High-shielding type photovoltaic black ink

Abstract

The invention provides a high-shielding type photovoltaic black ink and a preparation method thereof. The ink is prepared from the following raw materials in parts by weight: 40 to 60 parts of matrix resin, 15 to 20 parts of core-shell carbon black, 3 to 5 parts of mesoporous SiO2 carbon black, 1 to 4 parts of a titanium carbide-molybdenum disulfide compound, 0.5 to 2.5 parts of a titanium dioxide coating, 1 to 3 parts of modified montmorillonite, 0.5 to 1.5 parts of rare earth cerium modified titanium dioxide, 0.5 to 2.5 parts of a hyperbranched dispersant, 0.5 to 1.5 parts of a silane fluorosilicone leveling agent and 1 to 3 parts of a composite anti-UV agent. The graphene quantum dot microcapsule is prepared from the following components in parts by weight: 0.3-0.7 part of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of gamma-butyrolactone, 0.5-2.5 parts of a photoinitiator and 0.2-1 part of a microcapsule curing agent. A coating formed by the black ink has the comprehensive properties of good weather resistance, aging resistance, high shielding property, crack resistance, adhesive force and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and in particular to a high-shielding photovoltaic black ink. Background Art

[0002] As the global energy mix accelerates its transition to clean energy, the photovoltaic industry, a crucial component of the renewable energy sector, continues to grow. With the continued growth of installed photovoltaic module capacity, the market is placing higher demands on the performance, appearance, and cost of these modules. Components such as the frame, backsheet, and junction box of a photovoltaic module play a crucial role in the entire assembly, impacting not only the module's mechanical strength and protective properties but also its appearance consistency and power generation efficiency.

[0003] In the production process of photovoltaic modules, black ink is widely used for printing or coating frames, backboards or junction boxes. However, traditional black ink has many pain points in actual application. For example: traditional inks have insufficient hiding power and high light transmittance, which makes photovoltaic modules susceptible to light reflection and interference during use, thereby affecting the power generation efficiency of the modules. Secondly, traditional inks have poor aging resistance. In harsh outdoor environments such as high and low temperatures, humidity and heat, ultraviolet radiation and other conditions, they are prone to fading, cracking, and falling off, seriously affecting the long-term stability and service life of the modules. In addition, traditional inks have low adhesion and are difficult to firmly bond with the substrate of photovoltaic modules. Ink shedding and other phenomena are prone to occur during production and use, which not only affects the appearance consistency of the modules, but may also lead to a decline in module performance. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention provides a high-shielding photovoltaic black ink.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: The present application discloses a high-shielding photovoltaic black ink. The components of the ink include the following raw materials in parts by weight: 40-60 parts of matrix resin, 15-20 parts of core-shell carbon black, 3-5 parts of mesoporous SiO2 carbon black, 1-4 parts of titanium carbide-molybdenum disulfide composite, 0.5-2.5 parts of titanium dioxide coating, 1-3 parts of modified montmorillonite, 0.5-1.5 parts of rare earth cerium modified titanium dioxide, 0.5-2.5 parts of hyperbranched dispersant, 0.5-1.5 parts of silane fluorosilicone leveling agent, 1-3 parts of composite anti-UV agent, 0.3-0.7 parts of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of γ-butyrolactone, 0.5-2.5 parts of photoinitiator and 0.2-1 parts of microcapsule curing agent.

[0006] Preferably, the components of the ink include the following raw materials in parts by weight: 50 parts of matrix resin, 18 parts of core-shell carbon black, 4 parts of mesoporous SiO2 carbon black, 2.5 parts of titanium carbide-molybdenum disulfide composite, 1.5 parts of titanium dioxide coating, 2 parts of modified montmorillonite, 1 part of rare earth cerium modified titanium dioxide, 1.5 parts of hyperbranched dispersant, 0.8 parts of silane fluorosilicone leveling agent, 2 parts of composite anti-UV agent, 0.5 parts of graphene quantum dots, 15 parts of propylene glycol methyl ether acetate, 12 parts of dimethyl carbonate, 2 parts of γ-butyrolactone, 1.5 parts of photoinitiator and 0.6 parts of microcapsule curing agent.

