An antireflective coating solution and an antireflective photovoltaic glass

Abstract

This invention provides an antireflective coating solution and an antireflective photovoltaic glass, belonging to the field of antireflective coating technology. The antireflective coating solution provided by this invention comprises: mixing a silicate ester precursor, a coupling agent, and an organic solvent, then adding a catalyst or its aqueous solution to react, obtaining a reaction solution; adding a modified organosilicon resin to the reaction solution, reacting, and aging to obtain the antireflective coating solution. The modified organosilicon resin is an alkoxy-containing fluorinated organosilicon resin, which has alkoxy groups and fluorinated side chains. The alkoxy content of the alkoxy-containing fluorinated organosilicon resin is 20-55%, and the fluorinated side chain is CH2CH2(CF2). n CF3, n is 0 to 13. Since the main chain of the above resin is a flexible silicon-oxygen chain, it can give the modified coating better wear resistance; at the same time, the fluorine-containing side chain can give the modified coating good hydrophobic and oleophobic properties.

Description

Technical Field

[0001] This invention relates to the field of antireflection coating technology, specifically to an antireflection coating solution and an antireflection photovoltaic glass. Background Technology

[0002] Solar energy possesses characteristics such as being clean, widely distributed, inexhaustible, and readily available. Photovoltaic power generation, a technology that converts this renewable energy into electricity and heat, not only helps address the energy crisis but also significantly reduces greenhouse gas emissions and environmental pollution. Among all photovoltaic technologies, silicon solar cells, due to their high photoelectric conversion efficiency and low cost, still dominate large-scale production and application, becoming the most widely used type of solar cell. To further improve their photoelectric conversion efficiency and obtain more efficient silicon solar cells, besides developing silicon semiconductor technology, increasing the light transmittance of photovoltaic glass is another effective method. This anti-reflection technology generally involves adding an anti-reflection film to the photovoltaic glass and utilizing the principle of light interference to effectively reduce the loss of incident light, thereby improving photoelectric conversion efficiency.

[0003] With the expansion of solar cell application scenarios, especially in harsh environments such as outdoor, marine, or desert locations, more application standards have been put forward for antireflective films. They not only require high transmittance to ensure high photoelectric conversion efficiency, but also need to have good moisture resistance, salt spray resistance, acid resistance, washability, and stain resistance. This has become a core technical challenge that urgently needs to be solved in this field. Summary of the Invention

[0004] The present invention is made to solve the above-mentioned problems, and aims to provide an antireflective coating liquid that can improve various properties of photovoltaic glass, and an antireflective photovoltaic glass coated with the antireflective coating liquid that has good moisture resistance, salt spray resistance, acid resistance, washability and stain resistance.

[0005] This invention provides an antireflective coating solution, characterized by comprising: mixing a silicate ester precursor, a coupling agent, and an organic solvent, then adding a catalyst or an aqueous solution thereof to react and obtain a reaction solution; adding a modified organosilicon resin to the reaction solution, reacting, and aging to obtain the antireflective coating solution, wherein the modified organosilicon resin is an alkoxy-containing fluorinated organosilicon resin, the alkoxy-containing fluorinated organosilicon resin having alkoxy groups and fluorinated side chains, the alkoxy content of the alkoxy-containing fluorinated organosilicon resin being 20-55%, and the fluorinated side chain being CH2CH2(CF2). n CF3, where n is 0 to 13.

[0006] The antireflection coating solution provided by the present invention may also have the following feature: wherein the silicate ester precursor is selected from any one or more of methyl orthosilicate or ethyl orthosilicate.

[0007] The antireflection coating solution provided by the present invention may also have the following characteristics: wherein the catalyst is selected from acid catalysts or base catalysts, the acid catalyst is selected from any one or more of hydrochloric acid, boric acid, and acetic acid, and the base catalyst is ammonia water.

[0008] The antireflection coating solution provided by the present invention may also have the following feature: wherein the coupling agent is selected from any one or more of methyltrimethoxysilane or methyltriethoxysilane.

