A copper-doped titanium dioxide antibacterial skin care window film

Abstract

The present application relates to the technical field of functional film, in particular to a copper-doped titanium dioxide antibacterial skin-protecting window film; for solving the problems of low ultraviolet blocking rate and low antibacterial rate of the existing window film; the window film is prepared by adding copper-doped titanium dioxide antibacterial agent and fluorine-based benzophenone-based acrylate, copper ions are doped in titanium dioxide by anhydrous copper sulfate, the antibacterial performance is improved, the growth and reproduction of bacteria are effectively inhibited, so as to prevent the breeding of bacteria, by the reaction of isophorone diisocyanate with 4-fluoro-4'-hydroxybenzophenone and 2-hydroxyethyl acrylate, fluorine atoms and benzophenone groups are introduced into acrylate, the ultraviolet blocking ability is improved; the window film has excellent ultraviolet protection and skin care functions, can effectively protect the skin from ultraviolet damage, and has the advantages of broad-spectrum antibacterial, long-term stability, environmental friendliness, suitable for large-area construction and the like.

Description

A copper-doped titanium dioxide antibacterial skin care window film Technical Field

[0001] This invention relates to the field of functional thin film technology, specifically to a copper-doped titanium dioxide antibacterial skin care window film. Background Technology

[0002] With increasing demands for health and quality of life, UV-protective window films are widely used in vehicle and building windows to block ultraviolet rays, reduce skin damage and aging risks, and achieve a "skin-protecting" function. However, bacteria can easily grow on the surface of window films over long-term use, forming undetectable sources of pollution and posing health risks to the interior of vehicles or buildings. Existing antibacterial coatings are mostly achieved by adding antibacterial agents to ordinary coatings. These agents mainly include organic and inorganic antibacterial agents. While organic antibacterial agents possess highly effective and broad-spectrum antibacterial properties, they suffer from drawbacks such as volatility, poor chemical stability, insufficient thermal stability, and poor compatibility with the base material, making them difficult to apply in high-temperature curing processes. Inorganic antibacterial agents have better thermal stability, but silver ions are expensive and their biotoxicity is controversial; nano-titanium dioxide requires ultraviolet light irradiation to activate its antibacterial properties, and the atomic oxygen generated under light decomposes the coating resin, leading to coating degradation. Furthermore, inorganic antibacterial agents easily migrate from the coating to the surface over time, and their antibacterial ability diminishes or even disappears after wiping. This invention provides a copper-doped titanium dioxide antibacterial skin care window film, in which copper ions are doped into titanium dioxide, and fluorobenzophenone acrylate is synthesized and added to the coating, thereby improving the UV protection capability and enhancing the antibacterial performance of the window film. Summary of the Invention

[0003] In order to overcome the above-mentioned technical problems, the present invention aims to provide a copper-doped titanium dioxide antibacterial skin care window film, which solves the problems of low ultraviolet blocking rate and low antibacterial rate of existing window films.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] In a first aspect, this application provides a copper-doped titanium dioxide antibacterial skin care window film, comprising the following parts by weight:

[0006] The composition includes 10-25 parts of copper-doped titanium dioxide hybrid modified acrylate, 20-40 parts of aliphatic polyurethane acrylate, 6-14 parts of dipentaerythritol hexaacrylate, 9-21 parts of hydroxyethyl acrylate, 3-5 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5-8 parts of butyl acetate, 20-32 parts of ethyl acetate, and 0.5-1 parts of leveling agent.

[0007] The copper-doped titanium dioxide hybrid modified acrylate is prepared by the following steps:

[0008] Step A1: Add tetrabutyl titanate, triethanolamine and deionized water to a single-necked flask equipped with a stirrer, stir for 10-20 minutes to obtain the first solution;

[0009] Step A2: Add copper sulfate pentahydrate and deionized water to a single-necked flask equipped with a stirrer and stir for 5-10 min. Add the first solution and stir for 10-20 min. Add sodium hydroxide solution and stir for 20-30 min. After sealing, place in a forced-air drying oven at 130-150℃ for 48-96 h. Centrifuge and wash 3-5 times at 1000-1200 r / min. Calcinate in a muffle furnace at 450-550℃ for 1.5-2.5 h. Grind to obtain copper-doped titanium dioxide antibacterial agent.

[0010] Step A3: Add 4-fluoro-4'-hydroxybenzophenone and tetrahydrofuran to a single-necked flask equipped with a stirrer, stir for 5-10 minutes to obtain the second solution;

[0011] Step A4: Isophorone diisocyanate, dibutyltin dilaurate, and tetrahydrofuran were added to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Nitrogen gas was introduced for 30 minutes, and the second solution was added dropwise. The reaction was carried out at 80°C for 2-3 hours. Then, 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 2-hydroxyethyl acrylate were added. The reaction was carried out at 80°C for 2-3 hours. The mixture was purified by column chromatography with a mixed solvent of petroleum ether and ethyl acetate. The precipitate was settled three times and then precipitated by rotary evaporation to obtain fluorobenzophenone acrylate.

