Anti-dazzle tempered glass, preparation method thereof and photovoltaic panel
By generating a microporous structure inside the glass substrate and combining chemical etching and physical coating, the problem of poor anti-glare effect of anti-glare tempered glass has been solved, achieving a high light transmittance and durable anti-glare effect.
Patent Information
- Application Number
- CN202511035121.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-25
- Publication Date
- 2025-11-04
AI Technical Summary
Existing anti-glare tempered glass has poor anti-glare performance, the coating process is easy to fade and difficult to clean, the rolling technology is prone to dust accumulation, and the light spot phenomenon is obvious.
Laser engraving technology is used to create a microporous structure inside the glass substrate. Combined with chemical etching and physical coating, a staged tempering process is performed, including pre-tempering, acid etching and final tempering. A uniform anti-glare layer is formed using CeO2/TiO2 composite film and nano-silica particles.
It improves the uniformity and durability of the anti-glare effect, achieves a light transmittance of over 90%, enhances fingerprint resistance, and reduces etching time and cost.
Smart Images
Figure CN120887653A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of photovoltaic panel glass technology, and in particular to anti-glare tempered glass, its preparation method, and photovoltaic panels. Background Technology
[0002] Anti-glare glass, or AG glass for short, is a type of glass with a specially treated surface. The principle behind it is to process high-quality glass on one or both sides to give it a lower reflectivity compared to ordinary glass, thereby reducing interference from ambient light.
[0003] To control light pollution, most photovoltaic panels currently use AG glass, especially anti-glare tempered glass. However, current production methods for anti-glare photovoltaic tempered glass involve coating the glass surface with an anti-reflective layer (i.e., anti-glare film coating) or altering the shape and depth of the embossing during the glass rolling process to achieve low reflectivity. These coating processes, however, tend to wear off over time with use, resulting in a loss of anti-reflective function. While altering the shape of surface particles through rolling technology can maintain anti-glare effects long-term, the recessed areas are prone to dust accumulation and difficult to clean. Furthermore, current anti-glare tempered glass still exhibits light spots, indicating incomplete anti-glare performance. Summary of the Invention
[0004] The purpose of this application is to address the problem of poor anti-glare performance of existing anti-glare tempered glass. Therefore, this application provides anti-glare tempered glass, its preparation method, and a photovoltaic panel, which improves the anti-glare effect of the tempered glass through a synergistic "chemical + physical" approach.
[0005] This application provides a method for preparing anti-glare tempered glass, which includes performing the following processes in sequence:
[0006] S1. Pretreatment: A microporous structure is generated inside the glass substrate using laser engraving technology, and a pre-protective layer is sprayed on the surface of the glass substrate to reduce the impact of acid etching.
[0007] S2. Pre-tempering: The pre-treated glass substrate is tempered at 300-400℃.
[0008] S3, Acid Etching: The pre-tempered glass substrate is acid etched twice. The first acid etching is done by immersion treatment, and the second acid etching is done by spraying treatment. The second acid etching time is shorter than the first acid etching time.
[0009] S4. Dynamic atomization strengthening treatment: A CeO2 / TiO2 composite film is deposited on the surface of the glass substrate after acid etching by magnetron sputtering, and then nano-sized silica particles are atomized and sprayed. The film is then bonded to the glass substrate by high-temperature sintering.
[0010] S5. Final tempering: The glass substrate after coating is tempered at 680-720℃, and then subjected to gradient cooling.
[0011] In some embodiments, the etching solution for the first acid etching is: 25-30 wt% fluorosilicic acid, 8-12 wt% sodium fluoroborate, 5-8 wt% hydrofluoric acid, 0.5-1.5 wt% alum, 0.1-0.3 wt% surfactant CTAB, 3-5 wt% glycerol, and the balance being deionized water;
[0012] The temperature is 40-45℃, the soaking time is 3-5 minutes, and ultrasonic cleaning is used to remove residual liquid at a frequency of 20-35kHz.
[0013] In some embodiments, the etching solution for the second acid etching is: 15-18 wt% ammonium fluoride, 5-7 wt% oxalic acid, 3-5 wt% ammonium sulfate, 2-4 wt% nano-silica dispersion, 10-15 wt% ethanol, and the balance being deionized water.
[0014] The temperature is 25-30℃, the standing time after spraying is 1-2 minutes, and the water washing pressure to remove residual liquid is 0.2-1MPa.
