Anti-dazzle coating liquid, anti-dazzle film and preparation method of anti-dazzle film

Abstract

The invention provides an anti-dazzle coating liquid, an anti-dazzle film and a preparation method of the anti-dazzle film, and relates to the technical field of anti-dazzle materials. The preparation method of the anti-dazzle film comprises the following steps: uniformly mixing anti-dazzle particles and a cross-linking agent to prepare an anti-dazzle film coating solution; coating a substrate with the anti-dazzle coating liquid, and curing to form an anti-dazzle coating; the anti-dazzle particles are hollow nanometer titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles. The characteristic that the refractive indexes of the anti-dazzle particles and the cross-linking agent are different is utilized, so that light enters interfaces with different refractive indexes, the light propagation direction is changed, and the anti-dazzle effect is achieved; by utilizing the hollow parts of the titanium dioxide microspheres, light rays are refracted twice and reflected multiple times when passing through the anti-dazzle particles, the light ray dispersion effect is achieved in the anti-dazzle coating, the anti-dazzle effect does not need to be improved by means of the rough surface of the anti-dazzle film, and the surface of the anti-dazzle film is smooth; meanwhile, the glossiness and haze of the anti-dazzle film can be adjusted in a large range, and the anti-dazzle film is high in mechanical strength.

Description

Technical Field

[0001] The present application relates to the technical field of anti-glare materials, and in particular to an anti-glare coating liquid, an anti-glare film and a preparation method thereof. Background Art

[0002] In the display and photovoltaic fields, when a large amount of concentrated light is irradiated on the display glass surface or photovoltaic glass surface, the display glass surface or photovoltaic glass surface will produce strong specular reflection, causing light spots, halos and other phenomena. Such light spots and halos are glare, which affects vision and causes damage to human eyes. Anti-glare film can disperse concentrated transmitted and reflected light, thereby reducing or eliminating glare. The anti-glare effect of anti-glare film is mostly achieved through the roughness of the anti-glare film layer. When concentrated light passes through a rough surface, the direction of light propagation changes, thereby achieving the purpose of dispersing light and eliminating glare.

[0003] At present, anti-glare films are generally divided into two categories. One type of anti-glare film achieves an anti-glare effect by forming a rough surface on the glass surface through an etching process. This type of anti-glare film does not require the introduction of other materials, and the film layer has high mechanical strength. However, the current laser processing technology for anti-glare film is not mature, and the wet etching process uses strong acids such as hydrofluoric acid and concentrated sulfuric acid, which is not environmentally friendly. In addition, the surface of the anti-glare film is rough, which is easy to accumulate dust and cause dirt, and is not easy to clean. The other type of anti-glare film achieves an anti-glare effect by coating an anti-glare coating on the glass surface. However, the mechanical strength of this type of anti-glare film with a rough surface anti-glare coating is usually lower than that of glass, and when the glossiness of the anti-glare film is lower and the haze is higher, the surface roughness of the anti-glare coating is greater, and accordingly, the mechanical strength of the anti-glare coating deteriorates, that is, this type of anti-glare film with a rough surface anti-glare coating cannot adjust the glossiness and haze of the anti-glare film over a large range.

[0004] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide an anti-glare coating liquid, an anti-glare film and a preparation method thereof which have a smooth surface, are not prone to dust accumulation, are easy to clean, and have a glossiness and haze that can be adjusted over a wide range.

[0006] To achieve the above objectives, this application adopts the following technical solutions: A method for preparing an anti-glare film, comprising: The anti-glare particles and the cross-linking agent are mixed evenly to prepare an anti-glare coating liquid; Applying the anti-glare coating liquid on a substrate and curing the liquid to form an anti-glare coating; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

[0007] In some embodiments, the particle size of the hollow nano-titanium dioxide microspheres is 500 to 1200 nm; and / or The particle size of the silicon dioxide nanoparticles is 3-5 nm.

[0008] In some implementation methods, the anti-glare coating liquid further includes an organic solvent; the organic solvent includes one or more of an alcohol solvent, a ketone solvent, and an alcohol-water mixed solvent.