[0012] Step A5: Add fluorobenzophenone acrylate, methacrylate, acrylic acid, azobisisobutyronitrile and butyl acetate to a single-necked flask and sonicate for 20-30 min to obtain the third solution;

[0013] Step A6: Add copper-doped titanium dioxide antibacterial agent and butyl acetate to a beaker and sonicate for 20-40 min. Transfer to a reaction vessel, heat to 75℃, purge with nitrogen for 30-40 min to remove air, add the third solution to the reaction vessel through a dropping funnel, and react at 70℃ for 6 h. Settle the reaction solution with petroleum ether 3 times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate 3-5 times, and place in a drying oven to vacuum dry at 40℃ for 24 h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0014] As a further aspect of the present invention: the ratio of tetrabutyl titanate, triethanolamine and deionized water used in step A1 is 14-28 mL: 11-22 mL: 52.5-105 mL.

[0015] As a further aspect of the present invention: the ratio of copper sulfate pentahydrate, deionized water, the first solution and sodium hydroxide solution used in step A2 is 0.036-0.072g: 7.5-15mL: 77.5-155mL: 2.4-4.8mL.

[0016] As a further aspect of the present invention: the molar concentration of the sodium hydroxide solution in step A2 is 0.12 mol / L.

[0017] As a further aspect of the present invention: the ratio of 4-fluoro-4'-hydroxybenzophenone to tetrahydrofuran in step A3 is 0.006-0.012 mol: 62.5-125 mL.

[0018] As a further embodiment of the present invention: the ratio of isophorone diisocyanate, dibutyltin dilaurate, tetrahydrofuran, the second solution, 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution, and 2-hydroxyethyl acrylate in step A4 is 0.0126-0.0252 mol: 0.045-0.09 g: 12.5-25 mL: 62.5-125 mL: 5-10 mL: 0.0132-0.0264 mol.

[0019] As a further aspect of the present invention: the mass fraction of the 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution in step A4 is 1%.

[0020] As a further aspect of the present invention: the volume ratio of petroleum ether to ethyl acetate in the mixed solvent of petroleum ether and ethyl acetate in step A4 is 12:1.

[0021] As a further embodiment of the present invention: the ratio of the amount of fluorobenzophenone acrylate, methacrylate, acrylic acid, azobisisobutyronitrile and butyl acetate in step A5 is 7.5-15g: 6.25-12.5g: 2.5-5g: 0.75-1.5g: 1.75-3.5g.

[0022] As a further aspect of the present invention: the ratio of copper-doped titanium dioxide antibacterial agent, butyl acetate and the third solution in step A6 is 2.5-5g: 6.25-12.5g: 18.75-37.5g.

[0023] Secondly, this application provides a method for preparing a copper-doped titanium dioxide antibacterial skin care window film, comprising the following steps:

[0024] Step 1: Weigh out the following components by weight: 10-25 parts copper-doped titanium dioxide hybrid modified acrylate, 20-40 parts aliphatic polyurethane acrylate, 6-14 parts dipentaerythritol hexaacrylate, 9-21 parts hydroxyethyl acrylate, 3-5 parts 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5-8 parts butyl acetate, 20-32 parts ethyl acetate, and 0.5-1 parts leveling agent. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio. The 9-functional aliphatic polyurethane acrylate is of type B-919B. The 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702. The leveling agent is BYK-333 type siloxane leveling agent.

[0025] Step 2: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to a mixing cylinder and stir at 300-1500 r / min for 0.5-1 h. After filtration, store the mixed antibacterial skin care UV coating in a light-proof, sealed container and let it stand for later use.

[0026] Step 3: Apply a 6-15μm functional adhesive to one side of the 36-200μm original color PET substrate. After drying in an oven at 70-130℃ for 30-120s, cure to form a functional adhesive layer. Then, bond it to a 23-150μm transparent PET substrate. Apply a 6-30μm mounting adhesive to the other side of the original color PET substrate. After drying in an oven at 70-130℃ for 30-120s, cure to form a mounting adhesive layer. Then, bond it to a 23-75μm release film. Apply a 1-3μm antibacterial and skin-care UV coating to the outside of the transparent PET substrate. After evaporating the solvent at a low temperature of 60-80℃, perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0027] The beneficial effects of this invention are:

[0028] The present invention discloses a method for preparing a copper-doped titanium dioxide antibacterial skin care window film. By doping with copper ions, not only is titanium dioxide endowed with good ultraviolet absorption function, but its antibacterial properties are also enhanced. Fluorine atoms and benzophenone groups are introduced into acrylate to improve the material's ultraviolet blocking ability and antibacterial rate.

