Anti-dazzle and anti-reflection coating containing core-shell composite particles as well as preparation method and application of anti-dazzle and anti-reflection coating

Abstract

The invention relates to an anti-dazzle and anti-reflection coating containing core-shell composite particles as well as a preparation method and application of the anti-dazzle and anti-reflection coating. The anti-dazzle and anti-reflection coating comprises the core-shell composite particles A, the core-shell composite particles B, a mixed solvent, a dispersing agent, acrylic resin and a flatting agent, the core-shell composite particle A comprises a shell A with a cavity and an inner core A located in the cavity, the shell A comprises hollow SiO2 particles, and the inner core A comprises solid SiO2 particles; the core-shell composite particle B comprises an inner core B and an outer shell B coating the outer surface of the inner core B, the inner core B comprises hollow SiO2 particles, and the outer shell B comprises TiO2 particles. Through the synergistic effect of the core-shell composite particles A and the core-shell composite particles B, low reflection, high light transmittance, high wear resistance, high hardness and high weather resistance can be achieved, the compatibility with resin is good, and a coating is uniform and transparent.

Description

Technical Field

[0001] This invention relates to the field of optical thin film technology, specifically to an anti-glare and anti-reflective coating containing core-shell composite particles, its preparation method, and its application. Background Technology

[0002] Polymethyl methacrylate (PMMA) is widely used in optical displays, photovoltaic modules, and other fields due to its high light transmittance, good processability, and moderate cost. To meet the requirements for anti-glare and anti-reflection, the industry often uses functional coatings containing silica (SiO2) to modify the surface of PMMA. SiO2 has advantages such as low refractive index, excellent stability, and good transparency, and is a core functional filler in coatings.

[0003] However, in the existing process, the application of SiO2 to the optical coating of PMMA substrate has the following technical problems: (1) Using solid SiO2 nanoparticles, it is difficult to balance optical performance. The anti-glare and anti-reflection functions are mutually restrictive. Anti-reflection requires reducing the particle filling amount to adjust the refractive index, but this results in weak mechanical properties of the coating. Anti-glare requires increasing the particle size or filling amount, but this causes problems such as decreased light transmittance and particle agglomeration, which cannot meet the requirements of high-end scenarios for low reflection (≤2%) and high light transmittance; (2) Using single core-shell composite particles such as organic core-SiO2 shell, SiO2 core-oxide shell, etc., on the one hand, the organic core has poor weather resistance and is easily degraded under high temperature or ultraviolet light, shortening the service life of the coating. On the other hand, there is no hollow structure design, and the refractive index of the coating is too high, which cannot take into account both anti-glare and anti-reflection; (3) The particles and PMMA resin are mostly physically combined, with poor interface compatibility, insufficient wear resistance and weather resistance, and easy to fall off and crack under hot and cold cycles.

[0004] In summary, existing optical coatings generally suffer from problems such as difficulty in achieving both anti-glare and anti-reflection properties, and contradictions between optical properties and mechanical / weather resistance. There is an urgent need to develop a SiO2-based composite coating that is anti-glare, anti-reflection, wear-resistant, and weather-resistant to meet the high-end needs of the optical field. Summary of the Invention

[0005] To address the above problems, the present invention aims to provide an anti-glare and anti-reflective coating containing core-shell composite particles, its preparation method, and its application.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an anti-glare and anti-reflective coating containing core-shell composite particles, the anti-glare and anti-reflective coating comprising core-shell composite particles A, core-shell composite particles B, a mixed solvent, a dispersant, an acrylic resin, and a leveling agent;

[0008] The core-shell composite particle A includes a hollow outer shell A and a core A located within the hollow cavity. The outer shell A includes hollow SiO2 particles, and the core A includes solid SiO2 particles.

[0009] The core-shell composite particle B includes a core B and a shell B covering the outer surface of the core B. The core B includes hollow SiO2 particles, and the shell B includes TiO2 particles.

[0010] In this invention, the synergistic effect of core-shell composite particles A, core-shell composite particles B, mixed solvent, dispersant, acrylic resin, and leveling agent solves the problems of difficulty in simultaneously achieving anti-glare and anti-reflection, and the contradiction between optical and mechanical / weather resistance. Specifically, in core-shell composite particle A, solid SiO2 particles are encased in a shell composed of low-reflectivity hollow SiO2 particles, forming a high-refractive-index core-low-refractive-index shell composite structure. This structure reduces the overall equivalent refractive index of core-shell composite particle A, narrowing the refractive index difference with air or the resin matrix (PMMA), reducing interface and light reflection. The addition of core-shell composite particle A reduces the visible light reflectivity of the optical film, and the solid core-hollow shell structure achieves a balance between the low-refractive-index shell (hollow shell) and high mechanical strength (solid core), avoiding the problem of easy wear of pure hollow particles while maintaining anti-reflection performance. In the core-shell composite particle B, a high-refractive-index TiO2 particle shell is wrapped around the hollow SiO2 particles to construct a composite structure of hollow SiO2 core and high-refractive-index TiO2 shell. A low-to-high refractive index gradient is formed from the inside to the outside, which further optimizes the light propagation path, reduces reflection, and improves light absorption efficiency.

[0011] Preferably, the anti-glare and anti-reflective coating comprises, by weight, 7-9 parts of core-shell composite particles A, 2-5 parts of core-shell composite particles B, 30-50 parts of mixed solvent, 1-2 parts of dispersant, 50-70 parts of acrylic resin, and 0.5-1 parts of leveling agent.

[0012] In this invention, the core-shell composite particle A is 7-9 parts, for example, 7 parts, 7.5 parts, 8 parts, 8.5 parts, or 9 parts, but not limited to the listed values; other unlisted values ​​within the range are also applicable. The core-shell composite particle B is 2-5 parts, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, but not limited to the listed values; other unlisted values ​​within the range are also applicable. The dispersant is 1-2 parts, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, or 2 parts, but not limited to... The values ​​listed are applicable to any other values ​​not listed within the specified range; the acrylic resin is 50-70 parts, for example, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, or 70 parts, but not limited to the listed values, and any other values ​​not listed within the specified range are applicable; the leveling agent is 0.5-1 part, for example, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 part, but not limited to the listed values, and any other values ​​not listed within the specified range are applicable.

[0013] Preferably, the particle size of the kernel A is 10-100 nm.

[0014] Preferably, the particle size of the core-shell composite particle A is 80-150 nm.

[0015] Preferably, the particle size of the kernel B is 50-100 nm.

