Aging-resistant, dust-resistant and anti-reflection coating solution, preparation method and application thereof

Abstract

This invention belongs to the field of optical materials technology and discloses a coating solution with anti-aging, dust-resistant, and anti-reflective properties, its preparation method, and its application. The coating solution includes silica sol, antistatic and weather-resistant additives, and a template agent. The preparation process of the silica sol includes: mixing silicate ester with a diluent to obtain solution A; mixing water, a stabilizer, and an alkaline catalyst to obtain solution B; and reacting solution A and solution B to prepare the silica sol. In solution B, the mass of the stabilizer is less than 0.35% of the mass of water. The antistatic and weather-resistant additives include tin halides and antimony halides. The film layer formed on the glass surface using this coating solution enables the photovoltaic glass to simultaneously meet the performance requirements of anti-aging, dust-resistant, and anti-reflective properties, and further exhibits excellent antistatic performance.

Description

Technical Field

[0001] This invention belongs to the field of optical materials technology, and specifically relates to an aging-resistant, dust-resistant, and anti-reflective coating liquid, its preparation method, and its application. Background Technology

[0002] As a representative of new energy sources, the photovoltaic industry has seen its cumulative installed capacity increase by approximately 25 times over the past decade. It is projected that by 2030, more than 10% of the world's total electricity supply will be provided by solar photovoltaic power generation. However, solar panels operating in harsh environments for extended periods typically accumulate a thick layer of dust on their surface. This significantly reduces the transmittance of the coated glass on the photovoltaic modules, and the photoelectric conversion efficiency of the cells decreases exponentially with increasing dust density on the glass surface, severely impacting the normal power generation of the solar cells.

[0003] Chinese patent CN103044977A discloses a method for preparing a hydrophilic, self-cleaning, antireflective coating. It primarily addresses the issues of coatings lacking hydrophilic self-cleaning and antireflective / anti-reflective properties, while also requiring solutions for high-temperature curing. The method includes the following steps: 1) Mixing ammonia, alcohol, and deionized water at a volume ratio of 1:10–60:0.5–5 and heating to 30–90°C; 2) Mixing an organosilicon source and alcohol at a volume ratio of 1:1–30 to obtain a mixed solution; 3) Adding the reaction solution prepared in step 2) to the mixed solution prepared in step 1) in a single step, followed by reaction and other treatments to obtain the finished product. The resulting film is uniform, with a regular surface nanostructure and a high hydroxyl density on the particle surface, thus significantly improving light transmittance. When coated on one side, the light transmittance increases by more than 3%, while also exhibiting good hydrophilic self-cleaning properties. However, this film lacks antistatic or anti-accelerated aging properties, making it difficult to maintain stability over long-term use.

[0004] Chinese patent CN102153292A discloses a high-transmittance nano-silica antireflective film, its preparation method, and its application. Specifically, it includes the following steps: using tetraethyl orthosilicate, ethanol, and water as raw materials, and ammonia or hydrochloric acid as a catalyst, a silica sol is prepared according to a molar ratio of tetraethyl orthosilicate:ethanol:water:catalyst = 1:2-4:30-80:1-5. The silica sol is diluted, and polyvinylpyrrolidone stabilizer is added at a rate of 1-5 g / L of coating solution. A resin binder is added at a rate of 5-15 g / L of coating solution to obtain the coating solution. The coated glass is pre-cured at 100-200℃ for 20-300 s, followed by tempering. However, this film does not possess self-cleaning properties.

[0005] Chinese patent CN114772942A discloses a self-cleaning nano-coating for photovoltaic glass and its processing method. The raw materials include nano-silica, nano-titanium dioxide, waterborne polyurethane, polymer emulsion, dispersant, and siloxane. The nano-silica content is less than 4 / 5, and the nano-titanium dioxide content is not less than 3%. The processing steps include the construction and synthesis of a microstructure on the surface of core-shell nanoparticles. The core-shell nanoparticles are complex core-shell micro / nanomaterials with multi-layered core-shell structures. The film thickness of the microstructure is 1–3 micrometers. The microstructure is constructed using a three-dimensional cross-linking method, which forms the surface microstructure through covalent bonds, exhibiting swelling capacity. During the formation process, a linear polymer is first formed, followed by cross-linking through reactions between polymers. The core-shell nanoparticles are mass-produced through graft modification. An organic-inorganic cross-linking doping technique is used to dope conductive element intermediates and photocatalytic element intermediates. The conductive element doping results in a surface resistivity of the coated glass that is between 1 × 10⁻⁶. 4 Ω~1×10 11 Between Ω, the photocatalytic element intermediate is an inorganic intermediate. However, this film layer does not possess resistance to accelerated aging and is difficult to use for a long time in harsh environments.

