A photovoltaic backsheet glass frit and method of making the same

Abstract

The application discloses a kind of photovoltaic backboard glass glaze and its preparation method, it is related to photovoltaic module and glass glaze technical field, raw material includes 15-25 parts modified titanium dioxide, 7-17 parts titanium suboxide, 37-42 parts low melting point glass powder, 0.3-0.8 parts dispersing agent, 26-31 parts water-based ink oil according to weight part;The water-based ink oil raw material includes: 55-80 parts alcohol ether solvent, 25-35 parts water-based fluorine zirconium silicon modified acrylic resin, 1-3 parts rheological anti-sedimentation agent, 3-5 parts superhydrophobic carbon nanotube / silica composite material according to weight part.The photovoltaic backboard glass glaze provided by the application has excellent high reflectivity, high adhesion, weather resistance and superhydrophobicity and the like.

Description

Technical Field

[0001] This application relates to the fields of photovoltaic modules and glass glaze technology, and in particular to a photovoltaic backsheet glass glaze and its preparation method. Background Technology

[0002] To make fuller use of solar energy, photovoltaic glass modules are being upgraded from single-glass modules to double-glass modules. In this upgrade process, a white enamel is coated on the back of the solar panel glass to improve power generation efficiency. The main properties of this white enamel include good adhesion to glass, high chemical stability, high whiteness, and high reflectivity. When light enters the double-glass module, the white enamel reflects as much light as possible back onto the solar panel, thereby improving power generation efficiency.

[0003] The reflectivity of photovoltaic glass enamel directly affects the power generation of photovoltaic modules. Higher reflectivity results in greater power generation. However, during the handling and installation of photovoltaic glass, bumps and friction are inevitable, and photovoltaic modules require the sequential assembly of multiple materials during installation. Therefore, the enamel must possess a certain degree of adhesion after sintering to prevent scratches or peeling. Generally, the higher the reflectivity of the sintered enamel layer, the worse its adhesion; conversely, lower reflectivity results in better adhesion. Therefore, there is an urgent need to provide a new photovoltaic backsheet glass enamel that achieves a balance between high reflectivity and high adhesion. Summary of the Invention

[0004] In order to provide a photovoltaic backsheet glass glaze with excellent weather resistance, hydrophobicity, high reflectivity and adhesion, this application provides a photovoltaic backsheet glass glaze and its preparation method.

[0005] This application provides a photovoltaic backsheet glass glaze, which adopts the following technical solution:

[0006] A photovoltaic backsheet glass glaze, the raw materials by weight include 15-25 parts modified titanium dioxide, 7-17 parts titanium dioxide powder, 37-42 parts low melting point glass powder, 0.3-0.8 parts dispersant, and 26-31 parts water-based ink.

[0007] The water-based ink raw materials include, by weight: 55-80 parts alcohol ether solvent, 25-35 parts water-based fluorozirconium silicon modified acrylic resin, 1-3 parts rheology modifier, and 3-5 parts superhydrophobic carbon nanotube / silica composite material.

[0008] Preferably, the modified titanium dioxide is obtained by inorganic composite coating of rutile titanium dioxide.

[0009] Preferably, the softening temperature of the low melting point glass powder is 400-500℃.

[0010] Preferably, the waterborne fluorozirconium-silicon modified acrylic resin is prepared from the following raw materials in parts by weight: 12-24 parts methyl methacrylate, 10-20 parts butyl acrylate, 3.1-6.2 parts trifluoroethyl methacrylate, 2.2-4.4 parts zirconium-silicon resin, 20-40 parts 1,4-dioxane, 40-80 parts deionized water, and 0.115-0.23 parts initiator.

[0011] Preferably, the zirconium silicone resin is prepared from the following raw materials in parts by weight: 10.8-21.6 parts diphenylsilanediol, 8.2-16.4 parts vinyltrimethoxysilane, 0.03-0.06 parts barium hydroxide, 60-120 parts 1,4-dioxane, and 0.57-1.14 parts zirconium n-butoxide.