[0016] Preferably, the particle size of the core-shell composite particle B is 120-180 nm.

[0017] Preferably, the mixed solvent comprises ethyl acetate and ethanol in a volume ratio of 1:(1-2).

[0018] Preferably, the dispersant comprises silane dispersant KH-550.

[0019] Preferably, the leveling agent comprises an organosilicon leveling agent, polyether-modified polysiloxane.

[0020] In this invention, the dispersant used is silane dispersant KH550, which is used to graft and modify core-shell composite particles A and B. After the alkoxy groups of KH550 hydrolyze to generate silanol groups, they undergo a condensation reaction with the hydroxyl groups (-Si-OH, -Ti-OH) on the surface of core-shell composite particles A and B, forming stable covalent bonds. The amino groups of KH550 can form hydrogen bonds with the hydroxyl groups in the acrylic resin or generate polar interactions with the ester groups, enhancing the dispersion of particles in the system and the interfacial bonding strength between particles and resin. This effectively eliminates voids between particles and resin, preventing voids from increasing reflection, resulting in a denser interfacial structure, avoiding additional reflection at the particle-resin interface, and further reducing the total reflectivity. Furthermore, surface functional group modification can eliminate agglomeration caused by hydroxyl groups on the surface of SiO2 particles, ensuring uniform dispersion of particles in the system and preventing optical defects such as increased haze and decreased transmittance caused by agglomeration.

[0021] Secondly, the present invention provides a method for preparing an anti-glare and anti-reflective coating containing core-shell composite particles as described in the first aspect of the present invention, the preparation method comprising the following steps:

[0022] S1, Preparation of core-shell composite particle dispersion:

[0023] According to the formula, mix 7-9 parts of core-shell composite particles A, 2-5 parts of core-shell composite particles B and 10-20 parts of mixed solvent, and ultrasonically disperse for 30-40 minutes. Then add 1-2 parts of dispersant and stir for 10-20 minutes to obtain a core-shell composite particle dispersion.

[0024] S2, Preparation of resin-solvent system:

[0025] According to the formula, mix 50-70 parts of acrylic resin and 20-30 parts of mixed solvent, and stir for 10-20 minutes to obtain the resin-solvent system.

[0026] S3, Preparation of anti-glare and anti-reflective coating:

[0027] The core-shell composite particle dispersion obtained in step S1 and the resin-solvent system obtained in step S2 are mixed and stirred for 15-25 minutes. Then, 0.5-1 part of leveling agent is added and stirred for 5-10 minutes to obtain an anti-glare and anti-reflective coating.

[0028] In the preparation method of the anti-glare and anti-reflection coating provided by the present invention, the core-shell composite particles A and B are modified by adding a dispersant to increase the dispersibility of the particles and their compatibility with the system. Then, a leveling agent is added to make them easier to coat, which is conducive to forming a good anti-glare and anti-reflection film layer.

[0029] Preferably, the stirring speed in steps S1, S2, and S3 is 300-500 rpm.

[0030] Preferably, the preparation method of the core-shell composite particle A in step S1 includes the following steps:

[0031] S11, covered with a hollow SiO2 layer:

[0032] By weight, 1-2 parts of solid SiO2 particles and 100-200 parts of anhydrous ethanol are mixed and ultrasonically dispersed for 20-30 min. Then, 5-7 parts of ammonia water are added and stirred for 10-20 min. After that, 101-202 parts of template agent are added and stirred for 15-25 min to obtain dispersion A. Dispersion A is mixed with 78-91 parts of silicon source and reacted at 25-35℃. During the reaction, the mixture is stirred for 4-6 h. Then, the solid and liquid phases are separated and washed to obtain solid product A.

[0033] S12, calcined to remove the template agent, forms a hollow structure:

[0034] The solid product A obtained in step S11 is vacuum dried at 60-70°C for 1-2 hours, and then calcined at 500-600°C for 2-3 hours to obtain core-shell composite particles A.

[0035] In this invention, the mass concentration of the ammonia water is 25-28%. In this invention, by adding ammonia water and then stirring, the surface hydroxyl groups can be activated, enhancing the activity of subsequent reactions.

[0036] Preferably, the template agent comprises an aqueous solution of hexadecyltrimethylammonium bromide, comprising 1-2 parts by weight of hexadecyltrimethylammonium bromide and 100-200 parts by weight of water.

[0037] Preferably, the silicon source comprises an ethanol solution of tetraethyl silicate, comprising 8-11 parts by weight of tetraethyl silicate and 70-80 parts by weight of ethanol.

[0038] In this invention, the heating rate of calcination in step S12 is 2-5℃ / min.

[0039] The method for preparing the core-shell composite particle A provided by the present invention involves the adsorption of hexadecyltrimethylammonium bromide (CTAB) in the template agent onto the surface of solid SiO2 particles to form a template. In the silicon source, tetraethyl silicate (TEOS) is hydrolyzed and oligomerized in an alkaline water / alcohol phase to form a SiO2 shell on the outside of the CTAB template. By calcining and decomposing the template CTAB, the loose part inside the shell shrinks to form hollow SiO2 particles, thus obtaining the core-shell composite particle A with a solid SiO2 core and a hollow SiO2 particle shell.

[0040] In this invention, the solid-liquid separation method is not particularly limited and can be any commonly used solid-liquid separation method in the art, such as filtration or centrifugation. Taking centrifugation in step S11 as an example, the centrifugation speed is 8000-10000 rpm, the centrifugation time is 10-20 min, the supernatant is discarded after centrifugation, and the precipitate is washed with a mixed washing solution of ethanol and water to remove free CTAB and unreacted reagents. The volume ratio of ethanol to water in the washing solution is generally 1:1, and the number of washing cycles can be, for example, 2-3 times.

[0041] Preferably, the preparation method of the core-shell composite particle B in step S1 includes the following steps:

[0042] S11', Hollow SiO2 particle dispersion and surface activation:

[0043] Mix 1-2 parts of hollow SiO2 particles and 100-200 parts of anhydrous ethanol and disperse by ultrasonication for 20-30 minutes. Then add 2-3 parts of nitric acid and stir for 5-10 minutes to obtain dispersion B.

[0044] S12', titanium source solution coating:

[0045] The dispersion B obtained in mixing step S11' and 80-110 parts of titanium source are reacted at 25-35°C. During the reaction, the mixture is stirred for 1-2 hours. Then, the solid and liquid are separated and washed to obtain solid product B.

