Antireflection coating with high hardness, water repellency, oil repellency and self-cleaning properties, method for producing same and use thereof

Abstract

The present invention discloses an anti-reflection coating for solar cells that has high hardness, water-repellent properties, oil-repellent properties, and self-cleaning properties. The present invention provides an anti-reflection coating with high surface hardness, water-repellent properties, oil-repellent properties, and self-cleaning properties, which is applicable to solar cells. The anti-reflection coating comprises a low-refractive-index hollow nanoparticle phase and a low-refractive-index block copolymer phase. By rationally designing and combining the nanoparticle layer with a polymer filler, an anti-reflection coating with high surface hardness and excellent water-repellent properties, oil-repellent properties, and self-cleaning properties is obtained. The coating improves the light transmittance of the surface glass of solar panels, has water-repellent properties, maintains the surface clean, and improves power generation levels. It also resists external mechanical stress damage, extends the service life, and reduces costs associated with manual maintenance and cleaning.

Description

[Technical Field]

[0001] The present invention relates to the technical field of novel materials, particularly to anti-reflection coatings with high hardness, water repellency, oil repellency and self-cleaning properties, and their preparation method and use. [Background technology]

[0002] With the promotion and implementation of China's "dual carbon" policy, the solar power industry has developed rapidly in recent years as a new green energy source. According to statistics from the National Energy Administration of China, the new installed capacity of solar power generation nationwide in the first three quarters of 2023 was 128.94 million kilowatts, a 145% increase year-on-year. China's total installed capacity of solar power generation also reached 470 million kilowatts, ranking first in the world for the eighth consecutive year. As the main light energy capture interface of a power generation unit, the light transmittance of a solar panel directly affects the unit's power generation efficiency. Therefore, there is an increasing need to take effective measures to address the issue of reduced solar energy utilization efficiency caused by surface contamination and reduced transmittance due to light reflection. On the one hand, the adhesion of contaminants to the surface of solar panels reduces the amount of light absorbed. For example, the adhesion of sand, dust, bird droppings, pollen, and rainwater contaminates the surface of solar panels. On the other hand, light is refracted and scattered on the surface of solar panels, weakening the light energy actually absorbed by the solar photovoltaic module, which in turn leads to reduced power generation.

[0003] CN202310689178.0 discloses a hydrophilic coating for photovoltaic panels and a method for producing the same, which involves preparing a precursor sol by mixing a silica nanoparticle suspension, a titanium dioxide composite sol, and a non-ionic water-soluble polymer and then aging the mixture to treat the surface of the photovoltaic panel, adding a coupling agent, and then immersing the photovoltaic panel alternately in a PDDA solution and the precursor solution, followed by quenching. The resulting coating has superhydrophilic properties and a transmittance of up to 99.0%.

[0004] CN202310982606.9 discloses a hydrophilic coating for photovoltaic panels and its manufacturing method. The method involves adding an organic silicate ester and nanosilica to a hydrochloric acid solution for hydrolysis. After reacting for 2 to 5 hours, a magnesium fluoride acidic hydrolysis solution is added and hydrolysis is continued to obtain a mixed sol material of nanosilica and magnesium fluoride. A mixed alcohol solution and a nanotitania sol are added to the mixed sol material to obtain a nanosilicon titanium compound-complexed magnesium fluoride sol. Finally, the substrate is placed in acetone and deionized water, ultrasonically cleaned, and then dried. Finally, the resulting nanosilicon titanium compound-complexed magnesium fluoride sol is taken, applied to the substrate, and allowed to dry, resulting in a self-cleaning nanocoating.

[0005] However, all of the surface coatings for photovoltaics reported to date have only achieved either self-cleaning properties or improved transmittance, and their mechanical durability has not yet been fully explored. Therefore, it remains a challenge to develop a coating that combines self-cleaning properties due to its water- and oil-repellent surface with antireflection and antiglare properties, while also having excellent resistance to external physical damage. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] CN202310689178.0 [Patent Document 2] CN202310982606.9 Summary of the Invention

[0007] The purpose of this section is to summarize some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Some simplifications or omissions may be made in this section, the Abstract, and the Title of the present application so as not to obscure the purpose of this section, the Abstract, and the Title; however, such simplifications or omissions shall not be used to limit the scope of the present invention.

[0008] The present invention has been made in view of the above and / or the problems existing in the prior art.