[0012] Preferably, the method for preparing the zirconium silicate resin includes the following steps:

[0013] Diphenylsilanediol and vinyltrimethoxysilane were mixed, barium hydroxide and 1,4-dioxane were added, and the mixture was mechanically stirred at 80-85℃ and 300-500 rpm for 2-3 hours. Then zirconium butoxide was added dropwise and the reaction was continued for 6-7 hours. After cooling, barium hydroxide was removed by filtration, and impurities were removed by vacuum heating to obtain zirconium silicate resin.

[0014] Preferably, the preparation method of the waterborne fluorozirconium-silicon modified acrylic resin includes the following steps:

[0015] Methyl methacrylate, butyl acrylate, trifluoroethyl methacrylate, and zirconium silicate resin were mixed, and then 1,4-dioxane and deionized water were added. The mixture was refluxed and heated to 70-80°C with a stirring speed of 300-500 rpm. Nitrogen gas was then introduced, and an initiator was added. The mixture was kept at this temperature for 3-5 hours. Heating was then stopped, and the mixture was cooled to room temperature to obtain waterborne fluorozirconium silicate modified acrylic resin.

[0016] Preferably, the superhydrophobic carbon nanotube / silica composite material is prepared from the following raw materials in parts by weight: 4-6 parts carbon nanotube / silica composite material, 40-60 parts ethanol, 0.32-0.48 parts silane coupling agent, 40-60 parts water, and 0.48-0.72 parts perfluorodecyltrimethoxysilane;

[0017] The carbon nanotube / silica composite material is prepared from the following raw materials in parts by weight: 5-7.5 parts carboxylated carbon nanotubes, 40-60 parts tetraethyl orthosilicate, 35-53 parts ammonia, 350-525 parts isopropanol, and 150-225 parts deionized water.

[0018] Preferably, the preparation method of the superhydrophobic carbon nanotube / silica composite material includes the following steps:

[0019] Carboxylated carbon nanotubes were dissolved in a mixed solution of isopropanol and deionized water, ammonia was added and ultrasonically dispersed for 10-20 min, followed by slow dropwise addition of tetraethyl orthosilicate, and the reaction was carried out at 55-65℃ for 12-16 h. After the reaction was completed, the mixture was washed multiple times by centrifugation with deionized water and ethanol, and dried at 70-80℃ for 24-30 h. The mixture was then ground into powder to obtain the carbon nanotube / silica composite material.

[0020] The carbon nanotube / silica composite material was added to ethanol and stirred for 15-25 min. The silane coupling agent was added to water and ultrasonically dispersed for 15-23 min. Then, the aqueous solution of the silane coupling agent was mixed with the ethanol solution of the carbon nanotube / silica composite material, and perfluorodecyltrimethoxysilane was added dropwise. The mixture was magnetically stirred for 12-16 h. After the reaction was completed, the product was centrifuged, and the precipitate was washed several times with anhydrous ethanol and dried at 75-85℃ for 24-30 h. The product was then ground into powder to form the superhydrophobic carbon nanotube / silica composite material.

[0021] Preferably, the preparation method of the water-based ink adjuster includes the following steps:

[0022] The water-based ink modifier is obtained by mixing alcohol ether solvent, water-based fluorozirconium silicon modified acrylic resin, rheology modifier, and superhydrophobic carbon nanotube / silica composite material and stirring until homogeneous.

[0023] This application provides a method for preparing a photovoltaic backsheet glass glaze, which adopts the following technical solution:

[0024] A method for preparing a photovoltaic backsheet glass glaze includes the following steps:

[0025] Modified titanium dioxide, titanium dioxide powder, low melting point glass powder, dispersant, and water-based ink are mixed and stirred at 45-55℃ for 40-60 minutes to obtain photovoltaic backsheet glass glaze.

