Anti-reflection filler, anti-reflection coating, anti-reflection film and preparation method

Abstract

The invention discloses an anti-reflection filler, an anti-reflection coating, an anti-reflection film and a preparation method, the anti-reflection filler is formed by wrapping hollow silicon dioxide particles with aluminum oxide, and the mass of the aluminum oxide is 10-25% of that of the hollow silicon dioxide particles. The anti-reflection coating comprises the following raw materials in percentage by weight: 1%-3% of fluorine-containing acrylic resin, 0.6%-3% of anti-reflection filler, 0.05%-3% of a photoinitiator and the balance of a solvent. The anti-reflection coating is adopted to prepare the anti-reflection film, so that the anti-reflection film has the properties of high transmittance, low reflectivity and excellent wear resistance, and the reflectivity is slightly influenced by water vapor in air.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical films, and in particular relates to an anti-reflection filler, an anti-reflection coating, an anti-reflection film and a preparation method thereof. Background Art

[0002] With the rapid development of the display industry, people's requirements for displays are becoming increasingly higher. Liquid crystal displays (LCDs) are highly popular due to their large viewing area, excellent visual quality, and low energy consumption. The design of LCDs is also moving towards high definition and high contrast. However, because displays are easily affected by external light sources during use, it is necessary to reduce reflections caused by external light sources to improve their visual quality. Therefore, it is necessary to apply anti-reflection treatment to the surface of the display screen, using an anti-reflection hardened film layer to reduce reflections on the image display surface and improve its transmittance.

[0003] Currently, the anti-reflective films used on display screen surfaces on the market have various functions. However, they generally have the problem of insufficient wear resistance. Moreover, after long-term use, the film is easily affected by water vapor in the air, resulting in increased reflectivity and decreased transmittance. Therefore, the performance needs to be further improved. Summary of the Invention

[0004] The purpose of the present invention is to provide an anti-reflective filler, an anti-reflective coating, an anti-reflective film and a preparation method. The hollow silica particles are used to prepare the anti-reflective film, which can effectively improve the wear resistance and water resistance of the anti-reflective film.

[0005] In order to achieve the above object, a specific embodiment of the present invention provides the following technical solutions:

[0006] An anti-reflection filler comprises hollow silica particles coated with aluminum oxide, wherein the mass of the aluminum oxide is 10% to 25% of the mass of the hollow silica particles.

[0007] In one or more embodiments of the present invention, the particle size of the hollow silica particles is 50 nm-80 nm.

[0008] Another specific embodiment of the present invention provides a technical solution as follows:

[0009] A method for preparing an anti-reflective filler comprises the following steps:

[0010] The hollow silica particles, polyol and water are mixed, stirred for 1-2 hours, centrifuged and filtered, and treated at 110-130° C. for 1-3 hours to obtain pretreated hollow silica particles;

[0011] The pretreated hollow silica particles, soluble aluminum salt and water are mixed, then mixed with alkali to react for 0.7h-1.5h, treated at 110℃-130℃ for 1.5h-3h to remove water, and then calcined at 400℃-500℃ for 3h-5h to obtain hollow silica particles with aluminum oxide coated on the surface.

[0012] In one or more embodiments of the present invention, the mass ratio of the hollow silica particles to the polyol is 1:(5-15).

[0013] In one or more embodiments of the present invention, the polyol is at least one of aliphatic polyol, aromatic polyol, polyether polyol, polyester polyol, and polymer polyol.

[0014] In one or more embodiments of the present invention, the soluble aluminum salt is at least one of aluminum chloride hexahydrate, aluminum sulfate, and aluminum nitrate.

[0015] Another specific embodiment of the present invention provides a technical solution as follows:

[0016] An anti-reflective coating comprises the following raw materials in weight percentage: 1%-3% fluorine-containing acrylic resin, 0.6%-3% anti-reflective filler, 0.05%-3% photoinitiator, and the balance being solvent;

[0017] Wherein, the anti-reflection filler is the above-mentioned anti-reflection filler.

[0018] In one or more embodiments of the present invention, the mass of the anti-reflection filler is 60%-100% of the fluorine-containing acrylic resin.

[0019] In one or more embodiments of the present invention, the fluorine-containing acrylic resin is at least one of fluorine-containing polyurethane acrylate, fluorine-containing polyester acrylate, and fluorine-containing acrylate.