[0009] SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to overcome the drawbacks in the prior art and to provide an anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties, a method for producing the same and its use.

[0010] In order to solve the above technical problems, the present invention provides the following technical solution: The anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties is: a lower layer of small pore hollow silica nanoparticles; an upper layer of large pore hollow silica nanoparticles; a low refractive index fluorosilicone curable multi-block copolymer interstically filled in the particles; The small-pore hollow silica nanoparticles have a particle size of 40 to 45 nm, and the large-pore hollow silica nanoparticles have a particle size of 45 to 50 nm. In a preferred embodiment of the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties contains, in mass percent, the lower layer of the small-pore hollow silica nanoparticles contains 10 to 20 wt % of hexadecyltrimethylammonium bromide, 5 to 10 wt % of a 5% monodisperse polystyrene nanosphere-ethanol solvent emulsion having a particle size of 30 nm, and 10 to 20 wt % of vinyltrimethoxysilane; the upper layer of the large-pore hollow silica nanoparticles contains 10 to 20 wt % of a 5% monodisperse polystyrene nanosphere-ethanol solvent emulsion having a particle size of 45 nm, and 5 to 10 wt % of tetraethoxysilane; The low refractive index fluorosilicone curable multi-block copolymer comprises 10-20 wt% heptadecafluorodecyl acrylate, 1-6 wt% methacryloylpropyltrimethoxysilane, 5-15 wt% methyl methacrylate, 5-15 wt% methacryloyloxy-hedgehog-type silsesquioxane, and 0.01-1 wt% azobisisobutyronitrile.

[0011] Another object of the present invention is to overcome the drawbacks of the prior art and to provide a method for producing an anti-reflection coating that has high hardness, water repellency, oil repellency and self-cleaning properties.

[0012] In order to solve the above technical problems, the present invention provides the following technical means: The method for producing the anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties includes: Dissolve hexadecyltrimethylammonium bromide in ethanol, adjust the pH, and then stir uniformly; add a monodisperse polystyrene nanosphere emulsion with a particle size of 30 nm and mix uniformly; add vinyltrimethoxysilane dropwise to react with the emulsion to produce a lower layer of small-pore hollow silica nanoparticle suspension, which is designated as suspension A; After adjusting the pH with ethanol, add a monodisperse polystyrene nanosphere emulsion with a particle size of 45 nm and mix uniformly. Then, add tetraethoxysilane and react to produce a large pore hollow silica nanoparticle suspension as the upper layer, which is designated as suspension B. Dissolving heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate, and methacryloyloxy-cage silsesquioxane in tetrahydrofuran, adding azobisisobutyronitrile, introducing nitrogen gas to remove air, sealing the reaction vessel, and reacting at 25-45°C for 1-3 hours to prepare a low refractive index fluorosilicone curable multi-block copolymer solution, designated as Solution C; The method includes the steps of applying suspension A and suspension B to the surface of a cleaned glass substrate for a solar panel using a dip coating-pulling method, drying at 70-90°C for 1 hour, and then baking at 500-600°C for 1-3 hours to pretreat the solar panel and apply the suspension of hollow silica nanoparticles, and applying solution C using a spin coating method to complete the application of the low refractive index polymer to the solar panel, followed by drying at 70-90°C for 3-5 hours and curing.

[0013] In a preferred embodiment of the method for producing the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the step of adjusting the pH is a step of adjusting the pH to 10 to 11 by slowly adding 28% to 30% aqueous ammonia.

[0014] In a preferred embodiment of the method for producing the anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the step of sequentially adding tetraethoxysilane comprises: Dividing tetraethoxysilane into 5 equal parts and adding equal amounts of tetraethoxysilane dropwise to the reaction solution at intervals of 5 minutes, 10 minutes, 30 minutes, 1 hour, and 2 hours; The total reaction time of the tetraethoxysilane in the reaction system was 10 hours.

[0015] In a preferred embodiment of the method for producing the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the dip coating and pulling-up process is The method includes the steps of placing the suspension to be coated in a suitable container and ensuring that the liquid level is high enough to completely immerse the vertically placed glass substrate; completing the dip coating-pulling process using a dip coater, first fixing the glass substrate to a fixture of the dip coater and manually adjusting the height until the lower edge of the glass substrate is slightly higher than the surface of the suspension to be coated; and then setting the lowering speed to 50-650 μm / s, the dip coating time to 5-30 s, and the lifting speed to 50-650 μm / s.

