Optical resin copolymer-modified antireflection film for vehicle and method for manufacturing the same

Abstract

The application belongs to the field of optical protective films, and discloses an anti-reflection optical vehicle-mounted film and a preparation method thereof. The anti-reflection optical vehicle-mounted film comprises a directional light control copolymer layer, an anti-blue-light weather-resistant layer and an ultralow-reflection surface layer which are sequentially formed in situ from bottom to top. The surface of the directional light control copolymer layer has a one-dimensional micrograting or a microprism array. The directional light control copolymer layer, the anti-blue-light weather-resistant layer and the ultralow-reflection surface layer all use methyl methacrylate and aliphatic polyurethane acrylate as a base resin, and different copolymerization modification monomers are added for copolymerization modification. The application adopts a three-layer in-situ copolymerization integrated structure, realizes front high-transparency high-brightness and side low-brightness privacy through the directional light control copolymer layer, and realizes the synergistic improvement of multiple performances of the vehicle-mounted screen protective film in combination with the anti-blue-light weather-resistant copolymer layer and the ultralow-reflection surface layer.

Description

Technical Field

[0001] This invention belongs to the field of optical protective film technology, specifically relating to an anti-reflective light automotive film modified by optical resin copolymerization and its preparation method. Background Technology

[0002] A car infotainment screen is a display screen located on the center console of a vehicle. It displays various information and, in conjunction with electronic maps, can conveniently and accurately guide the driver to their destination, providing the shortest or fastest route. With the rapid development of automotive electronics technology, car infotainment screens have evolved from simple navigation displays to integrate entertainment, communication, intelligent driving, and other functions, becoming a core carrier of human-vehicle interaction. Currently, most car infotainment screens are touchscreens. Sharp objects scratching the screen surface can damage it, causing touchscreen malfunction. Furthermore, fingerprints are inevitably left on the screen when operating it, affecting visibility. Therefore, protective films are often applied to car infotainment screens.

[0003] Automotive screen protectors need to possess properties such as anti-reflection, anti-fingerprint, high hardness, resistance to high and low temperatures, and UV resistance. Existing products often focus on only one performance aspect. Furthermore, automotive screens need to ensure high brightness and clarity for driver-facing operation, while simultaneously limiting light transmittance at the side angles (30°~60°) to protect privacy and achieve a privacy protection effect. Current protectors mostly achieve light diffusion by adding ordinary inorganic microspheres, but the light control precision is low. Either the front light transmittance is insufficient, affecting screen brightness, or the side angle transmittance is too high, rendering the privacy protection effect ineffective. They cannot simultaneously meet the directional light control requirements of high brightness at the front and low brightness at the sides. In addition, blue light (400~420nm) from automotive screens can easily cause driver fatigue and damage. Automotive screen protectors have efficient blue light filtering capabilities, but traditional anti-blue light agents are mostly physical dopants, which have drawbacks such as poor compatibility with resins, easy migration and precipitation, and weak resistance to UV aging. Summary of the Invention

[0004] To address the shortcomings mentioned in the background art, the present invention aims to provide an anti-reflective automotive film modified by optical resin copolymerization and its preparation method. It adopts a three-layer in-situ copolymerization integrated structure, and achieves high transmittance and high brightness on the front and low brightness and privacy protection on the side through the directional light-controlled copolymerization layer. Combined with the anti-blue light and weather-resistant copolymerization layer and the ultra-low reflective surface layer, it realizes the multi-performance synergistic improvement of the automotive screen protection film.

[0005] The objective of this invention can be achieved through the following technical solutions: An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all based on methyl methacrylate and aliphatic polyurethane acrylate as matrix resins, with different copolymerizing monomers added for copolymerization modification. The copolymerized monomer of the directional light-controlling copolymer layer is a modified light-diffusing microsphere, which is a silica / polystyrene composite microsphere. After surface treatment with a silane coupling agent, it is doped with rare earth element Ce. 3+ ; The copolymer modification monomer of the anti-blue light weather-resistant layer is an anti-blue light monomer, which is an aromatic nitrogen-containing copolymer grafted with carbazole groups and then coated with ZnS quantum dots; The copolymerized monomers for the ultra-low reflectivity surface layer are perfluorohexyl allyl glycidyl ether, hydroxyethyl methacrylate, and butyl methacrylate.

[0006] Preferably, the directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 40-50 parts of aliphatic polyurethane acrylate, 30-35 parts of methyl methacrylate, 7-10 parts of fluorinated acrylate, 6-11 parts of bifunctional epoxy acrylate, 5-7 parts of modified light-diffusing microspheres, 1.2-1.5 parts of photoinitiator, 0.2-0.4 parts of anti-yellowing agent, 0.4-0.6 parts of anti-fingerprint agent, and 0.3-0.5 parts of leveling agent.

[0007] Preferably, the anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 30-35 parts aliphatic polyurethane acrylate, 20-25 parts methyl methacrylate, 10-12 parts anti-blue light monomer, 3-5 parts bifunctional epoxy acrylate, 0.7-0.9 parts photoinitiator, and 0.3-0.4 parts anti-yellowing agent.

[0008] Preferably, the ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 27-32 parts aliphatic polyurethane acrylate, 20-23 parts methyl methacrylate, 15-20 parts fluorinated acrylate, 3.5-5 parts perfluorohexyl allyl glycidyl ether, 1.5-1.7 parts hydroxyethyl methacrylate, 1.5-1.7 parts butyl methacrylate, 0.7-0.9 parts photoinitiator, 0.4-0.6 parts anti-fingerprint agent, and 0.3-0.5 parts leveling agent.

[0009] Preferably, the photoinitiator is a mixture of photoinitiator 1173 and photoinitiator 184 in a mass ratio of 1:1, the anti-yellowing agent is a hindered amine anti-yellowing agent, the anti-fingerprint agent is perfluorooctyltriethoxysilane, and the leveling agent is an acrylate leveling agent.