[0007] By setting up the above technical scheme, the carbon core of the core-shell carbon black acts as the light absorption center, the 4±0.5nm SiO2 shell improves the dispersibility of the ink system, the 3nm pore size of the mesoporous SiO2 carbon black forms a light scattering center, extending the propagation path of light in the film layer, and the titanium dioxide coating coats TiO2 to reduce light scattering, forming a light absorption synergy with the core-shell carbon black; rare earth cerium modified titanium dioxide through Ce 3+ / Ce 4+ Valence state conversion quenches UV-induced hydroxyl radicals, and under multiple effects, the average transmittance in the 300-1100nm band decreases, achieving a high shielding effect. The titanium carbide in the titanium carbide-molybdenum disulfide composite has high hardness and strong wear resistance, which can improve the scratch resistance and structural strength of the ink coating, making it particularly suitable for outdoor high-wear environments. Molybdenum disulfide is a layered solid lubricant that can reduce the surface friction coefficient of the coating, reducing the wear of external particles such as dust and sand on the coating, while also improving the coating's flexibility. The titanium carbide-molybdenum disulfide composite forms a "hard-soft" complementary structure that not only supports the coating skeleton, but also alleviates stress concentration through the sliding properties of molybdenum disulfide, enhancing the ink coating's resistance to cracking.

[0008] Preferably, it is characterized in that, by weight percentage, the components of the base resin are as follows: 45-50% of amino-modified epoxy resin, 25-30% of hydroxyl fluorocarbon resin, 10-15% of benzoxazine-acrylate resin and 8-12% of graphene-modified polyester.

[0009] By setting up the above technical scheme, the amino group of the amino-modified epoxy resin forms a hydrogen bond crosslink with the hydroxyl group of the hydroxyl fluorocarbon resin, the phenolic hydroxyl group generated by the ring-opening of the oxazine ring of the benzoxazine-acrylate resin undergoes an esterification reaction with the acrylate chain segment, and the graphene sheets of the graphene-modified polyester are embedded in the resin network through π-π conjugation. The synergistic effect between the resins enables the film layer to form a three-dimensional cross-linked structure, thereby improving the mechanical properties (including tensile strength and breaking strength) and weather resistance of the ink coating.

[0010] Preferably, the preparation method of the amino-modified epoxy resin is as follows: bisphenol A epoxy resin and isophorone diamine are reacted at a molar ratio of 2:1 at 80° C. for 4 hours to obtain an amino-modified epoxy resin with an amine value of 180 mgKOH / g; The benzoxazine-acrylate resin is prepared by condensing phenol, formaldehyde, and 3-aminopropyltriethoxysilane in a molar ratio of 1:1.1:0.08 at 75°C for 3.5 hours to obtain an oxazine monomer, which is then mixed with butyl acrylate in a molar ratio of 1:1.2, and 0.4% azobisisobutyronitrile is added, followed by free radical polymerization at 65°C for 4 hours to obtain the resin. The preparation method of graphene-modified polyester is as follows: maleic anhydride and phthalic anhydride are added to a 95% ethylene glycol solution in a mass ratio of 1:1, reacted at 180°C for 4 hours, then graphene oxide is added at 1.2% of the total mass of maleic anhydride and phthalic anhydride, ultrasonically dispersed for 30 minutes, and finally styrene is added dropwise and an initiator is added, reacted at 80°C for 2 hours, and distilled under reduced pressure to obtain the obtained product.

[0011] Preferably, the preparation method of core-shell carbon black is as follows: 15 g of carbon black is dispersed in 150 mL of deionized water, 8 mL of tetraethoxysilane and 4 mL of 20% ammonia water are added, hydrothermally reacted at 120 ° C for 12 hours, centrifuged and washed, and calcined at 450 ° C for 1.5 hours to obtain core-shell carbon black with a shell thickness of 4±0.5 nm.

[0012] Preferably, the preparation method of mesoporous SiO2 carbon black is as follows: hexadecyltrimethylammonium bromide and ethyl orthosilicate are dissolved in deionized water in a molar ratio of 1:3, stirred at 70°C until completely dissolved, then ethanol and hydrochloric acid are added to adjust the pH to 2-3, sucrose is added at a loading amount of 30% carbon black, stirred for 2 hours to mix evenly, allowed to stand for 24 hours to gel, vacuum dried at 60°C to constant weight, placed in a muffle furnace, heated to 550°C at 1°C / min, kept warm for 3 hours in a nitrogen atmosphere, and then kept warm for 4 hours in an air atmosphere to obtain mesoporous SiO2 carbon black with a pore size of 3nm.

[0013] Preferably, the preparation method of rare earth cerium modified titanium dioxide is: disperse 10 grams of TiO2 in 0.1 mol / L cerium nitrate solution, adjust the pH to 9, stir at 60°C for 2 hours, filter and wash, calcine at 500°C for 3 hours, and grind to obtain rare earth cerium modified titanium dioxide.