[0020] Another specific embodiment of the present invention provides a technical solution as follows:

[0021] An anti-reflection film is formed by using the above anti-reflection coating as a main raw material.

[0022] Compared to the prior art, the present invention uses aluminum oxide to encapsulate hollow silica particles. Leveraging the protective effect of aluminum oxide on the hollow silica particles, the present invention not only improves the wear resistance of the anti-reflection film but also prevents moisture from binding to the hollow silica particles, leading to increased humidity and, in turn, an increase in the reflectivity of the anti-reflection film. Furthermore, the addition of hollow silica particles to the anti-reflection film can reduce the film's refractive index, improving its transmittance and wear resistance. Furthermore, the use of a fluorine-containing acrylic resin in the anti-reflection film gives the film a compact, orderly internal structure, reducing light scattering and refraction within the film, thereby improving the film's transmittance, hardness, and wear resistance while reducing its reflectivity. DETAILED DESCRIPTION

[0023] To help those skilled in the art better understand the technical solutions of the present disclosure, the following clearly and completely describes the technical solutions in the embodiments of the present disclosure. Obviously, the described embodiments are only a portion of the embodiments of the present disclosure, not all of them. All other embodiments derived by those skilled in the art based on the embodiments of the present disclosure without creative effort should fall within the scope of protection of the present disclosure.

[0024] A specific embodiment of the present invention provides an anti-reflection filler, which is hollow silica particles coated with aluminum oxide, and the mass of the aluminum oxide is 10%-25% of the hollow silica particles.

[0025] Specifically, using alumina to encapsulate hollow silica particles can reduce the film's refractive index, increase its transmittance, and enhance its wear resistance when used to create an anti-reflective film. This reduces the impact of the high-refractive-index alumina on the film's reflectivity. Furthermore, the alumina coating prevents the increase in reflectivity caused by moisture combining with the hollow silica particles in high humidity.

[0026] Furthermore, the particle size of the hollow silica particles is 50 nm to 80 nm.

[0027] Specifically, when the particle size of the hollow silica particles is less than 50 nm, when used in anti-reflective coatings, the hollow silica particles do not refract light sufficiently and the reflectivity does not decrease significantly; when the particle size is higher than 80 nm, the hollow silica particles are easily precipitated from the coating surface, resulting in poor wear resistance of the coating, a decrease in the water contact angle, and a greater influence of water vapor.

[0028] Another specific embodiment of the present invention provides a method for preparing an anti-reflective filler, comprising steps 1-2.

[0029] Step 1: Mix hollow silica particles, polyol and water, stir for 1-2 hours, centrifuge and filter, and treat at 110-130° C. for 1-3 hours to obtain pretreated hollow silica particles.

[0030] Specifically, the stirring speed is 400 rpm-600 rpm, the mass ratio of the hollow silica particles to the polyol is 1:(5-15), the polyol is at least one of an aliphatic polyol, an aromatic polyol, a polyether polyol, a polyester polyol, and a polymer polyol, and specifically at least one of pentaerythritol, propylene glycol, glycerol, butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, xylitol, sorbitol, polyglycerol, polytetramethylene glycol, polycaprolactone polyol, diethylene glycol, dipropylene glycol, and polycarbonate diol.

[0031] Using polyols to wrap hollow silica particles can, on the one hand, increase the hydroxyl groups on the surface of the hollow silica and increase the number of its reactive groups. On the other hand, the polyols can also exist in the hollow pores of the hollow silica particles, playing a role in protecting the hollow pores.

[0032] Step 2: Mix the pretreated hollow silica particles, soluble aluminum salt and water, then mix with alkali to react for 0.7h-1.5h, treat at 110℃-130℃ for 1.5h-3h to remove water, and then calcine at 400℃-500℃ for 3h-5h to obtain hollow silica particles with alumina coated on the surface.

[0033] Specifically, the soluble aluminum salt is at least one of aluminum chloride hexahydrate (AlCl3·6H2O), aluminum sulfate (Al2(SO4)3), and aluminum nitrate (Al(NO3)3). The base can be sodium hydroxide or aqueous ammonia, with the base dosage being 3-3.5 times the mass of the soluble aluminum salt. Specifically, the pretreated hollow silica particles and the soluble aluminum salt are dispersed in water, with the base then added. The reaction is stirred at 150-250 rpm, allowing the generated aluminum hydroxide to slowly grow on the surface of the polyol-coated hollow silica. The resulting aluminum hydroxide is then heated and baked to evaporate and remove water.