[0026] In summary, this application includes at least one of the following beneficial technical effects:

[0027] 1. This application provides a compound of rutile titanium dioxide and titanium dioxide powder with a dense inorganic composite coating, which has the advantages of white color, resistance to yellowing, scratch resistance, and acid and alkali resistance. It not only ensures that the glaze has a high reflectivity and effectively improves the power generation efficiency of photovoltaic modules, but also reduces production costs.

[0028] 2. This application synthesizes a high-silicon-content zirconium silicone resin using vinyltrimethoxysilane, diphenylsilanediol, and zirconium n-butoxide as raw materials via a non-hydrolyzed sol-gel method. The synthesized zirconium silicone resin is then subjected to solution polymerization with acrylate and trifluoroethyl methacrylate to obtain an acrylic resin with a zirconium-silicon-oxygen structure. The zirconium-silicon-oxygen structure can effectively shield ultraviolet rays, inhibit photo-oxidative degradation, and significantly improve the weather resistance of the glaze. At the same time, the introduction of zirconium effectively enhances the thermal stability of the acrylic resin and significantly improves the stability of the ink at high temperatures.

[0029] 3. This application uses carboxyl carbon nanotubes as the matrix, tetraethyl orthosilicate as the silicon source, and ammonia water as a catalyst to provide an alkaline environment to effectively synthesize micro- and nano-scale carbon nanotube / silica composite materials. Furthermore, silane coupling agents and perfluorodecyltrimethoxysilane are used to hydrophobically modify the carbon nanotube / silica composite materials, reducing the surface energy. This results in the modified particles possessing superhydrophobicity and excellent wear resistance, effectively improving the self-cleaning performance and durability of the glaze. Detailed Implementation

[0030] The present application will be further described in detail below with reference to the embodiments.

[0031] The chemical reagents used in the preparation examples, embodiments, and comparative examples provided in this invention are all commercially available products, and their brands and manufacturers are as follows:

[0032] Sub-titanium powder, Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd.;

[0033] Rutile titanium dioxide, Huangshi Jingsheng Biotechnology Co., Ltd.;

[0034] Low melting point glass powder, Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., softening temperature is 450℃;

[0035] TEGO Dispers 755W, Shanghai Mengdihu Industrial Co., Ltd.

[0036] Preparation Example 1: Preparation of Waterborne Fluorozirconium Silicon Modified Acrylic Resin

[0037] Preparation Example 1.1

[0038] S1. Mix 10.8g of diphenylsilanediol and 8.2g of vinyltrimethoxysilane, add 0.03g of barium hydroxide and 60g of 1,4-dioxane, and mechanically stir at 80℃ and 300rpm for 2h; then add 0.57g of n-butoxide zirconium dropwise and continue stirring for 6h; after cooling, filter through a 0.45μm polytetrafluoroethylene filter to remove barium hydroxide, and remove volatile components by vacuum heating to obtain zirconium silicone resin;

[0039] S2. Mix 12g methyl methacrylate, 10g butyl acrylate, 3.1g trifluoroethyl methacrylate, and 2.2g zirconium silicate resin, then add 20g 1,4-dioxane and 40g deionized water. Reflux and heat to 70°C with a stirring speed of 300 rpm. Then introduce nitrogen gas and add 0.115g azobisisobutyronitrile. Continue the reaction at this temperature for 3 hours, then stop heating and cool to room temperature to obtain waterborne fluorozirconium silicate modified acrylic resin.

[0040] Preparation Example 1.2

[0041] S1. Mix 16.2g of diphenylsilanediol and 12.3g of vinyltrimethoxysilane, add 0.045g of barium hydroxide and 90g of 1,4-dioxane, and mechanically stir at 83℃ and 400rpm for 2.5h; then add 0.86g of zirconium butoxide dropwise and continue stirring for 6.5h; after cooling, filter through a 0.45μm polytetrafluoroethylene filter to remove barium hydroxide, and remove volatile components by vacuum heating to obtain zirconium silicone resin;

[0042] S2. Mix 18g methyl methacrylate, 15g butyl acrylate, 4.7g trifluoroethyl methacrylate, and 3.3g zirconium silicate resin, then add 30g 1,4-dioxane and 60g deionized water. Reflux and heat to 75°C with a stirring speed of 400 rpm. Then introduce nitrogen gas and add 0.173g azobisisobutyronitrile. Continue the reaction at this temperature for 4 hours, then stop heating and cool to room temperature to obtain waterborne fluorozirconium silicate modified acrylic resin.