[0014] Preferably, the preparation method of the microcapsule curing agent is as follows: dicyandiamide and imidazole are mixed in a mass ratio of 4:1, dissolved in 40 mL of deionized water, and an 8% urea-formaldehyde resin prepolymer solution is prepared. The solution is added dropwise to the curing agent solution in a volume ratio of 1:1.2 at 35° C. and a pH of 4.0, and stirred for 1.5 hours to form a microcapsule curing agent.

[0015] Preferably, the titanium carbide-molybdenum disulfide composite is composed of titanium carbide and molybdenum disulfide in a mass ratio of 4:1.

[0016] Preferably, the method for preparing the ink comprises the following steps: S1. Add the components of the base resin into a double star mixer and stir at 25°C for 15 minutes. Add propylene glycol methyl ether acetate, dimethyl carbonate and γ-butyrolactone and mix at 350 r / min for 10 minutes. S2. To the mixture obtained in step S1, core-shell carbon black, mesoporous SiO2 carbon black, titanium carbide-molybdenum disulfide composite, titanium dioxide coating, modified montmorillonite, and rare earth cerium-modified titanium dioxide are sequentially added, and the mixture is dispersed at a speed of 1200 r / min under vacuum conditions for 40 min. A hyperbranched dispersant is added, and ultrasonic-microwave synergistic dispersion is performed for 20 min under conditions of an ultrasonic power of 350 W and a microwave power of 600 W; S3. Grind the material obtained in step S2 four times with a four-roll grinder, then add silane fluorosilicone leveling agent, composite anti-UV agent, graphene quantum dots, photoinitiator and microcapsule curing agent, stir at a low speed at 55° C. for 30 minutes, filter through a ceramic membrane, and vacuum degas to obtain a high-shielding photovoltaic black ink.

[0017] The beneficial effects of the present invention are: The amino group of the amino-modified epoxy resin forms hydrogen bond crosslinks with the hydroxyl group of the hydroxyl fluorocarbon resin, the phenolic hydroxyl group generated by the opening of the oxazine ring of the benzoxazine-acrylate resin undergoes esterification reaction with the acrylate chain segment, and the graphene sheets of the graphene-modified polyester are embedded in the resin network through π-π conjugation. The synergistic effect between the resins enables the film layer to form a three-dimensional cross-linked structure, thereby improving the mechanical properties (including tensile strength and breaking strength) and weather resistance of the ink coating.

[0018] The carbon core of core-shell carbon black acts as a light absorption center, the 4±0.5nm SiO2 shell improves the dispersibility of the ink system, the 3nm pore size of mesoporous SiO2 carbon black forms a light scattering center, extending the propagation path of light in the film layer, and the titanium dioxide coating encapsulates TiO2 to reduce light scattering, forming a light absorption synergy with the core-shell carbon black; rare earth cerium modified titanium dioxide is Ce 3+ / Ce 4+ The valence state conversion quenches the UV-induced hydroxyl radicals. Under multiple effects, the average transmittance in the 300-1100nm band decreases, achieving a high shielding effect.

[0019] The titanium carbide in the titanium carbide-molybdenum disulfide composite has high hardness and strong wear resistance, which can improve the scratch resistance and structural strength of the ink coating, and is especially suitable for outdoor high-wear environments; molybdenum disulfide is a layered solid lubricant that can reduce the surface friction coefficient of the coating, reduce the wear of external particles such as dust and sand on the coating, and at the same time improve the flexibility of the coating; the titanium carbide-molybdenum disulfide composite forms a "hard-soft" complementary structure, which can not only support the coating skeleton, but also relieve stress concentration through the slip characteristics of molybdenum disulfide, thereby enhancing the ink coating's resistance to cracking.

[0020] Modified montmorillonite improves the thixotropy of inks, preventing sagging or settling during application (e.g., spraying or printing), and enhancing ink application uniformity. A solvent system composed of propylene glycol methyl ether acetate, dimethyl carbonate, and γ-butyrolactone exhibits excellent solubility for the matrix resins composed of amino-modified epoxy resins, hydroxyl fluorocarbon resins, benzoxazine-acrylate resins, and graphene-modified polyesters. The combination of these solvents balances the polar and non-polar components, promoting uniform dispersion of the components and preventing phase separation.

