Anti-reflection film, anti-reflection film manufacturing method and display device

Abstract

The invention provides an antireflection film with excellent wear resistance and ultralow reflectivity and a manufacturing method thereof.The antireflection film is composed of a base material layer, a hardened coating, a high-refractive-index coating and a low-refractive-index coating, the hardened coating is made of acrylic ultraviolet curing resin containing nanoscale silicon dioxide or polymethyl methacrylate particles, and the low-refractive-index coating is made of acrylic ultraviolet curing resin containing nanoscale silicon dioxide or polymethyl methacrylate particles; therefore, hardening and wear-resistant protection are provided. The solid nanoparticles are subjected to surface modification through vinyl silsesquioxane, so that the dispersity of the solid nanoparticles is improved, and the hardness, wear resistance and smoothness of the coating are enhanced by utilizing the cross-linking reaction of vinyl functional groups and acrylic resin. According to the manufacturing method, the dry coating technology and the wet coating technology are combined, the technological process is simplified, the ultralow reflectivity can be achieved only through one layer of high-refractive-index coating and one layer of low-refractive-index coating, and the reflectivity is stable at different visual angles. According to the technical scheme, the production cost is reduced, and the production efficiency and the product yield are improved.

Description

Technical Field

[0001] The present application relates to the field of display technology, and in particular to an anti-reflection film, an anti-reflection film manufacturing method and a display device. Background Art

[0002] With the vigorous development of the new energy vehicle industry, ultra-large display screens have become an important part of the interior of new energy vehicles, which not only improves the convenience of driving, but also greatly enriches the entertainment experience of passengers. However, as the size of the display screen increases, its reflection problem becomes increasingly prominent, especially in a strong light environment or when viewed from different angles. The reflection phenomenon of the screen will seriously affect the display effect and even threaten driving safety. Therefore, the development of efficient and low-cost anti-reflection film technology to improve the screen clarity under wide-angle viewing has become a key technical problem that needs to be solved urgently.

[0003] At present, the technology of anti-reflection film has made some progress, mainly prepared by two methods: magnetron sputtering (dry method) and coating process (wet method). Magnetron sputtering technology has shown significant advantages in the preparation of low-reflectivity anti-reflection film with its high precision, good coating uniformity and appearance characteristics. By precisely controlling the coating parameters, extremely low reflectivity can be achieved at a zero-degree viewing angle. However, this technology also has significant shortcomings, such as complex process, slow production speed, high cost, and difficulty in adapting to large-scale and continuous production needs.

[0004] In contrast, the wet coating process has the characteristics of low cost and high production efficiency, but the reflectivity of its single-layer coating is usually high, which is difficult to meet the low reflection requirements under wide-angle viewing. Although multi-layer coating technology can further reduce the reflectivity, it has extremely high requirements for equipment accuracy, coating surface flatness and solvent volatilization control, and it is difficult to achieve uniformity of the entire width and the first and last coating, thus affecting the overall performance of the product.

[0005] Therefore, a technical solution is needed to reduce the reflectivity while taking into account the comprehensive performance of the anti-reflection film, such as light transmittance, wear resistance, and weather resistance. Summary of the invention

[0006] The purpose of the present application is to provide an anti-reflection film, which can improve its wear resistance without affecting the reflectivity, the anti-reflection film comprising a substrate layer, a hardening coating, a high refractive index coating and a low refractive index coating; The low refractive index coating is an acrylic resin containing hollow nano-silicon dioxide particles and solid nano-particles; Wherein, the refractive index of the high refractive index coating is in the range of 2.1-2.5, and the refractive index of the low refractive index coating is in the range of 1.2-1.4.

[0007] In one embodiment, the particle size of the hollow nano-silica particles is in the range of 10-100 nm, the particle size of the solid nano-particles is in the range of 20-100 nm, and the solid nano-particle material includes at least one of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide particles.

[0008] In one embodiment, the surface of the solid nanoparticle is modified by polysilsesquioxane, and the structure of the polysilsesquioxane is irregular, ladder-shaped or cage-shaped. Preferably, the polysilsesquioxane is a cage-shaped polysilsesquioxane with vinyl functional groups.

