Anti-glare anti-reflective coating for displays

Abstract

An anti-glare anti-reflective film for displays includes, from bottom to top, a substrate (10), an AG coating (20), an HR coating (30), and an AR coating (40). The anti-glare AG coating (20), a high refractive HR coating (30), and a low refractive AR coating (40) are combined in a manner that defines a hierarchical structure. The components and morphology of the inorganic wear-resistant particles in the AG coating (20) are defined, and these are dispersed in a binder resin to achieve functions such as improving anti-glare and wear resistance. The particle size and morphology of the silica are defined, and the aggregated morphology partially forms an uneven shape on the coating surface after curing, and partially exists inside the coating, thereby improving the anti-glare effect.

Description

[Technical Field]

[0001] The present invention relates to the technical field of films, and in particular to anti-glare anti-reflective films for displays. [Background technology]

[0002] For example, display devices such as cathode ray tube display devices (CRT), plasma display devices (PDP), electroluminescent display devices (ELD), and liquid crystal display devices (LCD) are usually provided with an anti-reflection film on the outer surface of the display device to prevent a decrease in contrast due to reflection of external light and to prevent reflection of external light from entering an image.

[0003] Anti-reflection coatings, also known as AR coatings, are based on the wave nature and interference phenomenon of light. Their main function is to reduce or eliminate the reflected light on the surface of optical elements, thereby increasing the light transmittance of these elements and reducing or eliminating stray light in the system. Anti-reflection coatings occupy a very important position in the optical thin film industry.

[0004] Generally, antireflection coatings are formed by forming a multilayer antireflection layer on a transparent thin film substrate using chemical vapor deposition (CVD) or physical vapor deposition (PVD), as in the conventional Patent Document 1. The combination of a high-refractive index layer and a low-refractive index layer can achieve broadband antireflection. This technology has been realized using dry coating, but dry coating requires film formation in a vacuum, which has drawbacks such as complex production equipment structure, high capital investment, and low productivity. For this reason, wet coating technology, which enables low-cost coating of large areas and continuous production, has recently attracted attention. However, current conventional technology, such as Patent Documents 2 and 3, mainly uses single-layer antireflection coatings in wet coating.

[0005] In the field of wet coating, there is a problem that the film layer has high haze and cannot be used.

[0006] The light emitted by the liquid crystal display device itself and the light reflected by the display screen from the light source in the environment overlap to form glare, which affects the human eye over a long period of time, not only causing visual discomfort but also causing visual impairment if the glare is too strong. Therefore, an anti-glare film (AG film) is attached to the surface of each commercially available liquid crystal display device, and such a cured film must also have high abrasion resistance. For example, an anti-glare cured film for an electronic whiteboard must also have a good flash point and writing effect.

[0007] Therefore, current displays are required to have not only an optical film with anti-reflection function on the surface but also an optical film with anti-glare function, which can provide better visibility. Furthermore, the coating applied to the display cover plate must have high hardness and good abrasion resistance. However, currently, low refractive index layers produced by wet coating technology have low hardness, only reaching a maximum of 500 g / 1H, and poor abrasion resistance, only reaching 100 g / 10 times. This also limits the wider application of anti-reflection coatings. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Chinese Patent Application Publication No. 104614787 [Patent Document 2] Chinese Patent No. 1322338 [Patent Document 3] Taiwan Patent No. I515271 Summary of the Invention

[0009] In order to solve at least one of the above technical deficiencies, the present invention provides the following technical solutions:

[0010] The anti-glare anti-reflection coating for a display of the present application includes a substrate, an AG coating, an HR coating, and an AR coating, which are arranged in this order from bottom to top, The AG coating contains a binder resin, silica particles, organic particles, and inorganic wear-resistant particles. particle size as aggregates is 100nm- 2 000n m the organic particles are one or more of polymethyl methacrylate microparticles, polystyrene microparticles, polymethyl methacrylate-polystyrene copolymer microparticles, and polysilsesquioxane microparticles; and the inorganic wear-resistant particles are formed from one or more of nano-alumina, nano-zirconia, nano-diamond, and hexagonal boron nitride nanosheets. particle size as aggregates is 50-200n m can be, The refractive index of HR coating is 1.53-1.74, The refractive index of the AR coating is 1.2-1.48.

[0011] In this proposal, anti-glare AG coating, high refractive index HR coating, and low refractive index AR coating are combined in a hierarchical structure to integrate anti-glare and anti-reflection functions.

[0012] In AG coatings, inorganic abrasion-resistant particles with defined composition and morphology are dispersed in a binder resin to achieve improved anti-glare and abrasion resistance. Silica with defined particle size and morphology is preferred. Aggregated silica partially forms unevenness on the cured coating surface, while some of the aggregated silica remains internally, enhancing the anti-glare effect. Organic particles are preferably present internally, improving internal haze and reducing re-agglomeration of silica particle aggregates, reducing filler resin, and adjusting the refractive index difference between the particles and the resin, achieving a balanced internal and external haze. The films produced using this coating have improved performance, including hardness and abrasion resistance, as well as high resolution, a low flash point, and excellent whitening resistance.

[0013] Furthermore, the coating comprises a binder resin and inorganic metal oxide particles having a refractive index of 2.0-2.8, the inorganic metal oxide particles being aggregated in the coating to form particles having a particle diameter of 10-80 nm, the inorganic metal oxide particles being nano-zirconia or titanium oxide; The AR coating contains a binder resin and hollow silica particles with a refractive index of 1.15-1.40.

[0014] The addition of morphologically defined inorganic metal oxides to HR coatings reduces haze and contributes to improvements in the resolution and mechanical performance of the film layer. Hollow silica is added to AR coatings to adjust the refractive index, and the film layers made up of the above layers and components are stably bonded, resulting in new advances in performance such as hardness and abrasion resistance.