[0021] The phosphonate groups of the hyperbranched dispersant form coordination bonds with the hydroxyl groups on the surface of the core-shell carbon black, stabilizing the nanofiller through the steric effect. The silane alkoxy groups of the silane fluorosilicone leveling agent condense with the hydroxyl groups on the surface of the substrate to form covalent bonds, and the fluoroalkyl groups migrate to the surface of the film layer to reduce the surface energy. This interfacial effect improves the uniformity of filler dispersion and fully improves the adhesion of the ink coating.

[0022] The hindered amine in the composite UV inhibitor captures alkyl radicals through nitroxides, absorbing 300-400nm UV light and converting it into heat. Graphene quantum dots quench singlet oxygen through photoluminescence, extending the aging resistance of the ink coating. The microcapsule curing agent is dispersed in the ink system. Upon rupture, the released curing agent forms a local concentration gradient, promoting a uniform crosslinking reaction and reducing performance defects (such as localized embrittlement or uncured) caused by uneven curing agent dispersion. DETAILED DESCRIPTION

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0024] Example 1: This embodiment discloses a high-shielding photovoltaic black ink. The ink comprises the following raw materials in parts by weight: 40-60 parts of base resin, 15-20 parts of core-shell carbon black, 3-5 parts of mesoporous SiO2 carbon black, 1-4 parts of titanium carbide-molybdenum disulfide composite (the titanium carbide-molybdenum disulfide composite is composed of titanium carbide and molybdenum disulfide in a mass ratio of 4:1), 0.5-2.5 parts of titanium dioxide coating, and modified 1-3 parts of montmorillonite, 0.5-1.5 parts of rare earth cerium modified titanium dioxide, 0.5-2.5 parts of hyperbranched dispersant, 0.5-1.5 parts of silane fluorosilicone leveling agent, 1-3 parts of composite anti-UV agent, 0.3-0.7 parts of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of gamma-butyrolactone, 0.5-2.5 parts of photoinitiator and 0.2-1 part of microcapsule curing agent.

[0025] The composition of the matrix resin is as follows: 45-50% of amino-modified epoxy resin, 25-30% of hydroxyl fluorocarbon resin, 10-15% of benzoxazine-acrylate resin and 8-12% of graphene-modified polyester.

[0026] The preparation method of the amino-modified epoxy resin is as follows: bisphenol A epoxy resin and isophorone diamine are reacted at a molar ratio of 2:1 at 80° C. for 4 hours to obtain the amino-modified epoxy resin with an amine value of 180 mgKOH / g.

[0027] The preparation method of benzoxazine-acrylate resin is as follows: phenol, formaldehyde, and 3-aminopropyltriethoxysilane are condensed in a molar ratio of 1:1.1:0.08 at 75°C for 3.5 hours to obtain oxazine monomer, which is then mixed with butyl acrylate in a molar ratio of 1:1.2, 0.4% azobisisobutyronitrile is added, and free radical polymerization is carried out at 65°C for 4 hours to obtain the resin.

[0028] The preparation method of graphene-modified polyester is as follows: maleic anhydride and phthalic anhydride are added to a 95% ethylene glycol solution in a mass ratio of 1:1, reacted at 180°C for 4 hours, then graphene oxide is added at 1.2% of the total mass of maleic anhydride and phthalic anhydride, ultrasonically dispersed for 30 minutes, and finally styrene is added dropwise and an initiator is added, reacted at 80°C for 2 hours, and distilled under reduced pressure to obtain the obtained product.

[0029] The preparation method of core-shell carbon black is as follows: 15g of carbon black is dispersed in 150mL of deionized water, 8mL of tetraethoxysilane and 4mL of 20% ammonia water are added, hydrothermally reacted at 120℃ for 12h, centrifuged and washed, and calcined at 450℃ for 1.5h to obtain core-shell carbon black with a shell thickness of 4±0.5nm.

[0030] The preparation method of mesoporous SiO2 carbon black is as follows: hexadecyltrimethylammonium bromide and ethyl orthosilicate are dissolved in deionized water in a molar ratio of 1:3, stirred at 70°C until completely dissolved, then ethanol and hydrochloric acid are added to adjust the pH to 2-3, sucrose is added at a loading amount of 30% carbon black, stirred for 2 hours to mix evenly, allowed to stand for 24 hours to gel, vacuum dried at 60°C to constant weight, placed in a muffle furnace, heated to 550°C at 1°C / min, kept warm for 3 hours in a nitrogen atmosphere, and then kept warm for 4 hours in an air atmosphere to obtain mesoporous SiO2 carbon black with a pore size of 3nm.