[0029] To prepare a copper-doped titanium dioxide antibacterial skin-care window film, a copper-doped titanium dioxide antibacterial agent was first prepared. Butyl titanate underwent hydrolysis in water, forming a Ti-O-Ti network structure through dealcolysis condensation. Copper sulfate pentahydrate dissolved to provide copper ions into the Ti-O-Ti network structure. After calcination, copper-doped titanium dioxide was formed. The copper ions chemically react with bacterial proteins, interfering with bacterial metabolism and reproduction, thereby inhibiting bacterial growth. Under the catalysis of dibutyltin dilaurate, the isocyanate group of isophorone diisocyanate underwent nucleophilic addition with the hydroxyl group of 4-fluoro-4'-hydroxybenzophenone to form a carbamate bond. The hydroxyl group of 2-hydroxyethyl acrylate reacted with the remaining isophorone diisocyanate... The isocyanate group reacts to introduce acrylate double bonds, yielding fluorobenzophenone acrylate. The high electronegativity of the fluorine atom and the strong CF bond can form a "shielding layer" that reflects ultraviolet light, thereby enhancing the UV blocking ability. The benzophenone group can form covalent bonds with substrates such as metals, plastics, and wood, improving adhesion and preventing coating peeling. Furthermore, the benzophenone group can absorb ultraviolet light to generate reactive oxygen species, which can destroy bacterial cell membranes and improve the antibacterial rate. The resulting antibacterial skin-care UV coating has good adhesion and is scratch-resistant and abrasion-resistant. The copper-doped titanium dioxide antibacterial skin-care window film cured on the surface of PET substrate can be applied in high-end construction, automotive, aerospace, electronics, medical and other fields. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1:

[0032] This embodiment describes a method for preparing a copper-doped titanium dioxide antibacterial skin care window film, comprising the following steps:

[0033] Step A1: Add 14 mL of tetrabutyl titanate, 11 mL of triethanolamine and 52.5 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 10 min to obtain the first solution;

[0034] Step A2: Add 0.036g of copper sulfate pentahydrate and 7.5mL of deionized water to a single-necked flask equipped with a stirrer and stir for 5min. Add 77.5mL of the first solution and stir for 10min. Add 2.4mL of sodium hydroxide solution and stir for 20min. After sealing, place the flask in a forced-air drying oven at 130℃ for 48h. Wash the flask three times by centrifugation at 1000r / min. Calcinate the flask in a muffle furnace at 450℃ for 1.5h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0035] Step A3: Add 0.006 mol of 4-fluoro-4'-hydroxybenzophenone and 62.5 mL of tetrahydrofuran to a single-necked flask equipped with a stirrer, stir for 5 min, and obtain the second solution;

[0036] Step A4: Add 0.0126 mol isophorone diisocyanate, 0.045 g dibutyltin dilaurate, and 12.5 mL tetrahydrofuran to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Purge with nitrogen for 30 min, add 62.5 mL of the second solution dropwise, and react at 80 °C for 2 h. Add 5 mL of 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 0.0132 mol 2-hydroxyethyl acrylate, and react at 80 °C for 2 h. Purify by column chromatography with a mixed solvent of petroleum ether and ethyl acetate, precipitate three times, and evaporate the precipitate by rotary evaporation to obtain fluorobenzophenone acrylate.

[0037] Step A5: Add 7.5g of fluorobenzophenone acrylate, 6.25g of methacrylate, 2.5g of acrylic acid, 0.75g of azobisisobutyronitrile and 1.75g ​​of butyl acetate to a single-necked flask and sonicate for 20 minutes to obtain the third solution;

[0038] Step A6: Add 2.5g of copper-doped titanium dioxide antibacterial agent and 6.25g of butyl acetate to a beaker and sonicate for 20min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 30min to remove air. Add 18.75g of the third solution to the reaction vessel through a dropping funnel. React at 70℃ for 6h. Settle the reaction solution with petroleum ether three times. After centrifugation, remove petroleum ether and butyl acetate by rotary evaporation. Wash three times with ethyl acetate and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0039] Step A7: Weigh out 10 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 20 parts by weight of aliphatic polyurethane acrylate, 6 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of hydroxyethyl acrylate, 3 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5 parts by weight of butyl acetate, 20 parts by weight of ethyl acetate, and 0.5 parts by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0040] Step A8: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to the mixing cylinder and stir at 300 r / min for 0.5 h. After filtration, store the mixed antibacterial skin care UV coating in a light-proof, sealed container and let it stand for later use.