[0009] The antireflection coating solution provided by the present invention may also have the following feature: wherein the organic solvent is selected from any one or more of methanol, ethanol, isopropanol, n-butanol or ethylene glycol methyl ether.

[0010] The antireflective coating solution provided by this invention may also have the following characteristics. The preparation method includes the following steps: mixing 3-30 parts by weight of silicate ester precursor, 0.5-10 parts by weight of coupling agent and 20-70 parts by weight of organic solvent, heating to 30-120°C, and then adding 0.5-10 parts by weight of catalyst or its aqueous solution to react and obtain a reaction solution; adding 0.5-15 parts by weight of modified organosilicon resin to the reaction solution, reacting and aging to obtain the antireflective coating solution.

[0011] The antireflective coating solution provided by this invention may also have the following characteristics. The preparation method includes the following steps: mixing 3-30 parts by weight of silicate ester precursor, 0.5-10 parts by weight of coupling agent and 20-70 parts by weight of organic solvent, heating to 30-120°C, and then adding 0.5-10 parts by weight of catalyst or its aqueous solution to react for 1-10 hours to obtain a reaction solution; adding 0.5-15 parts by weight of modified organosilicon resin to the reaction solution, reacting for 1-10 hours, and aging for 5-10 days to obtain the antireflective coating solution.

[0012] The antireflective coating solution provided by this invention may also have the following characteristics. The preparation method includes the following steps: mixing 3-30 parts by weight of silicate ester precursor, 0.5-10 parts by weight of coupling agent, 0.5-15 parts by weight of modified organosilicon resin, and 20-70 parts by weight of organic solvent, heating to 30-120°C, slowly adding 0.5-10 parts by weight of catalyst or its aqueous solution, and reacting for 1-10 hours to obtain a reaction solution; adding alkoxy silicone oil to the reaction solution, reacting for 1-2 hours, aging for 1-10 days, and diluting to obtain the antireflective coating solution.

[0013] The present invention provides an antireflective photovoltaic glass, characterized in that at least a portion of at least one surface of the photovoltaic glass is coated with any of the above-mentioned antireflective coating liquid and then cured and sintered.

[0014] The antireflective photovoltaic glass provided by the present invention may also have the following feature: at least a portion of at least one surface of the photovoltaic glass is coated with any of the above-mentioned antireflective coating liquids, cured at 50-300°C, and sintered at 450-750°C to obtain the final product.

[0015] The role and effect of invention

[0016] According to the antireflection coating solution of the present invention, because an alkoxy-containing fluorinated organosilicon resin is selected, the alkoxy-containing fluorinated organosilicon resin can react and bond with the hydroxyl groups in the silica sol network structure, thereby modifying it. Compared with the traditional fluorocarbon silane coupling modification method, the main chain of the above resin is a flexible silica chain, which can impart better wear resistance to the modified coating; at the same time, the fluorinated side chains can give the modified coating good hydrophobic and oleophobic properties.

[0017] The antireflective photovoltaic glass according to the present invention, due to the use of the above-mentioned antireflective coating liquid, has better moisture resistance, salt spray resistance, acid resistance, washability and stain resistance than existing products. Attached Figure Description

[0018] Figure 1 The images show the effective transmittance spectra of solar light for the anti-reflection photovoltaic glass samples prepared in Example 1 and the comparative example of this invention (solid line represents Example 1, dashed line represents the comparative example). Detailed Implementation

[0019] To make the technical means, creative features, objectives and effects of this invention easy to understand, the invention will be specifically described below in conjunction with embodiments and accompanying drawings.

[0020] In the following embodiments, unless otherwise stated, all raw materials are commercially available products.

[0021] <Example 1>

[0022] An antireflective coating solution

[0023] This embodiment provides an antireflection coating solution, the preparation method of which is as follows:

[0024] (1) Mix 15g of methyl orthosilicate, 5g of methyltrimethoxysilane and 60g of isopropanol evenly, heat to 70°C, and slowly add hydrochloric acid aqueous solution (4g of 37% concentrated hydrochloric acid and 30g of water) over 1 hour, and continue the reaction for 6 hours to obtain the reaction solution.