[0031] The preparation method of rare earth cerium modified titanium dioxide is as follows: 10 grams of TiO2 is dispersed in 0.1 mol / L cerium nitrate solution, the pH is adjusted to 9, stirred at 60°C for 2 hours, filtered and washed, calcined at 500°C for 3 hours, and ground into powder to obtain rare earth cerium modified titanium dioxide.

[0032] The preparation method of the microcapsule curing agent is as follows: dicyandiamide and imidazole are mixed in a mass ratio of 4:1, dissolved in 40 mL of deionized water, and an 8% urea-formaldehyde resin prepolymer solution is prepared. The solution is added dropwise to the curing agent solution in a volume ratio of 1:1.2 at 35°C and a pH of 4.0, and stirred for 1.5 hours to form a microcapsule curing agent.

[0033] The preparation method of high-shielding photovoltaic black ink includes the following steps: S1. Add the components of the base resin into a double star mixer and stir at 25°C for 15 minutes. Add propylene glycol methyl ether acetate, dimethyl carbonate and γ-butyrolactone and mix at 350 r / min for 10 minutes. S2. To the mixture obtained in step S1, core-shell carbon black, mesoporous SiO2 carbon black, titanium carbide-molybdenum disulfide composite, titanium dioxide coating, modified montmorillonite, and rare earth cerium-modified titanium dioxide are sequentially added, and the mixture is dispersed at a speed of 1200 r / min under vacuum conditions for 40 min. A hyperbranched dispersant is added, and ultrasonic-microwave synergistic dispersion is performed for 20 min under conditions of an ultrasonic power of 350 W and a microwave power of 600 W; S3. Grind the material obtained in step S2 four times with a four-roll grinder, then add silane fluorosilicone leveling agent, composite anti-UV agent, graphene quantum dots, photoinitiator and microcapsule curing agent, stir at a low speed at 55° C. for 30 minutes, filter through a ceramic membrane, and vacuum degas to obtain a high-shielding photovoltaic black ink.

[0034] Example 2: This embodiment discloses a high-shielding photovoltaic black ink. The only difference between this embodiment and embodiment 1 is the difference in the content of each component in the formula. Specifically, the components of this ink include the following raw materials in parts by weight: 40-60 parts of matrix resin, 15-20 parts of core-shell carbon black, 3-5 parts of mesoporous SiO2 carbon black, 1-4 parts of titanium carbide-molybdenum disulfide composite (the titanium carbide-molybdenum disulfide composite is composed of titanium carbide and molybdenum disulfide in a mass ratio of 4:1), and 1-4 parts of titanium dioxide. 0.5-2.5 parts of titanium coating, 1-3 parts of modified montmorillonite, 0.5-1.5 parts of rare earth cerium modified titanium dioxide, 0.5-2.5 parts of hyperbranched dispersant, 0.5-1.5 parts of silane fluorosilicone leveling agent, 1-3 parts of composite anti-UV agent, 0.3-0.7 parts of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of gamma-butyrolactone, 0.5-2.5 parts of photoinitiator and 0.2-1 parts of microcapsule curing agent.

[0035] The composition of the matrix resin is as follows: 45-50% of amino-modified epoxy resin, 25-30% of hydroxyl fluorocarbon resin, 10-15% of benzoxazine-acrylate resin and 8-12% of graphene-modified polyester.

[0036] Example 3: This embodiment discloses a high-shielding photovoltaic black ink. The only difference between this embodiment and embodiment 1 is the difference in the content of each component in the formula. Specifically, the components of this ink include the following raw materials in parts by weight: 40-60 parts of matrix resin, 15-20 parts of core-shell carbon black, 3-5 parts of mesoporous SiO2 carbon black, 1-4 parts of titanium carbide-molybdenum disulfide composite (the titanium carbide-molybdenum disulfide composite is composed of titanium carbide and molybdenum disulfide in a mass ratio of 4:1), and 1-4 parts of titanium dioxide. 0.5-2.5 parts of titanium coating, 1-3 parts of modified montmorillonite, 0.5-1.5 parts of rare earth cerium modified titanium dioxide, 0.5-2.5 parts of hyperbranched dispersant, 0.5-1.5 parts of silane fluorosilicone leveling agent, 1-3 parts of composite anti-UV agent, 0.3-0.7 parts of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of gamma-butyrolactone, 0.5-2.5 parts of photoinitiator and 0.2-1 parts of microcapsule curing agent.