[0010] Preferably, the preparation method of the modified light-diffusing microspheres includes the following steps: (1) Styrene, polyvinylpyrrolidone and deionized water were added to the reaction vessel, and the oxygen was removed by purging with N2 for 20-40 min. Potassium persulfate was added, and the reaction was carried out at 70℃ for 22-26 h. After cooling to room temperature, the mixture was centrifuged, washed, and vacuum dried to obtain polystyrene microspheres. The polystyrene microspheres were redispersed in ethanol and water, sonicated for 20-40 min, and ammonia was added to adjust the pH value to 9-10. Tetraethyl orthosilicate was slowly added, and the reaction was stirred at room temperature for 6-12 h. After centrifugation, washing, and vacuum drying, silica / polystyrene composite microspheres were obtained. (2) Add silica / polystyrene composite microspheres to anhydrous ethanol, ultrasonically disperse for 20-40 min, add hydrochloric acid to adjust pH to 3.5, heat to 60℃, stir for 0.5-1.5 h, centrifuge, wash and vacuum dry to obtain pretreated microspheres; (3) Add the pretreated microspheres to toluene solvent, add 3-(methacryloyloxy)propyltrimethoxysilane, heat to 85°C, stir and reflux for 3-5 h, centrifuge, wash and vacuum dry to obtain silane coupling agent grafted microspheres. (4) Disperse the silane coupling agent-grafted microspheres in deionized water, add cerium nitrate, stir to dissolve, add ammonia to adjust the pH to 8.0, react at 50℃ for 1-3 hours, centrifuge to separate, wash with deionized water until neutral, vacuum dry, and then pulverize through a 200-mesh sieve to obtain modified light-diffusing microspheres.

[0011] Preferably, the mass ratio of styrene, polyvinylpyrrolidone, and potassium persulfate is 10:1.5:0.15; The mass ratio of polystyrene microspheres to tetraethyl orthosilicate is 1:2~4; The mass ratio of silica / polystyrene composite microspheres, 3-(methacryloyloxy)propyltrimethoxysilane, and cerium nitrate is 100:5:3.

[0012] Preferably, the preparation method of the anti-blue light monomer includes the following steps: A. N-vinylcarbazole and N-phenylmaleimide were added to toluene solvent and mixed evenly. Then azobisisobutyronitrile was added and reacted at 70℃ for 4-8 hours to obtain carbazole grafted modified aromatic nitrogen-containing monomer. B. Dissolve zinc chloride and sodium sulfide in deionized water, add 2wt% sodium citrate as a dispersant, stir at room temperature for 20-40 min, centrifuge, wash and vacuum dry to obtain ZnS quantum dots; C. Add ZnS quantum dots to deionized water and ultrasonically disperse for 15-25 min to form a uniform ZnS quantum dot dispersion. Add carbazole-grafted modified aromatic nitrogen-containing monomers to the ZnS quantum dot dispersion and ultrasonically disperse for 20-40 min. Stir and react at 45℃ for 2-4 h. Remove water and impurities by vacuum distillation and vacuum drying to obtain the anti-blue light monomer.

[0013] Preferably, the mass ratio of N-vinylcarbazole to N-phenylmaleimide is 1:3, and the azobisisobutyronitrile is 0.8% of the total mass of N-vinylcarbazole and N-phenylmaleimide; The molar ratio of zinc chloride to sodium sulfide is 1:1.2; The mass ratio of the azole-grafted modified aromatic nitrogen-containing monomer to ZnS quantum dots is 10:1.

[0014] A method for preparing an anti-reflective automotive film modified with optical resin copolymerization includes the following steps: S1. Prepare copolymer resin mixtures according to the formulations of the directional light-controlled copolymer layer, the anti-blue light weather-resistant layer and the ultra-low reflectivity surface layer. Add each raw material to a high-speed mixer according to the formulation ratio and stir for 20 to 40 minutes at 25°C and 800 r / min to obtain the copolymer resin mixtures corresponding to each layer. S2. Select a PET mold with a one-dimensional micro-grating array, with a grating spacing of 50~80μm and a height of 10~20μm. Perform plasma treatment on the mold surface, and then uniformly coat the pretreated mold surface with a photodynamic copolymer layer copolymer resin mixture. Apply the mixture at a wavelength of 365nm and a light intensity of 800mJ / cm². 2 Pre-curing under ultraviolet light for 20–40 seconds forms a directional light-controlled copolymer layer with a thickness of 80–90 μm. Then, an anti-blue light weather-resistant copolymer resin mixture is coated on its surface and cured under ultraviolet light for 30–50 seconds to form an anti-blue light weather-resistant layer with a thickness of 30–35 μm. Finally, an ultra-low reflectance surface copolymer resin mixture is coated and cured under ultraviolet light for 30–50 seconds to form an ultra-low reflectance surface layer with a thickness of 10–12 μm. S3. Demold the cured composite film from the mold and place it in a constant temperature oven. Keep it at 80℃ for 2-4 hours for post-curing treatment to remove residual stress. Then cut and grind the edges to obtain an optical resin copolymer modified anti-reflective automotive film.

[0015] The beneficial effects of this invention are: This invention relates to an optical resin copolymer-modified anti-reflective automotive film, employing a three-layer in-situ copolymer structure. Using high-transmittance methyl methacrylate / aliphatic polyurethane acrylate as the base resin, it incorporates fluorinated acrylate, bifunctional epoxy acrylate, modified light-diffusing microspheres, and anti-blue light monomers for copolymer modification. This significantly improves light control precision and blue light filtering stability. A directional light-control copolymer layer achieves high transmittance and brightness on the front, while providing low brightness and privacy protection on the sides. Combined with an anti-blue light weather-resistant copolymer layer and an ultra-low reflective surface layer, it achieves a synergistic improvement in multiple performance aspects of the automotive screen protector. This solves the technical problems of insufficient brightness on the front of the screen, privacy leaks on the sides, and screen reflections from rearview mirrors and windows interfering with driving in automotive scenarios. This invention's anti-reflective automotive film exhibits excellent optical performance: front transmittance ≥90%, providing sufficient brightness without affecting navigation and entertainment displays on the automotive screen; simultaneously, side transmittance ≤30%, offering good privacy protection; and a specular reflectivity <1.3%, preventing reflected light from interfering with the driver's vision and improving driving safety. This invention provides an anti-reflective automotive film with stable eye protection performance. It filters ≥35% of blue light below 420nm, effectively filtering high-energy harmful blue light and alleviating visual fatigue during prolonged driving. After 1000 hours of UV irradiation, the blue light filtration rate decreases by ≤2.8%, demonstrating strong weather resistance and maintaining excellent eye protection even with long-term use. The anti-reflective automotive film also boasts excellent mechanical properties, with a pencil hardness ≥6H, exhibiting superior scratch resistance and withstanding scratches from hard objects in daily use. Its stable film structure shows no cracking, yellowing, or delamination after 10 high-low temperature cycles (-40℃ to 85℃), making it suitable for extreme automotive environments.