[0006] In other words, the film formed by the coating solution in the existing technology cannot simultaneously meet the performance requirements of aging resistance, dust resistance and anti-reflection, which is not conducive to the application of coating solution in the photovoltaic industry.

[0007] Therefore, there is an urgent need to provide a new coating solution that enables the film formed by its application in the photovoltaic field to have the functions of aging resistance, dust resistance, and anti-reflection. Summary of the Invention

[0008] This invention aims to solve at least one of the technical problems existing in the prior art. To this end, this invention proposes a coating solution with aging resistance, dust resistance, and antireflection properties, its preparation method, and its application. The film layer formed by the coating solution of this invention simultaneously meets the performance requirements of aging resistance, dust resistance, and antireflection (or antireflection).

[0009] This invention primarily provides an aging-resistant, dust-resistant, and antireflective coating solution, aiming to solve the problem of dust accumulation on the surface of photovoltaic coated glass, leading to reduced power generation efficiency of photovoltaic modules. Traditional antireflective coatings for photovoltaic glass, in order to increase the hardness of the coating, are designed to form a dense structure, resulting in the coating easily adsorbing dust. Another type is a hydrophobic self-cleaning antireflective coating, prepared using inorganic-doped organic silica sol. This coating surface has superhydrophobic properties, allowing it to displace dust after rainfall, thus achieving a self-cleaning effect. However, this hydrophobic coating is easily damaged by ultraviolet light, leading to a deterioration in its hydrophobic properties. Furthermore, due to its hydrophobic nature, rainwater easily forms individual water droplets on the coating surface, which, after drying, become spots of mixed water and dust, significantly reducing the transmittance of the coated glass in that area.

[0010] The coating solution of this invention includes silica sol, template agent, and antistatic and weather-resistant additives. The coating solution is uniformly coated on the surface of the antireflective film layer of photovoltaic glass. After the glass is tempered, an anti-dust and antistatic antireflective film layer is formed, which gives the photovoltaic glass good anti-reflective, anti-dust, antistatic and anti-accelerated aging properties. The film layer can maintain good cleanliness after rain, mechanical vibration and air convection, which can enable the photovoltaic module to maintain stable power generation efficiency for a long time in harsh environments.

[0011] The membrane liquid preparation process in this invention is simple, easy to use, and has high stability, making it suitable for large-scale industrial production. It can endow photovoltaic glass with good anti-reflection, anti-dust, anti-static, and anti-accelerated aging properties, which can significantly extend the service life of photovoltaic glass and reduce its maintenance costs.

[0012] The first aspect of the present invention provides a coating liquid that is resistant to aging, dust, and has enhanced transparency.

[0013] Specifically, a coating solution that is resistant to aging, dust, and has enhanced transparency includes silica sol, antistatic weather-resistant additives, and template agents;

[0014] The preparation process of the silica sol includes: mixing silicate ester with diluent to obtain solution A; mixing water, stabilizer and alkaline catalyst to obtain solution B; and mixing solution A and solution B to react and prepare the silica sol.

[0015] In solution B, the mass of the stabilizer is less than 0.35% of the mass of the water;

[0016] The antistatic and weather-resistant additives include tin halides and antimony halides.

[0017] Preferably, the mass of the stabilizer is 0.01 to 0.35% of the mass of the water, for example, 0.01 to 0.33%, 0.1 to 0.33%, or 0.05 to 0.33%.

[0018] Preferably, the silicate ester is selected from at least one of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, trimethylmethoxysilane, or trimethylethoxysilane; more preferably, the silicate ester is selected from at least one of ethyl orthosilicate, methyltriethoxysilane, dimethyldiethoxysilane, or trimethylethoxysilane.

[0019] Preferably, the water is purified water or deionized water.

[0020] Preferably, the diluent is selected from at least one of methanol, ethanol, isopropanol or n-butanol.

[0021] Preferably, in solution A, the mass ratio of the silicate ester to the diluent is 15-30:(15-50), more preferably 15-30:(20-40).