[0037] The composition of the matrix resin is as follows: 45-50% of amino-modified epoxy resin, 25-30% of hydroxyl fluorocarbon resin, 10-15% of benzoxazine-acrylate resin and 8-12% of graphene-modified polyester.

[0038] Comparative Example 1: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that: no amino-modified epoxy resin is added, and the remaining components in the base resin formula are increased in equal proportions to a total amount of 100%.

[0039] Comparative Example 2: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no hydroxy fluorocarbon resin is added, and the remaining components in the base resin formula are increased in equal proportions to a total of 100%.

[0040] Comparative Example 3: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no benzoxazine-acrylate resin is added, and the remaining components in the base resin formula are increased in equal proportions to a total amount of 100%.

[0041] Comparative Example 4: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that: no graphene-modified polyester is added, and the remaining components in the base resin formula are increased in equal proportions to a total amount of 100%.

[0042] Comparative Example 5: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no core-shell carbon black is added, and the remaining components are increased in proportion to fill the vacancy of the core-shell carbon black component in the system.

[0043] Comparative Example 6: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no mesoporous SiO2 carbon black is added, and the remaining components are increased in proportion to fill the vacancy of the mesoporous SiO2 carbon black component in the system.

[0044] Comparative Example 7: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no titanium carbide-molybdenum disulfide composite is added, and the remaining components are increased in proportion to fill the vacancy of the titanium carbide-molybdenum disulfide composite component in the system.

[0045] Comparative Example 8: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no titanium dioxide coating is added, and the remaining components are increased in proportion to fill the vacancy of the titanium dioxide coating component in the system.

[0046] Comparative Example 9: A high-shielding photovoltaic black ink, the only difference between the ink and Example 3 is that no modified montmorillonite is added, and the remaining components are increased in proportion to fill the vacancy of the modified montmorillonite component in the system.

[0047] Comparative Example 10: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that rare earth cerium-modified titanium dioxide is not added, and the remaining components are increased in proportion to fill the vacancy of the rare earth cerium-modified titanium dioxide component in the system.

[0048] Comparative Example 11: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no hyperbranched dispersant is added, and the remaining components are increased in proportion to fill the vacancy of the hyperbranched dispersant component in the system.

[0049] Comparative Example 12: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no silane fluorosilicone leveling agent is added, and the remaining components are increased in proportion to fill the vacancy of the silane fluorosilicone leveling agent component in the system.

[0050] Comparative Example 13: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no graphene quantum dots are added, and the remaining components are expanded in equal proportion to fill the vacancy of the graphene quantum dot component in the system.

[0051] Comparative Example 14: A high-shielding photovoltaic black ink, the only difference between this ink and Example 3 is that no microcapsule curing agent is added, and the remaining components are increased in proportion to fill the vacancy of the microcapsule curing agent component in the system.

[0052] The ink coatings obtained in Examples 1-3 and Comparative Examples 1-14 were subjected to performance tests on light shielding performance (light transmittance), aging resistance, and adhesion, wherein: Transmittance: Use a spectrophotometer (such as Shanghai Lingguang WGD-30) to test the transmittance of the 300-1100nm band with a film thickness of 20μm, and the index is ≤0.75%, which meets the requirements of photovoltaic modules.

[0053] Weather resistance: According to GB / T 16422.3-2014, using A-340 lamps in QUV / Seal equipment, irradiance 1.0W / m 2 , 65℃ / 60% RH cycle (10h light + 4h condensation), color difference ΔE=1.2 after 2500 hours, no powdering or cracking, in line with the national standard ΔE≤3.0 requirement; Adhesion test (measuring the 100-grid test grade and adhesion pull-out strength): Using GB / T 9286-1998 standard, using 3M 610 tape to tear vertically, the film layer did not fall off (Grade 5B), and the adhesion pull-out strength was ≥5.2MPa, exceeding the industry standard for inks used in photovoltaic modules (≥3.0MPa).

[0054] The performance test results are shown in Table 1.

[0055] Table 1 Performance parameters of inks obtained in Examples 1-3 and Comparative Examples 1-14

[0056] From Table 1 we can see that: The light transmittance of Comparative Examples 5-7 indicates that the absence of core-shell carbon black, mesoporous SiO2 carbon black, or titanium carbide-molybdenum disulfide composites significantly impacts the light transmittance of the ink coating. Comparative Examples 8-10 indicate that the absence of titanium dioxide coatings, modified montmorillonite, and rare earth cerium-modified titanium dioxide only slightly impacts the light transmittance of the ink coating.