[0015] Further, the AG coating contains, by weight, 22-45 parts of binder resin, 3-7 parts of silica particles, 1-3 parts of organic particles, and 1-3 parts of inorganic wear-resistant particles; The HR coating contains, by weight, 40-200 parts binder resin and 20-75 parts nano-zirconia particles; The AR coating contains, by weight, 9-25 parts binder resin and 30-80 parts hollow silica particles.

[0016] The ratio of the amount of binder resin to the amount of functional particles is the basic component that constitutes the coating, and auxiliary agents such as lubricants, antifoaming agents, and leveling agents, and curing agents for hardening and molding can be freely added as needed.

[0017] Furthermore, the binder resins in the coating liquid components of the curable and molded AG coating, the curable and molded HR coating, and the curable and molded AR coating all contain a photocurable oligomer resin with six or more functional groups and a photocurable diluted monomer resin with three or more functional groups, The photocurable oligomer resin is one or more of polyurethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate and polyether acrylate, polyacrylic resin oligomer, epoxy resin polymer, oxygen-containing acrylate, uric acid acrylate; The light-curable diluted monomer resin is one or more of ethyl methacrylate, ethylhexyl methacrylate, styrene, methylstyrene, N-vinylpyrrolidone monofunctional monomer, polymethylolpropane trimethacrylate, diethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, hexanediol methacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, and neopentyl glycol dimethacrylate.

[0018] The resin component preferably has a limited structure, is convenient for photo-curing molding, and contributes to improving the hardness, flexibility, etc. of the coating.

[0019] The AR coating further comprises 2-8 parts of a fluorine-containing polymer, 5-30 parts of inorganic particles, and 5-23 parts of POSS. The inorganic particles are one or more of magnesium fluoride, boron nitride, silica, and alumina. The fluorine-containing polymer is one or more of partially fluorinated acrylate silicone copolymer, partially or fully fluorinated acrylic compound, and partially or fully fluorinated vinyl ether. The POSS is one or more of phenyl POSS, amino POSS, vinyl POSS, and acrylic POSS. The fluorine-containing polymer primarily increases the water contact angle and improves the abrasion resistance of the coating. The POSS increases the hardness of the AR coating. The inorganic particles improve the abrasion resistance of the AR coating.

[0020] Furthermore, the AG coating preferably contains, by mass percentage, 18%-38% of photocurable oligomer resin with 6 or more functional groups, 4%-7% of photocurable diluent monomer resin with 3 or more functional groups, 3%-7% of silica particles, 1%-3% of organic particles, 1%-3% of inorganic wear-resistant particles, 1%-5% of auxiliary agents, and 1%-3% of photoinitiator, and the solid content of the AG coating is 42%-55%. The HR coating contains, by mass percentage, 1%-2% of a photocurable oligomer resin with 6 or more functional groups, 0.3%-1% of a photocurable diluted monomer resin with 3 or more functional groups, 1%-3% of nanozirconia particles, 0.05%-0.2% of an auxiliary agent, and 0.1%-0.5% of a photoinitiator, and the solid content in the HR coating is preferably 3%-6%.

[0021] The AR coating contains, by weight, 0.25-0.5% hexafunctional or higher photocurable oligomer resin, 0.05-0.1% trifunctional or higher photocurable diluent monomer resin, 0.3-1.5% hollow silica particles, 0.1-1% solid silica particles, 0.1-1% POSS, and 0.1-0.5% photoinitiator. The solids content in the AR coating is preferably 2.0-5.0%.

[0022] The coating materials having the above-mentioned component ratios are preferably subjected to a photo-curing molding process. When used, each coating material is coated by a known coating technique such as slit coating, microgravure coating, blade coating, or roll coating, and then cured by one or a combination of two of ultraviolet curing, electron beam curing, and heat curing. The ultraviolet curing method is preferred because it has the advantage of allowing for a wider variety of selectable raw materials.

[0023] Examples of the auxiliary include a wetting leveling agent, an antifoaming agent, a polymerization inhibitor, and a surface control agent. Examples of the photoinitiator include acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ether. When an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, or a benzoin sulfonate ester is used, an active organic amine such as triethylamine or n-butylamine may be blended as a co-initiator.

[0024] Each of the above coatings is prepared by blending the corresponding components using a solvent. The solvent used can be, for example, a polar solvent or a non-polar solvent, specifically selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, methanol, ethanol, propanol, isopropanol, isobutanol, propylene glycol methyl ether, and n-butanol, and preferably selected from methyl isobutyl ketone, propylene glycol methyl ether, isobutanol, ethyl acetate, and butyl acetate. The solvent can be a single solvent or a mixed solvent of three or more solvents.

[0025] Furthermore, in AG coating, the silica particles are added as a dispersion liquid, and are mixed with a solvent to obtain a silica particle dispersion liquid with a secondary particle diameter of 100nm-2000nm, with a primary particle diameter of 10nm-50nm.

[0026] The inorganic wear-resistant particles are added as a dispersion, with a primary particle size of 10-50 nm, and mixed with a solvent to obtain a dispersion with a secondary particle size of 50-200 nm.

[0027] The particle diameter of the organic particles is 1 μm to 10 μm.

[0028] By limiting the particle shape and the type of addition, it was found through testing that this contributes to further improving the film layer performance.

[0029] Furthermore, the average particle size of the nano-zirconia particles is 5%-80% of the thickness of the HR coating, the average particle size of the hollow silica particles is 50-80nm, and the average particle size of the solid silica particles is 30%-100% of the thickness of the AR coating, contributing to improved film layer performance.