[0025] (2) Add 8g of alkoxy-containing fluorinated organosilicon resin (alkoxy content is 22.5%) to the reaction liquid, continue the reaction for 5 hours, and then age for 6 days to obtain an anti-reflection coating solution with a solid content of 4.5%.

[0026] The preparation process of the alkoxy-containing fluorinated organosilicon resin is as follows:

[0027] Under nitrogen protection, a vinyl-terminated trifluoropropylmethylsiloxane polymer ( 10g of n=6)triethoxysilane, 3.2g of triethoxysilane, 30ppm of Karstedt catalyst, and 40g of tetrahydrofuran were reacted at 70°C for 4 hours. The solvent and excess silane were removed under reduced pressure to obtain an alkoxy-containing fluorinated organosilicon resin.

[0028] <Comparative Example>

[0029] An antireflective coating solution

[0030] This comparative example provides an antireflection coating solution, the preparation method of which is as follows:

[0031] (1) Mix 15g of methyl orthosilicate, 5g of methyltrimethoxysilane and 60g of isopropanol evenly, heat to 70°C, slowly add hydrochloric acid aqueous solution (4g of hydrochloric acid and 12g of water) over 1 hour, continue the reaction for 5 hours, and then age for 6 days to obtain the anti-reflection coating solution.

[0032] <Application Example>

[0033] The antireflective coating solution prepared in Example 1 was applied to a single surface of the same photovoltaic glass using a roller coating method, with a coating amount of 6.7 g / m². 2 After curing at 200°C and tempering and sintering at 700°C, Sample 1 (coated with the antireflection coating liquid in Example 1) and Sample 2 (coated with the antireflection coating liquid in the comparative example) were obtained.

[0034] The performance of samples 1 and 2 was characterized using the following methods:

[0035] (1) Transmittance: The transmittance of sunlight in the 380–1100 nm wavelength band should be ≥93.5%.

[0036] (2) Moisture resistance: Tested according to standard JC / T 2170-2013(2017) / 6.12. The temperature is 85℃, the relative humidity is 85%, and the test time is 1000 hours. After the test, the average attenuation of the effective transmittance of sunlight should not be greater than 1%, and there should be no obvious peeling, flaking, or wrinkling of the film.

[0037] (3) Salt spray resistance: Tested according to standard JC / T 2170-2013(2017) / 6.9. A 50 g / L NaCl solution, pH: 7.0, was continuously sprayed at 35℃±2℃ for 96 hours. After the test, the average attenuation of the effective solar transmittance should not exceed 1%, and there should be no obvious peeling, flaking, or wrinkling of the film.

[0038] (4) Acid resistance: Tested according to standard JC / T 2170-2013(2017) / 6.8. The sample was placed in a 1mol / L hydrochloric acid solution at (23±2)℃ and immersed for 24h. After the test, the average attenuation of the effective transmittance of sunlight should not be greater than 1%, and there should be no obvious peeling, flaking, or wrinkling of the film.

[0039] (5) Washability: Tested according to standard JC / T 2170-2013(2017) / 6.7, using a 0.5% detergent solution with a pH of 10.3, for a total of 400 cycles. After the test, the average attenuation of the effective transmittance of sunlight should not be greater than 1%, and there should be no obvious peeling, flaking, or wrinkling of the film.

[0040] (6) Stain Resistance: The contaminant used in the test was a talc-based ash mixture, prepared by mixing talc and water at a mass ratio of 1:0.9. This ash was then evenly applied to the sample surface, with a coating amount of (6±0.1) g. After being placed in an environment of 23℃±2℃ and 50%±5% humidity for 2 hours, the sample was rinsed. The sample was then placed in the same environment at 23℃±2℃ and 50%±5% humidity until the next day, constituting one cycle (approximately 24 hours). The test was continued for five cycles. The average attenuation of the effective solar transmittance after the test should not exceed 1%.