[0016] In a preferred embodiment of the method for producing the anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion to vinyltrimethoxysilane is 1:1.125 to 4.5.

[0017] In a preferred embodiment of the method for producing the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to tetraethoxysilane is 1-4:2-1.

[0018] In a preferred embodiment of the method for producing the antireflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to the present invention, the mass ratio of the heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate and methacryloyloxy-cage-type silsesquioxane is 2-4:1-3:2-4:1-3, and the amount of azobisisobutyronitrile added is 0.2-1 wt % of the total mass of the heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate and methacryloyloxy-cage-type silsesquioxane monomers.

[0019] It is yet another object of the present invention to overcome the drawbacks in the prior art and to provide an anti-reflection coating with high hardness, water repellency, oil repellency and self-cleaning properties for use on the surface of a solar cell. [Effects of the Invention]

[0020] The beneficial effects of the present invention are as follows:

[0021] 1. Anti-reflection coatings with high hardness, water-repellent, oil-repellent and self-cleaning properties can reduce the loss of light due to reflection and refraction, increase the amount of light energy that can reach the core module of a solar cell, and further improve power generation.

[0022] 2. High hardness, water-repellent, oil-repellent and self-cleaning anti-reflection coating has excellent water-repellent, oil-repellent and self-cleaning properties, which helps keep the surface of solar panels clean for a long time, reduce the negative impact of contaminants on the light capture of the modules, and maintain a high level of power generation.

[0023] 3. High-hardness, water-repellent, oil-repellent and self-cleaning anti-reflection coatings have high surface hardness and good mechanical durability. The coatings can retain their inherent performance even after being worn and damaged by external stress for a certain period of time, thereby extending their service life. [Brief explanation of the drawings]

[0024] In order to more clearly describe the technical means of the embodiments of the present invention, the following will briefly describe the drawings necessary for describing the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention, and those skilled in the art can also obtain other drawings based on these drawings without any creative efforts. [Figure 1] 1 is a schematic diagram of a high-hardness, water-repellent, oil-repellent, and self-cleaning anti-reflection coating applied to a solar cell panel manufactured in Example 1 of the present invention. [Figure 2] 1 shows particle size distribution curves of two types of nanoparticles with different hollow pore diameters. [Figure 3] 1 is a comparison curve of the transmittance in the visible light region of the coated glass manufactured in Example 1 of the present invention and the original glass. [Figure 4] 1 shows the measurement of Vickers hardness of the coating surface produced in Example 1 of the present invention. [Figure 5] 1 shows the wet resistance of the coating produced in Example 1 of the present invention. [Figure 6] 1 shows the change curves of the water contact angle and sliding angle of the coating surface produced in Example 1 of the present invention during abrasion testing. [Figure 7] 1 shows the measurement of the amount of power generated by a solar panel after coating application manufactured in Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] In order to make the above objects, features and advantages of the present invention more apparent, specific embodiments of the present invention will be described in detail below with reference to examples in the specification.

[0026] In the following description, numerous specific details are set forth to facilitate a thorough understanding of the present invention; however, the present invention may be practiced in other ways than those described herein, and those skilled in the art may make similar generalizations without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

[0027] Next, "one example" or "example" as referred to herein refers to a particular feature, structure, or characteristic that may be included in at least one embodiment of the present invention. "In one example" appearing in different places in this specification does not necessarily refer to the same example, nor does it refer to an example that is mutually exclusive or alternatively exclusive with other examples.

[0028] The raw materials used in the present invention are all common commercially available products unless otherwise specified.

[0029] The coatings produced in the examples of the present invention are performance tested in the following manner.

[0030] Vickers hardness: The hardness of the coating surface is measured using a FALCON 507 Vickers microhardness tester. Vickers hardness is calculated based on the amount of pressure applied per unit surface area of ​​the indentation. A square diamond pyramid with an apex angle of 136° is used to press a square indentation into the test surface of the sample under a constant pressure. The lengths of the two diagonals of the indentation are measured using a microscope attached to the Vickers hardness tester, and the Vickers hardness value is looked up in the corresponding table based on the average length of the diagonals. Vickers hardness is indicated by the common symbol HV, where the number before HV is the Vickers hardness value and the number after HV is the test load.