[0030] Furthermore, the inorganic wear-resistant particles are formed by pre-treating hexagonal boron nitride nanosheets, and in the pre-treatment step, hexagonal boron nitride nanosheets having a primary particle size are stirred and mixed with a solvent and subjected to ultrasonic dispersion treatment to obtain a colloidal solution, and the colloidal solution is centrifuged to obtain a primary bottom solid; Repeating the above pretreatment process on the primary bottom solid to obtain a secondary bottom solid; The above pretreatment process is repeated for the secondary bottom solids, and the resulting centrifuged solution, a dispersion of inorganic wear-resistant particles, is collected. Tailoring the dispersion preparation process can contribute to uniform distribution and further improve the performance of the membrane layer.

[0031] Hexagonal boron nitride nanosheets can be obtained by known production methods, such as arc discharge, solvothermal, vapor deposition, and liquid phase methods. Because nanoparticles have high surface energy and tend to aggregate, their surfaces must be treated with, for example, a polymer dispersant or a coupling agent. Preferably, the surface treatment agent is a silane coupling agent with a reactive functional group that can contribute to the reaction of the resin.

[0032] Furthermore, the nano-zirconia particles are of one or a mixture of two or more of the tetragonal and cubic crystal types. Restricting the crystal type contributes to improving the film layer performance.

[0033] Furthermore, the nano-zirconia particles are added as a dispersion to the coating solution used to form the HR coating, and the dispersion of nano-zirconia particles is prepared as follows.

[0034] First, a zirconium-containing compound is mixed with a solvent and an organic acid mixture in a predetermined ratio, and the mixture is heated to 250-320°C and reacted at a constant temperature for 3-18 hours. Next, the filtrate obtained by the reaction is washed multiple times to obtain tetragonal or cubic nano-zirconia particles, The resulting nano-zirconia particles and dispersion aid are then added to a solvent and processed to obtain a transparent nano-zirconia dispersion, in which the nano-zirconia particles form an aggregated state with a secondary dispersed particle diameter of 10-50 nm.

[0035] The nanozirconia is crystalline nanozirconia produced by a solvothermal one-step synthesis method. The raw materials are a zirconium-containing compound and an organic solvent, or a mixture of an organic solvent and an organic acid. The zirconium-containing compound may be an organic zirconium compound such as zirconium n-propoxide, zirconium n-butoxide, or zirconium tetratert-butoxide, or an inorganic zirconium compound such as zirconium nitrate, zirconium chloride, or basic zirconium carbonate. An organic zirconium compound is preferred, and zirconium n-propoxide is more preferred. The organic solvent may be methanol, ethanol, butyl ether, benzyl alcohol, or the like, with methanol, ethanol, or benzyl alcohol being preferred. The organic acid may be formic acid, decylic acid, stearic acid, oleic acid, or the like, with formic acid and oleic acid being preferred.

[0036] The solvent used for the nanozirconia dispersion may be a polar solvent or a non-polar solvent, such as n-hexane, toluene, ethanol, butyl acetate, ethyl acetate, isopropanol, isobutanol, acetone, butanone, methyl isobutyl ketone, propylene glycol methyl ether, etc., and preferably toluene, butyl acetate, isopropanol, isobutanol, methyl isobutyl ketone, propylene glycol, methyl ether, etc.

[0037] When preparing this nanozirconia dispersion, it is necessary to add an appropriate amount of a dispersing aid. The dispersing aid may be a silane coupling agent, a titanate coupling agent, a high molecular weight polymer having surface affinity, an acrylate monomer, or an acrylate oligomer. It is preferable to disperse the zirconia powder in the high molecular weight polymer having surface affinity and the acrylate monomer.

[0038] In this process, the process flow and reaction temperature are limited, which contributes to obtaining nano-zirconia with the desired morphology.

[0039] Furthermore, the thickness of the AG coating is 2-50 μm, and the water contact angle of the surface of the AG coating is less than 80°, the optical thickness of the HR coating is 1 / 2λ0, and the optical thickness of the AR coating is 1 / 4λ0.

[0040] By limiting the optical thickness relationship of the coating, a broadband antireflection coating with a W-shaped reflectance curve is obtained.

[0041] The substrate may be one of triacetyl cellulose film (TAC), polyethylene terephthalate film (PET), polynorbornene film (COP), polymethyl methacrylate film (PMMA), polycarbonate film (PC), transparent polyimide film (CPI), etc., but triacetyl cellulose film (TAC) is preferred from the viewpoints of transparency and optical retardation. The thickness of the substrate is preferably 25 μm to 300 μm, and when used as a polarizing plate surface protection film, it is preferably 25 μm to 80 μm from the viewpoint of thinning.

[0042] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0043] The film layer of the present invention integrates anti-glare and anti-reflection functions, and the film layer has the advantages of high resolution, low flash point, good whitening prevention, high hardness, abrasion resistance, etc. [Brief explanation of the drawings]

[0044] In order to more clearly explain the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below. Obviously, the drawings in the following description are only some embodiments of the present invention, and those skilled in the art can obtain other drawings based on these drawings without creative work. [Figure 1] An explanatory diagram of the film layer structure of the AG-HR-AR film. [Figure 2] FIG. 1 is a cross-sectional view of the AG layer of the AG1-HR1-AR1 film of Example 1 taken by a scanning electron microscope. [Figure 3] 1 shows transmittance and reflectance spectra of an enlarged cross-sectional view of the AG layer of the AG2-HR1-AR1 film of Example 2, taken by a scanning electron microscope. [Figure 4] 1 shows transmittance and reflectance spectra of a cross section of the AR layer of the AG1-HR1-AR2 film of Comparative Example 1, taken by a scanning electron microscope. [Figure 5] Transmittance and reflectance spectra of the AG1-AR1 film of Comparative Example 2. [Figure 6] 1 shows transmittance and reflectance spectra of the AG1-HR1-AR1 film of Example 1. [Figure 7] 1 shows transmittance and reflectance spectra of the AG1-HR1-AR1 film of Example 1. [Figure 8] 1 shows transmittance and reflectance spectra of the AG1-HR1-AR1 film of Example 1. [Figure 9] Electron microscope photograph of crystalline nanozirconia of Example 7. [Figure 10] XRD pattern of crystalline nanozirconia of Example 7. [Figure 11] FIG. 10 is a particle size distribution diagram of the zirconia dispersion of Example 7.

