A glass treatment liquid and its use in the production of antireflection glass

Abstract

The application discloses a glass treatment liquid and application thereof in preparation of anti-reflective glass. The glass treatment liquid comprises an initial crack solution and / or a crack propagation solution. The initial crack solution is used for forming micro-cracks on the surface of a glass substrate, and the crack propagation solution is used for further expanding the micro-cracks on the surface of the glass substrate to form nano-sized hole structures, so that common glass can be prepared into anti-reflective glass with high light transmittance and low reflectivity. The prepared anti-reflective glass has a visible light transmittance of more than 95%, an average reflectivity of less than 4%, and a significantly reduced ultraviolet light transmittance, and can effectively block ultraviolet light.

Description

Technical Field

[0001] This invention relates to the field of antireflective glass preparation technology, and particularly to a glass treatment liquid and its application in the preparation of antireflective glass. Background Technology

[0002] Anti-reflective glass is a type of glass with high transmittance and low reflectance. It is made by processing one or both sides of the glass to change the roughness of the glass surface, reduce the mirror effect of the glass surface, reduce the full spectrum reflection of incident light on the glass surface, and enhance the transmission of incident light, thereby achieving the effect of improving transparency and reducing reflectance.

[0003] Compared to ordinary glass, anti-reflective glass has lower reflectivity and higher transmittance. In the visible light range, ordinary glass has a single-sided reflectivity of approximately 4% and a double-sided spectral reflectivity of approximately 8%, corresponding to an average visible light transmittance of approximately 91%. In contrast, anti-reflective glass has an average visible light transmittance exceeding 95% and an average reflectivity of less than 4%.

[0004] Due to its high light transmittance and low reflectance, anti-reflective glass makes objects appear clearer, with richer colors and a better visual effect when viewed through it. Initially, anti-reflective glass was mainly used in the manufacture of optical lenses for cameras and microscopes, limiting its applications. However, with technological advancements, it is now widely used in modern agricultural intelligent greenhouses, high-end display windows, museum display cases, picture frames, airport control towers, automotive glass, and scenic area viewing windows—fields with high requirements for eliminating reflected light. With the booming development of the solar photovoltaic industry, anti-reflective glass has also seen large-scale application as cover glass for solar photovoltaic systems. Furthermore, anti-reflective glass shows promising application prospects in LCD and plasma displays, primarily due to: its high light transmittance significantly improving the brightness of LCDs and plasma displays while reducing energy consumption; its low reflectance effectively mitigating the whitening effect caused by strong background light, resulting in clearer image quality, more vibrant colors, and stronger contrast; and its UV resistance effectively reducing the harmful effects of ultraviolet radiation on the eyes.

[0005] However, most anti-reflective glass currently on the market is achieved by coating the glass surface, which often faces the problem of coating aging and peeling. Summary of the Invention

[0006] To address the shortcomings of the existing technology, the first objective of this invention is to provide a glass treatment solution and its application in the preparation of antireflective glass; the second objective is to provide an antireflective glass and its preparation method. The antireflective glass prepared by this invention can effectively avoid the problem of film aging and peeling, and can achieve antireflection effects in specific wavelength bands.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] A glass processing solution includes an initial crack solution and / or a crack propagation solution. The initial crack solution is used to induce microcracks on the surface of a glass substrate, and the crack propagation solution is used to further propagate these microcracks on the glass substrate surface, forming a nanoscale porous structure. By combining these two solutions, ordinary glass can be processed into antireflective glass with high light transmittance and low reflectance.

[0009] The initial crack solution includes hydrofluoric acid, sulfuric acid, and nitric acid, with a volume ratio of hydrofluoric acid:sulfuric acid:nitric acid = 0.5-1:10-20:10-20.