[0009] In one embodiment, the coating liquid of the low refractive index coating includes the following components according to the weight ratio: 5-20 parts of photocurable acrylic resin, 5-15 parts of hollow nano-silica particles, 3-10 parts of vinyl silsesquioxane modified solid nano-particle solution, 60-85 parts of solvent, 2-5 parts of photoinitiator, 0.01-0.2 parts of leveling agent, and 1-6 parts of anti-reflection additive.

[0010] In one embodiment, the hardened coating is an acrylic ultraviolet light-curable resin coating containing nano-scale inorganic particles or nano-scale organic particles.

[0011] In one embodiment, the high refractive index coating is a niobium oxide coating. Preferably, the high refractive index coating is a niobium pentoxide coating.

[0012] In one embodiment, the thickness of the high refractive index coating is in the range of 5-20 nm, the thickness of the hardened coating is in the range of 2-8 μm, and the thickness of the low refractive index coating is in the range of 90-140 nm.

[0013] The present application further provides a method for manufacturing an anti-reflection film, comprising the following steps: Providing a substrate layer, and applying a hardening coating coating liquid on the substrate layer to form a hardening coating layer; forming a high refractive index coating layer on the hardened coating layer by sputtering or evaporation; A low refractive index coating liquid is prepared, wherein the coating liquid comprises hollow nano-silica particles and acrylic resin of solid nano-particles, wherein the solid nano-particle material comprises at least one of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide particles; Applying the low refractive index coating coating liquid on the high refractive index coating to form a low refractive index coating; The refractive index of the high refractive index coating formed is in the range of 2.1-2.5, and the refractive index of the low refractive index coating formed is in the range of 1.2-1.4.

[0014] In one embodiment, the manufacturing method also includes modifying the solid nanoparticles, specifically including taking 10-30 parts of solid nanoparticles and adding them to 30-60 parts of diluted vinyl silsesquioxane liquid, slowly adding 1-10 parts of diluted initiator during the dispersion process, reacting at a temperature of 50-100°C for 4-8h, and then terminating the reaction with a dodecanethiol chain transfer agent to obtain vinyl silsesquioxane modified solid nanoparticles.

[0015] Furthermore, the present application also provides a display device, which includes the aforementioned anti-reflection film.

[0016] Compared with the prior art, the present application has the following beneficial effects: The present application achieves ultra-low reflectivity by combining dry coating and wet coating. First, a hardened coating is formed on the surface of the substrate to meet the hardening and wear resistance requirements and provide a flat surface. Then a high-refractive niobium oxide coating is plated on the hardened coating, and then a low-refractive resin coating is applied. Through the design of the coating, only one layer of high-refractive index coating and one layer of low-refractive index coating are required to achieve ultra-low reflectivity at zero-degree angles. At the same time, the reflectivity of the anti-reflection film is also at a low value at a large angle, reaching or exceeding the reflectivity of only coating, coating or multi-layer coating plus coating. Coating only one layer of high-refractive index layer can greatly reduce the problems caused by the complexity of the coating process and the high cost. Moreover, since the coating is the accumulation and superposition of surface atoms, the coating thickness is consistent. Compared with coating one layer of high-refractive index resin layer, coating one layer of high-refractive index layer has a more uniform surface flatness, so that the coating of one layer of low-refractive index resin coating has better appearance and reflectivity.

[0017] Adding hollow silica particles and then adding solid nanoparticles to provide wear resistance, solid nanoparticles have poor dispersibility, and particle aggregation points caused by solid nanoparticles will appear during coating, resulting in poor spot appearance. The present application improves the wear resistance of a low-refractive index resin without affecting the reflectivity by adding solid nanoparticles modified with vinyl silsesquioxane, wherein the vinyl functional groups in the silsesquioxane undergo cross-linking reaction with the acrylic resin, further improving the hardness, wear resistance and smoothness of the surface layer.

[0018] Through the substrate layer, hardened coating, high refractive index coating, and low refractive index coating, the reflectivity is kept extremely low while ensuring the stability of the reflectivity at different viewing angles (including large angles such as 30° and 45°), improving the clarity of the display screen under different lighting conditions and viewing angles, and providing users with a more comfortable and realistic visual experience. Solid nanoparticles modified with vinyl silsesquioxane are introduced into the low refractive index coating. These modified particles maintain the low refractive index characteristics and enhance the wear resistance of the coating.