[0043] Preparation Example 1.3

[0044] S1. Mix 21.6g of diphenylsilanediol and 16.4g of vinyltrimethoxysilane, add 0.06g of barium hydroxide and 120g of 1,4-dioxane, and mechanically stir at 85℃ and 500rpm for 3h; then add 1.14g of n-butoxide zirconium dropwise and continue stirring for 7h; after cooling, filter through a 0.45μm polytetrafluoroethylene filter to remove barium hydroxide, and remove volatile components by vacuum heating to obtain zirconium silicone resin;

[0045] S2. Mix 24g methyl methacrylate, 20g butyl acrylate, 6.2g trifluoroethyl methacrylate, and 4.4g zirconium silicate resin, then add 40g 1,4-dioxane and 80g deionized water. Reflux and heat to 80°C with a stirring speed of 500 rpm. Then introduce nitrogen gas and add 0.23g azobisisobutyronitrile. Continue the reaction at this temperature for 5 hours, then stop heating and cool to room temperature to obtain waterborne fluorozirconium silicate modified acrylic resin.

[0046] Preparation Example 2: Preparation of Superhydrophobic Carbon Nanotube / Silica Composite Material

[0047] Preparation Example 2.1

[0048] 5g of carboxylated carbon nanotubes were dissolved in a mixed solution of 350g isopropanol and 150g deionized water. 35g of ammonia was added and the mixture was ultrasonically dispersed for 10min. Then, 40g of tetraethyl orthosilicate was slowly added dropwise and the mixture was reacted at 55℃ for 12h. After the reaction was completed, the mixture was washed three times by centrifugation with deionized water and ethanol and dried in a forced-air drying oven at 70℃ for 24h. The mixture was then ground into powder and passed through a 200-mesh sieve to obtain the carbon nanotube / silica composite material.

[0049] 4g of carbon nanotube / silica composite material was added to 40g of ethanol and stirred for 15min. 0.32g of silane coupling agent KH-550 was added to 40g of water and ultrasonically dispersed for 15min. Then, the aqueous solution of silane coupling agent was mixed with the ethanol solution of carbon nanotube / silica composite material, and 0.48g of perfluorodecyltrimethoxysilane was added dropwise. The mixture was magnetically stirred for 12h. After the reaction was completed, the product was centrifuged, and the precipitate was washed three times with anhydrous ethanol and dried in a 75℃ oven for 24h. The product was then ground into powder and passed through a 200-mesh sieve to obtain the superhydrophobic carbon nanotube / silica composite material.

[0050] Preparation Example 2.2

[0051] 6.25g of carboxyl carbon nanotubes were dissolved in a mixed solution of 440g isopropanol and 190g deionized water. 44g of ammonia was added and the mixture was ultrasonically dispersed for 15min. Then, 50g of tetraethyl orthosilicate was slowly added dropwise, and the mixture was reacted at 60℃ for 14h. After the reaction was completed, the mixture was washed four times by centrifugation with deionized water and ethanol, and dried in a forced-air drying oven at 75℃ for 27h. The mixture was then ground into powder and passed through a 200-mesh sieve to obtain the carbon nanotube / silica composite material.