[0045] The symbols are as follows:

[0046] 10 Substrate, 20 AG coating, 21 Organic fine particles, 22 Silica particle aggregates, 23 Inorganic wear-resistant particle aggregates, 30 HR coating, 31 Nano-zirconia particle aggregates, 40 AR coating, 41 Hollow silica particles, 42 Solid silica particles DETAILED DESCRIPTION OF THE INVENTION

[0047] The present invention will now be further described with reference to the drawings and specific examples.

[0048] 1. Preparation of Crystalline Nanozirconia Dispersion Example 1. Preparation of crystalline nanozirconia dispersion: Zirconium n-propoxide and benzyl alcohol were added to a kettle in a mass ratio of 0.6:1 (the total volume of the reactants did not exceed 60% of the kettle volume), the rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 275°C. After the reaction was complete, the resulting powder was washed multiple times with ethanol and propylene glycol methyl ether (3 times each). The zirconia powder was then ultrasonically dispersed using propylene glycol methyl ether as the solvent and a high molecular weight polymer (pigment affinity group-containing copolymer DISPERBYK2014, purchased from BYK) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia dispersed particle size was 57 nm, and the primary particle size was 5-10 nm. XRD analysis revealed that the nanozirconia crystal structure was a mixture of tetragonal and cubic.

[0049] Example 2. Preparation of crystalline nanozirconia dispersion: Zirconium n-butoxide and diacetone alcohol were added to a kettle in a mass ratio of 0.56:1 (the total volume of the reactants did not exceed 60% of the kettle volume), the rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 275°C. After the reaction was completed, the resulting powder was washed multiple times with ethanol and MIBK (methyl isobutyl ketone) (three times each). The zirconia powder was then ultrasonically dispersed using MIBK as the solvent and a polymer (pigment-affinity-containing structured copolymer DISPERBYK-2013, purchased from BYK) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia dispersed particles had a diameter of 42 nm, and the primary particle diameter was 8-12 nm. XRD analysis revealed that the nanozirconia crystal structure was a mixture of tetragonal and cubic.

[0050] Example 3. Preparation of crystalline nanozirconia dispersion: Zirconium carbonate and n-hexanol were added to a kettle in a mass ratio of 0.62:1 (the total volume of the reactants did not exceed 60% of the kettle volume), the rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 275°C. After the reaction was completed, the resulting powder was washed multiple times with ethanol and MIBK (methyl isobutyl ketone) (three times each). The zirconia powder was then ultrasonically dispersed using MIBK as the solvent and a polymer (pigment-affinity-containing structured copolymer DISPERBYK-2013, purchased from BYK) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia dispersed particles had a diameter of 45 nm, and the primary particle diameter was 8-12 nm. XRD analysis revealed that the nanozirconia crystal structure was a mixture of tetragonal and cubic.

[0051] Example 4. Preparation of crystalline nanozirconia dispersion: Zirconium n-butoxide and benzyl alcohol were added to a kettle in a mass ratio of 0.48:1 (the total volume of the reactants did not exceed 60% of the kettle volume), the rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 275°C. After the reaction was complete, the resulting powder was washed multiple times with ethanol and MIBK (methyl isobutyl ketone) (three times each). The zirconia powder was then ultrasonically dispersed using MIBK as the solvent and a polymer (pigment-affinity-containing structured copolymer DISPERBYK-2013, purchased from BYK) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia dispersed particles had a diameter of 45 nm, and the primary particle diameter was 8-12 nm. XRD analysis revealed that the nanozirconia crystal structure was a mixture of tetragonal and cubic.

[0052] Example 5. Preparation of crystalline nanozirconia dispersion: A mixture of zirconium nitrate, urea, and water was added to a kettle in a mass ratio of 0.48:1 (the total volume of the reactants did not exceed 60% of the kettle's volume). The rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 270°C. After the reaction was complete, the resulting powder was washed multiple times with ethanol and MIBK (methyl isobutyl ketone) (three times each). The zirconia powder was then ultrasonically dispersed using MIBK as the solvent and a high molecular weight polymer (pigment affinity group-containing copolymer DISPERSANT-2008, purchased from BYK) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia primary particle size was 20-25 nm, and XRD analysis revealed that the nanozirconia crystal structure was a mixture of monoclinic and tetragonal crystals. Because the reaction takes place in an aqueous solution, it is difficult to completely remove the water in post-treatment, and the resulting dispersion has large secondary particle diameters exceeding 100 nm, and is slightly cloudy and not transparent.

[0053] Example 6. Preparation of crystalline nanozirconia dispersion: Zirconium tetra tert-butoxide and benzyl alcohol were added to a kettle in a mass ratio of 0.6:1 (the total volume of the reactants did not exceed 60% of the kettle volume), the rotation speed was set to 450 rpm, and the maximum temperature of the kettle was set to 300°C. After the reaction was completed, the resulting powder was washed multiple times with ethanol and propylene glycol methyl ether (3 times each). The zirconia powder was then ultrasonically dispersed using propylene glycol methyl ether as the solvent and a high molecular weight polymer (pigment affinity group-containing copolymer UNIQ-SPERSE670U, purchased from Allnex Group, Germany) as a dispersing agent to obtain a nanozirconia dispersion with a solids content of 20%. The nanozirconia primary particle size was 15-25 nm, and XRD analysis showed that the nanozirconia crystal structure was primarily cubic. Nanozirconia prepared at too high a reaction temperature has a large primary particle size and is more difficult to disperse; the nanozirconia dispersion prepared under these conditions has a secondary particle size of more than 100 nm and is slightly cloudy and not transparent.