[0031] Visible light transmittance: The Shimadzu UV 3600 UV-Visible Spectrophotometer was used to measure the visible light transmittance of the samples (coated glass and original glass). The test sample size was 7.5 cm x 2.5 cm, and a glass slide of the same size was selected as a control sample during the test. The transmittance of air was used as the baseline for the test. The measurement wavelength range was 400 nm to 800 nm.

[0032] Contact angle: The KRUSS DSA25S optical contact angle analysis system is used to measure the contact angle of a water / oil droplet on a coating surface. To measure the contact angle in a non-moving state, a water / oil droplet (~5 μL) is first dropped onto the sample surface using a motor-controlled syringe. Once the droplet has stabilized, a side image is taken with a camera, and fitting calculations are performed using software to obtain the static contact angle of the water / oil droplet on the coating surface.

[0033] Sliding angle: The sliding angle of a water or oil droplet on the coating surface is measured using a KRUSS DSA25S optical contact angle analysis system. To measure the sliding angle, the sample is tilted using a motor-controlled, rotatable test stage, and the stage's rotation angle is displayed in real time on a computer connected to the motor. At the start of the test, the initial tilt angle of the stage is maintained at 0°. A water or oil droplet (~5 μL) is dispensed onto the coating surface using a syringe, and then the motor is controlled to rotate the stage. The moment the droplet begins to roll on the surface, the rotation stops, and the rotation angle displayed on the computer is recorded and used as the roll-off angle. Each sample is measured at three different positions to reduce data error.

[0034] The power generation of the solar panel after coating application: Cumulative measurement of the total power generation was performed using a WT5000 power analyzer. The solar panel used for the solar power performance test was a commercial silicon solar panel, and the test period was one month. During the test, the voltage input port was connected in parallel to the solar panel, and the current port was connected in series to the output port of the solar panel.

[0035] DI: deionized water, EtOH: absolute ethanol, THF: tetrahydrofuran, CTAB: hexadecyltrimethylammonium bromide, TEOS: tetraethoxysilane, PSNS: monodisperse polystyrene nanosphere emulsion (ethanol solvent, 5%, particle size 30, 45 nm), PFEA: heptadecafluorodecyl acrylate, KH-570: methacryloylpropyltrimethoxysilane, KH-171: vinyltrimethoxysilane, MMA: methyl methacrylate, M-POSS: methacryloyloxy-cage-type silsesquioxane, AIBN: azobisisobutyronitrile.

[0036] Example 1 This example provides a method for preparing an anti-reflection coating with high hardness, water repellency, oil repellency and self-cleaning properties, and is specifically as follows:

[0037] (1) 0.45 g of CTAB was weighed and dissolved in 55 mL of EtOH. 28%-30% aqueous ammonia was slowly added to adjust the pH to 10-11, and the mixture was stirred at room temperature for 30 min at 600 rpm. Next, 0.2 g of a monodisperse polystyrene nanosphere emulsion with a particle size of 30 nm was weighed and added to the above solution. After stirring for 10 min, 0.45 g of KH-171 was added dropwise. The mixture was allowed to react for 10 h with continued stirring. The resulting homogeneous suspension was designated Suspension A.

[0038] (2) 55 mL of EtOH was weighed into a round-bottom flask, and 28%–30% aqueous ammonia was slowly added to adjust the pH to 10–11. The mixture was stirred at 600 rpm for 30 min at room temperature. Next, 0.45 g of a monodisperse polystyrene nanosphere emulsion with a particle size of 45 nm was weighed and added to the above solution. The mixture was thoroughly mixed and stirred for 10 min to obtain a uniform emulsion. Then, 0.225 g of TEOS was divided into five equal portions on average, and each "equal portion" was added dropwise to the above emulsion at 10-min intervals. After a total of 50 min, the mixture was allowed to react for 10 h with continued stirring. The resulting uniform suspension was designated Suspension B.

[0039] (3) PFEA, KH-570, MMA, and M-POSS (mass percentages of 40 wt%, 10 wt%, 30 wt%, and 20 wt%, respectively) were weighed and dissolved in THF, and after stirring at room temperature for 10 minutes, the initiator AIBN (0.5 wt% of the total mass of the monomers) was added, and nitrogen gas was introduced to expel the air. The reaction vessel was sealed and then reacted at 35°C for 2 hours. The resulting polymer solution was designated Solution C.