[0019] The manufacturing method of the present application combines dry coating (sputtering or evaporation) with wet coating technology, and can achieve excellent anti-reflection effects through simplified process steps (only one layer of high refractive index coating and one layer of low refractive index coating). It reduces production complexity and cost, improves production efficiency and product yield, and provides strong support for large-scale commercial production. By selecting the substrate layer material, nanoparticle type and particle size, and the formula and process parameters of each coating, the anti-reflection film prepared in the present application has good light transmittance, weather resistance, scratch resistance and chemical stability while maintaining ultra-low reflectivity and wear resistance. The improvement of these comprehensive properties enables the anti-reflection film to adapt to various complex usage environments and meet diverse application needs. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is a schematic structural diagram of an anti-reflection film in one embodiment of the present application; Figure 2 It is a schematic flow chart of a method for manufacturing an anti-reflection film in one embodiment of the present application.

[0021] Explanation of reference numerals: 10, anti-reflection film; 100, substrate layer; 200, hardening coating layer; 300, high refractive index coating layer; 400, low refractive index coating layer. DETAILED DESCRIPTION

[0022] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail below in conjunction with the accompanying drawings. It is to be understood that the specific embodiments described herein are only used to explain the present application, rather than to limit the present application. It should also be noted that, for ease of description, only some structures related to the present application are shown in the accompanying drawings, rather than all structures. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0023] The terms "including" and "having" and any variations thereof in this application are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units not listed, or may optionally include other steps or units inherent to these processes, methods, products or devices.

[0024] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0025] The research and application of reflective films are particularly important. Anti-reflective film 10, through its unique structural design, aims to reduce the reflection of light on the screen surface, thereby enhancing the clarity and contrast of the image and improving the user's viewing experience. This introduction will focus on an innovative anti-reflective film 10 technology, which, through the ingenious design of combining multiple layers of coating, not only achieves ultra-low reflectivity, but also significantly improves the wear resistance of the coating without affecting this performance. Figure 1 As shown, an anti-reflection film 10 in a preferred embodiment of the present application improves its wear resistance without affecting the reflectivity, and achieves excellent anti-reflection effect through simplified process steps. The anti-reflection film 10 includes a substrate layer 100, a hardening coating 200, a high refractive index coating 300 and a low refractive index coating 400, wherein the low refractive index coating 400 is an acrylic resin coating containing hollow nano-silica particles and solid nano-particles; wherein the refractive index of the high refractive index coating 300 is in the range of 2.1-2.5, and the refractive index of the low refractive index coating 400 is in the range of 1.2-1.4.

[0026] The substrate layer 100 serves as the basic support for the entire anti-reflection film 10, ensuring the stability and durability of the film layer. The hardened coating 200 meets the requirements of hardening and wear resistance, while providing a smooth surface. Using advanced sputtering or evaporation technology, the oxide film layer formed is precisely controlled, and the refractive index difference between the high refractive index material and the air or the subsequent low refractive index coating 400 is used to achieve effective scattering and interference of light at the interface, thereby reducing reflected light and increasing light transmittance. The low refractive index coating 400 adopts a unique acrylic resin formula, which combines hollow nano-silica particles and solid nano-particles. With its extremely low refractive index (close to the refractive index of air) and unique microporous structure, it effectively reduces the overall refractive index of the coating, forms a closer refractive index match with air, and further weakens the interface reflection. The addition of solid nano-particles enhances the wear resistance of the coating and ensures stability and durability under long-term use.

[0027] By precisely controlling the refractive index range of high and low refractive index coatings, multiple interferences of light in the multi-layer film structure are achieved, which greatly reduces the surface reflectivity and improves the transmittance, making the light passing through the film layer clearer and brighter. The optimized anti-reflection effect not only reduces glare and reflection interference, but also enhances the contrast and color saturation of the image, bringing users a more realistic and delicate visual experience.