[0010] Preferably, the initial cracking solution is composed of the following components in volume fractions: 0.5%–1% hydrofluoric acid, 10%–20% sulfuric acid, 10%–20% nitric acid, and the balance water. This initial cracking solution, when used to immerse glass at room temperature and pressure, can induce microcracks on the glass surface without requiring stringent conditions, making it highly feasible.

[0011] The crack propagation solution comprises the following components by mass fraction: Na₂HPO₄, AlCl₃, NaH₂PO₄, and NaCl, in the following mass ratio:

[0012] Na2HPO4:AlCl3:NaH2PO4:NaCl=0.5~2:0.01~0.5:0.5~2:1~5.

[0013] Preferably, the crack propagation solution comprises the following components by mass fraction: Na₂HPO₄ 0.5%–2%, AlCl₃ 0.01%–0.5%, NaH₂PO₄ 0.5%–2%, NaCl 1%–5%, and water as the balance. This crack propagation solution is neutral, and under normal pressure, water bath heating can further propagate microcracks on the glass surface, forming a nanoscale porous structure. It requires no harsh conditions such as high pressure and is highly feasible.

[0014] The present invention also provides the application of the glass treatment solution in the preparation of antireflective glass.

[0015] The present invention also provides a method for preparing antireflective glass, which includes the following steps:

[0016] Clean the glass surface.

[0017] The cleaned glass is subjected to crack pretreatment, and the treatment solution used for crack pretreatment is the initial crack solution of the glass treatment solution mentioned above.

[0018] The glass, after crack pretreatment, is subjected to crack propagation treatment, and the treatment solution used for crack propagation treatment is the crack propagation solution of the aforementioned glass treatment solution.

[0019] Preferably, the crack pretreatment step includes immersing the glass in the initial crack solution at room temperature for 5-30 minutes. The treatment solution, treatment time, and treatment temperature all affect the formation of microcracks on the glass surface. Using the initial crack solution of this invention as the treatment solution, immersing the glass at room temperature and pressure for 5-30 minutes can effectively form microcracks on the glass surface. If the immersion time is too short, microcracks will not form on the glass surface; if the immersion time is too long, the cracks on the glass surface will be too severe, affecting the glass's light transmittance and reflectivity.

[0020] Preferably, the crack propagation treatment step includes: heating the glass in a water bath at 80-90°C for 10-24 hours using the crack propagation solution. The treatment solution, treatment time, and treatment temperature all affect the formation effect of the nanoporous structure on the glass surface. Using the crack propagation solution of this invention as the treatment solution, heating the pre-treated glass in a water bath at 80-90°C for 10-24 hours under normal pressure can form a good nanoporous structure on the glass surface, achieving a visible light transmittance of over 95% and an average reflectance of less than 4%, thus achieving a high anti-reflection effect. If the treatment time is too short or the water bath temperature is too low, the nanoporous structure on the glass surface will be too small, failing to achieve the anti-reflection effect; if the treatment time is too long or the water bath temperature is too high, the size of the formed pores on the glass surface will be too large, affecting the mechanical properties, transmittance, and reflectance of the glass.

[0021] Preferably, the method for preparing the antireflective glass further includes: cleaning the glass after crack pretreatment and then performing crack propagation treatment; and / or cleaning the glass after crack propagation treatment.

[0022] Preferably, the step of surface cleaning and / or washing the glass includes: rinsing and / or ultrasonically cleaning the glass with deionized water and / or anhydrous ethanol, and then drying it. Specifically, the glass can be immersed in deionized water, then rinsed sequentially with deionized water, anhydrous ethanol, and then deionized water, and finally dried. Alternatively, the glass can be ultrasonically cleaned with at least one of deionized water and anhydrous ethanol, and then dried. Or, the glass can be ultrasonically cleaned with anhydrous ethanol first, then rinsed with deionized water, and finally dried. In this way, dust, oil, and other impurities on the glass surface can be effectively removed, or residual treatment liquid on the glass surface can be removed.

[0023] Preferably, the glass is soda-lime-silicon glass.