[0022] Preferably, a diluent and / or a pore-forming agent are added during the preparation of liquid B.

[0023] Preferably, the stabilizer includes at least one selected from diethanolamine, dimethylethanolamine, dimethylformamide, or dimethylacetamide. When a stabilizer is present, the stability of the silica sol can be ensured when the silica sol, template agent, and antistatic weather-resistant additive are mixed.

[0024] Preferably, the alkaline catalyst includes at least one of ammonia, sodium hydroxide, or potassium hydroxide.

[0025] Preferably, the pore-forming agent is polyethylene glycol, and more preferably polyethylene glycol with a molecular weight of 200 to 1000.

[0026] Preferably, in solution B, the mass ratio of water to alkaline catalyst is 15-30:(0.1-1.0).

[0027] Preferably, when liquid B contains a diluent and a pore-forming agent, the mass ratio of water to diluent and pore-forming agent is 15-30:(10-50):(0.01-0.2), and more preferably 15-30:(20-40):(0.01-0.15).

[0028] Preferably, solution A is added to solution B at a constant speed at room temperature for 10-30 minutes, and then solution A and solution B react.

[0029] Preferably, the reaction of liquid A and liquid B is carried out at 15-40°C for 1-8 hours, and more preferably at room temperature for 2-8 hours.

[0030] Preferably, after the reaction between liquid A and liquid B is completed, the mixture is aged at room temperature for 2 to 6 days.

[0031] Preferably, the tin halide includes at least one of tin tetrachloride pentahydrate, tin tetrachloride, tin fluoride, and tin tetrabromide, and more preferably tin tetrachloride.

[0032] Preferably, the antimony halide includes at least one of antimony trichloride, antimony tribromide, and antimony pentafluoride, with antimony trichloride being more preferred.

[0033] The antistatic and weather-resistant additives not only improve the antistatic effect of the film formed by the coating solution, but also significantly enhance the aging resistance of the film.

[0034] Preferably, in the antistatic and weather-resistant additive, the mass ratio of tin halide to antimony halide is 20-100:1, more preferably 40-80:1.

[0035] Preferably, the antistatic and weather-resistant additive also includes a diluent.

[0036] Preferably, the template agent is silica core-shell microspheres. This template is prepared according to the method described in "2.2 Experimental Section" of Wan Yong's doctoral dissertation, "Preparation and Formation Mechanism Study of Silica Hollow Spheres and Core-Shell Structures," published by the University of Science and Technology of China.

[0037] Preferably, in the coating solution, the mass ratio of silica sol, antistatic weather-resistant agent and template agent, based on the effective solid content ratio, is 1:(0.1~1.0):(0.005~0.1); more preferably, it is 1:(0.1~0.8):(0.005~0.04).

[0038] The effective solid content ratio refers to the weight ratio of the remaining solid substances in a solution after a solid content test.

[0039] Preferably, the coating solution also includes a volatilization inhibitor.

[0040] Preferably, the volatile inhibitor is selected from at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, or diacetone.

[0041] Preferably, the volatile inhibitor accounts for 1-15% of the total mass of the coating solution, more preferably 4-8%.

[0042] A second aspect of the present invention provides a method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution.

[0043] Specifically, a method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0044] The coating solution is obtained by mixing silica sol with antistatic weather-resistant additives and template agents.

[0045] Preferably, tin halides are mixed with a diluent, and then antimony halides are added and stirred to obtain the antistatic and weather-resistant additive.

[0046] Preferably, tin tetrachloride pentahydrate is added to a diluent to prepare a solution with a molar concentration of 0.4–1.0 mol / L. Then, antimony trichloride is added at a mass ratio of tin tetrachloride pentahydrate to antimony trichloride of 20–100:1, and the solution is stirred and dissolved at room temperature. The solution is then stirred at a constant temperature of 60–100°C for 3–8 hours, cooled, and aged for 2–6 days to obtain an antistatic and weather-resistant additive.

[0047] Preferably, after mixing silica sol with antistatic weather-resistant additives and template agents, a diluent with a total solid content of 2-4% for silica sol, antistatic weather-resistant additives, and template agents is added to prepare a pre-coating solution. Finally, a volatilization inhibitor is added at 4-8% of the mass of the pre-coating solution to prepare the coating solution.