[0040] (4) First, the glass substrates for solar panels were rinsed twice alternately with EtOH and DI, and then dried. Next, Suspension A was applied to the surface of the glass substrate by dip coating and lifting, and the substrate was heated and dried in a blast oven at 80°C for 1 hour. Suspension B was then applied to the surface of the glass substrate by dip coating and lifting, and the substrate was similarly heated and dried in a blast oven at 80°C for 1 hour. After that, the PSNS and CTAB were baked at 550°C for 2 hours.

[0041] (5) Solution C was applied to the glass substrate prepared in the previous step by spin coating.

[0042] (6) The glass produced in the previous step was placed in a blast oven and dried at 80°C for 4 hours, resulting in an anti-reflection coating on the surface of the substrate that had high hardness, water repellency, oil repellency, and self-cleaning properties.

[0043] 1 is a schematic diagram of the anti-reflection coating with high hardness, water repellency, oil repellency, and self-cleaning properties applied to the solar cell panel manufactured in Example 1 of the present invention. As shown in the figure, a anti-reflection coating with a reflectance gradient is formed on the surface of a glass substrate, with a lower layer of small-pore hollow nanoparticles with a relatively high reflectance and an upper layer of large-pore hollow nanoparticles with a relatively low reflectance. The low-reflectance fluorine-containing multiblock copolymer is filled into the voids between the particles, improving the wetting resistance of the coating surface and also improving the mechanical stability between the particles and the substrate.

[0044] Figure 2 shows the particle size distribution curves of two types of hollow pore nanoparticles with different diameters. The diameters of the small-pore nanoparticles are mainly in the range of 40–45 nm, while the diameters of the large-pore nanoparticles are mainly in the range of 45–50 nm. This indicates that the diameter of the monodisperse polystyrene nanospheres directly affects the hollow inner diameter of the hollow nanoparticles, and that KH-171 is more likely to form a thicker outer wall than TEOS.

[0045] Furthermore, as shown in Figure 3, the test results showed that the anti-reflection coating produced by this invention, which has high hardness, water repellency, oil repellency, and self-cleaning properties, achieved an average transmittance of 95.3% in the visible light range, an increase of approximately 3% compared to the original substrate, demonstrating its anti-reflection effect. The Vickers hardness of the coating surface reached 414.03 HV0.02 (see Figure 4), indicating its high surface hardness. The contact angle of water droplets on the coating surface was 104.7° and the sliding angle was 13.8°, and the contact angle of oil droplets on the surface was 16.3° and the sliding angle was 1.12° (see Figure 5), indicating that the coating has excellent repellency against both oil and water. The coating maintained its performance and structural integrity even after Taber abrasion (see Figure 6). A comparison of the power generation of coated and untreated solar panels over time confirmed that the coating had an improved effect on the power generation of solar modules (see Figure 7).

[0046] Example 2 The difference between this example and Example 1 is that the mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion and KH-171 in the small pore nanoparticle suspension preparation process was adjusted to 1:1.125 (0.4 g of the 30 nm monodisperse polystyrene nanosphere emulsion and 0.45 g of KH-171 were weighed out). The rest of the preparation process was the same as in Example 1 to prepare the coating.

[0047] Example 3 The difference between this example and Example 1 is that the mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion to KH-171 in the preparation process of the small pore nanoparticle suspension was adjusted to 1:4.5 (0.2 g of the 30 nm monodisperse polystyrene nanosphere emulsion and 0.9 g of KH-171 were weighed out). The rest of the preparation process was the same as in Example 1 to prepare the coating.

[0048] The performance of the materials produced in the above examples was tested and the results compared with Example 1 are shown in Table 1.

[0049] [Table 1]

[0050] A slash in the table indicates that the data was not tested.

[0051] The above examples primarily examine the condition variables in the manufacturing process of the lower-layer small-pore hollow nanoparticles, primarily reflecting their effect on transmittance in the visible light region. As can be seen from the table, different amounts of monodisperse polystyrene nanosphere emulsion and KH-171 added affect the pore size and wall thickness of the resulting hollow nanoparticles. Increasing the mass of monodisperse polystyrene nanosphere emulsion alone increases the pore size of the resulting hollow nanoparticles. Without changing the amount or method of KH-171 added, the wall thickness does not change significantly, resulting in a decrease in the reflectivity of the hollow nanoparticles compared to Example 1. This increases the difference in reflectivity between the lower-layer small-pore hollow nanoparticle layer and the glass substrate, increasing interfacial reflection compared to Example 1 and decreasing light transmittance. When only the amount of KH-171 added was increased, the thickness of the sphere walls of the produced hollow nanoparticles increased. However, since the mass and addition method of the monodisperse polystyrene nanosphere emulsion were not changed, the inner diameter of the hollow nanoparticles did not change significantly. However, the reflection coefficient of the hollow nanoparticles increased compared to Example 1, and the difference in reflection coefficient between the lower small-pore hollow nanoparticle layer and the upper large-pore hollow nanoparticle layer increased. As a result, the interfacial reflection increased compared to Example 1, and the light transmittance decreased.