[0054] The results of the above examples and comparative examples show that the selection of different raw materials and solvents affects the primary particle size and crystal type of nano-zirconia, and the resulting dispersed particle size of nano-zirconia is larger. When this nano-zirconia dispersion is selected and added to an HR coating, the transmittance of the coating decreases, the haze increases, and the refractive index of the coating is affected (see Comparative Example 3 below). 2. Dispersion Preparation Silica particle dispersion: Commercially available solid silica particles (unsurface-treated) with a primary particle diameter of 10-50 nm are ground in an ethanol solvent using a ball mill to obtain a silica particle dispersion with a secondary dispersed particle diameter within a specified range. The secondary dispersed particle diameter can be adjusted by adjusting the solvent ratio, grinding parameters, etc., but this is not explained here.

[0055] Inorganic wear-resistant particle dispersion: First, in the pretreatment process, deionized water and ethanol are mixed in a volume ratio of 1:1, and commercially available hexagonal boron nitride nanosheets (without surface treatment) with a primary particle size of 10-50 nm are added while stirring. The mixture is stirred for 6-24 hours and then ultrasonically dispersed for approximately 10 minutes. The dispersion is then centrifuged at 6,000-10,000 rpm for 5-10 minutes, and the supernatant is discarded, leaving the lower layer (primary bottom solid).

[0056] Next, the above pretreatment steps (mixing with solvent, stirring, ultrasonication, centrifugation) are repeated with the primary bottom solid to obtain a secondary bottom solid for use.

[0057] Finally, the solvent (propylene glycol methyl ether) and the secondary bottom solid are subjected to the above pretreatment process to obtain a nano-hexagonal boron nitride dispersion, which is a centrifugal colloidal liquid.

[0058] The above pretreatment process is continued on the obtained bottom sediment, the centrifuged colloidal liquid is recovered, and the above pretreatment process is repeated on the centrifuged bottom solid sediment until no bottom sediment remains, and the recovered centrifuged colloidal liquid is a nano-hexagonal boron nitride dispersion.

[0059] 3. Preparation of coating solution used for coating Preparation of Coating Solution AG1: Prepare 10 kg of coating solution. The components, by mass, are 28% 10-functional polyurethane acrylate oligomer (JD8098, purchased from Shanghai Yangshi Industrial Co., Ltd.), 3% 6-functional polyurethane acrylate oligomer (EB1290, purchased from Allnex Group, Germany), 3% 3-functional acrylate monomer (pentaerythritol triacrylate), 3% 6-functional acrylate monomer (dipentaerythritol hexaacrylate), 2% thiol polymerization inhibitor (butylthiopentaerythritol), 8% silica with a dispersed particle size of 240 nm, and polysilsesquioxane microparticles (DF20A, purchased from Changxing Special Materials (Suzhou) Co., Ltd.). 0) accounts for 0.5%, hexagonal boron nitride nanosheets with a dispersed particle size of 80 nm account for 2%, a photoinitiator (photoinitiator 184, purchased from Shanghai Yinchang New Materials Co., Ltd.) accounts for 2%, and a mixed solvent of butyl acetate and isobutanol (butyl acetate accounts for 75% and isobutanol accounts for 25% by volume) accounts for the remaining proportions. Each component is added to the mixed solvent of butyl acetate and isobutanol and stirred until all components are completely dissolved, yielding coating solution AG1 with a solids content of 51.5%.

[0060] Preparation of Coating Solution AG2: Prepare 10 kg of coating solution. The components, by mass, are 21.5% 9-functional polyurethane acrylate oligomer (JR9929, purchased from Changzhou Qiaorun New Materials Technology Co., Ltd.), 2.8% 30-functional hyperbranched acrylate oligomer (BDT-4330, purchased from Shanghai Hesheng Industrial Group Co., Ltd.), 1.0% 3-functional acrylate monomer (pentaerythritol triacrylate), 2.4% 6-functional acrylate monomer (dipentaerythritol hexaacrylate), 2% thiol polymerization inhibitor (butylthiopentaerythritol), and polyethylene glycol (600, purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.). The composition consisted of 1.9% butyl acetate (DA), 8% silica with a dispersed particle size of 350 nm, 1% cross-linked polystyrene microparticles (purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.), 2% nanodiamond particles with a dispersed particle size of 100 nm, 2.1% photoinitiator 184, and a mixed solvent of butyl acetate and propylene glycol methyl ether (75% butyl acetate and 25% propylene glycol methyl ether by volume). Each component was added to the mixed solvent of butyl acetate and propylene glycol methyl ether and stirred until completely dissolved, yielding coating solution AG2 with a solids content of 44.7%.

[0061] Preparation of Coating Solution AG3: Prepare 10 kg of coating solution. The components, by mass, were 21.7% 9-functional polyurethane acrylate oligomer (SU5039, purchased from Kashan Trading (Shanghai) Co., Ltd.), 3.1% 30-functional hyperbranched acrylate oligomer (BDT-4330, purchased from Shanghai Hesheng Industrial Group Co., Ltd.), 1.2% 3-functional acrylate monomer (pentaerythritol triacrylate), 2.4% 6-functional acrylate monomer (dipentaerythritol hexaacrylate), 1.9% thiol polymerization inhibitor (butylthiopentaerythritol), and polyethylene glycol 60. The dispersion liquid contains 2% 0DA, 10% silica with a secondary particle diameter of 600 nm, 1.5% polymethyl methacrylate microparticles, 2% nanoalumina particles with a dispersed particle diameter of 80 nm, 2.1% photoinitiator 184, and a mixed solvent of butyl acetate and propylene glycol methyl ether (butyl acetate is 75% and propylene glycol methyl ether is 25% by volume). Each component is added to the mixed solvent of butyl acetate and propylene glycol methyl ether and stirred until the above components are completely dissolved, yielding coating liquid AG3 with a solids content of 47.9%.