[0041] The performance characterization results are shown in Table 1 and Figure 1 As shown.

[0042] Table 1 Performance Characterization

[0043]

[0044] The role and effect of the embodiments

[0045] According to the antireflection coating solution described in the above embodiments, because an alkoxy-containing fluorinated silicone resin is selected, this resin can react and bond with the hydroxyl groups in the silica sol network structure, thereby modifying it. Compared to traditional fluorocarbon silane coupling modification methods, the main chain of the above resin is a flexible silica chain, which can impart better wear resistance to the modified coating; at the same time, the fluorinated side chains can give the modified coating good hydrophobic and oleophobic properties.

[0046] Furthermore, since the organic components in the antireflective coating solution can carbonize during the subsequent curing and sintering process, thereby forming micropores, there is no need to add additional pore-forming agents.

[0047] The antireflective photovoltaic glass described in the above embodiments, due to the use of the aforementioned antireflective coating liquid, exhibits better moisture resistance, salt spray resistance, acid resistance, washability, and stain resistance than existing products.

[0048] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

Claims

1. An antireflective coating solution, characterized in that, Its preparation method includes the following steps: A reaction solution is obtained by mixing a silicate precursor, a coupling agent, and an organic solvent, then adding a catalyst or its aqueous solution. Modified organosilicon resin is added to the reaction solution, followed by reaction and aging to obtain the antireflection coating solution. The modified organosilicon resin is an alkoxy-containing fluorinated organosilicon resin, which has alkoxy groups and fluorinated side chains. The alkoxy content of the alkoxy-containing fluorinated organosilicon resin is 20-55%, and the fluorinated side chain is CH2CH2(CF2). n CF3, where n is 0 to 13.

2. The antireflective coating solution according to claim 1, characterized in that: in, The silicate precursor is selected from any one or more of methyl orthosilicate or ethyl orthosilicate.

3. The antireflective coating solution according to claim 1, characterized in that: in, The catalyst is selected from acid catalysts or base catalysts. The acid catalyst is selected from any one or more of hydrochloric acid, boric acid, and acetic acid. The alkaline catalyst is ammonia.

4. The antireflective coating solution according to claim 1, characterized in that: in, The coupling agent is selected from any one or more of methyltrimethoxysilane or methyltriethoxysilane.

5. The antireflective coating solution according to claim 1, characterized in that: in, The organic solvent is selected from any one or more of methanol, ethanol, isopropanol, n-butanol, or ethylene glycol methyl ether.

6. The antireflective coating solution according to claim 1, characterized in that, The preparation method includes the following steps: Mix 3-30 parts by weight of silicate precursor, 0.5-10 parts by weight of coupling agent and 20-70 parts by weight of organic solvent, heat to 30-120℃, and then add 0.5-10 parts by weight of catalyst or its aqueous solution to react and obtain reaction solution. Add 0.5-15 parts of modified organosilicon resin to the reaction solution, react, and age to obtain the antireflection coating solution.

7. The antireflective coating solution according to claim 1, characterized in that, The preparation method includes the following steps: Mix 3-30 parts by weight of silicate precursor, 0.5-10 parts by weight of coupling agent and 20-70 parts by weight of organic solvent, heat to 30-120℃, and then add 0.5-10 parts by weight of catalyst or its aqueous solution to react for 1-10 hours to obtain reaction solution. Add 0.5-15 parts of modified organosilicon resin to the reaction solution, react for 1-10 hours, and age for 5-10 days to obtain the antireflection coating solution.

8. An anti-reflective photovoltaic glass, characterized in that, At least a portion of at least one surface of a photovoltaic glass is coated with the antireflective coating liquid according to any one of claims 1-7 and then cured and sintered.

9. The photovoltaic glass according to claim 8, characterized in that, The preparation method is as follows: At least a portion of at least one surface of a photovoltaic glass is coated with the antireflective coating liquid according to any one of claims 1-7, cured at 50-300°C, and sintered at 450-750°C to obtain the coating.

Images