[0009] In some implementations, in the anti-glare coating solution, the mass percentage of the anti-glare particles is 3-10%, and the mass percentage of the cross-linking agent is 10-15%.

[0010] In some implementation methods, the pH value of the anti-glare coating solution is controlled at 2-3.

[0011] In some embodiments, the method for preparing the hollow nano-titanium dioxide microspheres includes a sacrificial template method; the method for preparing the hollow nano-titanium dioxide microspheres using the sacrificial template method includes: Silica microspheres were synthesized using ammonia water as initiator, tetraethyl orthosilicate as silicon source and ethanol aqueous solution as solvent. Using silane coupling agent KH-550 as a modifier, performing surface modification treatment on the silica microspheres to obtain modified silica microspheres; The modified silica microspheres are used as templates, tetrabutyl titanate is used as a titanium source, glacial acetic acid is used as an initiator, and ethanol aqueous solution is used as a solvent to synthesize titanium dioxide / silica microspheres; Sodium hydroxide solution is used as a template removal agent and ethanol aqueous solution is used as a solvent to dissolve the silicon dioxide microspheres coated in the titanium dioxide / silicon dioxide microspheres to form hollow nano titanium dioxide microspheres.

[0012] In some embodiments, the particle size of the prepared silica microspheres is 350 to 800 nm; The particle size of the prepared titanium dioxide / silicon dioxide microspheres is 500-1200 nm.

[0013] In some embodiments, the method for preparing the silicon dioxide nanoparticles comprises: using tetraethyl orthosilicate as a silicon source, hydrochloric acid as an initiator, and ethanol aqueous solution as a solvent to synthesize the silicon dioxide nanoparticles.

[0014] In some embodiments, the anti-glare coating liquid is coated on a substrate to form a coating layer with a thickness of 1000-2000 nm, and cured at 450-500° C. for 15-30 min to form the anti-glare coating.

[0015] The present application also provides an anti-glare coating liquid, comprising: anti-glare particles, a cross-linking agent; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

[0016] The present application also provides an anti-glare film, which is prepared by the above method; Or, the anti-glare coating liquid is coated on a substrate and then cured.

[0017] In the technical solution of the present application, hollow nano titanium dioxide microspheres with a refractive index of 2.5 are used as anti-glare particles, and silicon dioxide nanoparticles with a refractive index of 1.5 are used as cross-linking agents. The different refractive indices of the anti-glare particles and the cross-linking agent are used to make the light enter the interface with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve the anti-glare effect; the hollow part of the titanium dioxide microspheres is used to make the light refract twice and reflect multiple times when passing through the anti-glare particles, further improving the dispersion of the light, so that the light in the anti-glare The coating achieves a light dispersion effect, greatly improving the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean. At the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the multiple drawings represent the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings only depict some embodiments disclosed in the present application and should not be regarded as limiting the scope of the present application. Figure 1 Schematic diagram of the structure of the anti-glare film in the embodiment of the present application.

[0019] Numbers in the figure: 1, substrate; 2, anti-glare coating; 21, cross-linking agent; 22, anti-glare particles. DETAILED DESCRIPTION

[0020] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. In the accompanying drawings, for clarity, the sizes of layers, regions, elements and their relative sizes may be exaggerated. Wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be understood as limitations on the present application. It should be noted that, in the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0021] It should be understood that when an element or layer is referred to as "on ...", "adjacent to ...", "connected to" or "coupled to" other elements or layers, it can be directly on, adjacent to, connected to or coupled to other elements or layers, or there can be intervening elements or layers. On the contrary, when an element is referred to as "directly on ...", "directly adjacent to ...", "directly connected to" or "directly coupled to" other elements or layers, there is no intervening element or layer. It should be understood that although the terms first, second, third, etc. can be used to describe various elements, components, regions, layers and / or parts, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teachings of the present disclosure, the first element, component, region, layer or part discussed below can be represented as the second element, component, region, layer or part. And when the second element, component, region, layer or part is discussed, it does not mean that the present disclosure necessarily has the first element, component, region, layer or part.