[0062] Preparation of Coating Solution AG4: The difference from the preparation method of Coating Solution 3 is that no polymethyl methacrylate fine particles are added.

[0063] Preparation of Coating Solution AG5: The difference in the preparation method of Coating Solution 3 is that nano-alumina particles are not added.

[0064] Preparation of coating solution HR1: 10 kg of coating solution was prepared. Here, the weight percentages were: aliphatic hexaacrylate (EBECRYL purchased from Zhanxin Resin (China) Co., Ltd.) The total weight of the mixture was 1.24% (15 functional polyurethane acrylate prepolymer (W991 purchased from Guangzhou Wuxing Materials Technology Co., Ltd.), 0.165% (4 functional acrylate monomer (ditrimethylolpropane tetraacrylate)), 0.245% (3 functional acrylate monomer (trimethylolpropane trimethacrylate)), 1.4% (20 nm dispersed particle size nanozirconia (crystalline nanozirconia prepared in Example 1), 0.11% (leveling agent (BYK polyether-modified dimethylpolysiloxane BYK-378 purchased from BYK), 0.27% (photoinitiator) and propylene glycol methyl ether. Add each component to the propylene glycol methyl ether solvent and stir until completely dissolved to obtain coating solution HR1 with a solids content of 3.7%.

[0065] Preparation of Coating Liquid HR2: In the preparation method of Coating Liquid HR1, the zirconia dispersion liquid prepared in Example 5 having a dispersed particle diameter of more than 100 nm is selected.

[0066] Preparation of Coating Solution AR1: To prepare the coating solution, 0.314% by weight of 9-functional aliphatic polyurethane acrylate (JR9929, purchased from Changzhou Qiaorun New Materials Technology Co., Ltd.), 0.078% by weight of 2-functional epoxy acrylate (G5100, purchased from Guangzhou Wuxing Materials Technology Co., Ltd.), 1.26% by weight of 70 nm hollow silica, 0.27% by weight of solid silica, 0.5% by weight of POSS, 0.24% by weight of photoinitiator, and the remaining proportions of solvent were added to a mixture of methyl isobutyl ketone, propylene glycol methyl ether, isobutanol, ethyl acetate, and butyl acetate (volume ratio of each component: 1:4:3:4:8). Stir until the components are completely dissolved to obtain Coating Solution AR1 with a solids content of 2.7%.

[0067] Preparation of Coating Solution AR2: In the preparation method of Coating Solution AR1, the difference is that hollow silica of 20 nm is selected.

[0068] Preparation of Coating Solution AR3: The difference in the preparation method of Coating Solution AR1 is that solid silica is not added.

[0069] Preparation of coating solution AR4: The same method as in preparation of coating solution AR1 was used except that POSS was not added.

[0070] 4. Coating Preparation The film layer structure in each of the following examples is shown in Table 1.

[0071] Example 1 First, using a microgravure roll coater, the coating solution AG1 was applied to a triacetyl cellulose film having a thickness of 80 μm, and the film was dried at 80° C. Thereafter, under a nitrogen atmosphere, a high-pressure mercury lamp was used to apply 600 mJ / cm 2 The coating was cured with a curing energy of 0.05 to obtain a film AG1 with a coating thickness of 4 μm. The water contact angle of the surface of the corresponding AG coating is less than 80°.

[0072] Thereafter, the coating solution HR1 was applied to the AG1 film using a slit coater and dried at 80°C. Thereafter, a high-pressure mercury lamp was used to apply 600 mJ / cm2 under a nitrogen atmosphere. 2 The coating was cured with a curing energy of 0.05 to obtain a film AG1-HR1 having a HR coating thickness of (1 / 2)λ0.

[0073] Finally, the coating solution AR1 was applied to the AG1-HR1 film using a slit coater and dried at 80°C. Thereafter, a high-pressure mercury lamp was used to apply 600 mJ / cm2 under a nitrogen atmosphere. 2 The coating was cured with a curing energy of 1 / 4λ to obtain a film AG1-HR1-AR1 with an AR coating thickness of (1 / 4)λ0.

[0074] Example 2 In the method of Example 1, the coating thickness of HR was halved to 1 / 4λ0 to obtain a film AG1-HR1(1 / 4λ0)-AR1.

[0075] Example 3 In the method of Example 1, the coating liquid AG1 was replaced with AG2 (surface water contact angle less than 80°) to obtain a film AG2-HR1-AR1.

[0076] Example 4 In the method of Example 1, the coating liquid AG1 was replaced with AG3 (surface water contact angle of less than 80°) to obtain a film AG3-HR1-AR1.

[0077] Example 5 In the method of Example 1, the coating liquid AG1 was replaced with AG4 (surface water contact angle of less than 80°) to obtain a film AG4-HR1-AR1.

[0078] Example 6 In the method of Example 1, the coating liquid AG1 was replaced with AG5 (surface water contact angle of less than 80°) to obtain a film AG5-HR1-AR1.

[0079] Comparative Example 1 In the method of Example 1, the coating liquid AR1 was replaced with AR2 to obtain a film AG1-HR1-AR2.

[0080] Comparative Example 2 Membranes AG1-AR1 were obtained by the method of Example 1 without coating an HR layer.

[0081] Comparative Example 3 In the method of Example 1, the coating liquid HR1 was replaced with HR2 to obtain a film AG1-HR2-AR1.

[0082] Comparative Example 4 In the method of Example 1, the coating solution AG1 was replaced with AG2, and the coating solution AR1 was replaced with AR3 to obtain a film AG2-HR1-AR3.