[0016] The modified light-diffusing microspheres of this invention are silica / polystyrene composite microspheres with silane coupling agent surface treatment followed by doping with rare earth element Ce. 3+ Silane coupling agents, containing unsaturated double bonds at one end, can copolymerize with the matrix resin and other comonomers to form strong chemical bonds, eliminating interfacial defects between microspheres and resin, and significantly improving the dispersion stability of microspheres in the resin system. Rare earth element Ce... 3+With a unique electronic structure, after being doped onto the surface and interior of light-diffusing microspheres, the refractive index of the microspheres can be controlled to create a moderate difference between the refractive index of the microspheres and the refractive index of the resin matrix (the refractive index difference is controlled within 0.05-0.1). When light is incident, it can achieve a directional light control effect, ensuring straight light transmission from the front and attenuation of light scattering from the sides, thus ensuring high brightness from the front and preventing privacy from the sides. On the other hand, rare earth elements have a certain ultraviolet absorption capacity, which can capture free radicals induced by ultraviolet light, inhibit photoaging of the resin matrix and microspheres, reduce yellowing of the film, and improve the weather resistance and transmittance stability of the film. The composite-modified light-diffusing microspheres are uniformly dispersed in the directional light-control copolymer layer, combined with a micrograting or microprism array structure, forming a dual-redirection light control system of microstructure plus microsphere scattering. Light incident from the front (0°~10°) can pass through in a straight line along the gap between the microstructure and the microspheres, resulting in high light transmittance. Light incident from the side (30°~60°) is scattered by the microspheres and reflected and refracted by the micrograting / microprism structure, leading to significant light attenuation and thus achieving highly efficient privacy protection. Furthermore, the scattering process does not affect the uniformity and clarity of light transmission from the front. In addition, the hardness of the light-diffusing microspheres is much higher than that of the organic resin matrix. After composite modification, the microspheres form a strong chemical bond with the resin, which can act as a rigid support point to disperse the scratch stress on the film layer, reducing scratch damage and thus improving the pencil hardness of the film layer, enhancing scratch resistance, and extending the service life of the protective film.

[0017] The anti-blue light monomer of this invention is an aromatic nitrogen-containing comonomer grafted with a carbazole group and then coated with ZnS quantum dots. The aromatic heterocycle (carbazole) contains a conjugated π-electron system, whose π-π The transition energy matches the energy of high-energy blue light in the 400-420nm range, allowing for selective absorption of this wavelength while exhibiting no significant absorption of visible light above 420nm (such as green and red light). Therefore, it can efficiently filter harmful blue light while maintaining front-side transmittance and not affecting screen display performance. Aromatic heterocycles combine with aromatic nitrogen-containing copolymer monomers through grafting reactions, improving the compatibility between the anti-blue light monomer and the matrix resin, preventing the migration and precipitation of anti-blue light components, and ensuring uniform and stable blue light filtering. ZnS quantum dots possess a unique quantum size effect; their absorption wavelength can be precisely controlled by the quantum dot particle size, accurately absorbing high-energy blue light near 420nm. This synergistic effect with the selective absorption of aromatic heterocycles further enhances the blue light filtering rate. Simultaneously, the coating of quantum dots with anti-blue light monomers prevents quantum dot aggregation, improving their dispersion stability in the resin system. Furthermore, the coating layer protects the quantum dots from UV decomposition, extending their lifespan.

[0018] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Detailed Implementation

[0019] 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.

[0020] Example 1 A modified light-diffusing microsphere, comprising silica / polystyrene composite microspheres, surface-treated with a silane coupling agent and doped with rare earth element Ce. 3+ Its preparation method includes the following steps: (1) Add 10g styrene, 1.5g polyvinylpyrrolidone and 150mL deionized water to the reaction vessel, purge with N2 for 30min to remove oxygen, add 0.15g potassium persulfate, react at 70℃ for 24h, cool to room temperature, centrifuge and wash, vacuum dry to obtain polystyrene microspheres, redisperse 1g polystyrene microspheres in 100mL ethanol and 20mL water, sonicate for 30min, add ammonia to adjust pH to 9~10, slowly add 3mL tetraethyl orthosilicate, stir at room temperature for 8h, centrifuge, wash and vacuum dry to obtain silica / polystyrene composite microspheres; (2) Add 5.0g of silica / polystyrene composite microspheres to 50mL of anhydrous ethanol, sonicate for 30min, add hydrochloric acid to adjust the pH to 3.5, heat to 60℃, stir for 1h, centrifuge, wash and vacuum dry to obtain pretreated microspheres; (3) Add the pretreated microspheres to 60 mL of toluene solvent, add 0.25 g of 3-(methacryloyloxy)propyltrimethoxysilane, heat to 85 °C, stir and reflux for 4 h, centrifuge, wash and vacuum dry to obtain silane coupling agent grafted microspheres. (4) Disperse the silane coupling agent-grafted microspheres in 100 mL of deionized water, add 0.15 g of cerium nitrate, stir to dissolve, add ammonia to adjust the pH to 8.0, react at 50 °C for 2 h, centrifuge to separate, wash with deionized water until neutral, vacuum dry, and then pulverize through a 200 mesh sieve to obtain modified light-diffusing microspheres.

[0021] Example 2 An anti-blue light monomer, wherein the anti-blue light monomer is an aromatic nitrogen-containing comonomer grafted with a carbazole group and then coated with ZnS quantum dots, and its preparation method includes the following steps: A. Add 2.5g N-vinylcarbazole and 7.5g N-phenylmaleimide to 30mL toluene solvent and mix well. Then add 0.08g azobisisobutyronitrile and react at 70℃ for 6h to obtain carbazole grafted modified aromatic nitrogen-containing monomer. B. Dissolve 2.72 g zinc chloride and 1.44 g sodium sulfide in 50 mL deionized water, add 10 mL 2 wt% sodium citrate as a dispersant, stir at room temperature for 30 min, centrifuge, wash and vacuum dry to obtain ZnS quantum dots; C. Add 0.99g of ZnS quantum dots to 50mL of deionized water and sonicate for 20min to form a uniform ZnS quantum dot dispersion. Add 9.9g of carbazole-grafted modified aromatic nitrogen-containing monomer to the ZnS quantum dot dispersion and sonicate for 30min. Stir and react at 45℃ for 3h. Remove water and impurities by vacuum distillation and vacuum drying to obtain the anti-blue light monomer.