[0052] Test results showed that the average transmittance in the visible light region of the coatings produced in Examples 2 and 3 was approximately 94.7% and 93.6%, respectively. This is thought to be due to the change in the reflectance gradient caused by the change in the physical properties of the small-pore hollow nanoparticles, but the coating still has anti-reflection effect.

[0053] According to the results in the above table, in the process of preparing the small pore nanoparticle suspension of the present invention, when the mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion to KH-171 is 1:2.25, the optimum technical effect can be achieved.

[0054] Example 4 The difference between this example and Example 1 is that the mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to TEOS in the preparation of the large pore nanoparticle suspension was adjusted to 1:2 (0.45 g of the 45 nm monodisperse polystyrene nanosphere emulsion and 0.9 g of TEOS were weighed out). The rest of the preparation process was the same as in Example 1 to prepare the coating.

[0055] Example 5 The difference between this example and Example 1 is that the mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to TEOS in the preparation of the large pore nanoparticle suspension was adjusted to 4:1 (0.9 g of the 45 nm monodisperse polystyrene nanosphere emulsion and 0.225 g of TEOS were weighed out). The rest of the preparation process was the same as in Example 1 to prepare the coating.

[0056] The performance of the materials produced in the above examples was tested and the results compared with Example 1 are shown in Table 2.

[0057] [Table 2]

[0058] The above examples primarily examine the condition variables in the manufacturing process of the upper-layer large-pore hollow nanoparticles, primarily reflecting their effect on transmittance in the visible light region. As can be seen from the table above, varying the amount of 45 nm monodisperse polystyrene nanosphere emulsion and TEOS added affects the pore size and wall thickness of the resulting hollow nanoparticles. In Example 4, increasing the mass of TEOS alone did not significantly change the pore size of the resulting hollow nanoparticles, but increased the wall thickness, resulting in a higher reflection coefficient for the large-pore hollow nanoparticles compared to Example 1. This increased the difference in reflection coefficient between the upper-layer large-pore hollow nanoparticle layer and air, increasing interfacial reflection compared to Example 1 and decreasing light transmittance. Test results showed that the average transmittance in the visible light region of the coating manufactured in Example 4 was approximately 93.5%. Increasing only the mass of the 45 nm monodisperse polystyrene nanospheres increased the hollow pore diameter of the produced hollow nanoparticles, but the change in sphere wall thickness was small. The reflection coefficient of the large-pore hollow nanoparticles decreased compared to Example 1, and the difference in reflection coefficient between the upper large-pore hollow nanoparticle layer and the lower small-pore hollow nanoparticle layer increased, resulting in increased interfacial reflection compared to Example 1 and a decrease in light transmittance. Test results showed that the average transmittance in the visible light region of the coating produced in Example 4 was approximately 94.1%.

[0059] According to the results in the above table, in the process of preparing the small pore nanoparticle suspension of the present invention, when the mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to TEOS is 2:1, the optimum technical effect can be achieved.

[0060] Example 6 The difference between this example and Example 1 is that the mass percentages of PFEA, KH-570, MMA, and M-POSS in the preparation process of the fluorine-containing block copolymer were adjusted to 30 wt%, 13 wt%, 33 wt%, and 24 wt%, respectively. The remaining preparation processes were all the same as those in Example 1 to prepare the coating.

[0061] Example 7 The difference between this example and Example 1 is that the mass percentages of PFEA, KH-570, MMA, and M-POSS in the preparation process of the fluorine-containing block copolymer were adjusted to 40 wt%, 10 wt%, 40 wt%, and 10 wt%, respectively. The remaining preparation processes were all the same as those in Example 1 to prepare the coating.

[0062] The performance of the materials produced in the above examples was tested and the results compared with Example 1 are shown in Table 3.