[0022] In this application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0023] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein, for example. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0024] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for broadly including quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0025] The embodiment of the present application aims to provide an anti-glare coating liquid, an anti-glare film and a preparation method thereof, using hollow nano titanium dioxide microspheres with a refractive index of 2.5 as anti-glare particles, and using silicon dioxide nanoparticles with a refractive index of 1.5 as cross-linking agents, and utilizing the different refractive indices of the anti-glare particles and the cross-linking agent to allow light to enter interfaces with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve an anti-glare effect; utilizing the hollow part of the titanium dioxide microspheres to cause the light to undergo two refractions and multiple reflections when passing through the anti-glare particles, further improving the light The degree of dispersion makes the light achieve the effect of light dispersion inside the anti-glare coating, greatly improving the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean; at the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H.

[0026] The present application provides a method for preparing an anti-glare film, comprising: The anti-glare particles and the cross-linking agent are mixed evenly to prepare an anti-glare coating liquid; Applying the anti-glare coating liquid on a substrate and curing the liquid to form an anti-glare coating; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

[0027] In the embodiment of the present application, the substrate of the anti-glare film may include one or more of glass, ceramic tile, wood, leather, stone, alloy, paper, plastic, fiber, cotton fabric, etc.; a suitable substrate can be selected according to actual needs. In addition, the thickness of the substrate can be nanometer-level, micrometer-level, millimeter-level or centimeter-level, which can be set according to actual needs. In the embodiment of the present application, the thickness of the anti-glare coating can be nanometer-level, micrometer-level, millimeter-level or centimeter-level, and the thickness of the anti-glare coating can be limited according to actual needs.

[0028] In the embodiment of the present application, anti-glare particles and a cross-linking agent are added to an organic solvent or an adhesive and mixed evenly to prepare an anti-glare coating liquid. The type of organic solvent or adhesive can be selected according to actual needs. The method of coating the anti-glare coating liquid on the substrate can be selected from one or more of a spraying method, a roller coating method, and an immersion method.

[0029] In the embodiment of the present application, hollow nano titanium dioxide microspheres with a refractive index of 2.5 are used as anti-glare particles, and silicon dioxide nanoparticles with a refractive index of 1.5 are used as cross-linking agents. The different refractive indices of the anti-glare particles and the cross-linking agent are used to make the light enter the interface with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve the anti-glare effect; the hollow part of the titanium dioxide microspheres is used to make the light refract twice and reflect multiple times when passing through the anti-glare particles, further improving the dispersion of the light, so that the light is dispersed in the anti-glare coating. The light dispersion effect is achieved internally, which greatly improves the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean; at the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H (pencil hardness).

[0030] In an optional embodiment, the particle size of the hollow nano-titanium dioxide microspheres is 500-1200 nm (e.g., 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm); and / or The silica nanoparticles have a particle size of 3 to 5 nm (eg, 3.0 nm, 3.2 nm, 3.4 nm, 3.6 nm, 3.8 nm, 4.0 nm, 4.2 nm, 4.4 nm, 4.6 nm, 4.8 nm, 5.0 nm).

[0031] In the embodiment of the present application, the particle size of the anti-glare particles is optimized so that when light passes through the anti-glare coating, the light dispersion effect is better, thereby improving the anti-glare effect of the anti-glare film while allowing the anti-glare film to maintain a high mechanical strength.

[0032] In an optional embodiment, the anti-glare coating liquid further includes an organic solvent; the organic solvent includes one or more of an alcohol solvent, a ketone solvent, and an alcohol-water mixed solvent. In the embodiment of the present application, the addition of an organic solvent can adjust the viscosity and fluidity of the anti-glare coating liquid, which is beneficial to the coating process of the anti-glare coating liquid and reduces the coating difficulty of the anti-glare coating liquid.