[0083] Comparative Example 5 In the method of Example 1, the coating solution AG1 was replaced with AG3, and the coating solution AR1 was replaced with AR4, to obtain a film AG3-HR1-AR4.

[0084] 5. Exam As shown in Figure 1, the film layer structure of the present invention consists of a transparent substrate 10 at the bottom, on which an AG coating 20, an HR coating 30, and an AR coating 40 are sequentially arranged. The AG coating 20 contains organic microparticles 21, silica particle aggregates 22, and inorganic wear-resistant particle aggregates 23, with the silica particle aggregates 22 located on the surface. The HR coating 30 contains nano-zirconia particle aggregates 31, and the AR coating 40 contains hollow silica particles 41 and solid silica particles 42.

[0085] Test evaluation methodology description: (1) Optical performance of anti-reflection coating Measuring equipment: Ultraviolet spectrophotometer Measurement method: After coating, the flexible film is subjected to an optical performance test to measure the transmittance and reflectance of the film. The test range is 300-1100nm.

[0086] (2) Hydrophobic function of anti-reflection coating Measuring equipment: Contact angle tester Measurement method: After coating, the flexible film is subjected to a water contact angle test. The volume of the water droplet is 2 μL.

[0087] (3) Abrasion resistance of anti-reflective coating Measuring equipment: Abrasion resistance testing machine Testing method: The coated flexible film is subjected to abrasion resistance test, and weights are placed according to different requirements, and the number of times and speed of sliding are changed.

[0088] (4) Hardness of anti-reflective coating Measuring equipment: electric pencil hardness meter Measurement method: After coating, the flexible film is subjected to a hardness test under the following conditions: 500g, speed 40.

[0089] (5) Coating refractive index measurement: Measurement equipment: Ellipsometer Semilab SE-2000 Measurement method: The coating solution is applied to a silicon sheet by the pull-up coating method, and the silicon sheet is placed in an ellipsometer for measurement.

[0090] (6) Coating thickness: Measuring equipment: Thickness gauge Measurement method: Place the coated flexible film on a thickness gauge and measure.

[0091] (7) Coating Haze: Measuring equipment: Photoelectric haze meter WGW Measurement method: Place the coated flexible film on a haze meter and measure.

[0092] (8) Anti-glare film resolution and whitening suppression test Resolution: The outline of a fluorescent lamp is observed through the anti-glare film to evaluate the film's transmittance and diffusion.

[0093] ◎: The lamp is clearly visible, the outline is clear, and there is no diffusion effect.

[0094] ○: The lamp is visible and the outline is slightly blurred.

[0095] ×: The lamp is not clearly visible and the diffusion effect is obvious.

[0096] Whitening prevention: The anti-glare film is attached to a black acrylic plate and the degree of whitening of the coating is observed.

[0097] ⊚: Whitening prevention is extremely good.

[0098] ◯: Whitening suppression is good.

[0099] ×: Poor whitening suppression.

[0100] The test results are shown in Table 1 and Figures 2 to 11.

[0101] [Table 1]

[0102] As can be seen from the results of Example 1 and Comparative Example 1, when the AR coating selects hollow silica particles of 20 nm, the abrasion resistance is improved, but this affects the optical performance, so it is necessary to select hollow silica particles of an appropriate particle size.

[0103] As can be seen from the results of Example 1 and Comparative Example 2, the addition of an HR layer improves both the hardness and abrasion resistance of the coating, increases the transmittance, and decreases the reflectance, so it is necessary to select hollow silica particles with an appropriate particle size.

[0104] As can be seen from the results of Example 1 and Comparative Example 3, adding nano-zirconia particles with a dispersed particle size of more than 100 nm to the HR coating affects the optical transmittance of the coating film, so nano-zirconia particles with a dispersed particle size of less than 100 nm are preferred.

[0105] As can be seen from the results of Example 3 and Comparative Example 4, the absence of solid silica particles in the AR coating reduces the abrasion resistance of the coating.

[0106] As can be seen from the results of Example 4 and Comparative Example 5, if POSS is not added to the AR coating, both the hardness and abrasion resistance of the coating film decrease.

[0107] As can be seen from the results of Example 5, if organic particles are not added to the AG layer, internal scattering increases and internal haze cannot be obtained, resulting in a significant decrease in the total haze of the coating film.

[0108] As can be seen from the results of Example 6, the steel wool abrasion resistance of the coating film is significantly reduced if inorganic abrasion resistant particles are not added to the AG layer.

[0109] The above are merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited to the above examples, and any technical solutions that fall within the concept of the present invention are also within the scope of protection of the present invention. In addition, those skilled in the art may make various modifications or improvements without departing from the principles of the present invention, and these modifications or improvements should also be considered within the scope of protection of the present invention.

Claims

1. The coating includes a substrate, an AG coating, an HR coating, and an AR coating, which are arranged in this order from bottom to top, the AG coating comprises a binder resin, silica particles, organic particles, and inorganic abrasion-resistant particles, the particle size of the silica particles as aggregates being 100 nm to 2000 nm, the organic particles being one or more of polymethyl methacrylate fine particles, polystyrene fine particles, polymethyl methacrylate-polystyrene copolymer fine particles, and polysilsesquioxane fine particles, the inorganic abrasion-resistant particles being one or more of nano-alumina, nano-zirconia, nano-diamond, and hexagonal boron nitride nanosheets, the particle size of the inorganic abrasion-resistant particles as aggregates being 50 to 200 nm, The refractive index of the HR coating is 1.53-1.74, The refractive index of the AR coating is 1.2-1.48, The AG coating comprises, by weight, 22-45 parts of binder resin, 3-7 parts of silica particles, 1-3 parts of organic particles, and 1-3 parts of inorganic wear-resistant particles; The HR coating comprises, by weight, 40-200 parts binder resin and 20-75 parts nano-zirconia particles; The AR coating comprises, by weight, 9-25 parts binder resin and 30-80 parts hollow silica particles; An anti-glare anti-reflection film for a display, characterized in that

2. In the HR coating, the refractive index of the nano-zirconia particles is 2.0-2.8, and the nano-zirconia particles aggregate in the coating to form particles with a particle diameter of 10-80 nm. The refractive index of the hollow silica particles in the AR coating is 1.15-1.