[0015] In some embodiments, the acid etching solution used for both acid etching processes includes 0.05-0.1 wt% benzotriazole.
[0016] In some embodiments, the process further includes the following steps between the S3 acid etching and the S4 dynamic atomization enhancement treatment:
[0017] S31, Alkaline Etching: Etching is performed using an alkaline etching solution.
[0018] The alkaline etching solution consists of: 40-50 wt% sodium hydroxide, 5-8 wt% sodium silicate, 3-5 wt% potassium carbonate, 1-2 wt% ammonium dihydrogen phosphate, 0.5-1 wt% polyethylene glycol, and the balance being deionized water;
[0019] The temperature is 110-120℃, the soaking time is 150-200 minutes, and nitrogen is used to purge the surface of residual liquid.
[0020] In some embodiments, the process further includes the following prior to the S4 dynamic atomization enhancement process:
[0021] The glass substrate, after removing the residual liquid, is immersed in an ethanol solution containing 1-2% silane coupling agent.
[0022] In some embodiments, the pre-protective layer in the S1 pretreatment is an atomized coating containing nano-silica.
[0023] In some embodiments, laser engraving technology is used simultaneously in the S1 preprocessing to generate a chamfered preprocessing area inside the glass substrate.
[0024] This application also provides an anti-glare tempered glass, characterized in that it is prepared using any of the methods described above.
[0025] This application also provides a photovoltaic panel, including a photovoltaic module and glass covering thereon, wherein the glass is prepared using any of the methods described above.
[0026] Beneficial effects:
[0027] This application breaks through the traditional single chemical etching or spraying process for AG glass, achieving a synergistic anti-glare effect of "chemical + physical". Specifically, it uses laser internal engraving technology to generate a microporous structure inside the glass substrate, which can reduce the subsequent etching time by more than 30%, while avoiding local over-etching and improving the uniformity of micropore depression formation on the glass surface, thereby improving the uniformity of anti-glare. At the same time, it uses two acid etching processes to improve the etching effect. Furthermore, the first acid etching uses a compound system of fluorosilicic acid and sodium fluoroborate to simultaneously optimize the etching rate and surface morphology. The alum catalyst shortens the reaction time by 40%, and the surfactant CTAB encapsulates the reverse micelle solution of hydrofluoric acid, achieving an etching depth error of <5%. In addition, it uses a dual process of "magnetron sputtering + atomized spraying" to achieve a light transmittance of >90% for the anti-glare layer. Moreover, the tempering is divided into pre-tempering and final tempering, which improves the tempering effect and enhances the durability of the anti-glare layer.
[0028] Other features and corresponding beneficial effects of this application will be described in the latter part of the specification, and it should be understood that at least some of the beneficial effects will become obvious from the description in this application. Attached Figure Description
[0029] Figure 1 This is a schematic diagram of the preparation method of this application. Detailed Implementation
[0030] The invention will be more readily understood by referring to the following detailed description of preferred embodiments and included examples. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of conflict, the definitions in this specification shall prevail. As used herein, the term "prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.
[0031] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.
[0032] The singular form includes the plural objects of discussion unless the context clearly indicates otherwise. "Optional" or "any one" means that the matter or event described thereafter may or may not occur, and the description includes both the possibility that the event occurs and the possibility that the event does not occur.
[0033] Approximate terms used in the specification and claims to modify quantities indicate that the invention is not limited to that specific quantity, but also includes acceptable modifications close to that quantity that do not alter the relevant essential function. Correspondingly, the use of "about," "approximately," etc., to modify a numerical value means that the invention is not limited to that precise value. In some instances, approximate terms may correspond to the precision of the instrument used to measure the value. In this application's specification and claims, scope definitions can be combined and / or interchanged, unless otherwise stated, these scopes include all sub-scopes contained therein.
[0034] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of this invention do not impose any limitation on the quantity requirement (i.e., the number of times) of the elements or components. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers to the singular form.
[0035] Example 1:
[0036] Please see Figure 1 , Figure 1 This is a schematic diagram of the preparation method of this application.
[0037] This application provides a method for preparing anti-glare tempered glass, which can produce anti-glare tempered glass with an anti-glare layer haze of 20-95%, a gloss of 9.6 GU, and a bending strength ≥200 MPa after tempering.
[0038] This preparation method includes the following sequential processing:
[0039] S1. Pretreatment: A microporous structure is generated inside the glass substrate using laser engraving technology, and a pre-protective layer is sprayed on the surface of the glass substrate to reduce the impact of acid etching.