[0048] Preferably, the method for preparing the coating solution includes the following steps:

[0049] (1) Prepare solution A by premixing silicate ester and diluent at a mass ratio of 15-30:20-40, and prepare solution B by mixing purified water, diluent, pore-forming agent, stabilizer and ammonia at a mass ratio of 15-30:20-40:0.01-0.15:0.005-0.05:0.1-1.0;

[0050] (2) Add the A solution described in step (1) to the stirred B solution at a constant speed at room temperature for 10 to 30 minutes, and then continue to react at room temperature for 3 to 8 hours. After the reaction is completed, age at room temperature for 2 to 6 days to obtain silica sol.

[0051] (3) Add tin tetrachloride pentahydrate to a diluent to prepare a solution with a molar concentration of 0.4-1.0 mol / L. Then add antimony trichloride at a mass ratio of tin tetrachloride pentahydrate to antimony trichloride of 20-100:1 and stir to dissolve at room temperature. Then stir and react at a constant temperature of 60-100℃ for 3-8 hours. After cooling and aging for 2-6 days, an antistatic weather-resistant additive is obtained.

[0052] (4) The template agent was prepared according to the method described in "2.2 Experimental Section" of the doctoral dissertation of Wan Yong, University of Science and Technology of China, "Study on the Preparation and Formation Mechanism of Hollow Spheres and Core-Shell Structures of Silica".

[0053] (5) Mix silica sol, template agent and antistatic weathering agent in an effective solid content ratio of 1:0.1-0.8:0.005-0.04, and add diluent at 2-4% of the final solid content to prepare a pre-coating solution. Finally, add volatilization inhibitor at 4-8% of the mass of the pre-coating solution to prepare the coating solution.

[0054] A third aspect of the present invention provides an application of a coating solution that is resistant to aging, dust, and has enhanced transparency.

[0055] Specifically, a type of glass includes a film layer formed by the aforementioned coating solution.

[0056] Preferably, the glass includes photovoltaic glass.

[0057] A method for preparing photovoltaic glass includes the following steps:

[0058] The coating solution is applied to the glass using a roller coating method, then cured, and subsequently tempered to obtain the photovoltaic glass.

[0059] Preferably, the curing temperature is 140–160°C, and more preferably 150–160°C.

[0060] Preferably, the tempering temperature is 680–720°C, and more preferably 690–710°C.

[0061] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0062] The coating solution of this invention includes silica sol, antistatic and weather-resistant additives, and a template agent. The silica sol is prepared by a specific method of this invention. During the preparation of the silica sol, a stabilizer and an alkaline catalyst are required, and the stabilizer needs to be used in a specific amount. The antistatic and weather-resistant additives include tin halides and antimony halides. These antistatic and weather-resistant additives not only improve the antistatic effect of the film formed by the coating solution but also significantly enhance the aging resistance of the film. The film formed on the glass surface using this coating solution enables the photovoltaic glass to simultaneously meet the performance requirements of aging resistance, dust resistance, and antireflection (or anti-reflection), and further possesses excellent antistatic properties. Attached Figure Description

[0063] Figure 1 This is a cross-sectional view of the coated glass in Example 1;

[0064] Figure 2 This is a cross-sectional view of the coated glass in Comparative Example 2. Detailed Implementation

[0065] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0066] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0067] The solid content was tested according to the following method: Liquid A was quantitatively weighed into a beaker using a precision electronic balance, and the weight of the empty beaker, G, was recorded. 杯 and the weight of liquid A, G 液 The beaker containing solution A was placed in a 160℃ constant temperature drying oven for 1 hour. After being removed, it was transferred to a desiccator and cooled to room temperature. The total weight G of the beaker and the solid in it was then measured. 杯+固 Calculate the solid content = (G 杯+固 -G 杯 ) / G 液 .

[0068] Example 1: Preparation of Coating Solution

[0069] An aging-resistant, dust-resistant, and antireflective coating solution, comprising silica sol, antistatic weather-resistant additives, template agent, and ethylene glycol butyl ether;

[0070] 25g purified water, 25g ethanol, 0.05g dimethylformamide, 0.5g ammonia (20% by mass) and 0.06g polyethylene glycol were added sequentially to a conical flask equipped with a magnetic stirrer to form solution B. 20g tetraethyl orthosilicate and 30g ethanol were added to a constant pressure funnel to form solution A. Solution A in the constant pressure funnel was added dropwise to solution B in the conical flask under stirring at a constant rate over a period of 25 minutes. The mixture was then stirred at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 6.0 wt.% was obtained.