[0041] Step A9: Coat one side of the 36μm original color PET substrate with a 6μm functional adhesive, dry it in a 70℃ oven for 30 seconds to form a functional adhesive layer, and then bond it to a 23μm transparent PET substrate. Coat the other side of the original color PET substrate with a 6μm mounting adhesive, dry it in a 70℃ oven for 30 seconds to form a mounting adhesive layer, and then bond it to a 23μm release film. Coat the outside of the transparent PET substrate with a 1μm antibacterial and skin-care UV coating, evaporate the solvent at a low temperature of 60℃, and then perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0042] Example 2:

[0043] This embodiment describes a method for preparing a copper-doped titanium dioxide antibacterial skin care window film, comprising the following steps:

[0044] Step A1: Add 21 mL of tetrabutyl titanate, 16.5 mL of triethanolamine and 78.75 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 15 min to obtain the first solution;

[0045] Step A2: Add 0.054g of copper sulfate pentahydrate and 11.25mL of deionized water to a single-necked flask equipped with a stirrer and stir for 7min. Add 116.25mL of the first solution and stir for 15min. Add 3.6mL of sodium hydroxide solution and stir for 25min. After sealing, place the flask in a forced-air drying oven at 140℃ for 72h. Wash the flask four times by centrifugation at 1100r / min. Calcinate the flask in a muffle furnace at 500℃ for 2h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0046] Step A3: Add 0.009 mol of 4-fluoro-4'-hydroxybenzophenone and 93.75 mL of tetrahydrofuran to a single-necked flask equipped with a stirrer, stir for 7 min, and obtain the second solution;

[0047] Step A4: 0.0189 mol isophorone diisocyanate, 0.0675 g dibutyltin dilaurate, and 18.75 mL tetrahydrofuran were added to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Nitrogen gas was purged for 30 min, and 93.75 mL of the second solution was added dropwise. The mixture was reacted at 80 °C for 2.5 h. 7.5 mL of 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 0.0198 mol 2-hydroxyethyl acrylate were added, and the mixture was reacted at 80 °C for 2.5 h. The mixture was purified by column chromatography with a mixed solvent of petroleum ether and ethyl acetate. After precipitation three times, the precipitate was obtained by rotary evaporation to obtain fluorobenzophenone acrylate.

[0048] Step A5: Add 11.25g of fluorobenzophenone acrylate, 9.375g of methacrylate, 3.75g of acrylic acid, 1.125g of azobisisobutyronitrile and 2.625g of butyl acetate to a single-necked flask and sonicate for 25 minutes to obtain the third solution.

[0049] Step A6: Add 3.75g of copper-doped titanium dioxide antibacterial agent and 9.375g of butyl acetate to a beaker and sonicate for 30min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 35min to remove air. Add 28.125g of the third solution to the reaction vessel through a dropping funnel. React at 70℃ for 6h. Settle the reaction solution with petroleum ether three times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate four times and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0050] Step A7: Weigh out 17.5 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 30 parts by weight of aliphatic polyurethane acrylate, 10 parts by weight of dipentaerythritol hexaacrylate, 15 parts by weight of hydroxyethyl acrylate, 4 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 6.5 parts by weight of butyl acetate, 26 parts by weight of ethyl acetate, and 0.75 parts by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0051] Step A8: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to the mixing cylinder and stir at 900 r / min for 0.75 h. After filtration, store the mixed antibacterial skin care UV coating in a light-proof, sealed container and let it stand for later use.

[0052] Step A9: Coat one side of the 118μm original color PET substrate with a 9μm functional adhesive, dry it in a 100℃ oven for 75s to form a functional adhesive layer, and then bond it to an 86μm transparent PET substrate. Coat the other side of the original color PET substrate with an 18μm mounting adhesive, dry it in a 100℃ oven for 75s to form a mounting adhesive layer, and then bond it to a 49μm release film. Coat the outside of the transparent PET substrate with a 2μm antibacterial and skin-care UV coating, evaporate the solvent at a low temperature of 70℃, and then perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0053] Example 3:

[0054] This embodiment describes a method for preparing a copper-doped titanium dioxide antibacterial skin care window film, comprising the following steps:

[0055] Step A1: Add 28 mL of tetrabutyl titanate, 22 mL of triethanolamine and 105 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain the first solution;

[0056] Step A2: Add 0.072g of copper sulfate pentahydrate and 15mL of deionized water to a single-necked flask equipped with a stirrer and stir for 10min. Add 155mL of the first solution and stir for 20min. Add 4.8mL of sodium hydroxide solution and stir for 30min. After sealing, place the flask in a forced-air drying oven at 150℃ for 96h. Wash the flask five times by centrifugation at 1200r / min. Calcinate the flask in a muffle furnace at 550℃ for 2.5h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0057] Step A3: Add 0.012 mol of 4-fluoro-4'-hydroxybenzophenone and 125 mL of tetrahydrofuran to a single-necked flask equipped with a stirrer, stir for 10 min, and obtain the second solution;

[0058] Step A4: 0.0252 mol isophorone diisocyanate, 0.09 g dibutyltin dilaurate, and 25 mL tetrahydrofuran were added to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Nitrogen gas was purged for 30 min, and 125 mL of the second solution was added dropwise. The mixture was reacted at 80 °C for 3 h. Then, 10 mL of 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 0.0264 mol 2-hydroxyethyl acrylate were added. The mixture was reacted at 80 °C for 3 h. The mixture was purified by column chromatography with a mixed solvent of petroleum ether and ethyl acetate. After precipitation three times, the precipitate was obtained by rotary evaporation to obtain fluorobenzophenone acrylate.