[0028] Through the design of the coating, only one layer of high refractive index and one layer of low refractive index need to be coated to achieve ultra-low reflectivity at a zero-degree angle. At the same time, the anti-reflection film with low reflectivity at large angles can reach or exceed the reflectivity of only coating, coating, or multi-layer coating plus coating.

[0029] Specifically, the substrate layer 100 includes at least one of polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and cellulose triacetate, and the thickness of the substrate layer 100 is in the range of 20-150 μm. These materials have excellent mechanical strength, chemical stability, and thermal stability, and also have good optical transparency, which can ensure that light maintains high transmittance and is not distorted when passing through the substrate layer 100. In addition, the thickness range of the substrate layer 100 is set based on comprehensive considerations of optical performance, mechanical strength, and processing costs, which can reduce the absorption and scattering of light, further improve the transmittance, and facilitate subsequent coating processing and overall thickness control.

[0030] Specifically, the hardening coating 200 is an acrylic ultraviolet light curing resin system, embedded with at least one of nano-scale inorganic particles or nano-scale organic particles, which further enhances the hardness and wear resistance of the coating and effectively resists scratches and scrapes. The above-mentioned inorganic particles can be silica particles, and the above-mentioned organic particles can be polymethyl methacrylate particles. The particle size of the nano-scale silica particles or the polymethyl methacrylate particles is in the range of 5-50nm, and the acrylic ultraviolet light curing resin includes at least one of polyurethane acrylic resin, polyester acrylic resin, and epoxy acrylic resin. The introduction of nanoparticles improves the hardness and wear resistance of the hardening coating 200, and effectively resists external scratches and wear through the strong interaction between the nanoparticles and the resin matrix. The small size and uniform dispersion of the nanoparticles reduce the light scattering phenomenon, ensure the high optical transparency of the hardening coating 200, so that the anti-reflection film 10 maintains high light transmittance while also reducing the visual interference caused by the coating itself. The addition of some resin types, such as polyester acrylic resin, can also improve the weather resistance and chemical corrosion resistance of the hardened coating 200, so that the anti-reflection film 10 can maintain stable performance even in complex environments.

[0031] In one embodiment, the hardening coating coating liquid includes the following components according to weight ratio: 30-50 parts of ultraviolet light curing resin, 2-10 parts of nanometer-sized particles, 50-75 parts of solvent, 0.1-0.5 parts of leveling agent, and 3-5 parts of photoinitiator.

[0032] In order to achieve an efficient anti-reflection effect, the material of the high refractive index coating 300 is selected as niobium oxide. Preferably, the high refractive index coating material is niobium pentoxide, and the thickness of the high refractive index coating 300 is in the range of 5-20nm. As a high refractive index material, niobium pentoxide forms a large refractive index difference with the low refractive index coating 400. This difference causes the light to interfere and destructively interact at the interface of the two layers, thereby effectively reducing the intensity of the reflected light and enhancing the transmittance. At the same time, precise thickness control ensures the best effect of the interference effect and further improves the anti-reflection performance. Niobium pentoxide has good optical stability and can maintain a constant refractive index over a wide wavelength range. The anti-reflection film 10 can maintain stable performance under different lighting conditions. The thickness of the hardened coating 200 is in the range of 2-8μm, and is further preferably in the range of 3-5μm. The thickness of the low refractive index coating 400 is in the range of 90-140nm, and is further preferably in the range of 100-130nm, to ensure that the coating is neither too thick to affect the transmittance, nor too thin to lack sufficient protection effect.

[0033] Specifically, the particle size of the hollow nano silica particles is in the range of 10-100nm, preferably 20-80nm, and the particle size of the solid nano particles is in the range of 20-100nm, preferably 20-50nm. The particle size of the hollow nano silica particles is finely controlled within the range of 10-100nm, especially within the range of 20-80nm, which can balance the inhibitory effect of light scattering and the transparency of the coating. A smaller particle size can reduce light scattering and improve the transparency of the coating, but a too small particle size may increase the difficulty and cost of preparation; and a larger particle size may introduce unnecessary scattering and reduce the performance of the coating. The particle size of the solid nano particles is set within the range of 20-100nm, especially within the range of 20-50nm. Adding solid nano particles can improve the wear resistance of the coating. The reasonable combination of hollow nano-silica particles and solid nano-particles and the control of particle size achieve the precise control of the refractive index of the coating, which causes multiple interference and scattering of light inside the coating, effectively reducing the intensity of reflected light, increasing light transmittance and improving the wear resistance of the overall coating. By controlling the particle size of hollow nano-silica particles within an appropriate range, the occurrence of light scattering is reduced, ensuring the high transparency of the coating.