[0063] [Table 3]

[0064] The above examples mainly examine the condition variables in the manufacturing process of the fluorine-containing multi-block copolymer, mainly reflecting their effects on surface hardness and wetting resistance. As can be seen from the table above, different weight percentages of the four components in the fluorine-containing block copolymer affect the water repellency, oil repellency, and mechanical durability of the coating. In Example 6, the weight ratio of PFEA was reduced. Test results showed that the coating manufactured in Example 6 exhibited some reduction in both water and oil repellency. For example, the contact angle of water on the surface decreased to 98.6° and the sliding angle was 14.7°, while the contact angle of oil on the surface was 15.8° and the sliding angle was 2.1°. However, the coating still exhibited water repellency, oil repellency, and self-cleaning properties.

[0065] The coating produced in Example 7 has a reduced surface hardness, with a Vickers hardness of about 362.14 HV0.02, but the coating still has a high surface hardness and can resist damage caused by a certain amount of external stress.

[0066] From the above, the optimal mass ratio of PFEA, KH-570, MMA, and M-POSS is 4:1:3:2.

[0067] (Comparative Example 1) Original Glass FIG. 3 shows a comparison curve of the transmittance in the visible light range of the coated glass produced in Example 1 of the present invention and the original glass. The average transmittance in the visible light range of the original glass is 91.7%, while the average transmittance in the visible light range of Example 1 is 95.3%, indicating that the coating has a reflective and anti-reflection effect.

[0068] (Comparative Example 2) The difference between this example and Example 1 is that the dip coating-pull-up method in the manufacturing step (4) of this comparative example was changed to a spray gun spraying method, and all other manufacturing processes were the same as those of Example 1 to manufacture the coating.

[0069] The performance of the materials produced in the above comparative examples was tested and the results compared with Example 1 are shown in Table 4.

[0070] [Table 4]

[0071] Table 4 compares Example 1 with Comparative Examples 1 and 2, primarily comparing them with the original glass and examining the coating application process, primarily reflecting the effects on transmittance and wetting resistance in the visible light range. As can be seen from the table above, the coating produced in accordance with the present invention has a significant anti-reflection effect compared to the original glass. The coating produced in Comparative Example 2 is significantly thicker than Example 1, and its surface roughness also increases significantly, resulting in a sharp increase in the coating's reflectance, with a visible light transmittance of only 76.1%.

[0072] The present invention provides an anti-reflection coating that has high surface hardness, water-repellent properties, oil-repellent properties, and self-cleaning properties. The coating contains a low-refractive-index hollow nanoparticle phase and a low-refractive-index block copolymer phase. By rationally designing and combining the nanoparticle layer with a polymer filler, an anti-reflection coating with high surface hardness and excellent water-repellent properties, oil-repellent properties, and self-cleaning properties is obtained. The coating improves the light transmittance of the surface glass of a solar panel, has water-repellent properties, maintains the surface clean, and improves power generation. It also resists external mechanical stress damage, extends the service life, and reduces costs associated with manual maintenance and cleaning.

[0073] It should be noted that the above examples are merely for explaining the technical means of the present invention and are not intended to be limiting. The present invention has been described in detail with reference to preferred embodiments, but those skilled in the art may make modifications or equivalent substitutions to the technical means of the present invention without departing from the spirit and scope of the technical means of the present invention, and all of these should be included in the scope of the claims of the present invention.

Claims

1. a lower layer of small pore hollow silica nanoparticles; an upper layer of large pore hollow silica nanoparticles; a low refractive index fluorosilicone curable multi-block copolymer interstically filled in the particles; The anti-reflection coating has high hardness, water repellency, oil repellency and self-cleaning properties, characterized in that the small pore hollow silica nanoparticles have a particle size of 40 to 45 nm, and the large pore hollow silica nanoparticles have a particle size of 45 to 50 nm.

2. The formulation components of the high hardness, water-repellent, oil-repellent, self-cleaning anti-reflection coating, in weight percent, are: the lower layer of the small-pore hollow silica nanoparticles contains 10 to 20 wt % of hexadecyltrimethylammonium bromide, 5 to 10 wt % of a 5% monodisperse polystyrene nanosphere-ethanol solvent emulsion having a particle size of 30 nm, and 10 to 20 wt % of vinyltrimethoxysilane; the upper layer of the large-pore hollow silica nanoparticles contains 10 to 20 wt % of a 5% monodisperse polystyrene nanosphere-ethanol solvent emulsion having a particle size of 45 nm, and 5 to 10 wt % of tetraethoxysilane; 2. The high hardness, water-repellent, oil-repellent and self-cleaning anti-reflection coating of claim 1, wherein the low refractive index fluorosilicone curable multi-block copolymer comprises 10-20 wt % heptadecafluorodecyl acrylate, 1-6 wt % methacryloylpropyltrimethoxysilane, 5-15 wt % methyl methacrylate, 5-15 wt % methacryloyloxy-hedgehog-type silsesquioxane, and 0.01-1 wt % azobisisobutyronitrile.