[0034] Finally, calcination converts the aluminum hydroxide into aluminum oxide, while simultaneously removing the polyol that protects the pores within the hollow silica particles, leaving the pores intact and ensuring their reflectivity remains unchanged. The refractive index of the untreated hollow silica particles is 1.16-1.20, while the refractive index of the treated hollow silica particles is 1.21-1.25.

[0035] Another specific embodiment of the present invention provides an anti-reflective coating, comprising the following raw materials in weight percentage: 1%-3% fluorine-containing acrylic resin, 0.6%-3% anti-reflective filler, 0.05%-3% photoinitiator, and the balance being solvent, and the anti-reflective filler is the above-mentioned anti-reflective filler.

[0036] Specifically, adding anti-reflective fillers to the anti-reflective coating system can, on the one hand, reduce the refractive index of the coating and increase the transmittance of the coating. On the other hand, aluminum oxide, as a metal, can effectively improve the wear resistance and hardness of the coating. Moreover, aluminum oxide protects the hollow silica particles, preventing water vapor from reacting with the hydroxyl groups on the surface of the hollow silica particles, thereby reducing the possibility of the coating reflectivity being affected by water vapor.

[0037] Furthermore, the mass of the anti-reflection filler is 60%-100% of the fluorine-containing acrylic resin, preferably 70%-90%. Too much anti-reflection filler can easily reduce the wear resistance of the coating, while too little can result in a high reflectivity of the coating.

[0038] Furthermore, the fluorine-containing acrylic resin is at least one of fluorine-containing polyurethane acrylate, fluorine-containing polyester acrylate, and fluorine-containing acrylate.

[0039] Specifically, the refractive index of the fluorine-containing acrylic resin is 1.35-1.45. The fluorine-containing acrylic resin can give the coating low reflectivity, high water contact angle and excellent wear resistance, thereby improving the coating's ability to withstand the influence of water vapor.

[0040] Furthermore, the photoinitiator can be selected from common types, such as BASF DAROCUR1173; the solvent is specifically at least one of butyl acetate, methyl isobutyl ketone, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, cyclohexanone, diacetone alcohol, n-propanol, isopropanol, n-butanol, isobutanol, ethanol, ethylene glycol, and methanol.

[0041] Another specific embodiment of the present invention provides an anti-reflection film formed with the above anti-reflection coating as a main raw material.

[0042] Specifically, during the preparation, the anti-reflection coating is coated on the substrate, dried at 70° C.-90° C. for 1 min-3 min, and then irradiated with ultraviolet light to form an anti-reflection layer (LR layer) to prepare the anti-reflection film.

[0043] The substrate material is any one of polyethylene terephthalate (PET), cellulose triacetate (TAC), polymethyl methacrylate (PMMA), polyimide (PI), cycloolefin polymer (COP), polypropylene (PP), polyethylene (PE), and polycarbonate (PC) films, with a thickness of 20 μm to 100 μm, preferably 25 μm to 80 μm. By selecting a transparent substrate of appropriate thickness, the film achieves high transmittance and low reflectivity.

[0044] The thickness of the anti-reflective layer on the substrate is 80-120 nm, preferably 90-110 nm. When the solid content is 3%, the coating liquid coating thickness is 120 nm; when the solid content is 2%, the coating liquid coating thickness is 100 nm; and when the solid content is 1%, the coating liquid coating thickness is 80 nm. If the thickness of the anti-reflective layer is too thick or too thin, the refractive effect will be affected, thereby causing the transmittance to decrease, the reflectance to increase, and the rainbow stripe to be obvious. Moreover, if the thickness is too thin, the hollow silica particles will be exposed on the surface, resulting in poor surface wear resistance and a reduced water contact angle.

[0045] The application will be further described in detail below in combination with specific examples.