[0034] In order to further improve the dispersibility between solid nanoparticles, the surface of the solid nanoparticles is modified by polysilsesquioxane, and the structure of the polysilsesquioxane is irregular, ladder-shaped cage or cage-shaped. By modifying the surface of the solid nanoparticles, the surface of the solid nanoparticles is coated with multiple polysilsesquioxanes, thereby avoiding the solid nanoparticles from agglomerating with each other, and solving the problem of poor appearance such as point defects. Further preferably, the polysilsesquioxane is a cage-shaped polysilsesquioxane with vinyl functional groups, and the surface of the solid nanoparticles is modified by polysilsesquioxane. Polysilsesquioxane is a type of organic-inorganic hybrid material with a special three-dimensional cage structure, and its structural morphology is diverse, including but not limited to irregular, ladder-shaped cages and cage structures. These shapes are the shapes that can be obtained by polysilsesquioxane, which is determined by the specific polymerization method. Chemical bonding not only enhances the dispersibility and stability of the solid nanoparticles in the acrylic resin, but also improves the physical and optical properties of the entire low refractive index coating 400. The unique three-dimensional cage structure provides additional physical properties for the coating, such as hardness, wear resistance, scratch resistance, etc. These performance improvements enable the anti-reflection film 10 to perform well in a variety of application scenarios.

[0035] The present application further proposes an optimized method for manufacturing an anti-reflection film 10, which aims to achieve the preparation of a high-performance anti-reflection film 10 by finely regulating the composition and process parameters of each layer of material, and comprises the following steps: A substrate layer 100 is provided, and a coating liquid of a hardening coating layer 200 is coated on the substrate layer 100 to form a hardening coating layer 200, wherein the coating liquid of the hardening coating layer 200 includes nano-scale silica particles or nano-scale polymethyl methacrylate particles, and the coating thickness is in the range of 2-8 μm, preferably in the range of 3-5 μm; a high refractive index coating layer 300 is formed on the hardening coating layer 200 by sputtering or evaporation; a coating liquid of a low refractive index coating layer 400 is prepared, wherein the coating liquid includes an acrylic resin of hollow nano-silica particles and solid nano-particles, and the solid nano-particle material includes at least one of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide particles; the coating liquid of the low refractive index coating layer 400 is coated on the high refractive index coating layer 300 to form a low refractive index coating layer 400, wherein the refractive index of the formed high refractive index coating layer 300 is in the range of 2.1-2.5, and the refractive index of the formed low refractive index coating layer 400 is in the range of 1.2-1.4.

[0036] First, a substrate layer 100 with high light transmittance, good mechanical strength and chemical stability is selected, such as glass, plastic or polymer film. Ensure that the surface of the substrate layer 100 is flat and free of impurities, providing a good adhesion basis for subsequent coatings. The hardening coating 200 coating liquid containing nano-scale silica particles or nano-scale polymethyl methacrylate particles is evenly coated on the substrate layer 100. The introduction of nanoparticles not only enhances the hardness, wear resistance and scratch resistance of the coating.

[0037] On top of the hardening coating 200, a high-precision coating technology such as sputtering or evaporation is used to form a high-refractive index coating 300 to effectively reduce the reflection of light on the interface and improve the transmittance of light. A coating liquid for the low-refractive index coating 400 is prepared, which is an acrylic resin that combines hollow nano-silica particles and solid nano-particles. The hollow nano-silica particles can effectively reduce the refractive index of the coating due to their unique hollow shell structure; while the solid nano-particles enhance the mechanical properties and chemical stability of the coating.