[0052] 5g of carbon nanotube / silica composite material was added to 50g of ethanol and stirred for 20min. 0.4g of silane coupling agent KH-550 was added to 50g of water and ultrasonically dispersed for 19min. Then, the aqueous solution of silane coupling agent was mixed with the ethanol solution of carbon nanotube / silica composite material, and 0.6g of perfluorodecyltrimethoxysilane was added dropwise. The mixture was magnetically stirred for 14h. After the reaction was completed, the product was centrifuged, and the precipitate was washed four times with anhydrous ethanol and dried in an 80℃ oven for 27h. The product was then ground into powder and passed through a 200-mesh sieve to obtain the superhydrophobic carbon nanotube / silica composite material.

[0053] Preparation Example 2.3

[0054] 7.5g of carboxyl carbon nanotubes were dissolved in a mixed solution of 525g isopropanol and 225g deionized water. 53g of ammonia was added and the mixture was ultrasonically dispersed for 20min. Then, 60g of tetraethyl orthosilicate was slowly added dropwise, and the mixture was reacted at 65℃ for 16h. After the reaction was completed, the mixture was washed 5 times by centrifugation with deionized water and ethanol, and dried in a forced-air drying oven at 80℃ for 30h. The mixture was then ground into powder and passed through a 200-mesh sieve to obtain the carbon nanotube / silica composite material.

[0055] 6g of carbon nanotube / silica composite material was added to 60g of ethanol and stirred for 25min. 0.48g of silane coupling agent KH-550 was added to 60g of water and ultrasonically dispersed for 23min. Then, the aqueous solution of silane coupling agent was mixed with the ethanol solution of carbon nanotube / silica composite material, and 0.72g of perfluorodecyltrimethoxysilane was added dropwise. The mixture was magnetically stirred for 16h. After the reaction was completed, the product was centrifuged, and the precipitate was washed 5 times with anhydrous ethanol and dried in a forced-air drying oven at 85℃ for 30h. The product was then ground into powder and passed through a 200-mesh sieve to obtain the superhydrophobic carbon nanotube / silica composite material.

[0056] Preparation Example 3: Preparation of Modified Titanium Dioxide

[0057] Preparation Example 3.1

[0058] 150g of a 270g / L rutile titanium dioxide aqueous suspension was continuously stirred at 60℃ and 350rpm for 10min. 5.25mL of a 100g / L zirconium sulfate aqueous solution was added dropwise to the rutile titanium dioxide aqueous suspension. After the zirconium sulfate aqueous solution was added, the mixture was allowed to mature for 30min. The pH of the slurry was then adjusted to 9 with sodium aluminate solution. Subsequently, 60mL of sodium aluminate solution and 10% sulfuric acid were added for co-current coating. During the coating process, the amount of sulfuric acid added was adjusted to maintain a constant pH value. After the sodium aluminate solution was added, the mixture was allowed to mature for 60min. After maturation, the pH of the slurry was adjusted to 7.4 with sodium aluminate solution and matured for another 60min. The mixture was then filtered and washed with 2L of distilled water and dried at 120℃ for 18h to obtain modified titanium dioxide.

[0059] Example 1

[0060] 15g of modified titanium dioxide prepared in Preparation Example 3.1, 17g of titanium dioxide powder, 37g of low melting point glass powder, 0.3g of dispersant, and 31g of water-based ink were mixed and stirred at 45°C for 40 minutes to obtain photovoltaic backsheet glass glaze.

[0061] The dispersant is TEGO Dispers 755W;

[0062] The preparation method of the water-based ink adjuster includes the following steps:

[0063] 55g of diethylene glycol butyl ether, 25g of waterborne fluorozirconium silicate modified acrylic resin prepared in Preparation Example 1.1, 1g of ethyl cellulose, and 3g of superhydrophobic carbon nanotube / silica composite material prepared in Preparation Example 2.1 were mixed and stirred evenly to obtain waterborne ink.

[0064] Example 2

[0065] 20g of modified titanium dioxide prepared in Preparation Example 3.1, 12g of titanium dioxide powder, 39g of low melting point glass powder, 0.5g of dispersant, and 29g of water-based ink were mixed and stirred at 50°C for 50 minutes to obtain photovoltaic backsheet glass glaze.