[0046] Example 1

[0047] 2 g of hollow silica particles TL001 (Ningbo Te Particle, particle size 70 nm) and 20 g of pentaerythritol were dissolved in 200 g of distilled water, the solution was stirred at 500 rpm for 1 h, then the solid was centrifuged, and the pentaerythritol-coated hollow silica was obtained by baking at 120°C for 2 h. Then 1 g of the pentaerythritol-coated hollow silica powder and 0.5 g of aluminum sulfate solid were dissolved in 100 g of aqueous solution, then 32 g of 5% mass concentration sodium hydroxide solution was slowly added, and the mixture was stirred at 200 rpm for 1 h to allow the generated aluminum hydroxide to slowly grow on the surface of the pentaerythritol-coated hollow silica. After evaporation of the water solvent by baking at 120°C for 2 h, the pentaerythritol in the hollow pores was removed by calcination at 400°C in a muffle furnace, thereby obtaining aluminum oxide-coated hollow silica TL001-A.

[0048] 2 parts by weight of a fluorine-containing polyurethane acrylate resin (Sun Chemical SD339) was dissolved in a mixed solvent of methyl isobutyl ketone and diacetone alcohol at a mass ratio of 1:1, then 2 parts by weight of aluminum oxide-coated hollow silica TL001-A particles and 0.1 parts by weight of 1173 photoinitiator were added. The fluorine-containing polyurethane acrylate resin content in the system was adjusted to 2% using the mixed solvent, thereby obtaining an anti-reflective coating.

[0049] The anti-reflective coating was coated on a PET substrate (Japan Toyo Weave, product name TA048, thickness 80 μm), dried in a 80°C circulating oven for 2 min, and then irradiated with ultraviolet light at a dose of about 400 mJ / cm 2 for 10 s to obtain an anti-reflective film.

[0050] Example 2

[0051] Take 2g of hollow silica particles TL002 (Ningbo particles, particle size 50nm) and 20g of polyethylene glycol (molecular weight 200) and dissolve them in 200g of distilled water, stir the solution at 500rpm for 1h, then centrifuge the solid, and bake it at 120℃ for 2h to achieve polyethylene glycol-coated hollow silica, then take 1g of polyethylene glycol-coated hollow silica powder and 0.95g AlCl3·6H2O and dissolve them together in 100g of aqueous solution, then slowly add 58.714g of 5% mass concentration of sodium hydroxide solution, stir at 200rpm for 1h, so that the generated aluminum hydroxide slowly grows on the surface of the polyethylene glycol-coated hollow silica, bake at 120℃ for 2h to evaporate the water solvent, and then calcine at 400℃ in a muffle furnace to remove the polyethylene glycol in the hollow pores, thereby obtaining alumina-coated hollow silica TL002-A.

[0052] 1 part by weight of fluorinated acrylate resin (Hesheng Chemical 2304) was dissolved in propylene glycol methyl ether solvent, and then 0.6 parts by weight of alumina-coated hollow silica TL002-A particles and 0.05 parts by weight of 1173 photoinitiator were added. The fluorinated acrylate resin content in the system was adjusted to 1% using a solvent to obtain an anti-reflective coating.

[0053] The anti-reflective coating was coated on a PMMA substrate (Sichuan Longhua, product name PU-H404, thickness 40 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then exposed to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0054] Example 3

[0055] Take 2g of hollow silica particles TL003 (Ningbo particles, particle size 80nm) and 20g of glycerol and dissolve them in 200g of distilled water. The solution is stirred at 500rpm for 1h, then centrifuged to remove the solid, and baked at 120℃ for 2h to achieve glycerol-coated hollow silica. Then take 1g of glycerol-coated hollow silica powder and 1.04g of aluminum nitrate and dissolve them together in 100g of aqueous solution. Then, 72.8g of 5% mass concentration of sodium hydroxide solution is slowly added and stirred at 200rpm for 1h to allow the generated aluminum hydroxide to slowly grow on the surface of the glycerol-coated hollow silica. After baking at 120℃ for 2h to evaporate the water solvent, it is then calcined at 400℃ in a muffle furnace to remove the glycerol in the hollow pores to obtain alumina-coated hollow silica TL003-A.

[0056] 3 parts by weight of fluorine-modified polyurethane acrylate (Changxing Chemical 61998) was dissolved in propylene glycol methyl ether acetate solvent, and then 2 parts by weight of alumina-coated hollow silica TL003-A particles and 0.1 parts by weight of 1173 photoinitiator were added. The solvent was used to adjust the content of fluorine-modified polyurethane acrylate in the system to 3% to obtain an anti-reflective coating.