[0046] S13', calcination and crystallization:

[0047] The solid product B obtained in step S12' is vacuum dried at 60-70°C for 1-2 hours, and then calcined at 450-550°C for 1-2 hours to obtain core-shell composite particles B.

[0048] In this invention, the nitric acid has a mass concentration of 65-68%. In this invention, stirring after adding nitric acid activates the hydroxyl groups on the SiO2 surface under acidic conditions, enhancing the binding with the titanium source.

[0049] Preferably, the titanium source comprises an ethanol solution of tetrabutyl titanate, comprising 10-20 parts by weight of tetrabutyl titanate and 70-90 parts by weight of anhydrous ethanol.

[0050] In this invention, the heating rate of calcination in step S13' is 2-5℃ / min.

[0051] The preparation method of the core-shell composite particle B provided in this invention involves coating a hollow SiO2 particle with a shell composed of TiO2 particles. During calcination, the amorphous TiO2 is transformed into anatase phase, forming a high refractive index structure. This constructs a composite structure of hollow SiO2 core and high refractive index TiO2 particle shell, forming a low-to-high refractive index gradient from the inside out. This further optimizes the light propagation path, reduces reflection, and enhances light absorption efficiency.

[0052] In this invention, taking centrifugation in step S12' as an example, the centrifugation speed is 8000-10000 rpm, the centrifugation time is 10-20 min, the supernatant is discarded after centrifugation, and the precipitate is washed with a mixed washing solution of ethanol and water to remove free titanium. The volume ratio of ethanol to water in the washing solution is generally 1:1, and the number of washing times can be, for example, 2-3 times.

[0053] Thirdly, the present invention provides an anti-glare and anti-reflection film, wherein the anti-glare and anti-reflection film is prepared using the anti-glare and anti-reflection coating containing core-shell composite particles as described in the first aspect of the present invention.

[0054] The anti-glare and anti-reflective film provided by this invention has anti-reflective properties, anti-glare properties, wear resistance, hardness, and weather resistance, and has excellent comprehensive performance.

[0055] Fourthly, the present invention provides a polarizer comprising the anti-glare and anti-reflection film described in the third aspect of the present invention.

[0056] In this invention, the polarizer comprises a resin matrix, and the anti-glare and anti-reflective film described above is coated on the resin matrix, wherein the resin matrix comprises PMMA.

[0057] The polarizer provided by this invention uses the above-mentioned anti-glare and anti-reflection film, which has good anti-reflection, anti-glare, wear resistance, hardness and weather resistance properties, and has broad production prospects.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] (1) The anti-glare and anti-reflection coating containing core-shell composite particles provided by the present invention can be prepared into anti-glare and anti-reflection films and polarizers, which can effectively improve anti-reflection performance. The shell of core-shell composite particle A has an air-containing cavity, and the equivalent refractive index is reduced to 1.30. The equivalent refractive index of core-shell composite particle B is about 1.38. By mixing the above two core-shell composite particles, the equivalent refractive index of the anti-glare and anti-reflection film can be reduced to about 1.35, which is between air (1.0) and resin matrix such as PMMA (1.49). When light enters the film layer from the air, a continuous refractive index gradient is formed, and the reflected light undergoes destructive interference at the interface, rather than direct reflection. At the same time, the dispersant added in the present invention can covalently modify the core-shell composite particles A and B, which can eliminate the gaps between the particles and the resin, make the film layer more compact, avoid additional reflection at the particle-resin interface, and further reduce the total reflectivity.

[0060] (2) The anti-glare and anti-reflection coating containing core-shell composite particles provided by the present invention can be prepared into anti-glare and anti-reflection films and polarizers, which can effectively improve the anti-glare performance. In the present invention, the hollow SiO2 particles of core-shell composite particle A form a shell (the shell is a closed-pore structure), and the hollow SiO2 core layer of core-shell composite particle B form a shell with a significant difference in refractive index between the air inside and the SiO2 and TiO2 of the shell layer, respectively. The light undergoes multiple refractions and reflections at the air-inorganic shell layer interface, rather than single-interface scattering, thus making the scattering path more complex and significantly reducing the intensity of direct light. In the present invention, the particle size of core-shell composite particles A and core-shell composite particles B is further optimized to form a multi-level particle size distribution of small particle size + slightly larger particle size. When light irradiates the PMMA matrix, particles of different sizes can scatter visible light of different wavelengths (small particles scatter short waves, and large particles scatter long waves), thereby avoiding the scattering blind zone caused by a single particle size. At the same time, the refractive index difference between SiO2, TiO2 and PMMA is small, avoiding excessive light loss and maintaining light transmittance.

[0061] (3) The anti-glare and anti-reflective coating containing core-shell composite particles provided by the present invention can be prepared into anti-glare and anti-reflective films and polarizers, which can effectively improve wear resistance and hardness. The SiO2 of core-shell composite particle A and the TiO2 of core-shell composite particle B are both high-hardness inorganic materials. They are dispersed in acrylic resin to form a composite structure of resin + inorganic reinforcing particles. Thus, when subjected to external force or friction, the inorganic particles can bear part of the load, avoid wear of the PMMA matrix, and prevent crack propagation, thereby improving hardness. In the present invention, the core-shell composite particles A and B are covalently modified by a dispersant to form Si-O-Si or Si-O-Ti covalent bonds, which can prevent particles from falling off during friction, prevent particles from aggravating wear after falling off, reduce the voids at the particle-resin interface, make the coating denser, and make the wear resistance more durable.

[0062] (4) The anti-glare and anti-reflection coating containing core-shell composite particles provided by the present invention can be used to prepare anti-glare and anti-reflection films and polarizers, which can effectively improve weather resistance. In the present invention, the shell layer composed of hollow SiO2 particles of core-shell composite particle A and the core layer composed of hollow SiO2 particles of core-shell composite particle B are both closed-pore structures, which can block water vapor, oxygen, ultraviolet rays and other substances from entering the film layer, thereby preventing the PMMA resin matrix from hydrolyzing when exposed to water. In addition, ultraviolet rays are absorbed by the TiO2 shell layer, preventing the PMMA resin matrix from aging and yellowing. Furthermore, oxygen cannot enter, reducing the oxidative decomposition of the PMMA resin matrix.