[0071] In solution B, the mass of the stabilizer dimethylformamide is 0.2% of the mass of purified water.

[0072] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0073] (1) Add 25g purified water, 25g ethanol, 0.05g dimethylformamide, 0.5g ammonia (20% by mass) and 0.06g polyethylene glycol to a conical flask with a magnetic stirrer to form solution B. Add 20g tetraethyl orthosilicate and 30g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 25 minutes. Then continue stirring at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 6.0 wt.% is obtained.

[0074] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.21g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0075] (3) Silica core-shell microspheres were prepared as template agents according to the method described in "2.2 Experimental Section" of Wan Yong's doctoral dissertation "Preparation and Formation Mechanism of Silica Hollow Spheres and Core-Shell Structures". The solid content was 3.0 wt.%.

[0076] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.6:0.015, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0077] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0078] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0079] Example 2

[0080] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0081] (1) Add 15g purified water, 35g ethanol, 0.005g diethanolamine, 0.5g ammonia (20% by mass) and 0.15g polyethylene glycol to a conical flask with a magnetic stirrer to form solution B (the mass of the stabilizer diethanolamine in solution B is 0.03% of the mass of purified water). Add 20g tetraethyl orthosilicate and 30g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 20 minutes. Then continue stirring at room temperature for 4 hours. After aging for 3 days, a silica sol with a solid content of 6.2 wt.% is obtained.

[0082] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 15.75g of tin tetrachloride pentahydrate and 0.61g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.2wt.%.

[0083] (3) Same as the template agent in Example 1;

[0084] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.4:0.01, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 8% of the mass of the pre-coating solution to prepare the coating solution.

[0085] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0086] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0087] Example 3

[0088] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0089] (1) Add 30g purified water, 25g ethanol, 0.01g dimethylacetamide, 0.6g ammonia (20% by mass) and 0.01g polyethylene glycol to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylacetamide is 0.03% of the mass of purified water). Add 15g tetraethyl orthosilicate and 25g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 30 minutes. Then continue stirring at room temperature for 6 hours. After aging for 5 days, a silica sol with a solid content of 5.0 wt.% is obtained.

[0090] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 8.75g of tin tetrachloride pentahydrate and 0.12g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 1.8wt.%.

[0091] (3) Same as the template agent in Example 1;

[0092] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.3:0.04, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 4% of the mass of the pre-coating solution to prepare the coating solution.

[0093] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0094] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0095] Example 4

[0096] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0097] (1) Add 30g purified water, 25g ethanol, 0.025g dimethylformamide and 0.4g ammonia (ammonia concentration of 20%) to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylformamide is 0.08% of the mass of purified water). Add 20g tetraethyl orthosilicate, 1g methyltriethoxysilane and 25g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 20min. Then continue stirring at room temperature for 5h. After aging for 4 days, a silica sol with a solid content of 6.9wt.% is obtained.

[0098] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.16g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0099] (3) Same as the template agent in Example 1;

[0100] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.2:0.01, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add diethylene glycol butyl ether at 4% of the mass of the pre-coating solution to prepare the coating solution.

[0101] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0102] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0103] Example 5

[0104] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0105] (1) Add 25g purified water, 25g ethanol, 0.025g dimethylformamide, 0.5g ammonia (20% by mass) and 0.06g polyethylene glycol to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylformamide is 0.1% of the mass of purified water). Add 16g tetraethyl orthosilicate, 4g methyltriethoxysilane and 30g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 25 minutes. Then continue stirring at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 6.3 wt.% is obtained.

[0106] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.16g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0107] (3) Same as the template agent in Example 1;

[0108] (4) Mix silica sol, template agent and antistatic weathering agent in an effective solid content ratio of 1:0.1:0.005, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0109] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0110] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0111] Example 6

[0112] A method for preparing an aging-resistant, dust-resistant, and anti-reflective coating solution includes the following steps:

[0113] (1) Add 20g purified water, 25g ethanol, 0.01g dimethylformamide, and 0.6g ammonia (ammonia concentration of 20%) to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylformamide is 0.05% of the mass of purified water). Add 29g tetraethyl orthosilicate, 1g methyltriethoxysilane, and 25g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 20min. Then continue stirring at room temperature for 5h. After aging for 4 days, a silica sol with a solid content of 9.9wt.% is obtained.