[0022] Example 3 An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all copolymerized with methyl methacrylate and aliphatic polyurethane acrylate as the base resins, and different copolymerizing monomers are added for copolymerization modification.

[0023] The copolymer modification monomer of the directional light-controlling copolymer layer is the modified light-diffusing microsphere prepared in Example 1, and the copolymer modification monomer of the anti-blue light weather-resistant layer is the anti-blue light monomer prepared in Example 2; the copolymer modification monomer of the ultra-low reflectance surface layer is perfluorohexyl allyl glycidyl ether, hydroxyethyl methacrylate and butyl methacrylate.

[0024] The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 40 parts aliphatic polyurethane acrylate, 35 parts methyl methacrylate, 7 parts fluorinated acrylate, 11 parts bifunctional epoxy acrylate, 5 parts modified light-diffusing microspheres, 0.75 parts photoinitiator 1173, 0.75 parts photoinitiator 184, 0.2 parts hindered amine anti-yellowing agent, 0.6 parts perfluorooctyltriethoxysilane, and 0.3 parts acrylate leveling agent.

[0025] The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 35 parts aliphatic polyurethane acrylate, 20 parts methyl methacrylate, 12 parts anti-blue light monomer, 3 parts bifunctional epoxy acrylate, 0.45 parts photoinitiator 1173, 0.45 parts photoinitiator 184, and 0.3 parts hindered amine anti-yellowing agent.

[0026] The ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 32 parts aliphatic polyurethane acrylate, 20 parts methyl methacrylate, 20 parts fluorinated acrylate, 3.5 parts perfluorohexyl allyl glycidyl ether, 1.7 parts hydroxyethyl methacrylate, 1.5 parts butyl methacrylate, 0.45 parts photoinitiator 1173, 0.45 parts photoinitiator 184, 0.4 parts perfluorooctyltriethoxysilane, and 0.5 parts acrylate leveling agent.

[0027] The preparation method of the above-mentioned anti-reflective automotive film modified by optical resin copolymerization includes the following steps: S1. Prepare copolymer resin mixtures according to the formulations of the directional light-controlled copolymer layer, the anti-blue light weather-resistant layer and the ultra-low reflectivity surface layer. Add each raw material to a high-speed mixer according to the formulation ratio and stir for 20 minutes at 25°C and 800r / min to obtain the copolymer resin mixtures corresponding to each layer. S2. A PET mold with a one-dimensional micro-grating array was selected, with a grating spacing of 80 μm and a height of 10 μm. The mold surface was subjected to plasma treatment, and then a photodynamic copolymer layer copolymer resin mixture was uniformly coated onto the pretreated mold surface. The photodynamic copolymer layer was then applied at a wavelength of 365 nm and a light intensity of 800 mJ / cm². 2 Pre-curing under ultraviolet light for 40 seconds forms an 80μm thick directional light-controlled copolymer layer. Then, an anti-blue light weather-resistant copolymer resin mixture is coated on its surface and cured under ultraviolet light for another 50 seconds to form a 35μm thick anti-blue light weather-resistant layer. Finally, an ultra-low reflectance surface copolymer resin mixture is coated and cured under ultraviolet light for 50 seconds to form a 12μm thick ultra-low reflectance surface layer. S3. Demold the cured composite film from the mold, place it in a constant temperature oven, keep it at 80°C for 4 hours for post-curing treatment to remove residual stress, and then cut and grind the edges to obtain the optical resin copolymer modified anti-reflective light vehicle film.

[0028] Example 4 An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all copolymerized with methyl methacrylate and aliphatic polyurethane acrylate as the base resins, and different copolymerizing monomers are added for copolymerization modification.

[0029] The copolymer modification monomer of the directional light-controlling copolymer layer is the modified light-diffusing microsphere prepared in Example 1, and the copolymer modification monomer of the anti-blue light weather-resistant layer is the anti-blue light monomer prepared in Example 2; the copolymer modification monomer of the ultra-low reflectance surface layer is perfluorohexyl allyl glycidyl ether, hydroxyethyl methacrylate and butyl methacrylate.

[0030] The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 50 parts aliphatic polyurethane acrylate, 30 parts methyl methacrylate, 10 parts fluorinated acrylate, 6 parts bifunctional epoxy acrylate, 7 parts modified light-diffusing microspheres, 0.6 parts photoinitiator 1173, 0.6 parts photoinitiator 184, 0.4 parts hindered amine anti-yellowing agent, 0.4 parts perfluorooctyltriethoxysilane, and 0.5 parts acrylate leveling agent.

[0031] The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 30 parts aliphatic polyurethane acrylate, 25 parts methyl methacrylate, 10 parts anti-blue light monomer, 5 parts bifunctional epoxy acrylate, 0.35 parts photoinitiator 1173, 0.35 parts photoinitiator 184, and 0.4 parts hindered amine anti-yellowing agent.

[0032] The ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 27 parts aliphatic polyurethane acrylate, 23 parts methyl methacrylate, 15 parts fluorinated acrylate, 5 parts perfluorohexyl allyl glycidyl ether, 1.5 parts hydroxyethyl methacrylate, 1.7 parts butyl methacrylate, 0.35 parts photoinitiator 1173, 0.35 parts photoinitiator 184, 0.6 parts perfluorooctyltriethoxysilane, and 0.3 parts acrylate leveling agent.