[0057] The anti-reflective coating was coated on a TAC substrate (Hyosung, Korea, product name PG601F, thickness 60 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then exposed to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0058] Comparative Example 1

[0059] The difference between this comparative example and Example 3 is that 0.8 parts by weight of fluorine-modified polyurethane acrylate (Changxing Chemical 61998) is dissolved in propylene glycol methyl ether acetate solvent, and then 0.8 parts by weight of alumina-coated hollow silica TL003-A particles and 0.05 parts by weight of 1173 photoinitiator are added, and the solvent is used to adjust the content of fluorine-modified polyurethane acrylate in the system to 0.8% to obtain an anti-reflective coating.

[0060] The anti-reflective coating was coated on a TAC substrate (Hyosung, Korea, product name PG601F, thickness 60 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then exposed to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0061] Comparative Example 2

[0062] The difference between this comparative example and Example 3 is that 3.5 parts by weight of fluorine-modified polyurethane acrylate (Changxing Chemical 61998) is dissolved in propylene glycol methyl ether acetate solvent, and then 3 parts by weight of alumina-coated hollow silica TL003-A particles and 0.2 parts by weight of 1173 photoinitiator are added. The solvent is used to adjust the content of fluorine-modified polyurethane acrylate in the system to 3.5% to obtain an anti-reflective coating.

[0063] The anti-reflective coating was coated on a TAC substrate (Hyosung, Korea, product name PG601F, thickness 60 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then exposed to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0064] Comparative Example 3

[0065] The difference between this comparative example and Example 2 is that: 2 parts by weight of an aliphatic polyurethane acrylate resin (Changxing 61457) is dissolved in a butyl acetate solvent, and then 2 parts by weight of alumina-coated hollow silica TL002-A particles and 0.1 parts by weight of an 1173 photoinitiator are added, and the content of the aliphatic polyurethane acrylate resin in the system is adjusted to 2% using a solvent to obtain an anti-reflective coating.

[0066] Comparative Example 4

[0067] The difference between this comparative example and Example 3 is that 3 parts by weight of fluorine-modified polyurethane acrylate (Changxing Chemical 61998) is dissolved in propylene glycol methyl ether acetate solvent, and then 0.2 parts by weight of 1173 photoinitiator is added, and the solvent is used to adjust the content of fluorine-modified polyurethane acrylate in the system to 3% to obtain an anti-reflective coating.

[0068] Comparative Example 5

[0069] The difference between this comparative example and Example 3 is that: 3 parts by weight of fluorine-modified polyurethane acrylate (Changxing Chemical 61998) is dissolved in propylene glycol methyl ether acetate solvent, and then 3.3 parts by weight of alumina-coated hollow silica TL003-A particles and 0.1 parts by weight of 1173 photoinitiator are added, and the solvent is used to adjust the content of fluorine-modified polyurethane acrylate in the system to 3% to obtain an anti-reflective coating.

[0070] Comparative Example 6

[0071] The difference between this comparative example and Example 1 is that the surface of the hollow silica particles is not coated with aluminum oxide.

[0072] 2 parts by weight of a fluorinated polyurethane acrylate resin (Songda SD339) was dissolved in a mixed solvent of methyl isobutyl ketone and diacetone alcohol in a mass ratio of 1:1, and then 1.2 parts by weight of hollow silica particles TL001 (Ningbo particles, particle size 70 nm) and 0.1 parts by weight of a 1173 photoinitiator were added. The solvent was used to adjust the content of the fluorinated polyurethane acrylate resin in the system to 2% to obtain an anti-reflective coating.

[0073] Comparative Example 7

[0074] Take 2g of hollow silica particles TL004 (Ningbo particles, particle size 40nm) and 20g of pentaerythritol and dissolve them in 200g of distilled water, stir the solution at 500rpm for 1h, then centrifuge the solid, and bake it at 120℃ for 2h to achieve pentaerythritol-coated hollow silica, then take 1g of pentaerythritol-coated hollow silica powder and 0.5g of aluminum sulfate solid, dissolve them together in 100g of aqueous solution, then slowly add 32g of 5% mass concentration of sodium hydroxide solution, stir at 200rpm for 1h, so that the generated aluminum hydroxide slowly grows on the surface of the pentaerythritol-coated hollow silica, bake at 120℃ for 2h to evaporate the water solvent, and then calcine at 400℃ in a muffle furnace to remove the pentaerythritol in the hollow pores, and obtain alumina-coated hollow silica TL004-A.