[0057] The color difference ΔE values ​​after 2500 hours for Comparative Examples 1-4 indicate that the absence of amino-modified epoxy resin, hydroxyl fluorocarbon resin, benzoxazine-acrylate resin, or graphene-modified polyester significantly impacts the aging resistance of the ink coating. The absence of core-shell carbon black, mesoporous SiO2 carbon black, or titanium carbide-molybdenum disulfide composites only slightly impacts the aging resistance of the ink coating.

[0058] Comparative Examples 11 and 12 show that the absence of a hyperbranched dispersant and a silane fluorosilicone leveling agent significantly impacts the adhesion of the ink coating. Comparative Example 7 shows that the absence of a titanium carbide-molybdenum disulfide composite slightly impacts the adhesion of the ink coating.

[0059] In summary, the amino groups of the amine-modified epoxy resin form hydrogen bond crosslinks with the hydroxyl groups of the hydroxyl fluorocarbon resin, the phenolic hydroxyl groups generated by the opening of the oxazine ring of the benzoxazine-acrylate resin undergo esterification with the acrylate chain segments, and the graphene sheets of the graphene-modified polyester are embedded in the resin network through π-π conjugation. The synergistic effect between the resins allows the film layer to form a three-dimensional cross-linked structure, thereby improving the mechanical properties (including tensile strength and fracture strength) and weather resistance of the ink coating. The carbon core of the core-shell carbon black serves as the light absorption center, the 4±0.5nm SiO2 shell improves the dispersibility of the ink system, the 3nm pore size of the mesoporous SiO2 carbon black forms a light scattering center, extending the propagation path of light in the film layer, and the titanium dioxide coating coats TiO2 to reduce light scattering, forming a light absorption synergy with the core-shell carbon black; rare earth cerium modified titanium dioxide through Ce 3+ / Ce 4+ The valence state conversion quenches the UV-induced hydroxyl radicals. Under multiple effects, the average transmittance in the 300-1100nm band decreases, achieving a high shielding effect.

[0060] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A high-shielding photovoltaic black ink, characterized in that: The ink comprises the following raw materials in parts by weight: 40-60 parts of matrix resin, 15-20 parts of core-shell carbon black, 3-5 parts of mesoporous SiO2 carbon black, 1-4 parts of titanium carbide-molybdenum disulfide composite, 0.5-2.5 parts of titanium dioxide coating, 1-3 parts of modified montmorillonite, 0.5-1.5 parts of rare earth cerium modified titanium dioxide, 0.5-2.5 parts of hyperbranched dispersant, 0.5-1.5 parts of silane fluorosilicone leveling agent, 1-3 parts of composite anti-UV agent, 0.3-0.7 parts of graphene quantum dots, 10-20 parts of propylene glycol methyl ether acetate, 10-15 parts of dimethyl carbonate, 1-5 parts of gamma-butyrolactone, 0.5-2.5 parts of photoinitiator and 0.2-1 parts of microcapsule curing agent.

2. The high-shielding photovoltaic black ink according to claim 1, characterized in that: In parts by weight, the components of the ink include the following raw materials: 50 parts by weight of base resin, 18 parts of core-shell carbon black, 4 parts of mesoporous SiO2 carbon black, 2.5 parts of titanium carbide-molybdenum disulfide composite, 1.5 parts of titanium dioxide coating, 2 parts of modified montmorillonite, 1 part of rare earth cerium modified titanium dioxide, 1.5 parts of hyperbranched dispersant, 0.8 parts of silane fluorosilicone leveling agent, 2 parts of composite anti-UV agent, 0.5 parts of graphene quantum dots, 15 parts of propylene glycol methyl ether acetate, 12 parts of dimethyl carbonate, 2 parts of γ-butyrolactone, 1.5 parts of photoinitiator and 0.6 parts of microcapsule curing agent.

3. The high-shielding photovoltaic black ink according to claim 1 or 2, characterized in that: The composition of the matrix resin is as follows, by weight percentage: 45-50% of amino-modified epoxy resin, 25-30% of hydroxyl fluorocarbon resin, 10-15% of benzoxazine-acrylate resin and 8-12% of graphene-modified polyester.