[0063] (5) The anti-glare and anti-reflection coating containing core-shell composite particles provided by the present invention uses acrylic resin, which belongs to the same acrylic polymer as PMMA resin matrix. Both contain ester groups and have similar molecular structures. After coating, it is not easy to have compatibility problems such as delamination and pinholes, and can form a uniform and transparent coating. Detailed Implementation

[0064] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0065] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0066] Example 1

[0067] This embodiment provides an anti-glare and anti-reflective coating containing core-shell composite particles. The anti-glare and anti-reflective coating comprises, by weight, 7 parts core-shell composite particles A, 3 parts core-shell composite particles B, 30 parts mixed solvent (ethyl acetate-ethanol in a volume ratio of 1:1), 1 part dispersant KH-550, 50 parts acrylic resin (DKS 210 from Japan), and 0.5 parts polyether-modified polysiloxane silicone leveling agent (Sichuan Ruikaibang Chemical Materials Co., Ltd., brand name RianPont2903).

[0068] The core-shell composite particle A includes a hollow outer shell A and a core A located within the hollow cavity. The outer shell A includes hollow SiO2 particles, and the core A includes solid SiO2 particles. The particle size of the core A is 10-100 nm, and the particle size of the core-shell composite particle A is 80-150 nm.

[0069] The core-shell composite particle B includes a core B and a shell B covering the outer surface of the core B. The core B includes hollow SiO2 particles, and the shell B includes TiO2 particles. The particle size of the core B is 50-100 nm, and the particle size of the core-shell composite particle B is 120-180 nm.

[0070] This embodiment also provides a method for preparing the above-mentioned anti-glare and anti-reflection coating, the method comprising the following steps:

[0071] S1, Preparation of core-shell composite particle dispersion:

[0072] According to the formula, mix 7 parts of core-shell composite particles A, 3 parts of core-shell composite particles B and 10 parts of mixed solvent, and ultrasonically disperse for 30 minutes. Then add 1 part of dispersant and stir for 10 minutes to obtain a core-shell composite particle dispersion.

[0073] The preparation method of the core-shell composite particle A includes the following steps:

[0074] S11, by weight, 1 part of solid SiO2 particles with a particle size of 10-100 nm and 100 parts of anhydrous ethanol were mixed and ultrasonically dispersed for 20 min. Then, 5 parts of ammonia water (mass concentration of 25%) were added and stirred for 10 min. After that, 101 parts of an aqueous solution of hexadecyltrimethylammonium bromide (1 part CTAB dissolved in 100 parts deionized water) were added and stirred for 15 min to obtain dispersion A. 78 parts of an ethanol solution of tetraethyl orthosilicate (8 parts TEOS dissolved in 70 parts anhydrous ethanol) were added dropwise to dispersion A, and the reaction was carried out at 25 °C with stirring for 4 h. Then, the mixture was centrifuged at 8000 rpm for 10 min, the supernatant was discarded, and the precipitate was washed 3 times with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product A.

[0075] S12, the solid product A obtained in step S11 is vacuum dried at 60°C for 1 hour, and then calcined in a muffle furnace at 2°C / min to 500°C for 2 hours, and then naturally cooled to obtain core-shell composite particles A.

[0076] The preparation method of the core-shell composite particle B includes the following steps:

[0077] S11', mix 1 part of hollow SiO2 particles with a particle size of 50-100nm and 100 parts of anhydrous ethanol and ultrasonically disperse for 20min, then add 2 parts of nitric acid (mass concentration of 65%) and stir for 5min to obtain dispersion B.

[0078] S12', 80 parts of an ethanol solution of tetrabutyl titanate (10 parts TBOT dissolved in 70 parts anhydrous ethanol) were added dropwise to the dispersion B and the reaction was carried out at 25°C. During the reaction, the mixture was stirred for 1 h, then centrifuged at 10000 rpm for 10 min, the supernatant was discarded, and the precipitate was washed twice with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product B.

[0079] S13', the solid product B obtained in step S11' is vacuum dried at 60°C for 1 hour, then calcined at 450°C for 1 hour at a rate of 2°C / min, and then naturally cooled to obtain core-shell composite particles B.

[0080] S2, Preparation of resin-solvent system:

[0081] According to the formula, mix 50 parts of acrylic resin and 20 parts of mixed solvent, and stir for 10 minutes to obtain the resin-solvent system.

[0082] S3, Preparation of anti-glare and anti-reflective coating:

[0083] The core-shell composite particle dispersion obtained in step S1 and the resin-solvent system obtained in step S2 are mixed and stirred for 15 minutes. Then, 0.5 parts of polyether-modified polysiloxane-based silicone leveling agent are added and stirred for 5 minutes to obtain an anti-glare and anti-reflective coating.

[0084] In steps S1, S2, and S3 above, the stirring speed is 300 rpm.

[0085] Example 2

[0086] This embodiment provides an anti-glare and anti-reflective coating containing core-shell composite particles. The anti-glare and anti-reflective coating comprises, by weight, 9 parts of core-shell composite particles A, 2 parts of core-shell composite particles B, 50 parts of mixed solvent (ethyl acetate-ethanol in a volume ratio of 1:1), 2 parts of dispersant KH-550, 70 parts of acrylic resin (2561 from ADEKA Japan), and 1 part of polyether-modified polysiloxane-based silicone leveling agent (same as in Example 1).

[0087] The core-shell composite particle A includes a hollow outer shell A and a core A located within the hollow cavity. The outer shell A includes hollow SiO2 particles, and the core A includes solid SiO2 particles. The particle size of the core A is 10-100 nm, and the particle size of the core-shell composite particle A is 80-150 nm.

[0088] The core-shell composite particle B includes a core B and a shell B covering the outer surface of the core B. The core B includes hollow SiO2 particles, and the shell B includes TiO2 particles. The particle size of the core B is 50-100 nm, and the particle size of the core-shell composite particle B is 120-180 nm.

[0089] This embodiment also provides a method for preparing the above-mentioned anti-glare and anti-reflection coating, the method comprising the following steps:

[0090] S1, Preparation of core-shell composite particle dispersion:

[0091] According to the formula, mix 9 parts of core-shell composite particles A, 2 parts of core-shell composite particles B and 20 parts of mixed solvent, and ultrasonically disperse for 40 minutes. Then add 2 parts of dispersant and stir for 20 minutes to obtain a core-shell composite particle dispersion.