[0059] Step A5: Add 15g of fluorobenzophenone acrylate, 12.5g of methacrylate, 5g of acrylic acid, 1.5g of azobisisobutyronitrile and 3.5g of butyl acetate to a single-necked flask and sonicate for 30 minutes to obtain the third solution.

[0060] Step A6: Add 5g of copper-doped titanium dioxide antibacterial agent and 12.5g of butyl acetate to a beaker and sonicate for 40min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 40min to remove air. Add 37.5g of the third solution to the reaction vessel through a dropping funnel and react at 70℃ for 6h. Settle the reaction solution with petroleum ether three times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate five times and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0061] Step A7: Weigh out 25 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 40 parts by weight of aliphatic polyurethane acrylate, 14 parts by weight of dipentaerythritol hexaacrylate, 21 parts by weight of hydroxyethyl acrylate, 5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 8 parts by weight of butyl acetate, 32 parts by weight of ethyl acetate, and 1 part by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0062] Step A8: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to a mixing cylinder and stir at 1500 r / min for 1 h. After filtration, seal the mixed antibacterial skin care UV coating away from light and let it stand for later use.

[0063] Step A9: Coat one side of a 200μm original color PET substrate with a 15μm functional adhesive, dry it in a 130℃ oven for 120s and then cure it to form a functional adhesive layer. Then, bond it to a 150μm transparent PET substrate. Coat the other side of the original color PET substrate with a 30μm mounting adhesive, dry it in a 130℃ oven for 120s and then cure it to form a mounting adhesive layer. Then, bond it to a 75μm release film. Coat the outside of the transparent PET substrate with a 3μm antibacterial and skin-care UV coating. After evaporating the solvent at a low temperature of 80℃, perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0064] Comparative Example 1:

[0065] This comparative example illustrates a method for preparing a copper-doped titanium dioxide antibacterial skin-care window film, comprising the following steps:

[0066] Step A1: Add 28 mL of tetrabutyl titanate, 22 mL of triethanolamine and 105 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain the first solution;

[0067] Step A2: Add 0.072g of copper sulfate pentahydrate and 15mL of deionized water to a single-necked flask equipped with a stirrer and stir for 10min. Add 155mL of the first solution and stir for 20min. Add 4.8mL of sodium hydroxide solution and stir for 30min. After sealing, place the flask in a forced-air drying oven at 150℃ for 96h. Wash the flask five times by centrifugation at 1200r / min. Calcinate the flask in a muffle furnace at 550℃ for 2.5h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0068] Step A3: Add 15g butyl acrylate, 12.5g methacrylate, 5g acrylic acid, 1.5g azobisisobutyronitrile and 3.5g butyl acetate to a single-necked flask and sonicate for 30 minutes to obtain the third solution;

[0069] Step A4: Add 5g of copper-doped titanium dioxide antibacterial agent and 12.5g of butyl acetate to a beaker and sonicate for 40min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 40min to remove air. Add 37.5g of the third solution to the reaction vessel through a dropping funnel and react at 70℃ for 6h. Settle the reaction solution with petroleum ether three times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate five times and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0070] Step A5: Weigh out 25 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 40 parts by weight of aliphatic polyurethane acrylate, 14 parts by weight of dipentaerythritol hexaacrylate, 21 parts by weight of hydroxyethyl acrylate, 5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 8 parts by weight of butyl acetate, 32 parts by weight of ethyl acetate, and 1 part by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0071] Step A6: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to a mixing cylinder and stir at 1500 r / min for 1 h. After filtration, seal the mixed antibacterial skin care UV coating away from light and let it stand for later use.