[0033] In an optional embodiment, in the anti-glare coating liquid, the mass percentage of the anti-glare particles is 3-10% (for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%), and the mass percentage of the cross-linking agent is 10-15% (for example, 10%, 11%, 12%, 13%, 14%, 15%). In the embodiment of the present application, the dosage range of the anti-glare particles and the cross-linking agent is given, and the light transmission effect and anti-glare effect of the anti-glare film are better under this dosage range; in order to prepare an anti-glare film with a specific gloss and haze, the dosage of the anti-glare particles and the cross-linking agent can be continuously adjusted according to actual needs to obtain a good anti-glare effect and a suitable gloss and haze.

[0034] In an optional embodiment, the pH value of the anti-glare coating liquid is controlled at 2 to 3 (for example, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0). In the embodiment of the present application, controlling the pH value of the anti-glare coating liquid can make the anti-glare particles and the cross-linking agent disperse better in the anti-glare coating liquid, and at the same time make the curing effect of the anti-glare coating better, thereby improving the hardness and wear resistance of the anti-glare coating.

[0035] In the embodiment of the present application, the pH value of the anti-glare coating solution can be adjusted by an acidic solution and an alkaline solution. The acidic solution can include one or more of hydrochloric acid (HCl), sulfuric acid (H2SO4), acetic acid (CH3COOH), phosphoric acid, etc., for reducing the pH value of the solution; the alkaline solution can include one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonia water (NH3·H2O), sodium bicarbonate, etc., for increasing the pH value of the solution.

[0036] In an optional embodiment, the method for preparing the hollow nano-titanium dioxide microspheres includes a sacrificial template method; the method for preparing the hollow nano-titanium dioxide microspheres using the sacrificial template method includes: Silica microspheres were synthesized using ammonia water as initiator, tetraethyl orthosilicate as silicon source and ethanol aqueous solution as solvent. The silica microspheres are subjected to surface modification treatment using silane coupling agent KH-550 as a modifier to obtain modified silica microspheres; the silane coupling agent KH-550 is specifically 3-aminopropyltriethoxysilane; The modified silica microspheres are used as templates, tetrabutyl titanate is used as a titanium source, glacial acetic acid is used as an initiator, and ethanol aqueous solution is used as a solvent to synthesize titanium dioxide / silica microspheres; Sodium hydroxide solution is used as a template removal agent and ethanol aqueous solution is used as a solvent to dissolve the silicon dioxide microspheres coated in the titanium dioxide / silicon dioxide microspheres to form hollow nano titanium dioxide microspheres.

[0037] In the embodiments of the present application, the preparation method of hollow nano-titanium dioxide microspheres is optimized, which has the advantages of simple operation, low cost, and easy control of morphology and particle size. At the same time, the shell structure of the prepared hollow nano-titanium dioxide microspheres is stable, which plays a role in improving the hardness of the anti-glare coating.

[0038] In an optional embodiment, the particle size of the prepared silica microspheres is 350 to 800 nm (e.g., 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm); The particle size of the prepared titanium dioxide / silicon dioxide microspheres is 500-1200 nm (for example, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm).

[0039] In the embodiments of the present application, the particle size of the silica microspheres and the particle size of the titanium dioxide / silicon dioxide microspheres are optimized, so that the shell structure of the prepared hollow nano-titanium dioxide microspheres can be made more stable, thereby improving the hardness of the anti-glare coating.

[0040] In an optional embodiment, the method for preparing the silicon dioxide nanoparticles comprises: using tetraethyl orthosilicate as a silicon source, hydrochloric acid as an initiator, and ethanol aqueous solution as a solvent to synthesize the silicon dioxide nanoparticles. In the embodiment of the present application, the method for preparing the silicon dioxide nanoparticles is optimized to make the particle size of the prepared silicon dioxide nanoparticles more uniform, thereby further reducing the surface roughness of the anti-glare film.

[0041] In an optional embodiment, the anti-glare coating liquid is coated on a substrate to form a coating layer with a thickness of 1000-2000nm (for example, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, 1500nm, 1600nm, 1700nm, 1800nm, 1900nm, 2000nm), and cured at 450-500℃ (for example, 450℃, 460℃, 470℃, 480℃, 490℃, 500℃) for 15-30min (for example, 15min, 17min, 19min, 21min, 23min, 25min, 27min, 29min, 30min) to form the anti-glare coating. In the embodiment of the present application, optimizing the thickness and curing process of the anti-glare coating helps to improve the hardness and wear resistance of the anti-glare coating, thereby improving the mechanical properties and stability of the anti-glare coating.