[0033] The preparation method of the above-mentioned anti-reflective automotive film modified by optical resin copolymerization includes the following steps: S1. Prepare copolymer resin mixtures according to the formulations of the directional light-controlled copolymer layer, the anti-blue light weather-resistant layer and the ultra-low reflectivity surface layer respectively. Add each raw material to a high-speed mixer according to the formulation ratio and stir for 40 minutes at 25°C and 800r / min to obtain the copolymer resin mixtures corresponding to each layer. S2. A PET mold with a one-dimensional micro-grating array was selected, with a grating spacing of 50 μm and a height of 20 μm. The mold surface was subjected to plasma treatment, and then a mixture of phototropic copolymer resin was uniformly coated onto the pretreated mold surface. The photopolymer layer was then subjected to a wavelength of 365 nm and a light intensity of 800 mJ / cm². 2 Pre-curing under ultraviolet light for 20 seconds forms a 90μm thick directional light-controlled copolymer layer. Then, an anti-blue light weather-resistant copolymer resin mixture is coated on its surface and cured under ultraviolet light for another 30 seconds to form a 30μm thick anti-blue light weather-resistant layer. Finally, an ultra-low reflectance surface copolymer resin mixture is coated and cured under ultraviolet light for 30 seconds to form a 10μm thick ultra-low reflectance surface layer. S3. Demold the cured composite film from the mold, place it in a constant temperature oven, keep it at 80°C for 2 hours for post-curing treatment to remove residual stress, and then cut and grind the edges to obtain the optical resin copolymer modified anti-reflective light vehicle film.

[0034] Example 5 An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all copolymerized with methyl methacrylate and aliphatic polyurethane acrylate as the base resins, and different copolymerizing monomers are added for copolymerization modification.

[0035] The copolymer modification monomer of the directional light-controlling copolymer layer is the modified light-diffusing microsphere prepared in Example 1, and the copolymer modification monomer of the anti-blue light weather-resistant layer is the anti-blue light monomer prepared in Example 2; the copolymer modification monomer of the ultra-low reflectance surface layer is perfluorohexyl allyl glycidyl ether, hydroxyethyl methacrylate and butyl methacrylate.

[0036] The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 45 parts aliphatic polyurethane acrylate, 32.5 parts methyl methacrylate, 8.5 parts fluorinated acrylate, 8.5 parts bifunctional epoxy acrylate, 6 parts modified light-diffusing microspheres, 0.7 parts photoinitiator 1173, 0.7 parts photoinitiator 184, 0.3 parts hindered amine anti-yellowing agent, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0037] The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 32.5 parts aliphatic polyurethane acrylate, 22.5 parts methyl methacrylate, 11 parts anti-blue light monomer, 4 parts bifunctional epoxy acrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, and 0.35 parts hindered amine anti-yellowing agent.

[0038] The ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 29.5 parts aliphatic polyurethane acrylate, 21.5 parts methyl methacrylate, 18 parts fluorinated acrylate, 4.5 parts perfluorohexyl allyl glycidyl ether, 1.6 parts hydroxyethyl methacrylate, 1.6 parts butyl methacrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0039] The preparation method of the above-mentioned anti-reflective automotive film modified by optical resin copolymerization includes the following steps: S1. Prepare copolymer resin mixtures according to the formulations of the directional light-controlled copolymer layer, the anti-blue light weather-resistant layer and the ultra-low reflectivity surface layer. Add each raw material to a high-speed mixer according to the formulation ratio and stir for 30 minutes at 25°C and 800r / min to obtain the copolymer resin mixtures corresponding to each layer. S2. A PET mold with a one-dimensional micro-grating array was selected, with a grating spacing of 65 μm and a height of 15 μm. The mold surface was subjected to plasma treatment, and then a mixture of phototropic copolymer resin was uniformly coated onto the pretreated mold surface. The photopolymer layer was then subjected to a wavelength of 365 nm and a light intensity of 800 mJ / cm². 2 Pre-curing under ultraviolet light for 30 seconds forms an 85μm thick directional light-controlled copolymer layer. Then, an anti-blue light weather-resistant copolymer resin mixture is coated on its surface and cured under ultraviolet light for another 40 seconds to form a 32μm thick anti-blue light weather-resistant layer. Finally, an ultra-low reflectance surface copolymer resin mixture is coated and cured under ultraviolet light for 40 seconds to form a 10μm thick ultra-low reflectance surface layer. S3. Demold the cured composite film from the mold, place it in a constant temperature oven, keep it at 80°C for 3 hours for post-curing treatment to remove residual stress, and then cut and grind the edges to obtain the optical resin copolymer modified anti-reflective light vehicle film.

[0040] Comparative Example 1 An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all based on methyl methacrylate and aliphatic polyurethane acrylate resins.

[0041] The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 45 parts aliphatic polyurethane acrylate, 32.5 parts methyl methacrylate, 8.5 parts fluorinated acrylate, 8.5 parts bifunctional epoxy acrylate, 0.7 parts photoinitiator 1173, 0.7 parts photoinitiator 184, 0.3 parts hindered amine anti-yellowing agent, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0042] The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 32.5 parts aliphatic polyurethane acrylate, 22.5 parts methyl methacrylate, 11 parts anti-blue light monomer, 4 parts bifunctional epoxy acrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, and 0.35 parts hindered amine anti-yellowing agent.

[0043] The ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 29.5 parts aliphatic polyurethane acrylate, 21.5 parts methyl methacrylate, 18 parts fluorinated acrylate, 4.5 parts perfluorohexyl allyl glycidyl ether, 1.6 parts hydroxyethyl methacrylate, 1.6 parts butyl methacrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0044] The preparation method of the above-mentioned optical resin copolymer modified anti-reflective light vehicle film is the same as that in Example 5, except that the modified light-diffusing microspheres are not added to the copolymer resin mixture of the directional light-controlling copolymer layer in step S1.

[0045] Comparative Example 2 An optical resin copolymer-modified anti-reflective automotive film includes, from bottom to top, an in-situ copolymerized directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflective surface layer. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflective surface layer are all based on methyl methacrylate and aliphatic polyurethane acrylate resins.

[0046] The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 45 parts aliphatic polyurethane acrylate, 32.5 parts methyl methacrylate, 8.5 parts fluorinated acrylate, 8.5 parts bifunctional epoxy acrylate, 0.7 parts photoinitiator 1173, 0.7 parts photoinitiator 184, 0.3 parts hindered amine anti-yellowing agent, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0047] The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 32.5 parts aliphatic polyurethane acrylate, 22.5 parts methyl methacrylate, 4 parts difunctional epoxy acrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, and 0.35 parts hindered amine anti-yellowing agent.

[0048] The ultra-low reflectance surface layer comprises the following raw materials in parts by weight: 29.5 parts aliphatic polyurethane acrylate, 21.5 parts methyl methacrylate, 18 parts fluorinated acrylate, 4.5 parts perfluorohexyl allyl glycidyl ether, 1.6 parts hydroxyethyl methacrylate, 1.6 parts butyl methacrylate, 0.4 parts photoinitiator 1173, 0.4 parts photoinitiator 184, 0.5 parts perfluorooctyltriethoxysilane, and 0.4 parts acrylate leveling agent.