[0072] Step A7: Coat one side of a 200μm original color PET substrate with a 15μm functional adhesive, dry it in a 130℃ oven for 120s to form a functional adhesive layer, and then bond it to a 150μm transparent PET substrate. Coat the other side of the original color PET substrate with a 30μm mounting adhesive, dry it in a 130℃ oven for 120s to form a mounting adhesive layer, and then bond it to a 75μm release film. Coat the outside of the transparent PET substrate with a 3μm antibacterial and skin-care UV coating, evaporate the solvent at a low temperature of 80℃, and then perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0073] Comparative Example 2:

[0074] This comparative example illustrates a method for preparing a copper-doped titanium dioxide antibacterial skin-care window film, comprising the following steps:

[0075] Step A1: Add 28 mL of tetrabutyl titanate, 22 mL of triethanolamine and 105 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain the first solution;

[0076] Step A2: Add 0.072g of copper sulfate pentahydrate and 15mL of deionized water to a single-necked flask equipped with a stirrer and stir for 10min. Add 155mL of the first solution and stir for 20min. Add 4.8mL of sodium hydroxide solution and stir for 30min. After sealing, place the flask in a forced-air drying oven at 150℃ for 96h. Wash the flask five times by centrifugation at 1200r / min. Calcinate the flask in a muffle furnace at 550℃ for 2.5h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0077] Step A3: Add 0.0252 mol of 2-fluoroisocyanate, 0.09 g of dibutyltin dilaurate, and 25 mL of tetrahydrofuran to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Purge with nitrogen for 30 min, then add 10 mL of 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 0.0252 mol of 2-hydroxyethyl acrylate. React at 80 °C for 3 h. Purify by column chromatography with a mixed solvent of petroleum ether and ethyl acetate. After precipitation three times, the precipitate is obtained by rotary evaporation to obtain fluoroacrylate.

[0078] Step A4: Add 15g of fluoroacrylate, 12.5g of methacrylate, 5g of acrylic acid, 1.5g of azobisisobutyronitrile and 3.5g of butyl acetate to a single-necked flask and sonicate for 30 minutes to obtain the third solution;

[0079] Step A5: Add 5g of copper-doped titanium dioxide antibacterial agent and 12.5g of butyl acetate to a beaker and sonicate for 40min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 40min to remove air. Add 37.5g of the third solution to the reaction vessel through a dropping funnel and react at 70℃ for 6h. Settle the reaction solution with petroleum ether three times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate five times and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0080] Step A6: Weigh out 25 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 40 parts by weight of aliphatic polyurethane acrylate, 14 parts by weight of dipentaerythritol hexaacrylate, 21 parts by weight of hydroxyethyl acrylate, 5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 8 parts by weight of butyl acetate, 32 parts by weight of ethyl acetate, and 1 part by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0081] Step A7: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to a mixing cylinder and stir at 1500 r / min for 1 h. After filtration, seal the mixed antibacterial skin care UV coating away from light and let it stand for later use.

[0082] Step A8: Coat one side of a 200μm original color PET substrate with a 15μm functional adhesive, dry it in a 130℃ oven for 120s to form a functional adhesive layer, and then bond it to a 150μm transparent PET substrate. Coat the other side of the original color PET substrate with a 30μm mounting adhesive, dry it in a 130℃ oven for 120s to form a mounting adhesive layer, and then bond it to a 75μm release film. Coat the outside of the transparent PET substrate with a 3μm antibacterial and skin-care UV coating, evaporate the solvent at a low temperature of 80℃, and then perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0083] Comparative Example 3:

[0084] This comparative example illustrates a method for preparing a copper-doped titanium dioxide antibacterial skin-care window film, comprising the following steps:

[0085] Step A1: Add 28 mL of tetrabutyl titanate, 22 mL of triethanolamine and 105 mL of deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain the first solution;

[0086] Step A2: Add 0.072g of copper sulfate pentahydrate and 15mL of deionized water to a single-necked flask equipped with a stirrer and stir for 10min. Add 155mL of the first solution and stir for 20min. Add 4.8mL of sodium hydroxide solution and stir for 30min. After sealing, place the flask in a forced-air drying oven at 150℃ for 96h. Wash the flask five times by centrifugation at 1200r / min. Calcinate the flask in a muffle furnace at 550℃ for 2.5h. After grinding, obtain copper-doped titanium dioxide antibacterial agent.

[0087] Step A3: Add 0.012 mol of 2,4-dihydroxybenzophenone and 125 mL of tetrahydrofuran to a single-necked flask equipped with a stirrer, stir for 10 min, and obtain the second solution;

[0088] Step A4: Add 0.0252 mol isophorone diisocyanate, 0.09 g dibutyltin dilaurate, and 25 mL tetrahydrofuran to a three-necked flask equipped with a mechanical stirrer, condenser, and thermometer. Purge with nitrogen for 30 min, add 125 mL of the second solution dropwise, and react at 80 °C for 3 h. Add 10 mL of 2,6-di-tert-butyl-p-cresol-tetrahydrofuran solution and 0.0264 mol 2-hydroxyethyl acrylate, and react at 80 °C for 3 h. Purify by column chromatography with a mixed solvent of petroleum ether and ethyl acetate, precipitate three times, and evaporate the precipitate by rotary evaporation to obtain benzophenone acrylate.