[0066] The dispersant is TEGO Dispers 755W;

[0067] The preparation method of the water-based ink adjuster includes the following steps:

[0068] 55g of diethylene glycol butyl ether, 25g of waterborne fluorozirconium silicate modified acrylic resin prepared in Preparation Example 1.1, 1g of ethyl cellulose, and 3g of superhydrophobic carbon nanotube / silica composite material prepared in Preparation Example 2.1 were mixed and stirred evenly to obtain waterborne ink.

[0069] Example 3

[0070] 25g of modified titanium dioxide prepared in Preparation Example 3.1, 7g of titanium dioxide powder, 42g of low melting point glass powder, 0.8g of dispersant, and 26g of water-based ink were mixed and stirred at 55°C for 60 minutes to obtain photovoltaic backsheet glass glaze.

[0071] The dispersant is TEGO Dispers 755W;

[0072] The preparation method of the water-based ink adjuster includes the following steps:

[0073] 55g of diethylene glycol butyl ether, 25g of waterborne fluorozirconium silicate modified acrylic resin prepared in Preparation Example 1.1, 1g of ethyl cellulose, and 3g of superhydrophobic carbon nanotube / silica composite material prepared in Preparation Example 2.1 were mixed and stirred evenly to obtain waterborne ink.

[0074] Example 4

[0075] 15g of modified titanium dioxide prepared in Preparation Example 3.1, 7g of titanium dioxide powder, 37g of low melting point glass powder, 0.3g of dispersant, and 26g of water-based ink were mixed and stirred at 45°C for 40 minutes to obtain photovoltaic backsheet glass glaze.

[0076] The dispersant is TEGO Dispers 755W;

[0077] The preparation method of the water-based ink adjuster includes the following steps:

[0078] 68g of diethylene glycol butyl ether, 30g of waterborne fluorozirconium silicate modified acrylic resin prepared in Preparation Example 1.1, 2g of ethyl cellulose, and 4g of superhydrophobic carbon nanotube / silica composite material prepared in Preparation Example 2.1 were mixed and stirred evenly to obtain waterborne ink.

[0079] Example 5

[0080] 15g of modified titanium dioxide prepared in Preparation Example 3.1, 7g of titanium dioxide powder, 37g of low melting point glass powder, 0.3g of dispersant, and 26g of water-based ink were mixed and stirred at 45°C for 40 minutes to obtain photovoltaic backsheet glass glaze.

[0081] The dispersant is TEGO Dispers 755W;

[0082] The preparation method of the water-based ink adjuster includes the following steps:

[0083] 80g of diethylene glycol butyl ether, 35g of waterborne fluorozirconium silicate modified acrylic resin prepared in Preparation Example 1.1, 3g of ethyl cellulose, and 5g of superhydrophobic carbon nanotube / silica composite material prepared in Preparation Example 2.1 were mixed and stirred evenly to obtain waterborne ink.

[0084] Example 6

[0085] The difference between Example 6 and Example 1 is that the waterborne fluorozirconium-silicon modified acrylic resin used in Example 6 was prepared from Preparation Example 1.2.

[0086] Example 7

[0087] The difference between Example 7 and Example 1 is that the waterborne fluorozirconium-silicon modified acrylic resin used in Example 7 was prepared from Preparation Example 1.3.

[0088] Example 8

[0089] The difference between Example 8 and Example 1 is that the superhydrophobic carbon nanotube / silica composite material used in Example 8 was prepared by Example 2.2.

[0090] Example 9

[0091] The difference between Example 9 and Example 1 is that the superhydrophobic carbon nanotube / silica composite material used in Example 9 was prepared by Example 2.3.

[0092] Comparative Example 1

[0093] The difference between Comparative Example 1 and Example 1 is that the titanium dioxide used in Comparative Example 1 is unmodified rutile titanium dioxide.

[0094] Comparative Example 2

[0095] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 uses an equal amount of acrylic resin instead of the waterborne fluorozirconium silicon modified acrylic resin prepared in Preparation Example 1.1.