[0049] The preparation method of the above-mentioned optical resin copolymer modified anti-reflective light vehicle film is the same as that in Example 5, except that the anti-blue light weather-resistant layer copolymer resin mixture in step S1 does not contain anti-blue light monomers.

[0050] Performance testing The optical resin copolymerized anti-reflective automotive films prepared in Examples 3-5 and Comparative Examples 1 and 2 were cut into 10cm×15cm samples. Three parallel samples were prepared for each group of samples, and the average value of the test results was taken to ensure the reliability of the data.

[0051] (1) Transmittance detection A UV-Vis spectrophotometer was used. The instrument was turned on and preheated for 30 minutes. Using air as a blank reference, the instrument transmittance was calibrated to 100% at a wavelength of 550 nm to ensure detection accuracy. Three parallel samples were cut into 2cm × 2cm squares. The sample surfaces were wiped with anhydrous ethanol to remove dust and fingerprints, and allowed to air dry naturally before being fixed on the instrument's sample holder. The sample surfaces were ensured to be flat, wrinkle-free, and bubble-free, and perpendicular to the incident light. The incident light angle was adjusted to 0°, and the sample transmittance was tested and the data recorded. The angle was then adjusted to 5° and 10°, and the test was repeated. Each angle was tested three times, and the average of the three angles was taken as the final result of the front transmittance of the sample. The incident light angle was then adjusted to 30°, 45°, and 60°. After each adjustment, the sample holder was fixed, ensuring the angle between the sample and the incident light was accurate, and the transmittance at each angle was tested three times. The average of the three angles was taken as the final result of the side transmittance of the sample. (2) Specular reflectance A specular reflectance meter was used. The instrument was turned on and preheated for 20 minutes. The instrument was calibrated with a standard reflector (100% reflectance) to ensure detection accuracy. The sample was cut into a 3cm×3cm square, and after cleaning the surface, it was fixed flat on the sample stage, ensuring that the sample surface was free of scratches and stains and perpendicular to the test probe. The test probe was aligned with the center of the sample, and the test was started. Five different points were tested for each sample (one at the center and one at each of the four corners). The reflectance data of each point was recorded, and the average value of the five points was taken as the final result of the specular reflectance of the sample. (3) Blue light filtering rate A UV-Vis spectrophotometer was used. The instrument was turned on and preheated for 30 minutes. Using air as a blank reference, the instrument transmittance was calibrated to 100% in the 400–420 nm wavelength range. Three parallel samples were cut into 2 cm × 2 cm squares, and their surfaces were wiped with anhydrous ethanol to remove dust and fingerprints. After air drying, they were fixed on the instrument's sample holder, ensuring the sample surface was flat, wrinkle-free, bubble-free, and perpendicular to the incident light. The instrument wavelength range was adjusted to 400–420 nm, and the sample transmittance was measured every 5 nm. The transmittance data at each wavelength was recorded, and the average transmittance in the 400–420 nm wavelength range was calculated. Finally, the blue light filtration rate (%) was calculated as: Blue light filtration rate = 100% - Average transmittance in the 400–420 nm wavelength range. (4) Pencil hardness Use a pencil hardness tester equipped with standard pencils (HB, 2H, 3H, 4H, 5H, 6H, 7H). Fix the sample flat on the test platform. Select standard pencils of different hardnesses, sharpen the pencils to a 45° bevel, ensure that the pencil leads are not damaged or loose, and polish the tips of the leads with sandpaper to make them flat. Adjust the load of the pencil hardness tester to 750 g. Hold the tip of the pencil perpendicular to the surface of the sample and move it uniformly for 50 mm. Test 3 parallel scratches for each hardness grade, and the scratch spacing should be ≥5 mm. Observe the scratches. If there are no obvious scratches on the sample surface and no film peeling, then this hardness grade is qualified. Gradually increase the pencil hardness until obvious scratches (scratch width ≥0.1 mm) or film peeling occur. At this time, the previous hardness grade is the pencil hardness of the sample; (5) High and low temperature cycle resistance Cut 3 parallel samples into squares with a size of 5 cm × 5 cm respectively. After cleaning the surface, label the sample numbers with tags and place them on the sample rack in the high and low temperature test chamber, ensuring that the samples do not touch or overlap each other. Set the high and low temperature cycle program, specifically: keep at -40°C for 2 h → heat up to 25°C (heating rate 5°C / min), keep at 25°C for 30 min → heat up to 85°C (heating rate 5°C / min), keep at 85°C for 2 h → cool down to 25°C (cooling rate 5°C / min), keep at 25°C for 30 min, and complete 1 cycle; set a total of 10 cycles. Start the test chamber and conduct high and low temperature cycle tests according to the set program. Observe the state of the samples during the test to avoid sample detachment and collision. After the cycle is completed, take out the samples and let them cool naturally to room temperature (25°C). Observe with the naked eye whether there are defects such as cracking, yellowing, delamination, and bubbles on the sample surface. At the same time, gently peel the film layer by hand to observe whether there is delamination, and record the defect situation; (6) Dispersion stability Cut 3 parallel samples into squares with a size of 3 cm × 3 cm respectively. After cleaning the surface, place them on the sample rack in the high temperature oven, ensuring that the samples are flat and do not overlap. Set the oven temperature to 85°C and keep them at a constant temperature for 72 h. Observe the surface state of the samples every 24 h during this period and record whether there are phenomena such as haze change and yellowing. After the high temperature placement is completed, take out the samples and let them cool naturally to room temperature. Cut the cross-section of the samples (in the thickness direction), after sputtering with gold, put them into the SEM and magnify them 2000 times to observe the dispersion state of the modified light diffusion microspheres in the resin system, and record whether there are microsphere agglomeration and sedimentation phenomena. Use a haze meter to measure the haze values of the samples before and after high temperature placement, and calculate the haze change rate (%). The haze change rate = (haze after high temperature - haze before high temperature) / haze before high temperature × 100%. If the haze change rate ≤5% and there is no obvious agglomeration and sedimentation, it is considered dispersion stable; (7) Anti-blue light weather resistance stability Three parallel samples were cut into 2cm × 2cm squares. After cleaning the surfaces, the initial blue light filtration rate (below 420nm) was tested and the initial data were recorded. The samples were then placed in a UV aging test chamber, with the irradiation wavelength set to 340nm and the irradiation intensity to 0.89W / m². 2 At a temperature of 40℃ and a humidity of 50%, samples were continuously irradiated for 1000 hours. During this period, samples were taken out every 200 hours, cooled to room temperature, and the blue light filtration rate was tested and the data was recorded. The blue light filtration rate attenuation rate (%) was calculated as follows: Blue light filtration rate attenuation rate = (initial blue light filtration rate - blue light filtration rate after 1000 hours of UV irradiation) / initial blue light filtration rate × 100%. Each sample was calculated three times, and the average value was taken as the final attenuation rate. After the UV irradiation ended, the sample surface was observed for yellowing, cracking, delamination, or other phenomena, and the appearance was recorded.