[0040] Preferably, the microporous structure is a microporous tubular structure, which has a better anti-glare effect and better light transmittance compared to the conventional microporous spherical structure.
[0041] Laser engraving technology is a technique that uses high-energy pulsed lasers to precisely create tiny burst points or modified particles inside transparent materials. It controls the pulsed laser to focus inside the glass and uses micron-level burst points to form a three-dimensional image without damaging the material surface. Its core principle is to adjust the laser energy density so that the intensity of the focused area exceeds the glass damage threshold, forming a fine array of white dots.
[0042] This method achieves a synergistic effect of "chemical + physical" by forming a microporous structure inside the glass and cooperating with subsequent etching. Since the existing microporous structure can achieve a certain degree of anti-glare, the corrosion thickness on the glass surface can be reduced compared to conventional anti-glare glass (conventional corrosion is 2.2-3.2um, while in this embodiment it can be only 0.6um). This can speed up subsequent etching and reduce subsequent etching time by more than 30%. At the same time, due to the small etching thickness, it is beneficial to avoid local over-etching and improve the uniformity of microporous depression formation on the glass surface, thereby improving the uniformity of glass anti-glare.
[0043] Preferably, the pre-protective layer is an atomized coating containing nano-silica. By covering the glass surface with the pre-protective layer, the direct impact of the subsequent etching solution can be reduced, thereby preventing the internally carved micropores from being corroded and damaged.
[0044] Preferably, the thickness of the pre-protective layer is 50-60 nanometers.
[0045] S2. Pre-tempering: The pre-treated glass substrate is tempered at 300-400℃ to improve the crack resistance of the glass substrate.
[0046] S3. Acid etching: The pre-tempered glass substrate is acid etched twice. The first acid etching is done by immersion treatment, and the second acid etching is done by spraying treatment. The second acid etching time is shorter than the first acid etching time, which can form a spherical micro-bump structure of 0.08-2.0μm, avoid flash point problems and improve the anti-glare effect of the glass.
[0047] S4. Dynamic Atomization Enhancement Treatment: A CeO2 / TiO2 composite film is deposited on the surface of the acid-etched glass substrate using magnetron sputtering to enhance transparency. The next step involves spraying nano-sized silica particles as the coating liquid for AG glass. After curing, the film is bonded to the glass substrate through high-temperature sintering. This dual-process combination of magnetron sputtering and atomization spraying achieves a transmittance of >90% for the anti-glare layer compared to traditional spraying processes, while achieving 85% transmittance. It also enhances diffuse reflection and fingerprint resistance.
[0048] It should be noted that the anti-glare layer is the uneven structure formed by acid etching and the coating layer formed in step S4.
[0049] S5. Final tempering: The glass substrate after coating is tempered at 680-720℃, and then a gradient cooling is used after tempering, such as air cooling followed by liquid nitrogen rapid cooling, in order to balance the stability of the anti-glare layer and the strength of the glass.
[0050] Furthermore, the tempering process is divided into pre-tempering and final tempering, which improves the tempering effect and enhances the durability of the anti-glare layer.
[0051] In one embodiment, the etching solution for the first acid etching is: 25-30 wt% fluorosilicic acid (H2SiF6), 8-12 wt% sodium fluoroborate (NaBF4), 5-8 wt% hydrofluoric acid (HF), 0.5-1.5 wt% alum (potassium aluminum sulfate), 0.1-0.3 wt% surfactant CTAB, 3-5 wt% glycerol, and the balance being deionized water. That is, fluorosilicic acid (H2SiF6) and sodium fluoroborate (NaBF4) are compounded, alum (potassium aluminum sulfate) is added as a catalyst, and the surfactant CTAB is introduced to encapsulate the hydrofluoric acid to form a reverse micelle solution. The addition of glycerol can prevent splashing. This formulation can accelerate the deposition of fluorosilicates, refine the grains, and thus improve the surface roughness uniformity. Specifically, the composite system of fluorosilicic acid and sodium fluoroborate can simultaneously optimize the etching rate and surface morphology, and the alum catalyst shortens the reaction time by 40%. The surfactant CTAB encapsulates the reverse micelle solution of hydrofluoric acid, achieving an etching depth error of <5%, while the error of traditional processes can reach 15-20%.
[0052] In one embodiment, the first acid etching temperature is 40-45°C, the soaking time is 3-5 minutes, and the residual liquid is removed by ultrasonic cleaning at a frequency of 20-35kHz.