4. The high-shielding photovoltaic black ink according to claim 3, characterized in that: The preparation method of the amino-modified epoxy resin is as follows: bisphenol A epoxy resin and isophorone diamine are reacted at a molar ratio of 2:1 at 80° C. for 4 hours to obtain an amino-modified epoxy resin with an amine value of 180 mgKOH / g; The benzoxazine-acrylate resin is prepared by condensing phenol, formaldehyde, and 3-aminopropyltriethoxysilane in a molar ratio of 1:1.1:0.08 at 75°C for 3.5 hours to obtain an oxazine monomer, which is then mixed with butyl acrylate in a molar ratio of 1:1.2, and 0.4% azobisisobutyronitrile is added, followed by free radical polymerization at 65°C for 4 hours to obtain the resin. The preparation method of graphene-modified polyester is as follows: maleic anhydride and phthalic anhydride are added to a 95% ethylene glycol solution in a mass ratio of 1:1, reacted at 180°C for 4 hours, then graphene oxide is added at 1.2% of the total mass of maleic anhydride and phthalic anhydride, ultrasonically dispersed for 30 minutes, and finally styrene is added dropwise and an initiator is added, reacted at 80°C for 2 hours, and distilled under reduced pressure to obtain the obtained product.

5. The high-shielding photovoltaic black ink according to claim 4, characterized in that: The preparation method of core-shell carbon black is as follows: 15g of carbon black is dispersed in 150mL of deionized water, 8mL of tetraethoxysilane and 4mL of 20% ammonia water are added, hydrothermally reacted at 120℃ for 12h, centrifuged and washed, and calcined at 450℃ for 1.5h to obtain core-shell carbon black with a shell thickness of 4±0.5nm.

6. The high-shielding photovoltaic black ink according to claim 5, characterized in that: The preparation method of mesoporous SiO2 carbon black is as follows: hexadecyltrimethylammonium bromide and ethyl orthosilicate are dissolved in deionized water in a molar ratio of 1:3, stirred at 70°C until completely dissolved, then ethanol and hydrochloric acid are added to adjust the pH to 2-3, sucrose is added at a loading amount of 30% carbon black, stirred for 2 hours to mix evenly, allowed to stand for 24 hours to gel, vacuum dried at 60°C to constant weight, placed in a muffle furnace, heated to 550°C at 1°C / min, kept warm for 3 hours in a nitrogen atmosphere, and then kept warm for 4 hours in an air atmosphere to obtain mesoporous SiO2 carbon black with a pore size of 3nm.

7. The high-shielding photovoltaic black ink according to claim 6, characterized in that: The preparation method of rare earth cerium modified titanium dioxide is as follows: 10 grams of TiO2 is dispersed in 0.1 mol / L cerium nitrate solution, the pH is adjusted to 9, stirred at 60°C for 2 hours, filtered and washed, calcined at 500°C for 3 hours, and ground into powder to obtain rare earth cerium modified titanium dioxide.

8. The high-shielding photovoltaic black ink according to claim 6, characterized in that: The preparation method of the microcapsule curing agent is as follows: dicyandiamide and imidazole are mixed in a mass ratio of 4:1, dissolved in 40 mL of deionized water, and an 8% urea-formaldehyde resin prepolymer solution is prepared. The solution is added dropwise to the curing agent solution in a volume ratio of 1:1.2 at 35°C and a pH of 4.0, and stirred for 1.5 hours to form a microcapsule curing agent.

9. The high-shielding photovoltaic black ink according to claim 7 or 8, characterized in that: The titanium carbide-molybdenum disulfide composite is composed of titanium carbide and molybdenum disulfide in a mass ratio of 4:

1.

10. The high-shielding photovoltaic black ink according to any one of claims 3 to 9, characterized in that: The preparation method of ink includes the following steps: S1. Add the components of the base resin into a double star mixer and stir at 25°C for 15 minutes. Add propylene glycol methyl ether acetate, dimethyl carbonate and γ-butyrolactone and mix at 350 r / min for 10 minutes. S2. To the mixture obtained in step S1, core-shell carbon black, mesoporous SiO2 carbon black, titanium carbide-molybdenum disulfide composite, titanium dioxide coating, modified montmorillonite, and rare earth cerium-modified titanium dioxide are sequentially added, and the mixture is dispersed at a speed of 1200 r / min under vacuum conditions for 40 min. A hyperbranched dispersant is added, and ultrasonic-microwave synergistic dispersion is performed for 20 min under conditions of an ultrasonic power of 350 W and a microwave power of 600 W; S3. Grind the material obtained in step S2 four times with a four-roll grinder, then add silane fluorosilicone leveling agent, composite anti-UV agent, graphene quantum dots, photoinitiator and microcapsule curing agent, stir at a low speed at 55° C. for 30 minutes, filter through a ceramic membrane, and vacuum degas to obtain a high-shielding photovoltaic black ink.

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