40. characterized in that The anti-glare anti-reflection film for a display according to claim 1.

3. The binder resins in the AG coating, HR coating, and AR coating all contain a photocurable oligomer resin having 6 or more functional groups and a photocurable diluent monomer resin having 3 or more functional groups, The photocurable oligomer resin is one or more of polyurethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate and polyether acrylate, polyacrylic acid resin oligomer, epoxy resin polymer, oxygen-containing acrylate, uric acid acrylate; The photocurable diluted monomer resin is one or more of ethyl methacrylate, ethylhexyl methacrylate, styrene, methylstyrene, N-vinylpyrrolidone monofunctional monomer, polymethylolpropane trimethacrylate, diethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, hexanediol methacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, and neopentyl glycol dimethacrylate; characterized in that The anti-glare anti-reflection film for a display according to claim 1.

4. The AR coating comprises 2-8 parts of a fluorine-containing polymer, 5-30 parts of inorganic particles, and 5-23 parts of POSS, wherein the inorganic particles are one or more of magnesium fluoride, boron nitride, silica, and alumina, the fluorine-containing polymer is one or more of a partially fluorinated acrylate silicone copolymer, a partially or fully fluorinated acrylic compound, and a partially or fully fluorinated vinyl ether, and the POSS is one or more of a phenyl POSS, an amino POSS, a vinyl POSS, and an acrylic POSS. characterized in that The anti-glare anti-reflection film for a display according to claim 1.

5. The coating solution used to form the AG coating contains, by mass percentage, 18%-38% of a photocurable oligomer resin having 6 or more functional groups, 4%-7% of a photocurable diluent monomer resin having 3 or more functional groups, 8%-12% of silica particles, 1%-3% of organic particles, 1%-3% of inorganic wear-resistant particles, 1%-5% of an auxiliary agent, and 1%-3% of a photoinitiator. characterized in that The anti-glare anti-reflection film for a display according to claim 1.

6. The coating solution used to form the HR coating contains, by mass percentage, 1%-3% of a photocurable oligomer resin having 6 or more functional groups, 0.3%-1% of a photocurable diluent monomer resin having 3 or more functional groups, 1%-3% of nano-zirconia particles, 0.05%-0.2% of an auxiliary agent, and 0.1%-0.5% of a photoinitiator. characterized in that The anti-glare anti-reflection film for a display according to claim 1.

7. The coating solution used to form the AR coating contains, by mass percentage, 0.25%-0.5% of a photocurable oligomer resin having 6 or more functional groups, 0.05%-0.1% of a photocurable diluted monomer resin having 3 or more functional groups, 0.3%-1.5% of hollow silica particles, 0.1%-1% of solid silica particles, 0.1%-1% of POSS, and 0.1%-0.5% of a photoinitiator. characterized in that The anti-glare anti-reflection film for a display according to claim 1.

8. The average particle size of the nano-zirconia particles is 5%-80% of the thickness of the HR coating, the particle size of the hollow silica is 50-80 nm, and the average particle size of the solid silica is 30%-100% of the thickness of the AR coating. characterized in that The anti-glare anti-reflection film for a display according to claim 7.

9. The nano-zirconia particles are one or a mixture of two or more of tetragonal and cubic crystal types. characterized in that The anti-glare anti-reflection film for a display according to claim 2.

10. 10. The method for producing an anti-glare anti-reflection coating for a display according to claim 9, wherein the nano-zirconia particles are added as a dispersion to a coating liquid used to form an HR coating; The dispersion of nano-zirconia particles is First, a zirconium-containing compound, a solvent, and a mixture of an organic acid are mixed in a predetermined ratio, heated to 250-320°C, and reacted at a constant temperature for 3-18 hours. Next, the filtrate obtained by the reaction is washed multiple times to obtain tetragonal or cubic nano-zirconia particles, The resulting nano-zirconia particles and a dispersing aid are then added to a solvent and processed to obtain a transparent nano-zirconia dispersion, in which the nano-zirconia particles form an aggregated state with a secondary dispersed particle diameter of 10-50 nm. It is prepared as follows: characterized in that Manufacturing method of anti-glare anti-reflection coating.

11. A method for producing the anti-glare anti-reflection film for a display according to claim 5, comprising the steps of: In the coating liquid used to form the AG coating, the silica particles are added as a dispersion, and are mixed with a solvent to obtain a dispersion of silica particles having a primary particle diameter of 10 nm to 50 nm and a secondary particle diameter of 100 nm to 2000 nm; The inorganic wear-resistant particles are added as a dispersion, and are mixed with a solvent with a primary particle size of 10-50 nm to obtain a dispersion with a secondary particle size of 50-200 nm; The particle size of the organic particles is 1 μm to 10 μm. characterized in that Manufacturing method of anti-glare anti-reflection coating.

12. The inorganic wear-resistant particles are formed by pre-treating hexagonal boron nitride nanosheets. In the pre-treatment step, hexagonal boron nitride nanosheets having a primary particle size are stirred and mixed with a solvent, and then subjected to ultrasonic dispersion treatment to obtain a colloidal solution. The colloidal solution is centrifuged to obtain a primary bottom solid. Repeating the above pretreatment process on the primary bottom solid to obtain a secondary bottom solid; repeating the above pretreatment process on the secondary bottom solids and collecting the resulting centrate, a dispersion of inorganic wear-resistant particles; characterized in that A method for producing the anti-glare anti-reflection coating according to claim 11.

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