[0053] It is important to note that acid etching requires strict control of the fluorosilicic acid concentration gradient, and 2-3% fresh stock solution should be added for each batch to maintain activity.
[0054] In one embodiment, the etching solution for the second acid etching comprises: 15-18 wt% ammonium fluoride (NH4F), 5-7 wt% oxalic acid (C2H2O4), 3-5 wt% ammonium sulfate ((NH4)2SO4), 2-4 wt% nano-silica dispersion, 10-15 wt% ethanol, and the balance being deionized water. This formulation allows for fine etching, and the ethanol accelerates evaporation and film formation, shortening the etching time.
[0055] Preferably, the nano-silica dispersion is pre-adjusted with ammonia water at pH 9.5 to prevent aggregation.
[0056] In one embodiment, the second acid etching temperature is 25-30°C, the standing time after spraying is 1-2 minutes, and the water washing pressure to remove residual liquid is 0.2-1 MPa.
[0057] In one embodiment, the acid etching solution used for both acid etching processes includes 0.05-0.1 wt% benzotriazole, thereby inhibiting excessive dissolution of sodium ions from the glass and reducing white fogging.
[0058] In one embodiment, the process further includes the following steps between the S3 acid etching and the S4 dynamic atomization enhancement treatment:
[0059] S31. Alkaline etching: Alkaline etching solution is used for etching. After the acid etching solution forms a preset rough layer and is cleaned, the microcracks are expanded by alkaline liquid to form a multi-level porous structure, thereby improving the uniformity of diffuse reflection.
[0060] In one embodiment, the alkaline etching solution comprises: 40-50 wt% sodium hydroxide (NaOH), 5-8 wt% sodium silicate (Na2SiO3), 3-5 wt% potassium carbonate (K2CO3), 1-2 wt% ammonium dihydrogen phosphate (NH4H2PO4), 0.5-1 wt% polyethylene glycol (PEG-400), and the balance being deionized water. Ammonium dihydrogen phosphate acts as a grain boundary inhibitor, and polyethylene glycol acts as a wetting agent.
[0061] In one embodiment, the alkaline etching temperature is 110-120°C, the immersion time is 150-200 minutes, and nitrogen is used to purge the surface residual liquid.
[0062] It should be noted that the tank used for alkaline etching must be equipped with a titanium alloy heating tube to avoid high-temperature corrosion from NaOH.
[0063] In one embodiment, the process further includes the following prior to the S4 dynamic atomization enhancement treatment:
[0064] The glass substrate, after removing residual liquid, is immersed in an ethanol solution containing 1-2% silane coupling agent to improve the adhesion of subsequent coatings.
[0065] In one embodiment, laser engraving technology is used simultaneously in the S1 preprocessing to generate a chamfer preprocessing area inside the glass substrate to facilitate subsequent glass chamfering.
[0066] Detection Example:
[0067] S1. Pretreatment: A microporous structure is generated inside the glass substrate using laser engraving technology, and a pre-protective layer is sprayed on the surface of the glass substrate to reduce the impact of acid etching.
[0068] S2. Pre-tempering: The pre-treated glass substrate is tempered at 300-400℃.
[0069] S3, Acid Etching: The pre-tempered glass substrate is acid etched twice. The first acid etching is done by immersion treatment, and the second acid etching is done by spraying treatment. The second acid etching time is shorter than the first acid etching time.
[0070] The etching solution for the first acid etching consisted of: 27 wt% fluorosilicic acid, 10 wt% sodium fluoroborate, 5 wt% hydrofluoric acid, 1.0 wt% alum, 0.1 wt% surfactant CTAB, 3 wt% glycerol, and the remainder being deionized water.
[0071] The temperature was 40℃, the soaking time was 4 minutes, and ultrasonic cleaning was used to remove residual liquid at a frequency of 28kHz.
[0072] In some embodiments, the etching solution for the second acid etching is: 16 wt% ammonium fluoride, 7 wt% oxalic acid, 5 wt% ammonium sulfate, 3 wt% nano-silica dispersion, 10 wt% ethanol, and the balance being deionized water.
[0073] The temperature was 27℃, the standing time after spraying was 1 minute, and the water washing pressure to remove residual liquid was 0.2MPa.
[0074] S4. Dynamic atomization strengthening treatment: A CeO2 / TiO2 composite film is deposited on the surface of the glass substrate after acid etching using magnetron sputtering, and nano-sized silica particles are sprayed simultaneously by atomization. The film is then bonded to the glass substrate by high-temperature sintering.