[0092] The preparation method of the core-shell composite particle A includes the following steps:

[0093] S11, by weight, 2 parts of solid SiO2 particles with a particle size of 10-100 nm and 200 parts of anhydrous ethanol were mixed and ultrasonically dispersed for 30 min. Then, 7 parts of ammonia water (mass concentration of 28%) were added and stirred for 20 min. After that, 202 parts of an aqueous solution of hexadecyltrimethylammonium bromide (2 parts of CTAB dissolved in 200 parts of deionized water) were added and stirred for 25 min to obtain dispersion A. 91 parts of an ethanol solution of tetraethyl orthosilicate (11 parts of TEOS dissolved in 80 parts of anhydrous ethanol) were added dropwise to dispersion A and the reaction was carried out at 35 °C. During the reaction, the mixture was stirred for 6 h. Then, the mixture was centrifuged at 8000 rpm for 20 min, the supernatant was discarded, and the precipitate was washed 3 times with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product A.

[0094] S12, the solid product A obtained in step S11 is vacuum dried at 70°C for 2 hours, and then calcined in a muffle furnace at 600°C at a rate of 2°C / min for 3 hours, and then naturally cooled to obtain core-shell composite particles A.

[0095] The preparation method of the core-shell composite particle B includes the following steps:

[0096] S11', mix 2 parts of hollow SiO2 particles with a particle size of 50-100nm and 200 parts of anhydrous ethanol and ultrasonically disperse for 30min, then add 3 parts of nitric acid (mass concentration of 68%) and stir for 10min to obtain dispersion B;

[0097] S12', 110 parts of an ethanol solution of tetrabutyl titanate (20 parts TBOT dissolved in 90 parts anhydrous ethanol) were added dropwise to the dispersion B and the reaction was carried out at 35°C. The mixture was stirred for 2 hours during the reaction, and then centrifuged at 10,000 rpm for 20 minutes. The supernatant was discarded, and the precipitate was washed three times with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product B.

[0098] S13', the solid product B obtained in step S11' is vacuum dried at 70°C for 2 hours, then calcined at 550°C at a rate of 2°C / min for 2 hours, and then naturally cooled to obtain core-shell composite particles B.

[0099] S2, Preparation of resin-solvent system:

[0100] According to the formula, mix 70 parts of acrylic resin and 30 parts of mixed solvent, and stir for 20 minutes to obtain the resin-solvent system.

[0101] S3, Preparation of anti-glare and anti-reflective coating:

[0102] The core-shell composite particle dispersion obtained in step S1 and the resin-solvent system obtained in step S2 are mixed and stirred for 25 minutes. Then, 1 part of polyether-modified polysiloxane organosilicon leveling agent is added and stirred for 10 minutes to obtain an anti-glare and anti-reflective coating.

[0103] In steps S1, S2, and S3 above, the stirring speed is 500 rpm.

[0104] Example 3

[0105] This embodiment provides an anti-glare and anti-reflective coating containing core-shell composite particles. The anti-glare and anti-reflective coating comprises, by weight, 8 parts of core-shell composite particles A, 4 parts of core-shell composite particles B, 40 parts of mixed solvent (ethyl acetate-ethanol in a volume ratio of 1:1), 1.5 parts of dispersant KH-550, 60 parts of acrylic resin (same as in Example 1), and 0.8 parts of polyether-modified polysiloxane-based silicone leveling agent (same as in Example 1).

[0106] The core-shell composite particle A includes a hollow outer shell A and a core A located within the hollow cavity. The outer shell A includes hollow SiO2 particles, and the core A includes solid SiO2 particles. The particle size of the core A is 10-100 nm, and the particle size of the core-shell composite particle A is 80-150 nm.

[0107] The core-shell composite particle B includes a core B and a shell B covering the outer surface of the core B. The core B includes hollow SiO2 particles, and the shell B includes TiO2 particles. The particle size of the core B is 50-100 nm, and the particle size of the core-shell composite particle B is 120-180 nm.

[0108] This embodiment also provides a method for preparing the above-mentioned anti-glare and anti-reflection coating, the method comprising the following steps:

[0109] S1, Preparation of core-shell composite particle dispersion:

[0110] According to the formula, mix 8 parts of core-shell composite particles A, 4 parts of core-shell composite particles B and 15 parts of mixed solvent, and ultrasonically disperse for 35 minutes. Then add 1.5 parts of dispersant and stir for 15 minutes to obtain a core-shell composite particle dispersion.

[0111] The preparation method of the core-shell composite particle A includes the following steps:

[0112] S11, by weight, 1 part of solid SiO2 particles with a particle size of 10-100 nm and 200 parts of anhydrous ethanol were mixed and ultrasonically dispersed for 25 min. Then, 6 parts of ammonia water (mass concentration of 26%) were added and stirred for 15 min. After that, 151.5 parts of an aqueous solution of hexadecyltrimethylammonium bromide (1.5 parts of CTAB dissolved in 150 parts of deionized water) were added and stirred for 20 min to obtain dispersion A. 84 parts of an ethanol solution of tetraethyl orthosilicate (9 parts of TEOS dissolved in 75 parts of anhydrous ethanol) were added dropwise to dispersion A and the reaction was carried out at 30 °C. During the reaction, the mixture was stirred for 5 h. Then, the mixture was centrifuged at 8000 rpm for 15 min, the supernatant was discarded, and the precipitate was washed 3 times with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product A.

[0113] S12, the solid product A obtained in step S11 is vacuum dried at 65°C for 1.5 h, then calcined in a muffle furnace at 550°C at a rate of 2°C / min for 2.5 h, and then naturally cooled to obtain core-shell composite particles A.

[0114] The preparation method of the core-shell composite particle B includes the following steps:

[0115] S11', mix 1.5 parts of hollow SiO2 particles with a particle size of 50-100nm and 150 parts of anhydrous ethanol and ultrasonically disperse for 25min, then add 2.5 parts of nitric acid (mass concentration of 66%) and stir for 10min to obtain dispersion B;

[0116] S12', 95 parts of an ethanol solution of tetrabutyl titanate (15 parts TBOT dissolved in 80 parts anhydrous ethanol) were added dropwise to the dispersion B and the reaction was carried out at 30°C. The mixture was stirred for 1.5 h during the reaction, and then centrifuged at 10000 rpm for 15 min. The supernatant was discarded, and the precipitate was washed three times with an ethanol-water washing solution with a volume ratio of 1:1 to obtain solid product B.

[0117] S13', the solid product B obtained in step S11' is vacuum dried at 65°C for 1.5h, then calcined at 500°C for 1.5h at a rate of 2°C / min, and then naturally cooled to obtain core-shell composite particles B.