[0075] Preparation of anti-reflective coating: 3 parts by weight of fluorinated polyurethane acrylate resin (Songda SD339) was dissolved in a mixed solvent of methyl isobutyl ketone and diacetone alcohol in a mass ratio of 1:1, and then 3 parts by weight of alumina-coated hollow silica TL004-A particles and 0.2 parts by weight of 1173 photoinitiator were added. The content of fluorinated polyurethane acrylate resin in the system was adjusted to 2% using solvent to obtain an anti-reflective coating.

[0076] The anti-reflective coating was coated on a PET substrate (Toyobo, Japan, product name TA048, thickness 80 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then subjected to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0077] Comparative Example 8

[0078] Take 2g of hollow silica particles TL005 (Ningbo particles, particle size 90nm) and 20g of pentaerythritol and dissolve them in 200g of distilled water. The solution is stirred at 500rpm for 1h, then the solid is centrifuged and baked at 120℃ for 2h to achieve pentaerythritol-coated hollow silica. Then, take 1g of pentaerythritol-coated hollow silica powder and 0.5g of aluminum sulfate solid and dissolve them together in 100g of aqueous solution. Then, 32g of 5% mass concentration of sodium hydroxide solution is slowly added and stirred at 200rpm for 1h to allow the generated aluminum hydroxide to slowly grow on the surface of the hollow silica coated with pentaerythritol. After baking at 120℃ for 2h to evaporate the water solvent, the solution is calcined at 400℃ in a muffle furnace to remove the pentaerythritol in the hollow pores, thereby obtaining alumina-coated hollow silica TL005-A.

[0079] Preparation of anti-reflective coating: 3 parts by weight of fluorinated polyurethane acrylate resin (Songda SD339) was dissolved in a mixed solvent of methyl isobutyl ketone and diacetone alcohol in a mass ratio of 1:1, and then 3 parts by weight of alumina-coated hollow silica TL005-A particles and 0.2 parts by weight of 1173 photoinitiator were added. The content of fluorinated polyurethane acrylate resin in the system was adjusted to 2% using solvent to obtain an anti-reflective coating.

[0080] The anti-reflective coating was coated on a PET substrate (Toyobo, Japan, product name TA048, thickness 80 μm), placed in an 80 ° C circulation oven to dry for 2 minutes, and then subjected to a dose of about 400 mJ / cm 2 The anti-reflection film was prepared by irradiating the film with ultraviolet light for 10 seconds.

[0081] The following tests were performed on the membrane materials in each embodiment and each comparative example:

[0082] (1) Test the total light transmittance and haze according to JIS K7105-1981 "Test methods for optical properties of plastics";

[0083] (2) Test the water contact angle according to GB / T 30693-2014 “Measurement of the contact angle of plastic films with water”;

[0084] (3) Test pencil hardness according to JIS K5400-1990 "Determination of adhesion properties of powder coatings";

[0085] (4) The wear resistance of the film was tested according to HG / T 4303-2012 "Test method for wear resistance of surface hardened polyester film" using 0000# steel wool, 500gf / cm 2 Load, by testing the wear resistance limit of the diaphragm surface without scratches, to determine the wear resistance of the film. The higher the wear resistance, the better the effect.

[0086] (5) Test the reflectivity of the film according to the standard HG / T 4915-2016 “Determination of reflectivity of white reflective film”;

[0087] (6) The film thickness of the HC layer and the LR layer of the film was measured by scanning electron microscopy.

[0088] (7) According to the standard of GB / T 30693-2014 “Measurement of the contact angle of plastic film with water”, the water contact angle is tested; the rainbow pattern of the material is determined by measuring the red and green difference under the reflected light of the film attached to a black screen, where ○ represents no rainbow pattern, □ represents slight rainbow pattern, and × represents severe rainbow pattern.

[0089] Table 1 Performance test results

[0090]

[0091]

[0092] From table 1, using fluorine-containing acrylic resin to prepare anti-reflective coating, due to the low refractive index of fluorine-containing resin, the interference effect can offset the reflected light, and the fluorine resin forms a nanoscale rough surface or porous structure after film forming, which reduces the scattering and refraction phenomenon of light propagation in the resin, thereby improving the transmittance, water contact angle, pencil hardness and wear resistance of the material, and reducing the reflectivity.