[0024] The present invention also provides an anti-reflective glass, which is prepared by the method for preparing the anti-reflective glass described above.

[0025] Compared with existing technologies, the beneficial effects of this invention are as follows: By controlling the formulation and component ratio of the initial crack solution and crack propagation solution, as well as the time and temperature of crack pretreatment and crack propagation treatment, this invention effectively prepares ordinary glass into anti-reflective glass with high light transmittance and low reflectance. The anti-reflective glass prepared by this invention achieves a visible light transmittance of over 95%, an average reflectance of less than 4%, and a significantly reduced transmittance in the ultraviolet spectral region, effectively blocking ultraviolet rays. The method for preparing anti-reflective glass by this invention is simple to operate, requires no harsh conditions, is highly feasible, has good repeatability, high safety, and controllable anti-reflection effect. By adjusting the composition, treatment time, and treatment temperature of the initial crack solution and crack propagation solution within the process conditions provided by this invention, anti-reflective glass with different anti-reflection effects can be obtained, which can be applied to photovoltaic, catalytic, and display glass fields. Attached Figure Description

[0026] Figure 1 This is a comparison chart of the transmittance of the antireflective glass obtained in Examples 1, 2, and 3 of the present invention (with varying the initial crack solution's action time);

[0027] Figure 2 This is a comparison chart of the transmittance of the antireflective glass obtained in Examples 4, 5, and 6 of the present invention (changing the action time of the crack propagation solution);

[0028] Figure 3 This is a comparison chart of the transmittance of the antireflective glass obtained in Examples 6, 7, and 8 of the present invention (changing the operating temperature of the crack propagation solution);

[0029] Figure 4 This is a comparison chart of the transmittance of the antireflective glass obtained in Examples 5, 9, and 10 of the present invention (changing the composition of the crack propagation solution);

[0030] Figure 5 This is a comparison chart of the transmittance of the antireflective glass obtained in Examples 1-5;

[0031] Figure 6 This is the AFM image of the antireflective glass obtained in Example 1. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] This embodiment provides a method for preparing antireflective glass, which includes the following steps:

[0035] (1) Surface cleaning: Sodium calcium silicate glass substrate is soaked in deionized water for cleaning, then rinsed three times with deionized water, anhydrous ethanol and deionized water respectively, and then dried in a forced-air drying oven.

[0036] (2) Crack pretreatment: The glass treated in step (1) is immersed in the initial crack solution at room temperature for 5 minutes, then ultrasonically treated in anhydrous ethanol for 30 minutes, rinsed three times with deionized water, and finally dried in a forced-air drying oven; the initial crack solution is composed of the following components in volume fraction: hydrofluoric acid 0.5%, sulfuric acid 10%, nitric acid 10% and deionized water balance.

[0037] (3) Crack propagation treatment: The glass treated in step (2) is placed in a crack propagation solution and heated in a water bath at 80°C for 20 hours. The crack propagation solution consists of the following components in terms of mass fraction: Na2HPO4 0.5%, AlCl3 0.01%, NaH2PO4 1%, NaCl 1%, and deionized water as the balance.

[0038] (4) Cleaning: The glass treated in step (3) is ultrasonically cleaned with deionized water, anhydrous ethanol and deionized water for 10 min respectively, and then placed in a drying oven to dry to obtain anti-reflective glass.

[0039] Example 2

[0040] This embodiment provides a method for preparing antireflective glass. The only difference between this method and Embodiment 1 is the crack pretreatment time. The immersion time for crack pretreatment in Embodiment 2 is 10 minutes, while the rest is the same as in Embodiment 1.

[0041] Example 3

[0042] This embodiment provides a method for preparing antireflective glass. The only difference between this method and Embodiment 1 is the crack pretreatment time. The immersion time for crack pretreatment in Embodiment 3 is 15 minutes, while the rest is the same as in Embodiment 1.