[0118] S2, Preparation of resin-solvent system:

[0119] According to the formula, mix 60 parts of acrylic resin and 25 parts of mixed solvent, and stir for 15 minutes to obtain the resin-solvent system.

[0120] S3, Preparation of anti-glare and anti-reflective coating:

[0121] The core-shell composite particle dispersion obtained in step S1 and the resin-solvent system obtained in step S2 are mixed and stirred for 20 minutes. Then, 0.8 parts of polyether-modified polysiloxane organosilicon leveling agent are added and stirred for 10 minutes to obtain an anti-glare and anti-reflective coating.

[0122] In steps S1, S2, and S3 above, the stirring speed is 400 rpm.

[0123] Example 4

[0124] This embodiment provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Embodiment 1 is that the particle size of the core A of the core-shell composite particles A is 200-300 nm.

[0125] In this embodiment, the difference between the preparation method of the core-shell composite particle A and that in Example 1 is that the solid SiO2 particles are replaced with solid SiO2 particles with a particle size of 200-300 nm.

[0126] Example 5

[0127] This embodiment provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Embodiment 1 is that the particle size of the core B of the core-shell composite particles B is 200-300 nm.

[0128] In this embodiment, the difference between the preparation method of the core-shell composite particle B and that in Example 1 is that the hollow SiO2 particles are replaced with hollow SiO2 particles with a particle size of 200-300 nm.

[0129] Comparative Example 1

[0130] This comparative example provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Example 1 is that the core-shell composite particles A are replaced with an equal weight of solid SiO2 particles with a particle size of 80-150 nm, and the core-shell composite particles B are replaced with an equal weight of solid SiO2 particles with a particle size of 120-180 nm.

[0131] Comparative Example 2

[0132] This comparative example provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Example 1 is that the core-shell composite particles A are replaced with an equal weight of hollow SiO2 particles with a particle size of 80-150 nm, and the core-shell composite particles B are replaced with an equal weight of hollow SiO2 particles with a particle size of 120-180 nm.

[0133] Comparative Example 3

[0134] This comparative example provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Example 1 is that the core-shell composite particles B are replaced with an equal weight of core-shell composite particles A.

[0135] Comparative Example 4

[0136] This comparative example provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference from Example 1 is that the core-shell composite particles A are replaced with an equal weight of core-shell composite particles B.

[0137] Comparative Example 5

[0138] This comparative example provides an anti-glare and anti-reflective coating containing core-shell composite particles. The only difference between this and Example 1 is that the dispersant KH550 is not added.

[0139] Performance testing:

[0140] The anti-glare and anti-reflective coatings provided in the above embodiments and comparative examples were applied to a transparent substrate layer made of polymethyl methacrylate with a thickness of 60 μm using a roller coating method, resulting in an anti-glare and anti-reflective film with a thickness of 5 μm after drying. Then, a 260 mJ / cm² coating was applied. 2 The anti-glare and anti-reflective film was cured by UV irradiation to obtain a polarizer, and its performance was tested.

[0141] (1) Anti-glare test method:

[0142] A black acrylic sheet was attached to the reverse side of the polarizer. An LED fluorescent lamp was then shone onto the surface of the anti-glare and anti-reflective film, and the blurring effect of the reflected light was evaluated. A 30W LED fluorescent lamp with a color temperature of 6500K was used, positioned 50cm away from the sample and illuminated vertically. Three professional evaluators judged the film according to the following criteria, and the consensus result among the three evaluators was taken as the final grade.

[0143] LV5-6: The outline of the fluorescent lamp is completely and uniformly blurred, with good anti-glare performance;

[0144] LV3-4: Fluorescent lights are blurry but retain their outlines; anti-glare performance is average.

[0145] LV1-2: The outline of the fluorescent lamp can be clearly seen, or it may be uneven and blurry, with poor anti-glare performance.

[0146] (2) Total haze test method:

[0147] The procedure was performed in accordance with GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics": each group of anti-glare and anti-reflective films was cut into 50mm×50mm squares, and three parallel samples were prepared for each group. The surface was wiped with a lint-free cloth soaked in anhydrous ethanol to remove oil and dust, and placed in a standard environment of 23℃±2℃ and 50%±5% RH for 24 hours.

[0148] A transmittance haze meter (NDH-5000W) was used with visible light at a wavelength of 550nm as the light source. The instrument was calibrated first, and then the test was conducted. The sample was laid flat on the instrument test stage to ensure complete adhesion without air bubbles. Each sample was tested at 3 different locations, and the average value was taken as the final result.

[0149] (3) Anti-reflective testing method:

[0150] Reflectivity was measured using a SolidSpec 3700 manufactured by SHIMADZU. Black tape (472Black vinyl tape, manufactured by 3M) was applied to the side of the polarizer without the anti-glare and anti-reflection coating to prevent light from entering. Under conditions of a sampling interval of 1 mm, a time constant of 0.1 s, a slit width of 20 nm, and a scan rate of 300 nm / min, the anti-glare and anti-reflection coating was illuminated with light of wavelengths from 380 nm to 780 nm in 100T mode, and the average reflectivity was measured.

[0151] (4) Abrasion resistance test method:

[0152] The surface pencil hardness of the anti-glare and anti-reflective film of the polarizer was tested using the method described in the test of optical film scratch resistance (GB / T-34261-2017).

[0153] (5) Weather resistance test:

[0154] Cut the anti-glare and anti-reflective film into 100mm×100mm squares and attach them to black PET, preparing three parallel samples. Before testing, place the samples in an environment of 23℃±2℃ and 50%±5% RH for 24 hours, and clean the surface with a lint-free cloth. Then, irradiate them in a UV aging tester with a UV-B light source and an irradiation intensity of 500W / m². 2 (300-700nm) Stop the machine at 48h, 96h, 144h, 192h, and 240h to perform a 100-cross cross-cut test.

[0155] The results of the above tests are shown in Table 1.

[0156] Table 1

[0157]

[0158] As can be seen from the data in Table 1:

[0159] (1) As can be seen from the data of Examples 1-3, the anti-glare and anti-reflection film and polarizer prepared by the anti-glare and anti-reflection coating containing core-shell composite particles provided by the present invention have an anti-glare performance of LV6, a total haze of less than 1.5%, a visible light reflectance of less than 0.8%, a pencil hardness of 5H, and a weather resistance of 240h, indicating that the anti-glare and anti-reflection performance, light transmittance, scratch resistance and weather resistance are excellent.