[0038] Specifically, the manufacturing method also includes preparing modified solid nanoparticles, specifically including taking 10-30 parts of solid nanoparticles and adding them into 30-60 parts of diluted vinyl silsesquioxane liquid, slowly adding 1-10 parts of diluted initiator during the dispersion process, reacting at a temperature of 50-100°C for 4-8h, and then terminating the reaction with a dodecanethiol chain transfer agent to obtain vinyl silsesquioxane modified solid nanoparticles.

[0039] Specifically, the coating liquid of the hardening coating 200 includes the following components according to the weight ratio: 30-50 parts of ultraviolet light-curing resin, 2-10 parts of nano-scale particles, 50-75 parts of solvent, 0.1-0.5 parts of leveling agent, and 3-5 parts of photoinitiator. The coating liquid of the low refractive index coating 400 includes the following components according to the weight ratio: 5-20 parts of photocurable acrylic resin, 5-15 parts of hollow nano-silica particles, 3-10 parts of vinyl silsesquioxane modified solid nanoparticle solution, 60-85 parts of solvent, 2-5 parts of photoinitiator, 0.01-0.2 parts of leveling agent, and 1-6 parts of anti-reflection additive.

[0040] Furthermore, the present application also provides a display device, which includes the aforementioned anti-reflection film 10 .

[0041] Specific embodiments: The technical effects of the present application scheme are further described below through specific implementation methods combined with comparative examples. In the following embodiments and comparative examples, the leveling agent is BYK 333, BYK 307, BYK 377 and BYK 358, or a combination of at least two of them. The substrate TAC is a Japanese Fuji substrate, the PET substrate is a Japanese Toray substrate, the photoinitiator is BASF 184 photoinitiator, and the solvents are all commercially available conventional solvents.

[0042] Example 1 HC Hard Coating Preparation: 40 parts of UV light-curing resin (Kenmet Acu-Coat UV7700), 5 parts of 30nm nano-silicon dioxide particles (Evonik R972), 20 parts of propylene glycol methyl ether and 30 parts of ethyl acetate, 0.1 parts of leveling agent (BYK333), and 5 parts of photoinitiator were mixed and dispersed evenly by homogenizer. The HC hardening coating liquid was coated on the TAC substrate by gravure coating, and the HC hardening coating was prepared by oven baking and UV irradiation polymerization. The thickness of the TAC substrate was 60um and the dry coating thickness was 4um.

[0043] Preparation of high refractive index coating: Nb2O5 was coated on the surface of HC hardening coating by sputtering, with a coating thickness of 7nm and a refractive index of 2.3.

[0044] Preparation of low refractive index coating: Octavidinyl silsesquioxane modified solid nanoparticles: Take 15 parts of solid nanoparticles and add them to 60 parts of diluted octavinyl silsesquioxane (Forsman Technology Company) liquid, disperse them by mechanical dispersion or ultrasonic dispersion, slowly add 4 parts of diluted azobisisobutyronitrile initiator during the dispersion process, react at 70°C for 5h, and finally add 1 part of diluted dodecanethiol chain transfer agent to terminate the reaction to obtain octavinyl silsesquioxane modified solid nanoparticle solution. The dilution solvent is toluene, and the dilution ratio is 1:9. Finally, the solid content of octavinyl silsesquioxane modified solid nanoparticle solution with a solid content of about 26% is obtained.

[0045] Then, 15 parts of low refractive index resin (Kyoeisha, SL023, refractive index 1.32), 10 parts of hollow nano silica particles, 8 parts of octavinyl silsesquioxane modified alumina solid nanoparticle solution, 75 parts of solvent, 3 parts of photoinitiator, and 0.1 parts of leveling agent were mixed and dispersed evenly by homogenizer. The low refractive index coating liquid was coated on the high refractive index coating layer by gravure coating, first baked in an oven and then polymerized by UV irradiation to prepare a low refractive index coating with a dry coating thickness of 127nm.

[0046] The prepared anti-reflection film.

[0047] Example 2 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: The thickness of the high refractive index coating is 15nm.

[0048] Example 3 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: The low refractive index resin in the low refractive index coating is ELCOM-5062 of JGC Catalyst Co., Ltd., with a refractive index of 1.38.