[0089] Step A5: Add 15g benzophenone acrylate, 12.5g methacrylate, 5g acrylic acid, 1.5g azobisisobutyronitrile and 3.5g butyl acetate to a single-necked flask and sonicate for 30 minutes to obtain the third solution;

[0090] Step A6: Add 5g of copper-doped titanium dioxide antibacterial agent and 12.5g of butyl acetate to a beaker and sonicate for 40min. Transfer to a reaction vessel, heat to 75℃ and purge with nitrogen for 40min to remove air. Add 37.5g of the third solution to the reaction vessel through a dropping funnel and react at 70℃ for 6h. Settle the reaction solution with petroleum ether three times, centrifuge, and then remove petroleum ether and butyl acetate by rotary evaporation. Wash with ethyl acetate five times and place in a drying oven to vacuum dry at 40℃ for 24h to obtain copper-doped titanium dioxide hybrid modified acrylate.

[0091] Step A7: Weigh out 25 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 40 parts by weight of aliphatic polyurethane acrylate, 14 parts by weight of dipentaerythritol hexaacrylate, 21 parts by weight of hydroxyethyl acrylate, 5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 8 parts by weight of butyl acetate, 32 parts by weight of ethyl acetate, and 1 part by weight of leveling agent, and set aside. The aliphatic polyurethane acrylate is composed of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate in a 1:3 ratio; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is BYK-333 type siloxane leveling agent.

[0092] Step A8: Add copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent to a mixing cylinder and stir at 1500 r / min for 1 h. After filtration, seal the mixed antibacterial skin care UV coating away from light and let it stand for later use.

[0093] Step A9: Coat one side of a 200μm original color PET substrate with a 15μm functional adhesive, dry it in a 130℃ oven for 120s and then cure it to form a functional adhesive layer. Then, bond it to a 150μm transparent PET substrate. Coat the other side of the original color PET substrate with a 30μm mounting adhesive, dry it in a 130℃ oven for 120s and then cure it to form a mounting adhesive layer. Then, bond it to a 75μm release film. Coat the outside of the transparent PET substrate with a 3μm antibacterial and skin-care UV coating. After evaporating the solvent at a low temperature of 80℃, perform UV curing to form an antibacterial and skin-care coating. Finally, a copper-doped titanium dioxide antibacterial and skin-care window film is obtained.

[0094] Performance testing:

[0095] The antibacterial skin-care UV coating provided by this invention has a dry film thickness of 3±0.5μm and its performance was tested according to the following method:

[0096] Adhesion: Performed according to ASTM D3359-22 standard. The specific procedure is to use a crisscross tool to draw a square grid on the UV-cured coating surface, with 2mm spacing between the cuts, for a total of six cuts. Apply 3M 810 tape smoothly to the grid, leaving no gaps. Then, holding the free end of the tape, quickly (not forcefully pull) peel it off at an angle as close to 180° as possible in the opposite direction. Observe the edges of the crisscross for any delamination. No delamination is rated 5B; delamination between 0-5% is 4B; between 5-15% is 3B; between 15-35% is 2B; between 35-65% is 1B; and above 65% is 0B.

[0097] Pencil hardness: Performed in accordance with the standard GB / T 6739-2022 Determination of paint film hardness by pencil method, using a coating film hardness tester obtained by pencil scratching.

[0098] Antibacterial test method: The antibacterial rate of the window films prepared in each example and comparative example was tested according to the test standard GB / T 31402-2023 Determination of antibacterial activity of plastics and other non-porous materials. The selected bacterial species were Staphylococcus aureus and Escherichia coli, respectively.

[0099] UV blocking rate: Tested using an LS162A solar film tester.

[0100] Table 1 shows the performance test results of the coatings cured on PET base films provided in the examples and comparative examples.

[0101]

[0102] Referring to the table above, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has good adhesion and ultraviolet blocking ability.

[0103] Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has a higher antibacterial rate of Escherichia coli than the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and acrylate. This indicates that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has excellent antibacterial properties.

[0104] Based on the comparison between Example 3 and Comparative Example 2, it can be seen that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has a higher antibacterial rate of Escherichia coli than the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate. This indicates that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has excellent antibacterial properties.

[0105] Based on the comparison between Example 3 and Comparative Example 3, it can be seen that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has a higher Escherichia coli antibacterial rate than the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate. This indicates that the antibacterial skin care UV coating prepared by adding copper-doped titanium dioxide antibacterial agent and fluorobenzophenone acrylate has excellent antibacterial properties.