[0042] The present application also provides an anti-glare coating liquid, comprising: anti-glare particles, a cross-linking agent; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

[0043] In the embodiment of the present application, hollow nano titanium dioxide microspheres with a refractive index of 2.5 are used as anti-glare particles, and silicon dioxide nanoparticles with a refractive index of 1.5 are used as cross-linking agents. The different refractive indices of the anti-glare particles and the cross-linking agent are used to make the light enter the interface with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve the anti-glare effect; the hollow part of the titanium dioxide microspheres is used to make the light refract twice and reflect multiple times when passing through the anti-glare particles, further improving the dispersion of the light, so that the light can be dispersed in the anti-glare effect. The light dispersion effect is achieved inside the optical coating, which greatly improves the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean; at the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H.

[0044] The present application also provides an anti-glare film, which is prepared by the above method; Or, the anti-glare coating liquid is coated on a substrate and then cured.

[0045] In the embodiment of the present application, an anti-glare film (such as Figure 1 As shown in FIG. 1 , the anti-glare film comprises a substrate 1 and an anti-glare coating 2 stacked on the substrate 1, wherein the anti-glare coating 2 is made of a cross-linking agent 21 and anti-glare particles 22. The advantages of the above anti-glare film are also possessed by the anti-glare film, which will not be described in detail here.

[0046] The following specific examples further illustrate the present application, but should not be construed as limiting the present application. Without departing from the spirit and substance of the present application, modifications or replacements made to the methods, steps or conditions of the present application are within the scope of the present application.

[0047] Example 1 A method for preparing an anti-glare film, comprising: (1) Synthesis of anti-glare particles: ① Add 10 ml of 25 wt% ammonia water to 100 g of ethanol aqueous solution, the mass ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 9 / 1 (i.e. 90 g of anhydrous ethanol and 10 g of deionized water), stir magnetically at 400 r / min for 5 min to mix evenly, then add 8 g of tetraethyl orthosilicate dropwise, continue stirring at room temperature for 12 h, synthesize silica nanospheres with a particle size of 350-500 nm, and wash with deionized water by centrifugation for 3-5 times; ② The silica nanospheres from which the alkali solution was removed by centrifugal water washing were redispersed in an ethanol-water solution with a mass ratio of 9 / 1, and the silane coupling agent KH-550 was added to the mixture, heated to 50°C, and magnetically stirred at a speed of 500 r / min for 60 min; ③ Add diluted glacial acetic acid solution to the mixed solution in step ②, adjust the solution pH to 2, increase the magnetic stirring speed to 900r / min, maintain a constant temperature water bath at 50°C, dilute 12g of tetrabutyl titanate with 50ml of deionized water, and dropwise add it into the mixed solution. After continuous stirring at room temperature for 2h, silica / titanium dioxide microspheres with a particle size of 500-800nm ​​are formed, and centrifugal washing is performed with deionized water for 3-5 times; ④ Re-disperse the silica / titanium dioxide microspheres from which the acid solution has been removed by centrifugation in 50 ml of deionized water, add 10 g of a 2 mol / L NaOH solution, place in a 50°C constant temperature water bath, stir magnetically at 500 r / min for 6 h, and then centrifuge and wash with water for 3-5 times to obtain hollow titanium dioxide microspheres from which the silica template has been removed; ⑤ The hollow titanium dioxide microspheres from which the alkali solution has been removed are redispersed in 20 g of an ethanol aqueous solution with a mass ratio of 9 / 1, which is recorded as solution A.