[0093] The thickness of the anti-reflective layer (LR layer) in the anti-reflective film is within a certain range, the transmittance is high, the reflectivity is low, the wear resistance is good, the water contact angle is high, and the rainbow stripe is good, the thickness of the LR layer is too thin or too thick, the refraction effect will be poor, resulting in a decrease in transmittance, an increase in reflectivity and a more obvious rainbow stripe. The thinner the LR layer, the more the hollow silica particles are exposed on the surface, resulting in poor surface wear resistance and reduced water contact angle.

[0094] The present application adds a certain amount and particle size of hollow silica particles within a certain range in the anti-reflective coating, which changes the refraction of light inside the coating, thereby improving the transmittance, reducing the reflectivity and improving the rainbow stripe.

[0095] The present application can ensure the chemical stability of the material surface by coating the hollow silica with aluminum oxide, enhance the rigidity and conductivity of the surface, thereby improving the wear resistance, hardness and antistatic property of the material, further improve the wear resistance and water contact angle of the material, and further reduce the influence of water vapor on the reflectivity of the material. In addition, if the particle size of the hollow silica is too large or too small, the refraction of light will be weakened, resulting in a decrease in transmittance and an increase in reflectivity. Therefore, the present application selects hollow silica particles with a particle size within a certain range, which effectively ensures that the anti-reflective film has a low reflectivity.

[0096] It is apparent to those skilled in the art that the present disclosure is not limited to the details of the foregoing exemplary embodiments, and that the present disclosure can be implemented in other concrete forms without departing from the spirit or essential characteristics of the present disclosure. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, the scope of the present disclosure being defined by the appended claims rather than the foregoing description, and it is intended to encompass all changes and modifications that fall within the meaning and scope of equivalents of the claims.

[0097] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. An anti-reflective filler, characterized in that: The hollow silica particles are coated with alumina, and the mass of the alumina is 10%-25% of the hollow silica particles.

2. The anti-reflection filler according to claim 1, wherein The particle size of the hollow silica particles is 50nm-80nm.

3. A method for preparing an anti-reflective filler, characterized in that: The steps include: The hollow silica particles, polyol and water are mixed, stirred for 1-2 hours, centrifuged and filtered, and treated at 110-130° C. for 1-3 hours to obtain pretreated hollow silica particles; The pretreated hollow silica particles, soluble aluminum salt and water are mixed, then mixed with alkali to react for 0.7h-1.5h, treated at 110℃-130℃ for 1.5h-3h to remove water, and then calcined at 400℃-500℃ for 3h-5h to obtain hollow silica particles with aluminum oxide coated on the surface.

4. The method for preparing the anti-reflective filler according to claim 3, wherein: The mass ratio of the hollow silica particles to the polyol is 1:(5-15).

5. The method for preparing the anti-reflective filler according to claim 3, wherein: The polyol is at least one of aliphatic polyol, aromatic polyol, polyether polyol, polyester polyol and polymer polyol.

6. The method for preparing the anti-reflective filler according to claim 3, wherein: The soluble aluminum salt is at least one of aluminum chloride hexahydrate, aluminum sulfate, and aluminum nitrate.

7. An anti-reflective coating, characterized in that: The raw materials include the following weight percentages: 1%-3% fluorine-containing acrylic resin, 0.6%-3% anti-reflective filler, 0.05%-3% photoinitiator, and the balance is solvent; Wherein, the anti-reflection filler is the anti-reflection filler according to any one of claims 1-2 or the anti-reflection filler prepared by the preparation method according to any one of claims 3-6.

8. The anti-reflective coating according to claim 7, wherein: The mass of the anti-reflection filler is 60%-100% of the fluorine-containing acrylic resin.

9. The anti-reflective coating according to claim 7, wherein: The fluorine-containing acrylic resin is at least one of fluorine-containing polyurethane acrylate, fluorine-containing polyester acrylate, and fluorine-containing acrylate.

10. An anti-reflection film, characterized in that: The anti-reflective coating is mainly made of the anti-reflective coating according to any one of claims 7 to 9.

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