[0114] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.16g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0115] (3) Same as the template agent in Example 1;

[0116] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.8:0.03, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0117] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0118] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0119] Comparative Example 1

[0120] The Yishang dustproof coating liquid, purchased from Shenzhen Yishang Nanotechnology Co., Ltd., was applied to photovoltaic glass using a roller coating method. The glass was then baked and cured at 160°C, followed by tempering at 710°C to obtain the coated glass.

[0121] Comparative Example 2

[0122] A method for preparing a coating solution includes the following steps:

[0123] (1) Add 20g of purified water, 25g of ethanol and 0.4g of hydrochloric acid (concentration of hydrochloric acid is 0.2mol / L) to a conical flask with a magnetic stirrer to form solution B. Add 30g of tetraethyl orthosilicate and 25g of ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 20min. Then continue stirring at room temperature for 4h. After aging for 4 days, a silica sol with a solid content of 15.4wt.% is obtained.

[0124] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.21g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0125] (3) Same as the template agent in Example 1;

[0126] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.8:0.02, and add ethanol to adjust the solid content to 4wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0127] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0128] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0129] Comparative Example 3

[0130] A method for preparing a coating solution includes the following steps:

[0131] (1) Add 20g purified water, 25g ethanol, 0.1g dimethylformamide and 0.6g ammonia (20% mass fraction of ammonia) to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylformamide is 0.5% of the mass of purified water). Add 25g tetraethyl orthosilicate and 25g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 25 minutes. Then continue stirring at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 11.7 wt.% is obtained.

[0132] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.21g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0133] (3) Same as the template agent in Example 1;

[0134] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.6:0.02, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0135] A method for preparing coated glass includes the following steps:

[0136] The above coating solution was applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and subsequently tempered at 710°C to obtain coated glass.

[0137] Comparative Example 4

[0138] A method for preparing a coating solution includes the following steps:

[0139] (1) Add 20g of purified water, 25g of ethanol and 0.6g of ammonia (20% by mass) to a conical flask with a magnetic stirrer to form solution B. Add 20g of tetraethyl orthosilicate and 25g of ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 25 minutes. Then continue stirring at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 11.3 wt.% is obtained.

[0140] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 12.25g of tin tetrachloride pentahydrate and 0.21g of antimony trichloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 2.0wt.%.

[0141] (3) Same as the template agent in Example 1;

[0142] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.6:0.02, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0143] A method for preparing coated glass includes the following steps:

[0144] The above coating solution was applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and subsequently tempered at 710°C to obtain coated glass.

[0145] Comparative Example 5

[0146] A method for preparing a coating solution includes the following steps:

[0147] (1) Add 20g of purified water, 25g of ethanol, 0.01g of dimethylformamide and 0.5g of ammonia (ammonia concentration of 20%) to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylformamide is 0.05% of the mass of purified water). Add 30g of tetraethyl orthosilicate and 25g of ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 25 minutes. Then continue stirring at room temperature for 5 hours. After aging for 4 days, a silica sol with a solid content of 10.6 wt.% is obtained.

[0148] (2) Same as the template agent in Example 1;

[0149] (3) Mix silica sol and template agent at an effective solid content ratio of 1:0.6, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 5% of the mass of the pre-coating solution to prepare the coating solution.

[0150] A method for preparing coated glass includes the following steps:

[0151] The above coating solution was applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and subsequently tempered at 710°C to obtain coated glass.

[0152] Comparative Example 6

[0153] A method for preparing a coating solution includes the following steps:

[0154] (1) Add 30g purified water, 25g ethanol, 0.01g dimethylacetamide, 0.6g ammonia (20% by mass) and 0.01g polyethylene glycol to a conical flask with a magnetic stirrer to form solution B (in solution B, the mass of the stabilizer dimethylacetamide is 0.03% of the mass of purified water). Add 15g tetraethyl orthosilicate and 25g ethanol to a constant pressure funnel to form solution A. Add solution A from the constant pressure funnel to solution B in the conical flask under stirring at a constant rate for 30 minutes. Then continue stirring at room temperature for 6 hours. After aging for 5 days, a silica sol with a solid content of 5.0 wt.% is obtained.