[0048] (2) Preparation of anti-glare coating liquid: ① Dissolve 0.1g of 36wt% concentrated hydrochloric acid in 50g of 9 / 1 ethanol aqueous solution, mix well, add 10g of ethyl orthosilicate dropwise, stir magnetically at room temperature for 6h, and synthesize silica nanoparticles, which is recorded as solution B; ② Mix solution A and solution B in a specific ratio to obtain an anti-glare coating solution, which is recorded as solution C. Use hydrochloric acid and ammonia water to adjust the pH value of solution C to 2.

[0049] (3) Preparation of anti-glare film: Solution C was taken and coated on a clean glass surface by spraying to form an anti-glare coating with a thickness of 1500 nm. The anti-glare coating was cured at 480°C for 20 min to obtain an anti-glare film. The prepared anti-glare film was as follows: Figure 1 shown.

[0050] Example 2-Example 4 The anti-glare films of Examples 2 to 4 were prepared by referring to the preparation method of Example 1, except that the mass ratios of solution A and solution B were different when preparing solution C in step (2). The mass ratios of solution A and solution B in solution C in Examples 1 to 4 are shown in Table 1.

[0051] Example 5 A method for preparing an anti-glare film, comprising: (1) Anti-glare particles and a cross-linking agent are mixed uniformly, and the pH value of the anti-glare coating liquid is controlled at 2.5 to prepare an anti-glare coating liquid, wherein the mass percentage of the anti-glare particles is 10%, the mass percentage of the cross-linking agent is 10%, and the balance is an ethanol aqueous solution with a mass ratio of 9 / 1; the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles; the particle size of the hollow nano titanium dioxide microspheres is 500-1200 nm; the particle size of the silicon dioxide nanoparticles is 3-5 nm; (2) Preparation of anti-glare film: Take the anti-glare coating liquid, and use the spraying process to apply the anti-glare coating liquid on the clean glass surface to form an anti-glare coating layer with a thickness of 1500 nm. Curing at 480°C for 20 minutes to prepare the anti-glare film.

[0052] Example 6 The anti-glare film of Example 6 was prepared by referring to the preparation method of Example 5, except that: The step (1) in Example 6 is: the anti-glare particles and the cross-linking agent are mixed uniformly, and the pH value of the anti-glare coating liquid is controlled at 1.5 to prepare the anti-glare coating liquid, wherein the mass percentage of the anti-glare particles is 10%, the mass percentage of the cross-linking agent is 10%, and the remainder is an ethanol aqueous solution with a mass ratio of 9 / 1; the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles; the particle size of the hollow nano titanium dioxide microspheres is 500-1200 nm; and the particle size of the silicon dioxide nanoparticles is 3-5 nm.

[0053] Example 7 The anti-glare film of Example 7 was prepared by referring to the preparation method of Example 5, except that: The step (1) in Example 7 is: the anti-glare particles and the cross-linking agent are mixed uniformly, and the pH value of the anti-glare coating liquid is controlled at 3.5 to prepare the anti-glare coating liquid, wherein the mass percentage of the anti-glare particles is 10%, the mass percentage of the cross-linking agent is 10%, and the remainder is an ethanol aqueous solution with a mass ratio of 9 / 1; the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles; the particle size of the hollow nano titanium dioxide microspheres is 500-1200 nm; the particle size of the silicon dioxide nanoparticles is 3-5 nm.

[0054] Example 8 The anti-glare film of Example 8 was prepared by referring to the preparation method of Example 5, except that: The step (1) in Example 8 is: the anti-glare particles and the cross-linking agent are mixed uniformly, and the pH value of the anti-glare coating liquid is controlled at 2.5 to prepare the anti-glare coating liquid, wherein the mass percentage of the anti-glare particles is 10%, the mass percentage of the cross-linking agent is 10%, and the remainder is an ethanol aqueous solution with a mass ratio of 9 / 1; the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles; the particle size of the hollow nano titanium dioxide microspheres is 300-700 nm; and the particle size of the silicon dioxide nanoparticles is 3-5 nm.