3. Dissolving hexadecyltrimethylammonium bromide in ethanol, adjusting the pH, and then uniformly stirring; then adding a monodisperse polystyrene nanosphere emulsion with a particle size of 30 nm and mixing uniformly; adding vinyltrimethoxysilane dropwise and reacting to produce a lower layer of small pore hollow silica nanoparticle suspension, which is called suspension A; After adjusting the pH with ethanol, add a monodisperse polystyrene nanosphere emulsion with a particle size of 45 nm and mix uniformly. Then, add tetraethoxysilane and react to produce a large pore hollow silica nanoparticle suspension as the upper layer, which is designated as suspension B. Dissolving heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate, and methacryloyloxy-cage silsesquioxane in tetrahydrofuran, adding azobisisobutyronitrile, introducing nitrogen gas to remove air, sealing the reaction vessel, and reacting at 25-45°C for 1-3 hours to prepare a low refractive index fluorosilicone curable multi-block copolymer solution, designated as Solution C; 3. The method for manufacturing a high-hardness, water-repellent, oil-repellent, and self-cleaning anti-reflection coating according to claim 2, further comprising the steps of: applying suspension A and suspension B to the surface of a cleaned glass substrate for a solar panel by a dip coating-pulling method; drying at 70-90°C for 1 hour; and baking at 500-600°C for 1-3 hours to pretreat the solar panel and coat the suspension of hollow silica nanoparticles; and applying solution C by a spin coating method; completing the coating of the low refractive index polymer on the solar panel; and then drying at 70-90°C for 3-5 hours to coat the surface.

4. 3. The method for producing an anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to claim 2, wherein the step of adjusting the pH is a step of adjusting the pH to 10-11 by slowly adding 28%-30% ammonia water.

5. The step of sequentially adding tetraethoxysilane comprises: Dividing tetraethoxysilane into five equal portions and adding equal amounts of tetraethoxysilane dropwise to the reaction solution at intervals of 5 minutes, 10 minutes, 30 minutes, 1 hour, and 2 hours; 3. The method for producing an anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to claim 2, wherein the total reaction time of the tetraethoxysilane in the reaction system is 10 hours.

6. The dip coating-pulling process is 3. The method for manufacturing a high-hardness, water-repellent, oil-repellent, and self-cleaning anti-reflection coating according to claim 2, comprising the steps of: pouring the suspension to be coated into a suitable container and ensuring a liquid level high enough to completely immerse the glass substrate placed vertically; and completing the dip coating-pull-up process using a dip coater, first fixing the glass substrate to a fixture of the dip coater and manually adjusting the height until the lower edge of the glass substrate is slightly higher than the surface of the suspension to be coated; and then setting the lowering speed to 50-650 μm / s, the dip coating time to 5-30 s, and the pull-up speed to 50-650 μm / s.

7. The method for producing an anti-reflection coating with high hardness, water repellency, oil repellency and self-cleaning properties as claimed in claim 2, characterized in that the mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion to vinyltrimethoxysilane is 1:1.125-4.

5.

8. The method for producing an anti-reflection coating with high hardness, water repellency, oil repellency and self-cleaning properties as claimed in claim 2, characterized in that the mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to tetraethoxysilane is 1-4:2-1.

9. 3. The method for producing a high-hardness, water-repellent, oil-repellent, and self-cleaning anti-reflection coating according to claim 2, wherein the mass ratio of the heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate, and methacryloyloxy-cage-type silsesquioxane is 2-4:1-3:2-4:1-3, and the amount of azobisisobutyronitrile added is 0.2-1 wt % of the total mass of the heptadecafluorodecyl acrylate, methacryloylpropyltrimethoxysilane, methyl methacrylate, and methacryloyloxy-cage-type silsesquioxane monomers.

10. 10. Use of the anti-reflection coating having high hardness, water repellency, oil repellency and self-cleaning properties according to claim 1 on the surface of a solar cell.

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