[0043] Example 4

[0044] This embodiment provides a method for preparing antireflective glass. The only difference between this method and that of Embodiment 2 is the temperature and time of the crack propagation treatment. In Embodiment 4, the crack propagation treatment is a water bath heating treatment at 85°C for 16 hours, while the rest is the same as in Embodiment 2.

[0045] Example 5

[0046] This embodiment provides a method for preparing antireflective glass. The only difference between this method and Embodiment 2 is the temperature and time of the crack propagation treatment. In Embodiment 5, the crack propagation treatment is a water bath heating treatment at 85°C for 18 hours, while the rest is the same as in Embodiment 2.

[0047] Example 6

[0048] This embodiment provides a method for preparing antireflective glass. The only difference between this method and Embodiment 2 is the temperature and time of the crack propagation treatment. In Embodiment 6, the crack propagation treatment is a water bath heating treatment at 85°C for 20 hours. The rest is the same as in Embodiment 2.

[0049] Example 7

[0050] This embodiment provides a method for preparing antireflective glass. The only difference between this embodiment and Embodiment 2 is the temperature and time of the crack propagation treatment. In Embodiment 7, the crack propagation treatment is a water bath heating treatment at 75°C for 20 hours, while the rest is the same as in Embodiment 2.

[0051] Example 8

[0052] This embodiment provides a method for preparing antireflective glass. The only difference between this embodiment and Embodiment 2 is the temperature and time of the crack propagation treatment. In Embodiment 8, the crack propagation treatment is a 90°C water bath heating treatment for 20 hours, while the rest is the same as in Embodiment 2.

[0053] Example 9

[0054] This embodiment provides a method for preparing antireflective glass, which differs from Example 6 only in the crack propagation solution; otherwise, it is the same as Example 5. The crack propagation solution of Example 9 consists of the following components by mass fraction: Na₂HPO₄ 1%, AlCl₃ 0.2%, NaH₂PO₄ 1.5%, NaCl 1.5%, and deionized water as the balance.

[0055] Example 10

[0056] This embodiment provides a method for preparing antireflective glass, which differs from Example 6 only in the crack propagation solution; otherwise, it is the same as Example 5. The crack propagation solution of Example 10 consists of the following components by mass fraction: Na₂HPO₄ 2%, AlCl₃ 0.5%, NaH₂PO₄ 2%, NaCl 2%, and deionized water as the balance.

[0057] Comparative Example 1

[0058] The only difference between Comparative Example 1 and Example 2 is the initial crack solution; everything else is the same as in Example 2. The initial crack solution of Comparative Example 1 consisted of the following components by mass fraction: 20% sulfuric acid, 20% nitric acid, and the balance being deionized water.

[0059] Comparative Example 2

[0060] The only difference between Comparative Example 2 and Example 2 is the crack propagation solution; everything else is the same as Example 2. The crack propagation solution of Comparative Example 2 consists of the following components by mass fraction: Na2HPO4 1.5%, AlCl3 1.01%, and deionized water as the balance.

[0061] Comparative Example 3

[0062] The only difference between Comparative Example 3 and Example 2 is the crack propagation solution; everything else is the same as Example 2. The crack propagation solution of Comparative Example 3 consists of the following components by mass fraction: 1.5% NaH2PO4, 1.01% NaCl, and the balance being deionized water.

[0063] Comparative Example 4

[0064] The only difference between Comparative Example 4 and Example 2 is that Comparative Example 4 underwent two crack pretreatments, each lasting 10 minutes, and no crack propagation treatment was performed. Otherwise, it was the same as Example 2.

[0065] Comparative Example 5

[0066] The only difference between Comparative Example 5 and Example 2 is that Comparative Example 5 did not undergo crack pretreatment; otherwise, it was the same as Example 2.

[0067] The specific process conditions for Examples 1-10 and Comparative Examples 1-5 are shown in the table below. Transmittance tests were performed on the glasses prepared in Examples 1-10 and Comparative Examples 1-5, with the sodium-calcium-silicon glass substrate serving as a blank control group. The test results are shown in the table below and attached. Figures 1-5 As shown.