[0075] S5. Final tempering: The glass substrate after coating is tempered at 680-720℃, and then subjected to gradient cooling.
[0076] Table 1:
[0077] index Detection Examples Existing anti-glare tempered glass Improvement effect Surface roughness Ra 0.8-1.2μm 0.3-0.6μm 100％ Adjustable haze range 25-90％ 15-70％ Expand by 30% Light transmittance loss <5％ 8-12％ Reduce by 60% fingerprint resistance Contact angle >110° Contact angle <90° Increased by 22%
[0078] As shown in Table 1, the anti-glare tempered glass prepared by this method has a higher surface roughness, a higher upper limit of the adjustable haze range, and less light transmittance loss, thus achieving better anti-glare effect and better fingerprint resistance.
[0079] Example 2:
[0080] This application also provides an anti-glare tempered glass, which is prepared using the method of Example 1.
[0081] Example 3:
[0082] This application also provides a photovoltaic panel, including a photovoltaic module and glass covering it, wherein the glass is prepared using the method of Example 1.
[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A method for preparing anti-glare tempered glass, characterized in that, This includes performing the following processes in sequence: S1. Pretreatment: A microporous structure is generated inside the glass substrate using laser engraving technology, and a pre-protective layer is sprayed on the surface of the glass substrate to reduce the impact of acid etching. S2. Pre-tempering: The pre-treated glass substrate is tempered at 300-400℃. S3, Acid Etching: The pre-tempered glass substrate is acid etched twice. The first acid etching is done by immersion treatment, and the second acid etching is done by spraying treatment. The second acid etching time is shorter than the first acid etching time. S4. Dynamic atomization strengthening treatment: A CeO2 / TiO2 composite film is deposited on the surface of the glass substrate after acid etching by magnetron sputtering, and then nano-sized silica particles are atomized and sprayed. The film is then bonded to the glass substrate by high-temperature sintering. S5. Final tempering: The glass substrate after coating is tempered at 680-720℃, and then subjected to gradient cooling.
2. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, The etching solution for the first acid etching is: 25-30 wt% fluorosilicic acid, 8-12 wt% sodium fluoroborate, 5-8 wt% hydrofluoric acid, 0.5-1.5 wt% alum, 0.1-0.3 wt% surfactant CTAB, 3-5 wt% glycerol, and the balance being deionized water; The temperature is 40-45℃, the soaking time is 3-5 minutes, and ultrasonic cleaning is used to remove residual liquid at a frequency of 20-35kHz.
3. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, The etching solution for the second acid etching is: 15-18 wt% ammonium fluoride, 5-7 wt% oxalic acid, 3-5 wt% ammonium sulfate, 2-4 wt% nano-silica dispersion, 10-15 wt% ethanol, and the balance being deionized water. The temperature is 25-30℃, the standing time after spraying is 1-2 minutes, and the water washing pressure to remove residual liquid is 0.2-1MPa.
4. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, The acid etching solutions used in both acid etching processes contained 0.05-0.1 wt% benzotriazole.
5. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, Between the S3 acid etching and the S4 dynamic atomization enhancement treatment, there is also: S31, Alkaline Etching: Etching is performed using an alkaline etching solution. The alkaline etching solution consists of: 40-50 wt% sodium hydroxide, 5-8 wt% sodium silicate, 3-5 wt% potassium carbonate, 1-2 wt% ammonium dihydrogen phosphate, 0.5-1 wt% polyethylene glycol, and the balance being deionized water; The temperature is 110-120℃, the soaking time is 150-200 minutes, and nitrogen is used to purge the surface of residual liquid.
6. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, Prior to the S4 dynamic atomization enhancement process, the following were also included: The glass substrate, after removing the residual liquid, is immersed in an ethanol solution containing 1-2% silane coupling agent.
7. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, The pre-protective layer in the S1 pretreatment is an atomized coating containing nano-silica.
8. The method for preparing anti-glare tempered glass according to claim 1, characterized in that, In the S1 pretreatment, laser engraving technology is used simultaneously to generate a chamfered pretreatment area inside the glass substrate.
9. An anti-glare tempered glass, characterized in that, Prepared using the method described in any one of claims 1-8.
10. A photovoltaic panel, comprising a photovoltaic module and glass covering thereon, characterized in that, The glass is prepared using the method described in any one of claims 1-8.