[0096] Comparative Example 3

[0097] The difference between Comparative Example 3 and Example 1 is that no superhydrophobic carbon nanotube / silica composite material is added in Comparative Example 3.

[0098] Performance testing

[0099] The photovoltaic backsheet glass enamels obtained in Examples 1-9 and Comparative Examples 1-3, with a thickness of 15 μm, were coated onto the photovoltaic module glass. The coated glass was then cured in a 180°C drying oven for 15 min, followed by tempering in a 700°C muffle furnace for 5 min to obtain the enamel-coated backsheet glass. The following tests were then performed:

[0100] 1. Appearance: Visually inspect whether the surface is smooth, free of cracks, and whether the color is uniform;

[0101] II. Reflectivity: The reflectivity of the glazed back glass in the 380-730nm range was measured using an ERX30 spectrophotometer;

[0102] III. Adhesion: The adhesion of the glaze is tested using the cross-cut test with a cross-cutting knife.

[0103] IV. UV Resistance: According to JC / T 2170-2013, the total radiation of the enamel-coated backing glass at 60℃ is 15 kWh / m². 2 After radiation treatment under certain conditions, the change in reflectivity after radiation treatment was tested. Yellowing index ;

[0104] V. Aging Resistance: After treating the enamel-coated backing glass at a temperature of 121℃, relative humidity of 100%, and a test time of 48 hours, the change in glass reflectivity after treatment was tested. ;

[0105] The results are shown in Table 1.

[0106] The specific test results are as follows:

[0107] Table 1 Performance Test Results

[0108]

[0109] As can be seen from the test results in Table 1, the photovoltaic backsheet glass glaze provided in this application has a high reflectivity, and compared with the comparative example, the adhesion, UV resistance and aging resistance of the examples are significantly improved.

[0110] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A photovoltaic backsheet glass enamel, characterized in that: The raw materials, by weight, include 15-25 parts modified titanium dioxide, 7-17 parts titanium dioxide powder, 37-42 parts low melting point glass powder, 0.3-0.8 parts dispersant, and 26-31 parts water-based ink thinner; The water-based ink raw materials include, by weight: 55-80 parts alcohol ether solvent, 25-35 parts water-based fluorozirconium silicon modified acrylic resin, 1-3 parts rheology modifier, and 3-5 parts superhydrophobic carbon nanotube / silica composite material. The waterborne fluorozirconium-silicon modified acrylic resin is prepared from the following raw materials in parts by weight: 12-24 parts methyl methacrylate, 10-20 parts butyl acrylate, 3.1-6.2 parts trifluoroethyl methacrylate, 2.2-4.4 parts zirconium-silicon resin, 20-40 parts 1,4-dioxane, 40-80 parts deionized water, and 0.115-0.23 parts initiator; The zirconium silicone resin is prepared from the following raw materials in parts by weight: 10.8-21.6 parts diphenylsilanediol, 8.2-16.4 parts vinyltrimethoxysilane, 0.03-0.06 parts barium hydroxide, 60-120 parts 1,4-dioxane, and 0.57-1.14 parts zirconium n-butoxide; The method for preparing the zirconium-silicon resin includes the following steps: Diphenylsilanediol and vinyltrimethoxysilane were mixed, barium hydroxide and 1,4-dioxane were added, and the mixture was mechanically stirred at 80-85℃ and 300-500 rpm for 2-3 hours. Then zirconium butoxide was added dropwise and the reaction was continued for 6-7 hours. After cooling, barium hydroxide was removed by filtration, and impurities were removed by vacuum heating to obtain zirconium silicone resin. The method for preparing the modified titanium dioxide includes the following steps: 150g of a 270g / L rutile titanium dioxide aqueous suspension was continuously stirred at 60℃ and 350rpm for 10min. 5.25mL of a 100g / L zirconium sulfate aqueous solution was added dropwise to the rutile titanium dioxide aqueous suspension. After the zirconium sulfate aqueous solution was added, the mixture was allowed to mature for 30min. The pH of the slurry was then adjusted to 9 with sodium aluminate solution. Subsequently, 60mL of sodium aluminate solution and 10% sulfuric acid were added for co-current coating, adjusting the amount of sulfuric acid added during the coating process to maintain a constant pH. After the sodium aluminate solution was added, the mixture was allowed to mature for 60min. After maturation, the pH of the slurry was adjusted to 7.4 with sodium aluminate solution and matured for another 60min. The mixture was then filtered and washed with 2L of distilled water and dried at 120℃ for 18h to obtain modified titanium dioxide. The preparation method of the waterborne fluorozirconium-silicon modified acrylic resin includes the following steps: Methyl methacrylate, butyl acrylate, trifluoroethyl methacrylate, and zirconium silicate resin were mixed, and then 1,4-dioxane and deionized water were added. The mixture was refluxed and heated to 70-80°C with a stirring speed of 300-500 rpm. Nitrogen gas was then introduced, and an initiator was added. The mixture was kept at this temperature for 3-5 hours. Heating was then stopped, and the mixture was cooled to room temperature to obtain waterborne fluorozirconium silicate modified acrylic resin.