[0055] Example 9 The anti-glare film of Example 9 was prepared by referring to the preparation method of Example 5, except that: The step (1) in Example 9 is: the anti-glare particles and the cross-linking agent are mixed uniformly, and the pH value of the anti-glare coating liquid is controlled at 2.5 to prepare the anti-glare coating liquid, wherein the mass percentage of the anti-glare particles is 10%, the mass percentage of the cross-linking agent is 10%, and the remainder is an ethanol aqueous solution with a mass ratio of 9 / 1; the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles; the particle size of the hollow nano titanium dioxide microspheres is 1000-1600 nm; and the particle size of the silicon dioxide nanoparticles is 3-5 nm.

[0056] Comparative Example 1-Comparative Example 4 The anti-glare films of Comparative Examples 1-4 were prepared according to the preparation method of Example 1, except that: The preparation method of solution A in specific embodiment 1 is changed, the anti-glare particle synthesis step ④ is removed, and the silica template is not removed, that is, the silica-coated titanium dioxide microspheres are directly used as anti-glare particles.

[0057] Comparative Example 5-Comparative Example 8 A conventional anti-glare coating liquid on the market is used, and a rough surface is formed on a clean glass surface by spraying to achieve an anti-glare effect and form an anti-glare film. The difference between Comparative Examples 5 to 8 is that the optical properties of the anti-glare film are adjusted by adjusting the spraying parameters and the coating thickness. When the glossiness is lower and the haze is higher, the surface roughness of the coating is higher. The spraying parameters and coating thickness parameters of Comparative Examples 5 to 8 are detailed in Table 3.

[0058] The test results of the anti-glare films prepared in the above examples and comparative examples are shown in Tables 1 to 3 below.

[0059] Table 1

[0060] Table 2

[0061] Table 3

[0062] Referring to the test data of the above-mentioned Examples 1-9 and Comparative Examples 1-8, it can be seen that hollow nano titanium dioxide microspheres with a refractive index of 2.5 are used as anti-glare particles, and silicon dioxide nanoparticles with a refractive index of 1.5 are used as cross-linking agents. The different refractive indices of the anti-glare particles and the cross-linking agent are utilized to make the light enter the interface with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve the anti-glare effect; the hollow part of the titanium dioxide microspheres is utilized to make the light refract twice and reflect multiple times when passing through the anti-glare particles, further improving the dispersion degree of the light. The degree of glare dispersion can achieve the effect of light dispersion inside the anti-glare coating, greatly improving the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean; at the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H.

[0063] Referring to the test data of the above-mentioned Example 5 and Examples 6-7, it can be known that controlling the pH value of the anti-glare coating liquid can make the anti-glare particles and the cross-linking agent dispersed in the anti-glare coating liquid better, and at the same time make the curing effect of the anti-glare coating better, thereby improving the hardness and wear resistance of the anti-glare coating.

[0064] Referring to the test data of the above-mentioned Example 5 and Examples 8-9, it can be seen that when the particle size of the anti-glare particles is larger, the mechanical strength of the coating decreases, and when the particle size is smaller, the anti-glare effect decreases; by optimizing the particle size of the anti-glare particles, when light enters the anti-glare coating, a good light dispersion effect can be achieved while maintaining a high mechanical strength.

[0065] In summary, the present invention uses hollow nano titanium dioxide microspheres with a refractive index of 2.5 as anti-glare particles and silicon dioxide nanoparticles with a refractive index of 1.5 as cross-linking agents, and utilizes the different refractive indices of the anti-glare particles and the cross-linking agent to allow light to enter interfaces with different refractive indices, change the propagation direction of the light, and then disperse the concentrated incident light to achieve an anti-glare effect; utilizes the hollow part of the titanium dioxide microspheres to cause the light to refract twice and reflect multiple times when passing through the anti-glare particles, further improving the degree of light dispersion and making the light more effective in the anti-glare effect. The light dispersion effect is achieved inside the optical coating, which greatly improves the anti-glare effect of the anti-glare film. There is no need to use the rough surface of the anti-glare film to improve the anti-glare effect, so that the surface of the anti-glare film is smooth (surface roughness Ra≤0.05), not easy to accumulate dust, and easy to clean; at the same time, due to the presence of the hollow part of the titanium dioxide microspheres, the gloss and haze of the anti-glare film can be adjusted in a wide range. The gloss control range of the anti-glare film is 30-140%, and the haze control range is 0-30%. The anti-glare coating has high mechanical strength and a hardness of 7-9H.