[0049] Example 4 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: The substrate selected is optical grade PET substrate Japan Toray U483, with a thickness of 50μm.

[0050] Example 5 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: 4 parts of octavinylsilsesquioxane modified solid nanoparticle solution.

[0051] Comparative Example 1 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: The anti-reflection layer is prepared by vacuum coating on the HC hardened coating by sequentially stacking a first niobium pentoxide layer, a silicon dioxide layer, a second niobium pentoxide layer, and a silicon dioxide layer, wherein the first niobium pentoxide layer has a thickness of 10 nm, the silicon dioxide layer has a thickness of 40 nm, the second niobium pentoxide layer has a thickness of 120 nm, and the silicon dioxide layer has a thickness of 90 nm, and then an anti-fouling layer is coated on the coating, the anti-fouling layer has a thickness of 20 nm, and thus a anti-reflection film is obtained.

[0052] Comparative Example 2 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: A bulk low-refractive-index coating liquid (Arakawa Chemical, SL046B, refractive index 1.36) was applied on the HC hard coating to a film thickness of 100 nm.

[0053] Comparative Example 3 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: No vinyl silsesquioxane modification is added to the low refractive index coating. The hollow nano-silica particles and the solid nano-particles are added together into a resin solvent for dispersion.

[0054] Comparative Example 4 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: The solid nanoparticles in the low refractive index coating are not modified by vinyl silsesquioxane. The hollow nano-silica particles, the solid nanoparticles and octavinyl silsesquioxane are added together into a resin solvent for dispersion.

[0055] Comparative Example 5 This embodiment is different from Embodiment 1 in the following features, and the rest of the features are the same as Embodiment 1: Solid nanoparticles in low refractive index coatings are modified with vinylsiloxane KH570 Test Method Transmittance: Refer to JIS K7361 test method. Haze: Refer to JIS K7361 test method.

[0056] Abrasion resistance test: 0000# steel wool, 1000g load, 2cm*2cm contact area, friction speed 50 times / min. Reflectivity test: Cut the reflective film into 10cm*10cm size, stick a black film on the back of the anti-reflective film, use Lambda950 to test the reflectivity of the anti-reflective film at 0°, 30°, and 45° at 400-700nm, and calculate the average reflectivity of 420-680nm.

[0057] Through the test results of the above embodiments and comparative examples, it can be found that the present application achieves ultra-low reflectivity by combining dry coating and wet coating, and also has higher wear resistance. Although the comparative example also has high wear resistance, its reflectivity is relatively high. In comparative example 2, only the coating liquid of the first refractive index is applied, the wear resistance decreases and the reflectivity increases significantly. It can be found in comparative example 3 that no modification will lead to low wear resistance, white spots will appear, and the appearance is unqualified. It can also be found through comparative example 4 that the required wear resistance and low refractive index requirements cannot be achieved without modification in advance. In addition, other modified substances cannot achieve the technical effect of using silsesquioxane modification.

[0058] From the foregoing, it can be seen that the present application proposes an anti-reflection film preparation technology that combines the advantages of dry coating and wet coating processes, aiming to achieve ultra-low reflectivity while ensuring stable control of reflectivity at different viewing angles (especially large angles such as 30° and 45°), thereby significantly improving the visual effects and user experience of the display.

[0059] Specifically, a hardened coating is first constructed on the surface of the substrate, which not only meets the hardening and wear resistance requirements of the substrate, but also a high-refractive-index niobium oxide coating is deposited on the hardened coating using dry coating technology, which simplifies the process and reduces production costs. At the same time, it avoids the uneven thickness and interface defects that may be caused by multi-layer coatings, and applies a low-refractive-index resin coating on the high-refractive-index coating using wet coating technology. In order to further improve the wear resistance of the coating, the present application introduces solid nanoparticles modified with vinyl silsesquioxane, which, while maintaining the low-refractive-index characteristics, enhances the hardness, wear resistance and smoothness of the coating through the cross-linking reaction between the vinyl functional group and the acrylic resin, effectively solving the problem of poor appearance caused by poor dispersibility of traditional solid nanoparticles.