[0160] (2) A comparison of Examples 1 and 4-5 shows that when the core particle size of core-shell composite particle A or core particle B exceeds the preferred range of this invention, the performance of the resulting coating decreases significantly. Large-diameter particles themselves act as scattering centers, causing excessive light scattering, leading to a sharp increase in haze (Example 4: 8.5%, Example 5: 11.2%) and a decrease in anti-glare effect (Example 4: LV4, Example 5: LV3). Simultaneously, large particles are more prone to uneven distribution in the coating, disrupting the precise refractive index gradient constructed by the synergistic interaction of core-shell composite particles A and B, resulting in increased reflectivity. Furthermore, large particles may affect the coating's density, leading to a decrease in pencil hardness and weather resistance. This underscores the necessity of controlling the particle core size within a specific range (e.g., core A: 10-100 nm, core B: 50-100 nm) for achieving the superior overall effect of this invention.

[0161] (3) As can be seen from the comparison between Example 1 and Comparative Example 1, the solid SiO2 particles in Comparative Example 1 do not have hollow cavities or TiO2 high refractive index shells compared with the core-shell composite particles A and B in this invention, resulting in low light scattering efficiency and a lower anti-glare level than Example 1. This indicates that Comparative Example 1 does not use the core-shell composite particles provided in this application, resulting in insufficient light scattering and poor anti-glare performance.

[0162] Compared to the synergistic effect of core-shell composite particles A and B in this invention, the fixed refractive index of solid SiO2 particles in Comparative Example 1 is 1.46, which cannot form the refractive index gradient of air-anti-glare and anti-reflection film-PMMA in this invention. The reflectivity is much higher than that in Example 1, indicating that the core-shell composite particles A and B provided by this invention play a key role in anti-reflection.

[0163] Compared to the synergistic effect of core-shell composite particles A and B in this invention, the surface hydroxyl activity of solid SiO2 in Comparative Example 1 is insufficient. The silane coupling agent can only achieve physical bonding and cannot achieve chemical reinforcement of covalent bonds. Its pencil hardness is significantly lower than that of Example 1, indicating that the core-shell composite particles A and B provided by this invention have good strength and can form a strong interfacial bond with the silane coupling agent, thereby improving wear resistance.

[0164] Compared to the synergistic effect of core-shell composite particles A and B used in this invention, the solid SiO2 particles in Comparative Example 1 have a hollow structure without closed pores and a TiO2 shell, making them more susceptible to resin erosion by moisture and ultraviolet radiation. Their weather resistance is shorter than that of Example 1, indicating that the core-shell composite particles A and B provided by this invention can improve impermeability and weather resistance.

[0165] (4) A comparison between Example 1 and Comparative Example 2 shows that although the hollow SiO2 particles used in Comparative Example 2 have a certain scattering ability, their simple structure lacks the design of the core-shell composite particles of this invention. First, the absence of a high-refractive-index TiO2 shell (a key feature of core-shell composite particle B) results in insufficient refractive index contrast with air, leading to lower light scattering efficiency and a lower anti-glare level (LV3) than Example 1 (LV6). Second, although its effective refractive index is lower than that of solid SiO2, its refractive index system is singular, making it impossible to construct a broad, gradually changing refractive index matching layer through the synergy of core-shell composite particles A and B as in this invention. Therefore, its reflectivity (4.9%) is much higher than that of Example 1 (0.8%). Third, the lack of a solid SiO2 core support weakens the particle's mechanical strength, significantly reducing its pencil hardness (HB). Fourth, the absence of a TiO2 shell provides UV shielding, resulting in poorer weather resistance (96h). This fully demonstrates the structural advancement and synergistic performance of the core-shell composite particles A and B designed in this invention.

[0166] (5) Comparing Example 1 and Comparative Example 3, it can be seen that Comparative Example 3 only uses core-shell composite particles A, without core-shell composite particles B to provide a high refractive index difference between the TiO2 shell and air. The scattering efficiency is lower than that of Example 1, indicating that the present invention uses core-shell composite particles A and core-shell composite particles B in synergy to improve the anti-glare effect.

[0167] Compared to Example 3, which utilizes the synergistic effect of core-shell composite particles A and B in this invention, although core-shell composite particles A can create a partial refractive index gradient, it lacks the low-to-high refractive index gradient change from the inside to the outside of core-shell composite particles B. Therefore, its reflectivity is higher than that of Example 1. This demonstrates that this invention uses core-shell composite particles A and B to synergistically regulate the refractive index, thereby reducing reflection.

[0168] Compared to the synergistic effect of core-shell composite particles A and B in this invention, Comparative Example 3 lacks the TiO2 shell provided by core-shell composite particles B, which makes it easier for ultraviolet rays to penetrate the anti-glare and anti-reflection film, resulting in a significantly shorter weather resistance time than Example 1. This demonstrates that the synergistic effect of core-shell composite particles A and B provided by this invention can improve weather resistance.

[0169] (6) Comparing Example 1 and Comparative Example 4, it can be seen that Comparative Example 4 only uses core-shell composite particles B. Although its TiO2 shell can improve the scattering effect (LV5), indicating that core-shell composite particles B is one of the keys to improving the anti-glare effect, the equivalent refractive index of core-shell composite particles B is low and cannot be gradually changed as in the present invention, resulting in a higher reflectivity than in Example 1. This indicates that the present invention reduces reflection through the synergistic effect of core-shell composite particles A and core-shell composite particles B.

[0170] Compared to the present invention, which uses the synergistic effect of core-shell composite particles A and B, Comparative Example 4 lacks the solid SiO2 core support provided by core-shell composite particles A, resulting in insufficient mechanical strength of the particles and a lower pencil hardness than Example 1. This demonstrates that the present invention improves wear resistance through the synergistic effect of core-shell composite particles A and B.

[0171] (7) As can be seen from the comparison between Example 1 and Comparative Example 5, Comparative Example 5 does not have dispersant KH550, which results in the surface hydroxyl groups of core-shell composite particles A and B not being modified. Hydrogen bonds lead to agglomeration, forming optical defects. The haze is significantly higher than that of Example 1, the transmittance is lower than that of Example 1, and the reflectance is higher than that of Example 1. This shows that the dispersant provided by the present invention can modify the core-shell composite particles and improve the dispersibility and interface density of the particles.