[0106] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0107] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A copper-doped titanium dioxide antibacterial skin-care window film, characterized in that, The product comprises the following components by weight: 10-25 parts copper-doped titanium dioxide hybrid modified acrylate, 20-40 parts aliphatic polyurethane acrylate, 6-14 parts dipentaerythritol hexaacrylate, 9-21 parts hydroxyethyl acrylate, 3-5 parts 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5-8 parts butyl acetate, 20-32 parts ethyl acetate, and 0.5-1 parts leveling agent; wherein the copper-doped titanium dioxide hybrid modified acrylate is prepared by the following steps: Step A1: Stir 14-28 mL of butyl titanate, 11-22 mL of triethanolamine, and 52.5-105 mL of deionized water to obtain a first solution; Step A2: Stir 0.036-0.072 g of copper sulfate pentahydrate and 7.5-15 mL of deionized water, add 77.5-155 mL of the first solution, and add 2.4-4.8 mL of... Stirring, drying, centrifuging and washing, calcining, and grinding yields copper-doped titanium dioxide antibacterial agent; Step A3: Stirring 0.006-0.012 mol 4-fluoro-4'-hydroxybenzophenone and 62.5-125 mL tetrahydrofuran to obtain a second solution; Step A4: Plugging nitrogen gas into 0.0126-0.0252 mol isophorone diisocyanate, 0.045-0.09 g dibutyltin dilaurate, and 12.5-25 mL tetrahydrofuran, adding 62.5-125 mL of the second solution to react, and then adding 5-10 mL of 1%... 2,6-Di-tert-butyl-p-cresol-tetrahydrofuran solution was reacted with 0.0132-0.0264 mol of 2-hydroxyethyl acrylate, purified, precipitated, and precipitated by rotary evaporation to obtain fluorobenzophenone acrylate; Step A5: Fluorobenzophenone acrylate, methacrylate, acrylic acid, azobisisobutyronitrile and butyl acetate were sonicated to obtain a third solution; Step A6: Copper-doped titanium dioxide antibacterial agent and butyl acetate were sonicated, heated and purged with nitrogen, the third solution was added to react, precipitated, centrifuged, rotary evaporated, washed and dried to obtain copper-doped titanium dioxide hybrid modified acrylate.

2. The copper-doped titanium dioxide antibacterial skin-care window film according to claim 1, characterized in that, The ratio of fluorobenzophenone acrylate, methacrylate, acrylic acid, azobisisobutyronitrile and butyl acetate used in step A5 is 7.5-15g: 6.25-12.5g: 2.5-5g: 0.75-1.5g: 1.75-3.5g.

3. The copper-doped titanium dioxide antibacterial skin-care window film according to claim 1, characterized in that, The ratio of copper-doped titanium dioxide antibacterial agent, butyl acetate, and the third solution in step A6 is 2.5-5g: 6.25-12.5g: 18.75-37.5g.

4. A method for preparing a copper-doped titanium dioxide antibacterial skin-care window film, characterized in that, The preparation of the copper-doped titanium dioxide antibacterial skin-care window film as described in any one of claims 1-3 comprises the following steps: Step 1: Weigh out 10-25 parts by weight of copper-doped titanium dioxide hybrid modified acrylate, 20-40 parts by weight of aliphatic polyurethane acrylate, 6-14 parts by weight of dipentaerythritol hexaacrylate, 9-21 parts by weight of hydroxyethyl acrylate, 3-5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5-8 parts by weight of butyl acetate, 20-32 parts by weight of ethyl acetate, and 0.5-1 parts by weight of leveling agent, and set aside; Step 2: Add the copper-doped titanium dioxide hybrid modified acrylate, aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, hydroxyethyl acrylate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, butyl acetate, ethyl acetate, and leveling agent into a feed cylinder at 300-1500 r / Stir for 0.5-1 hour at a low temperature, filter, and store the mixed antibacterial skin care UV coating in a light-proof, sealed container for later use. Step 3: Coat one side of the 36-200μm original color PET substrate with a 6-15μm functional adhesive, dry in an oven at 70-130℃ for 30-120 seconds to form a functional adhesive layer, and then bond it to a 23-150μm transparent PET substrate. Coat the other side of the original color PET substrate with a 6-30μm mounting adhesive, dry in an oven at 70-130℃ for 30-120 seconds to form a mounting adhesive layer, and then bond it to a 23-75μm release film. Coat the outside of the transparent PET substrate with a 1-3μm antibacterial skin care UV coating, evaporate the solvent at a low temperature of 60-80℃, and then perform UV curing to form an antibacterial skin care coating. Finally, a copper-doped titanium dioxide antibacterial skin care window film is obtained.

5. The method for preparing a copper-doped titanium dioxide antibacterial skin care window film according to claim 4, characterized in that, in, The aliphatic polyurethane acrylate is composed of a 1:3 ratio of 6-functional aliphatic polyurethane acrylate and 9-functional aliphatic polyurethane acrylate; the 9-functional aliphatic polyurethane acrylate is of type B-919B; the 6-functional aliphatic polyurethane acrylate is of type Ebecryl8702; and the leveling agent is a BYK-333 type siloxane leveling agent.

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