[0060] In summary, this application achieves a combination of ultra-low reflectivity and excellent wear resistance through a four-layer structure (substrate layer, hardened coating, high refractive index coating, and low refractive index coating) while simplifying the process flow and reducing costs. The anti-reflection film can exhibit excellent clarity and visual effects under different lighting conditions and viewing angles, and has good light transmittance, weather resistance, scratch resistance and chemical stability.

[0061] The above is only a specific implementation of the present application, and any other improvements made based on the concept of the present application are deemed to be within the protection scope of the present application.

Claims

1. An anti-reflection film (10), characterized in that: It comprises a substrate layer (100), a hardening coating layer (200), a high refractive index coating layer (300) and a low refractive index coating layer (400); The low refractive index coating (400) is an acrylic resin coating containing hollow nano-silicon dioxide particles and solid nano-particles; The refractive index of the high refractive index coating (300) is within the range of 2.1-2.5, and the refractive index of the low refractive index coating (400) is within the range of 1.2-1.

4.

2. The anti-reflection film (10) according to claim 1, characterized in that: The particle size of the hollow nano-silica particles is in the range of 10-100 nm, the particle size of the solid nano-particles is in the range of 20-100 nm, and the solid nano-particle material includes at least one of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide particles.

3. The anti-reflection film (10) according to claim 1, characterized in that: The surface of the solid nanoparticle is modified by polysilsesquioxane, and the structure of the polysilsesquioxane is irregular, ladder-shaped or cage-shaped. Preferably, the polysilsesquioxane is a cage-shaped polysilsesquioxane with vinyl functional groups.

4. The anti-reflection film (10) according to claim 3, characterized in that: The coating liquid of the low refractive index coating (400) comprises the following components in terms of weight ratio: 5-20 parts of photocurable acrylic resin, 5-15 parts of hollow nano silica particles, 3-10 parts of vinyl silsesquioxane modified solid nano particle solution, 60-85 parts of solvent, 2-5 parts of photoinitiator, 0.01-0.2 parts of leveling agent, and 1-6 parts of anti-reflection auxiliary agent.

5. The anti-reflection film (10) according to claim 1, characterized in that: The hardened coating (200) is an acrylic ultraviolet curing resin coating containing at least one of nanometer-scale inorganic particles or nanometer-scale organic particles.

6. The anti-reflection film (10) according to claim 1, characterized in that: The high refractive index coating (300) is a niobium oxide coating, and preferably, the high refractive index coating is a niobium pentoxide coating.

7. The anti-reflection film (10) according to claim 1, characterized in that: The thickness of the high refractive index coating (300) is in the range of 5-20 nm, the thickness of the hardened coating (200) is in the range of 2-8 μm, and the thickness of the low refractive index coating (400) is in the range of 90-140 nm.

8. A method for manufacturing an anti-reflection film (10), characterized in that: The steps include: Providing a substrate layer (100), and coating a coating liquid of a hardening coating layer (200) on the substrate layer (100) to form a hardening coating layer (200); forming a high refractive index coating layer (300) on the hardened coating layer (200) by sputtering or evaporation; A coating liquid of a low refractive index coating (400) is prepared, wherein the coating liquid comprises an acrylic resin of hollow nano-silicon dioxide particles and solid nano-particles, wherein the solid nano-particle material comprises at least one of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide particles; Applying the low refractive index coating (400) coating liquid on the high refractive index coating (300) to form a low refractive index coating (400); The refractive index of the formed high-refractive-index coating (300) is within the range of 2.1-2.5, and the refractive index of the formed low-refractive-index coating (400) is within the range of 1.2-1.

4.

9. The method for manufacturing an anti-reflection film (10) according to claim 8, characterized in that: The method also includes modifying the solid nanoparticles, specifically including taking 10-30 parts of solid nanoparticles and adding them into 30-60 parts of diluted vinyl silsesquioxane liquid, slowly adding 1-10 parts of diluted initiator during the dispersion process, reacting at a temperature of 50-100° C. for 4-8 hours, and then terminating the reaction with a dodecanethiol chain transfer agent to obtain vinyl silsesquioxane-modified solid nanoparticles.

10. A display device, characterized in that: Comprising the anti-reflection film (10) as described in any one of claims 1 to 7.

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