2. The photovoltaic backsheet glass enamel material according to claim 1, characterized in that: The superhydrophobic carbon nanotube / silica composite material is prepared from the following raw materials in parts by weight: 4-6 parts carbon nanotube / silica composite material, 40-60 parts ethanol, 0.32-0.48 parts silane coupling agent, 40-60 parts water, and 0.48-0.72 parts perfluorodecyltrimethoxysilane. The carbon nanotube / silica composite material is prepared from the following raw materials in parts by weight: 5-7.5 parts carboxylated carbon nanotubes, 40-60 parts tetraethyl orthosilicate, 35-53 parts ammonia, 350-525 parts isopropanol, and 150-225 parts deionized water.

3. The photovoltaic backsheet glass enamel material according to claim 2, characterized in that: The preparation method of the superhydrophobic carbon nanotube / silica composite material includes the following steps: Carboxylated carbon nanotubes were dissolved in a mixed solution of isopropanol and deionized water, ammonia was added and ultrasonically dispersed for 10-20 min, followed by slow dropwise addition of tetraethyl orthosilicate, and the reaction was carried out at 55-65℃ for 12-16 h. After the reaction was completed, the mixture was washed multiple times by centrifugation with deionized water and ethanol, and dried at 70-80℃ for 24-30 h. The mixture was then ground into powder to obtain the carbon nanotube / silica composite material. The carbon nanotube / silica composite material was added to ethanol and stirred for 15-25 min. The silane coupling agent was added to water and ultrasonically dispersed for 15-23 min. Then, the aqueous solution of the silane coupling agent was mixed with the ethanol solution of the carbon nanotube / silica composite material, and perfluorodecyltrimethoxysilane was added dropwise. The mixture was magnetically stirred for 12-16 h. After the reaction was completed, the product was centrifuged, and the precipitate was washed several times with anhydrous ethanol and dried at 75-85℃ for 24-30 h. The product was then ground into powder to form the superhydrophobic carbon nanotube / silica composite material.

4. The photovoltaic backsheet glass enamel material according to claim 1, characterized in that: The preparation method of the water-based ink adjuster includes the following steps: The water-based ink modifier is obtained by mixing alcohol ether solvent, water-based fluorozirconium silicon modified acrylic resin, rheology modifier, and superhydrophobic carbon nanotube / silica composite material and stirring until homogeneous.

5. A method for preparing a photovoltaic backsheet glass enamel according to any one of claims 1-4, characterized in that: Includes the following steps: Modified titanium dioxide, titanium dioxide powder, low melting point glass powder, dispersant, and water-based ink are mixed and stirred at 45-55℃ for 40-60 minutes to obtain photovoltaic backsheet glass glaze.

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