[0155] (2) Add 39.45g of ethanol to another conical flask with a magnetic stirrer, then add 8.75g of tin tetrachloride pentahydrate and 0.12g of aluminum chloride to the ethanol, stir to dissolve at room temperature, then stir at 80℃ for 5h, cool and age for 4 days to obtain an antistatic weather-resistant additive with a solid content of 1.8wt.%.

[0156] (3) Same as the template agent in Example 1;

[0157] (4) Mix silica sol, template agent and antistatic weather-resistant agent in an effective solid content ratio of 1:0.3:0.04, and add ethanol to adjust the solid content to 3wt.% to prepare a pre-coating solution. Finally, add ethylene glycol butyl ether at 4% of the mass of the pre-coating solution to prepare the coating solution.

[0158] A method for preparing dust-resistant, anti-static, and anti-reflective coated glass includes the following steps:

[0159] The above coating solution is applied to photovoltaic glass by roller coating, then baked and cured at 160°C, and then tempered at 710°C to obtain dust-resistant, anti-static, and anti-reflective coated glass.

[0160] Product effectiveness test

[0161] Observation of the film layers formed by the coating solutions of Example 1 and Comparative Example 2 Figure 1 This is a cross-sectional view of the coated glass in Example 1; Figure 2 This is a cross-sectional view of the coated glass in Comparative Example 2. From... Figure 1-2 It can be seen that the film formed by the coating solution in Example 1 has a microscopic mountain-like structure, while the film formed by the coating solution in Comparative Example 1 is relatively flat.

[0162] The coated glasses prepared in the above embodiments and comparative examples were subjected to the following performance tests:

[0163] (1) Transmittance test: The transmittance (T) of the film layer was measured using the Beijing Aobotai GST-3 air-floating tabletop patterned glass spectral transmittance measuring instrument. The coated glass was placed on the measuring table with the film surface facing up and moved to the measuring point. When the instrument started measuring, the glass was moved to continuously measure 12 transmittance data at different positions. The maximum and minimum values ​​were removed and the average value was taken. The transmittance (ΔT) was obtained by subtracting the transmittance of the substrate glass from the measured transmittance.

[0164] (2) Dust Adhesion Test: Prepare a clean coated glass with dimensions of 300×300mm and a clean crucible with an inner area of ​​S. First, weigh the crucible on a balance with an area of ​​0.01%. Then, add 3g of talcum powder to the crucible and record the total weight G'. Next, use a fixing ring and an antistatic elastic rope to invert the crucible onto the coating surface of the coated glass. Turn it over several times to ensure that the talcum powder is fully in contact with and adheres to the coating surface. After the test, remove the crucible and weigh it to obtain G”. Calculate the dust adhesion amount according to the following formula:

[0165] Dust accumulation amount = (G' - G”) / S, unit: g / m 2 .

[0166] Tests were conducted on three different areas of three different coated glass pieces, and the final average value was taken.

[0167] (3) Antistatic test: The MODEL-100 surface resistance tester was used to test at least 12 different areas on the same coated glass, and the median of the final result was taken.

[0168] (4) PCT high pressure accelerated aging test: The coated glass to be tested is cut into square pieces of 300×300mm, and then placed vertically in the high pressure accelerated aging test chamber with a 3cm gap between the glass pieces. Then, under the test conditions of temperature 121℃, humidity 100% and 2 standard atmospheres, it is continuously tested for 48 hours. The test results represent the service life of the film layer of about 20 years.

[0169] The test results are shown in Table 1.

[0170] Table 1

[0171]

[0172]

[0173] As can be seen from Table 1, all embodiments have good dust and antistatic properties and can pass the PCT accelerated aging test. After the accelerated aging test, the membrane surface permeability decreased less and maintained the same dust resistance as before the accelerated aging test, which can ensure long-term stability in harsh environments.

[0174] Comparative Example 1 showed good dust resistance and high transmittance, but failed the PCT accelerated aging test, with a significant decrease in transmittance and dust resistance before and after the test. Comparative Example 2 used hydrochloric acid as a catalyst, resulting in a film surface with poor dust resistance. Comparative Example 3 had excessive stabilizer in the coating solution, leading to excessively large silica sol particles, which significantly reduced the transmittance of the film. Comparative Example 4 did not add stabilizer to the coating solution, resulting in poor silica sol stability, low transmittance, and poor dust resistance. Comparative Example 5 did not add antistatic and weather-resistant additives to the coating solution, resulting in high surface resistivity and failure to pass the PCT accelerated aging test. In Comparative Example 6, antimony trichloride was replaced with aluminum chloride in the coating solution, resulting in poor antistatic and weather-resistant properties.