[0052] The obtained data is shown in Table 1 below.

[0053] Table 1. Performance test results of anti-reflective automotive film modified with optical resin copolymer. As can be seen from the data in Table 1, the front transmittance of Comparative Example 1 is slightly lower than that of Examples 3-5, indicating that the introduction of microspheres optimizes the light path, reduces light loss inside the resin, and improves the front transmittance. This is because the modified light-diffusing microspheres can control the direction of light propagation, allowing incident light to pass through in a straight line as much as possible, reducing refraction loss within the resin. Simultaneously, the doping of rare earth elements can slightly absorb ultraviolet light, preventing a decrease in transmittance due to ultraviolet aging. Therefore, Examples 1-3 have higher front transmittance. Comparative Example 1 has a side transmittance as high as 47%, indicating that without the addition of light-diffusing microspheres, light cannot be effectively scattered and directionally controlled, significantly reducing the privacy protection effect. The modified light-diffusing microspheres of this invention, after being grafted with a silane coupling agent and modified with rare earth element doping, can be uniformly dispersed in a directional light-controlling copolymer layer. When light is incident at a side angle of 30° to 60°, it is scattered by the microspheres, resulting in light attenuation and thus achieving a privacy protection effect. In contrast, Comparative Example 1, without the addition of modified light-diffusing microspheres, allows light from the side angle to pass directly through the film layer without scattering attenuation, rendering the privacy protection effect completely ineffective. Simultaneously, the hardness of Comparative Example 1 decreased to 5H, indicating that the hardness of the modified light-diffusing microspheres is higher than that of the resin matrix. After grafting with the silane coupling agent, a strong chemical bond is formed with the resin, which can disperse the scratch stress on the film layer, thereby improving the overall hardness and enhancing scratch resistance.

[0054] In Comparative Example 2, the blue light filtering rate was only 11.3%, far lower than other groups, indicating that the anti-blue light monomer is the core of achieving efficient blue light filtering. The anti-blue light monomer of this invention adopts a composite structure of heterocyclic grafting and quantum dot coating, with the aromatic heterocyclic π-π The transition selectively absorbs high-energy blue light in the 400-420nm range, and the quantum size effect of quantum dots further enhances the precise absorption of this wavelength. The synergistic effect of both achieves highly efficient blue light filtering. In contrast, Comparative Example 2, without the addition of an anti-blue light monomer, relies solely on the weak absorption of the matrix resin and anti-yellowing agent, failing to effectively filter harmful blue light, resulting in a significant decrease in blue light filtration efficiency. Furthermore, Comparative Example 2 exhibits a blue light attenuation rate of 9.2%, far exceeding that of Examples 1-3, and shows slight yellowing, indicating that the composite modification of the anti-blue light monomer significantly improves UV aging resistance. The aromatic heterocyclic structure of the anti-blue light monomer in this invention forms a synergistic stable system with quantum dots, which can capture free radicals induced by UV light, inhibiting resin aging and the decomposition of the anti-blue light component, thereby reducing the attenuation of the blue light filtration efficiency. In contrast, Comparative Example 2, lacking an anti-blue light monomer, is prone to photoaging under UV irradiation, leading to film yellowing and a further decrease in blue light filtering capacity.

[0055] 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.

[0056] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An anti-reflective automotive film modified with optical resin copolymerization, characterized in that, It includes a directional light-controlling copolymer layer, an anti-blue light weather-resistant layer, and an ultra-low reflectivity surface layer, which are sequentially copolymerized in situ from bottom to top. The surface of the directional light-controlling copolymer layer has a one-dimensional micro-grating or micro-prism array. The directional light-controlling copolymer layer, the anti-blue light weather-resistant layer, and the ultra-low reflectivity surface layer are all based on methyl methacrylate and aliphatic polyurethane acrylate as matrix resins, and different copolymerizing modifying monomers are added for copolymerization modification. The copolymerized monomer of the directional light-controlling copolymer layer is a modified light-diffusing microsphere, which is a silica / polystyrene composite microsphere doped with rare earth element Ce after surface treatment with a silane coupling agent. 3+ ; The copolymer modification monomer of the anti-blue light weather-resistant layer is an anti-blue light monomer, which is an aromatic nitrogen-containing copolymer grafted with a carbazole group and then coated with ZnS quantum dots. The copolymerized monomers of the ultra-low reflectivity surface layer are perfluorohexyl allyl glycidyl ether, hydroxyethyl methacrylate, and butyl methacrylate.

2. The optical resin copolymer-modified anti-reflective automotive film according to claim 1, characterized in that, The directional light-controlled copolymer layer comprises the following raw materials in parts by weight: 40-50 parts of aliphatic polyurethane acrylate, 30-35 parts of methyl methacrylate, 7-10 parts of fluorinated acrylate, 6-11 parts of bifunctional epoxy acrylate, 5-7 parts of modified light-diffusing microspheres, 1.2-1.5 parts of photoinitiator, 0.2-0.4 parts of anti-yellowing agent, 0.4-0.6 parts of anti-fingerprint agent, and 0.3-0.5 parts of leveling agent.

3. The optical resin copolymer-modified anti-reflective automotive film according to claim 1, characterized in that, The anti-blue light weather-resistant layer comprises the following raw materials in parts by weight: 30-35 parts aliphatic polyurethane acrylate, 20-25 parts methyl methacrylate, 10-12 parts anti-blue light monomer, 3-5 parts bifunctional epoxy acrylate, 0.7-0.9 parts photoinitiator, and 0.3-0.4 parts anti-yellowing agent.