[0066] It should be noted that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present application. The orientation words "inside" and "outside" refer to the inside and outside relative to the outline of each component itself. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Therefore, the exemplary term "above..." can include both "above..." and "below..." orientations. The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used here are interpreted accordingly.

[0067] It should also be noted that "one embodiment", "another embodiment", "embodiment", etc. mentioned in this application refer to the specific features, structures or characteristics described in conjunction with the embodiment included in at least one embodiment generally described in this application. The same expression appearing in multiple places in the specification does not necessarily refer to the same embodiment. Further, when describing a specific feature, structure or characteristic in conjunction with any embodiment, it is claimed that the realization of such feature, structure or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0068] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0069] It should also be noted that the above are only preferred embodiments of the present application, and the patent protection scope of the present application is not limited thereto. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for preparing an anti-glare film, characterized in that: include: The anti-glare particles and the cross-linking agent are mixed evenly to prepare an anti-glare coating liquid; Applying the anti-glare coating liquid on a substrate and curing the liquid to form an anti-glare coating; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

2. The method according to claim 1, characterized in that: The particle size of the hollow nano titanium dioxide microspheres is 500 to 1200 nm; and / or The particle size of the silicon dioxide nanoparticles is 3-5 nm.

3. The method according to claim 1, characterized in that The anti-glare coating liquid also includes an organic solvent; the organic solvent includes one or more of an alcohol solvent, a ketone solvent, and an alcohol-water mixed solvent.

4. The method according to claim 1, characterized in that: In the anti-glare coating liquid, the mass percentage of the anti-glare particles is 3-10%, and the mass percentage of the cross-linking agent is 10-15%.

5. The method according to claim 1, characterized in that The pH value of the anti-glare coating liquid is controlled at 2-3.

6. The method according to claim 1, characterized in that The method for preparing the hollow nano titanium dioxide microspheres includes a sacrificial template method; the method for preparing the hollow nano titanium dioxide microspheres using the sacrificial template method includes: Silica microspheres were synthesized using ammonia water as initiator, tetraethyl orthosilicate as silicon source and ethanol aqueous solution as solvent. Using silane coupling agent KH-550 as a modifier, performing surface modification treatment on the silica microspheres to obtain modified silica microspheres; The modified silica microspheres are used as templates, tetrabutyl titanate is used as a titanium source, glacial acetic acid is used as an initiator, and ethanol aqueous solution is used as a solvent to synthesize titanium dioxide / silica microspheres; Sodium hydroxide solution is used as a template removal agent and ethanol aqueous solution is used as a solvent to dissolve the silicon dioxide microspheres coated in the titanium dioxide / silicon dioxide microspheres to form hollow nano titanium dioxide microspheres.

7. The method according to claim 6, characterized in that The particle size of the prepared silica microspheres is 350 to 800 nm; The particle size of the prepared titanium dioxide / silicon dioxide microspheres is 500-1200 nm.

8. The method according to claim 1, characterized in that The method for preparing silicon dioxide nanoparticles comprises: using tetraethyl orthosilicate as a silicon source, hydrochloric acid as an initiator and ethanol aqueous solution as a solvent to synthesize the silicon dioxide nanoparticles.

9. The method according to claim 1, characterized in that: The anti-glare coating liquid is coated on a substrate to form a coating layer with a thickness of 1000-2000 nm, and the anti-glare coating layer is cured at 450-500° C. for 15-30 minutes to form the anti-glare coating layer.

10. An anti-glare coating liquid, characterized in that: include: Anti-glare particles, cross-linking agent; Wherein, the anti-glare particles are hollow nano titanium dioxide microspheres, and the cross-linking agent is silicon dioxide nanoparticles.

11. An anti-glare film, characterized in that: Prepared by the method according to any one of claims 1 to 9; Or, the anti-glare coating liquid as claimed in claim 10 is coated on a substrate and then cured.

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