[0175] Traditional antireflective coatings for photovoltaic glass, in order to achieve high hardness, are designed to form a dense structure, which makes them prone to dust adsorption. Another type is the hydrophobic self-cleaning antireflective coating, prepared using inorganic-doped organic silica sol, which gives the coating superhydrophobic properties, allowing it to repel surface dust after rainfall and achieve self-cleaning. However, this type of hydrophobic coating is easily damaged by ultraviolet light, leading to performance degradation; furthermore, after being washed by rain, the coating easily forms individual water droplets, which, after drying, become spots of mixed water and dust, significantly reducing the transmittance of the coated glass in that area.

[0176] This invention utilizes a sol-gel method under alkaline catalytic conditions to form a granular silica sol with a particle size that can be freely controlled through formulation variations. When this silica sol is combined with a template agent and an antistatic agent and coated onto the surface of photovoltaic glass, it creates a microscopic, uneven mountain-like structure on the glass surface, imparting excellent dust-resistant properties to the film. Simultaneously, the antistatic and weather-resistant additives provide good electrical conductivity to the film, effectively preventing electrostatic adsorption caused by dust friction. Furthermore, the combination of silica sol and antistatic and weather-resistant additives gives the film excellent weather resistance. After passing the PCT accelerated aging test, the film still maintains high transmittance and good dust and antistatic properties, ensuring a clean surface for long-term use of the photovoltaic glass in harsh environments, extending the lifespan of the photovoltaic module and maintaining stable power generation efficiency.

Claims

1. A plating solution, characterized by comprising: Including silica sol, antistatic and weather-resistant additives, and template agents; The preparation process of the silica sol includes: mixing silicate ester with diluent to obtain solution A; mixing water, stabilizer and alkaline catalyst to obtain solution B; and mixing solution A and solution B to react and prepare the silica sol. In solution B, the mass of the stabilizer is 0.01~0.35% of the mass of the water, and the mass ratio of the water to the alkaline catalyst is 15~30:(0.1~1.0). The antistatic and weather-resistant additives include tin halides and antimony halides; The stabilizer includes at least one of diethanolamine, dimethylethanolamine, dimethylformamide, or dimethylacetamide; The template agent is silica core-shell microspheres.

2. The plating solution according to claim 1, wherein The silicate ester is selected from at least one of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, trimethylmethoxysilane, or trimethylethoxysilane.

3. The plating solution of claim 1, wherein In the preparation of liquid B, a diluent and / or a pore-forming agent are also added.

4. The coating solution according to claim 1, characterized in that, The alkaline catalyst includes at least one of ammonia, sodium hydroxide, or potassium hydroxide.

5. The plating solution of claim 3, wherein The pore-forming agent is polyethylene glycol.

6. The plating solution of claim 3, wherein When solution B contains diluent and pore-forming agent, the mass ratio of water to diluent and pore-forming agent is 15~30:(10~50):(0.01~0.2).

7. The plating solution of claim 1, wherein The reaction of solution A and solution B is carried out at 15-40°C for 1-8 hours; and / or, after the reaction of solution A and solution B is completed, the mixture is aged at room temperature for 2-6 days; and / or, the tin halide includes at least one of tin tetrachloride pentahydrate, tin tetrachloride, tin fluoride, and tin tetrabromide; and / or, the antimony halide includes at least one of antimony trichloride, antimony tribromide, and antimony pentafluoride.

8. The plating solution of claim 1, wherein In the coating solution, the mass ratio of silica sol, antistatic weather-resistant agent, and template agent, based on the effective solid content ratio, is 1:(0.1~1.0):(0.005~0.1); and / or, the coating solution also includes a volatilization inhibitor.

9. The method of claim 1-8, wherein the plating solution is prepared by the steps of: Includes the following steps: The silica sol is mixed with an antistatic and weather-resistant additive and a template agent to obtain the coating solution.

10. A glass characterized by, The film layer formed by the coating solution according to any one of claims 1-8.

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