4. The optical resin copolymer-modified anti-reflective automotive film according to claim 1, characterized in that, The ultra-low reflectivity surface layer comprises the following raw materials in parts by weight: 27-32 parts aliphatic polyurethane acrylate, 20-23 parts methyl methacrylate, 15-20 parts fluorinated acrylate, 3.5-5 parts perfluorohexyl allyl glycidyl ether, 1.5-1.7 parts hydroxyethyl methacrylate, 1.5-1.7 parts butyl methacrylate, 0.7-0.9 parts photoinitiator, 0.4-0.6 parts anti-fingerprint agent, and 0.3-0.5 parts leveling agent.

5. The optical resin copolymer-modified anti-reflective automotive film according to any one of claims 2 to 4, characterized in that, The photoinitiator is a mixture of photoinitiator 1173 and photoinitiator 184 in a mass ratio of 1:1; the anti-yellowing agent is a hindered amine anti-yellowing agent; the anti-fingerprint agent is perfluorooctyltriethoxysilane; and the leveling agent is an acrylate leveling agent.

6. The optical resin copolymer-modified anti-reflective automotive film according to claim 1, characterized in that, The method for preparing the modified light-diffusing microspheres includes the following steps: (1) Styrene, polyvinylpyrrolidone and deionized water were added to the reaction vessel, and the oxygen was removed by purging with N2 for 20-40 min. Potassium persulfate was added, and the reaction was carried out at 70℃ for 22-26 h. After cooling to room temperature, the mixture was centrifuged, washed, and vacuum dried to obtain polystyrene microspheres. The polystyrene microspheres were redispersed in ethanol and water, sonicated for 20-40 min, and ammonia was added to adjust the pH value to 9-10. Tetraethyl orthosilicate was slowly added, and the reaction was stirred at room temperature for 6-12 h. After centrifugation, washing, and vacuum drying, silica / polystyrene composite microspheres were obtained. (2) Add silica / polystyrene composite microspheres to anhydrous ethanol, ultrasonically disperse for 20-40 min, add hydrochloric acid to adjust pH to 3.5, heat to 60℃, stir for 0.5-1.5 h, centrifuge, wash and vacuum dry to obtain pretreated microspheres; (3) Add the pretreated microspheres to toluene solvent, add 3-(methacryloyloxy)propyltrimethoxysilane, heat to 85°C, stir and reflux for 3-5 h, centrifuge, wash and vacuum dry to obtain silane coupling agent grafted microspheres. (4) Disperse the silane coupling agent-grafted microspheres in deionized water, add cerium nitrate, stir to dissolve, add ammonia to adjust the pH to 8.0, react at 50℃ for 1-3 hours, centrifuge to separate, wash with deionized water until neutral, vacuum dry, and then pulverize through a 200-mesh sieve to obtain modified light-diffusing microspheres.

7. The optical resin copolymer-modified anti-reflective automotive film according to claim 6, characterized in that, The mass ratio of styrene, polyvinylpyrrolidone, and potassium persulfate is 10:1.5:0.15; The mass ratio of the polystyrene microspheres to tetraethyl orthosilicate is 1:2~4; The mass ratio of the silica / polystyrene composite microspheres, 3-(methacryloyloxy)propyltrimethoxysilane, and cerium nitrate is 100:5:

3.

8. The optical resin copolymer-modified anti-reflective automotive film according to claim 1, characterized in that, The preparation method of the anti-blue light monomer includes the following steps: A. N-vinylcarbazole and N-phenylmaleimide were added to toluene solvent and mixed evenly. Then azobisisobutyronitrile was added and reacted at 70℃ for 4-8 hours to obtain carbazole grafted modified aromatic nitrogen-containing monomer. B. Dissolve zinc chloride and sodium sulfide in deionized water, add 2wt% sodium citrate as a dispersant, stir at room temperature for 20-40 min, centrifuge, wash and vacuum dry to obtain ZnS quantum dots; C. Add ZnS quantum dots to deionized water and ultrasonically disperse for 15-25 min to form a uniform ZnS quantum dot dispersion. Add carbazole-grafted modified aromatic nitrogen-containing monomers to the ZnS quantum dot dispersion and ultrasonically disperse for 20-40 min. Stir and react at 45℃ for 2-4 h. Remove water and impurities by vacuum distillation and vacuum drying to obtain the anti-blue light monomer.

9. The optical resin copolymer-modified anti-reflective automotive film according to claim 8, characterized in that, The mass ratio of N-vinylcarbazole to N-phenylmaleimide is 1:3, and the azobisisobutyronitrile is 0.8% of the total mass of N-vinylcarbazole and N-phenylmaleimide. The molar ratio of zinc chloride to sodium sulfide is 1:1.2; The mass ratio of the azole-grafted modified aromatic nitrogen-containing monomer to ZnS quantum dots is 10:

1.

10. The method for preparing the optical resin copolymer-modified anti-reflective automotive film according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. Prepare copolymer resin mixtures according to the formulations of the directional light-controlled copolymer layer, the anti-blue light weather-resistant layer and the ultra-low reflectivity surface layer. Add each raw material to a high-speed mixer according to the formulation ratio and stir for 20 to 40 minutes at 25°C and 800 r / min to obtain the copolymer resin mixtures corresponding to each layer. S2. Select a PET mold with a one-dimensional micro-grating array, with a grating spacing of 50~80μm and a height of 10~20μm. Perform plasma treatment on the mold surface, and then uniformly coat the pretreated mold surface with a photodynamic copolymer layer copolymer resin mixture. Apply the mixture at a wavelength of 365nm and a light intensity of 800mJ / cm². 2 Pre-curing under ultraviolet light for 20–40 seconds forms a directional light-controlled copolymer layer with a thickness of 80–90 μm. Then, an anti-blue light weather-resistant copolymer resin mixture is coated on its surface and cured under ultraviolet light for 30–50 seconds to form an anti-blue light weather-resistant layer with a thickness of 30–35 μm. Finally, an ultra-low reflectance surface copolymer resin mixture is coated and cured under ultraviolet light for 30–50 seconds to form an ultra-low reflectance surface layer with a thickness of 10–12 μm. S3. Demold the cured composite film from the mold and place it in a constant temperature oven. Keep it at 80°C for 2-4 hours for post-curing treatment to remove residual stress. Then cut and grind the edges to obtain the optical resin copolymer modified anti-reflective light vehicle film.

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