[0068] Transmittance test method: The transmittance of the glass substrate before and after etching was measured using a Lambda 950 UV-Vis-NIR spectrophotometer manufactured by PerkinElmer, USA, equipped with an integrating sphere. For details, please refer to GB / T 2680-1994.

[0069]

[0070]

[0071] Note: "-" in the table indicates that this step was not performed.

[0072] Based on the data in the table above and Figures 1-5 It can be seen that:

[0073] Figure 1 This is a comparison of the transmittance of antireflective glasses obtained by controlling the interaction time between the original glass sheet and the initial crack solution in Embodiments 1, 2, and 3 of this invention. As shown in the figure, the transmittance of the antireflective glass prepared by this invention is improved compared to that of the original glass sheet. Furthermore, the transmittance of the antireflective glass shows a trend of first increasing and then decreasing with the extension of the interaction time of the initial crack solution.

[0074] Figure 2 These are comparison graphs of the transmittance of antireflective glass obtained by controlling the interaction time between the original glass sheet and the crack propagation solution in Embodiments 4, 5, and 6 of the present invention. As shown in the graphs, the transmittance of the antireflective glass exhibits a trend of first increasing and then remaining essentially flat as the interaction time with the crack propagation solution increases.

[0075] Figure 3 These are comparison graphs of the transmittance of antireflective glass obtained by controlling the interaction temperature between the original glass sheet and the crack propagation solution in Embodiments 6, 7, and 8 of the present invention. As shown in the graphs, the transmittance of the antireflective glass exhibits a trend of first increasing and then decreasing with the increase of the interaction temperature of the crack propagation solution.

[0076] Figure 4 These are comparison graphs of the transmittance of antireflective glass obtained by controlling the concentrations of the original glass sheet and the crack propagation solution in Embodiments 5, 9, and 10 of the present invention. As shown in the graphs, the transmittance of the antireflective glass exhibits a trend of first decreasing and then increasing with the increase of the crack propagation solution concentration.

[0077] Figure 5 Comparative Examples 1-5 of this invention, compared with the embodiments, show that using the initial crack solution and the crack propagation solution alone, as well as changing the composition of the two solutions, can improve the transmittance of the original glass sheet, but the increase is low and the anti-reflection effect is not obvious.

[0078] According to the preparation method provided by the present invention, the average transmittance of the obtained antireflective glass in the solar light band range of 250nm to 1300nm is increased by more than 5% compared with the original glass sheet, and the change in transmittance can be controlled and adjusted by controlling the process parameters.

[0079] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing antireflective glass, characterized in that, It is made by the following steps: Clean the glass surface. The cleaned glass is subjected to crack pretreatment. The treatment solution used for crack pretreatment is an initial crack solution, which is composed of the following components in volume fractions: 0.5%~1% hydrofluoric acid, 10%~20% sulfuric acid, 10%~20% nitric acid and water balance. The crack pretreatment step includes: immersing the glass in the initial crack solution at room temperature for 5-30 minutes; The glass after crack pretreatment is cleaned and dried, and then crack propagation treatment is performed. The treatment solution used for crack propagation treatment is a crack propagation solution, which is composed of the following components by mass fraction: Na2HPO4 0.5%~2%, AlCl3 0.01%~0.5%, NaH2PO4 0.5%~2%, NaCl 1%~5%, and water balance. The steps of the crack propagation treatment include: heating the glass in a water bath at 80-90°C for 10-24 hours with the crack propagation solution; The glass, after the crack propagation treatment, is cleaned and dried.

2. The method of making a reduced reflection glass according to claim 1, wherein, The glass is sodium-calcium-silicon glass.

3. An antireflective glass, characterized by, It is prepared by the method for preparing antireflective glass according to any one of claims 1 to 2.

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