second part of the solvent and ultrasonically disperse for 30-90 minutes. Add the resulting mixture 2 to mixture 1 under stirring, then add the photoinitiator and auxiliary agent, and stir for 5-30 minutes to obtain the antibacterial enhanced multi-functional coating liquid.

9. The method for preparing the antibacterial multifunctional optical film according to any one of claims 1-8, characterized in that, The particle size of mesoporous silica is 50-500 nm.

10. The method for preparing the antibacterial multifunctional optical film according to any one of claims 1-8, characterized in that, The organic solvent is at least one of acetone and methyl ethyl ketone; the photoinitiator is at least one of photoinitiator TPO, photoinitiator TPO-L, photoinitiator 907, photoinitiator 1173, photoinitiator 184, and photoinitiator OXE-01; the emulsifier is at least one of emulsifier OP-13, emulsifier OP-10, sodium dodecylbenzene sulfonate, and polyoxyethylene stearate; the additives include one or more of leveling agents, defoamers, and dispersants.

Images