[0172] A comparison of Example 1 and Comparative Example 5 shows that, in the absence of dispersant KH550, the core-shell composite particles severely agglomerate due to the action of surface hydroxyl groups, forming macroscopic optical defects in the coating and causing a sharp increase in haze to 35.4%. The agglomerates also disrupt the uniform refractive index distribution, resulting in an increase in reflectivity to 3.5%. More importantly, the particles and the resin matrix rely solely on physical adsorption, resulting in numerous voids at the interface and weak bonding. This not only affects optical performance but also directly leads to a significant decrease in pencil hardness (H) and weather resistance (96h). This comparison strongly demonstrates that dispersant KH550, through chemical bonding, achieves particle surface modification and interface strengthening, making it an indispensable key component of this invention.

[0173] In summary, the anti-glare and anti-reflective coatings made from the core-shell composite particle anti-glare and anti-reflective coatings provided by this invention possess anti-reflective properties, anti-glare properties, wear resistance, hardness, and weather resistance, exhibiting excellent comprehensive performance and broad production prospects.

[0174] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An anti-glare anti-reflection coating containing core-shell composite particles, characterized by, The anti-glare anti-reflection coating comprises core-shell composite particle A, core-shell composite particle B, mixed solvent, dispersant, acrylic resin and leveling agent; The core-shell composite particle A comprises shell A with cavity and inner core A in the cavity, the shell A comprises hollow SiO2 particle, and the inner core A comprises solid SiO2 particle; The core-shell composite particle B comprises inner core B and shell B coated on the outer surface of the inner core B, the inner core B comprises hollow SiO2 particle, and the shell B comprises TiO2 particle.

2. The anti-glare anti-reflection coating according to claim 1, characterized in that, The anti-glare anti-reflection coating comprises, by weight fraction, 7-9 parts of core-shell composite particle A, 2-5 parts of core-shell composite particle B, 30-50 parts of mixed solvent, 1-2 parts of dispersant, 50-70 parts of acrylic resin, and 0.5-1 part of leveling agent.

3. Anti-glare anti-reflection coating according to claim 1 or 2, characterized in that The particle size of the inner core A is 10-100 nm; Preferably, the particle size of the core-shell composite particle A is 80-150 nm.

4. Anti-glare anti-reflection coating according to any one of claims 1 to 3, characterized in that, The particle size of the inner core B is 50-100 nm; Preferably, the particle size of the core-shell composite particle B is 120-180 nm.

5. Anti-glare anti-reflection coating according to any one of claims 1 to 4, characterized in that, The mixed solvent comprises ethyl acetate and ethanol in a volume ratio of 1:(1-2); Preferably, the dispersant comprises silane dispersant KH-550; Preferably, the leveling agent comprises organosilicon leveling agent polyether modified polysiloxane.

6. A process for the production of an anti-glare anti-reflection coating containing core-shell composite particles according to any one of claims 1 to 5, characterized in that The preparation method comprises the following steps: S1, preparation of core-shell composite particle dispersion liquid: According to the formula amount, 7-9 parts of core-shell composite particle A, 2-5 parts of core-shell composite particle B and 10-20 parts of mixed solvent are mixed, ultrasonic dispersion is performed for 30-40 min, then 1-2 parts of dispersant is added, stirring is performed for 10-20 min, and a core-shell composite particle dispersion liquid is obtained; S2, preparation of resin-solvent system: According to the formula amount, 50-70 parts of acrylic resin and 20-30 parts of mixed solvent are mixed, stirring is performed for 10-20 min, and a resin-solvent system is obtained; S3, preparation of anti-glare anti-reflection coating: The core-shell composite particle dispersion liquid obtained in step S1 and the resin-solvent system obtained in step S2 are mixed, stirring is performed for 15-25 min, then 0.5-1 part of leveling agent is added, stirring is performed for 5-10 min, and an anti-glare anti-reflection coating is obtained; Preferably, the stirring rate in steps S1, S2 and S3 is 300-500 rpm.

7. The production method according to claim 6, wherein The preparation method of the core-shell composite particle A in step S1 comprises the following steps: S11, coating hollow SiO2 layer: According to weight fraction, 1-2 parts of solid SiO2 particle and 100-200 parts of anhydrous ethanol are mixed and ultrasonic dispersion is performed for 20-30 min, then 5-7 parts of ammonia water is added and stirring is performed for 10-20 min, then 101-202 parts of template agent is added and stirring is performed for 15-25 min, and a dispersion liquid A is obtained; the dispersion liquid A and 78-91 parts of silicon source are mixed and reacted at 25-35℃, the reaction is stirred for 4-6 h, then solid-liquid separation and washing are performed, and a solid product A is obtained; S12, calcination to remove template agent and form hollow structure: The solid phase product A obtained in step S11 is vacuum dried at 60-70℃ for 1-2h, and then calcined at 500-600℃ for 2-3h to obtain the core-shell composite particle A; Preferably, the template agent comprises an aqueous solution of cetyltrimethylammonium bromide, which comprises cetyltrimethylammonium bromide 1-2 parts and water 100-200 parts by weight fraction; Preferably, the silicon source comprises a tetraethyl silicate ethanol solution, which comprises tetraethyl silicate 8-11 parts and ethanol 70-80 parts by weight fraction.

8. The production method according to claim 6 or 7, characterized by, The preparation method of the core-shell composite particle B in step S1 comprises the following steps: S11', hollow SiO2 particle dispersion and surface activation: 1-2 parts of hollow SiO2 particles and 100-200 parts of anhydrous ethanol are mixed and ultrasonically dispersed for 20-30min, then 2-3 parts of nitric acid is added and stirred for 5-10min to obtain dispersion liquid B; S12', titanium source solution coating: The dispersion liquid B obtained in step S11' and 80-110 parts of a titanium source are mixed and reacted at 25-35℃, the reaction is stirred for 1-2h, then solid-liquid separation and washing are performed to obtain a solid phase product B; S13', calcination and crystallization: The solid phase product B obtained in step S12' is vacuum dried at 60-70℃ for 1-2h, and then calcined at 450-550℃ for 1-2h to obtain the core-shell composite particle B; Preferably, the titanium source comprises a tetrabutyl titanate ethanol solution, which comprises tetrabutyl titanate 10-20 parts and anhydrous ethanol 70-90 parts by weight fraction.

9. An anti-glare anti-reflection film, characterized by The anti-glare anti-reflection film is prepared by using the anti-glare anti-reflection coating containing the core-shell composite particle according to any one of claims 1-5.

10. A polarizing sheet characterized by comprising: The polarizing sheet comprises the anti-glare anti-reflection film according to claim 9.

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