An AG glass and its wet etching method and application

Abstract

This invention belongs to the field of AG glass technology and discloses an AG glass, its wet etching method, and its application. The method includes glass substrate processing, coating layer, and multi-stage solution etching steps. A first-type solution containing inorganic fluoride, oxidant, inorganic acid, and surfactant is used, followed by a second-type inorganic strong acid solution and a third-type fluorine-containing mixed solution for sequential etching. Through a multi-stage synergistic etching mechanism, precise control of the glass surface microstructure is achieved. The AG glass prepared by this invention has a regular and uniform micron-level surface structure, with an opening size of 4~6μm, a depth of 0.7~1.5μm, a surface roughness Sa value of 0.20~0.35μm, and a maximum contour undulation value below 3.0μm, while also exhibiting excellent anti-glare performance.

Description

Technical Field

[0001] This invention belongs to the field of AG glass technology, specifically relating to an AG glass and its wet etching method and application. Background Technology

[0002] Anti-glare glass, also known as AG glass, is a type of glass product that uses chemical wet etching, sandblasting, or laser-induced etching to create a micron-level roughness structure on the glass surface. This causes diffuse reflection of incident light, significantly reducing specular reflection. Its core advantage is reducing glare interference caused by ambient light and improving viewing comfort.

[0003] Currently, the etching process for AG glass products mostly uses chemical solution wet etching. This is because, compared to physical methods such as sandblasting or laser-induced etching, wet etching can form a finer AG structure on the glass surface.

[0004] Chemical wet etching (AG) processes can be further divided into frosted AG etching and photochromic AG etching. Frosted etching originated from glass decoration techniques in the early 20th century. With the rise of the display industry, frosted AG etched cover glass has been widely used in anti-glare processing.

[0005] As an anti-glare treatment process for glass surfaces, frosted AG etching has the advantages of low cost, no need for expensive equipment, and suitability for large-area glass surface frosting treatment. However, due to the same process limitations, frosted AG products have obvious graininess on the surface, the opening size is difficult to control and is prone to being too large, and the AG etching effect on corrosion-resistant glass is difficult to control. These are the disadvantages of frosted AG etching.

[0006] To meet the increasingly stringent screen quality requirements of the display industry, yellow-light AG etching has gradually become the mainstream AG processing method. The advantage of yellow-light AG is its ability to be combined with optical design to meet more refined and specific anti-glare product needs. However, the equipment costs involved in the yellow-light AG etching process are substantial, resulting in high costs for yellow-light AG products. Summary of the Invention

[0007] The purpose of this invention is to provide an AG glass and its wet etching method, which uses a multi-stage chemical solution synergistic etching process to control the microstructure of the glass surface, thereby obtaining an AG glass product with excellent anti-glare performance.

[0008] Another objective of this invention is to provide an application of AG glass in cover screens of consumer electronics products.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] 1. A wet etching method for AG glass, the wet etching method specifically comprising the following steps:

[0011] 1) Glass substrate processing; 2) Coating layer; 3) Etching process;

[0012] In step 3), the etching process refers to sequentially performing solution etching, barrier layer removal, and polishing using a first type of solution, a second type of solution, and a third type of solution, respectively; wherein the first type of solution is prepared from inorganic fluorides, oxidants, inorganic acids, and surfactants.

[0013] In step 1), the substrate is first rinsed with deionized water, and dust and organic impurities are removed from the substrate surface by means of a soft brush or ultrasonic waves. The temperature range of the treatment is 20-100℃ and the treatment time is 1-10 minutes.

[0014] In step 1), the glass substrate is one of soda-lime glass, aluminosilicate glass, lithium aluminosilicate glass, or high-alumina glass.

[0015] In step 2), the material of the film layer includes one of a metal film layer or a metal compound film layer, wherein the metal film layer is one or more of Al, Cr, Ni, Mo or Cu; and the metal compound film layer is one or more of Nb2O5, CrNO, Cr2O3, MgF2 or ITO.

[0016] In step 2), the film preparation method includes one or more of physical vapor deposition, chemical vapor deposition, or sputtering deposition.

[0017] In step 2), the thickness of the film is 600Å-2000Å.

[0018] In step 3), the inorganic fluoride is one or more of NH4F, HF, NaF or NH4HF2, and the amount used is 5wt%-20wt%.

[0019] In step 3), the oxidant is one or more of K2Cr2O7, H2O2, FeCl3, HNO3, KMnO4 or HClO2, and the amount used is 0.5-2wt%.

[0020] In step 3), the inorganic acid is one or more of HCl, H2SO4 or H3PO4, and the total amount used is 20wt%-40wt%.

[0021] In step 3), the surfactant is one or more of ethanol, propanol, glycerol, sodium dodecyl sulfate (SDS), polyethylene glycol (PEG), alkyl glycoside (APG) or polyoxyethylene lauryl ether (AEO), and the amount used is 0.1wt%-1.0wt%.

[0022] According to a specific embodiment of the present invention, preferably, the molecular weight of the polyethylene glycol is 2000.

[0023] In step 3), the second type of solution is an inorganic strong acid with a mass fraction of 15-25%, wherein the inorganic strong acid is one or more of H2SO4, H3PO4 or HCl.

[0024] In step 3), the third type of solution is a mixed solution of HF, NH4F and H2SO4, wherein the total mass fraction of HF and NH4F is 10-20 wt% and the mass fraction of H2SO4 is 5-15 wt%.

[0025] In step 3), the etching time of the first type of solution used in the solution etching is 3-10 min and the etching temperature is 25-35℃; the removal of the barrier layer using the second type of solution is 5-15 min and the etching temperature is 25-35℃; and the etching time of the third type of solution used in the polishing is 3-20 min and the etching temperature is 25-35℃.

[0026] The present invention provides an AG glass prepared using the above-described wet etching method, wherein the AG glass has an opening size of 4-6 μm, a surface roughness Sa value of 0.20-0.35 μm, and a maximum profile undulation value of less than 3.0 μm.

[0027] The present invention also provides the application of the above-mentioned AG glass in cover screens of consumer electronics products, including mobile phones, tablets and computers.

[0028] The first type of solution is responsible for etching a rough texture with anti-glare effect onto the glass surface coated with a film. The oxidant preferentially destroys the barrier layer, thereby improving the etching uniformity of the corrosion-resistant glass surface. The second type of solution is responsible for reacting and removing the residual film layer from the glass surface. The formulation of the second type of solution contains inorganic acids but no inorganic fluorides. The third type of solution is responsible for polishing and adjusting the roughness of the glass surface. The third type of solution contains both inorganic acids and inorganic fluorides.

[0029] The first type of solution is responsible for etching the coated aluminosilicate glass, forming a micron-sized structure with anti-glare properties on the glass surface. The same etching effect can be achieved by immersing the coated glass in the first type of solution or by spraying the first type of solution onto the glass surface.

[0030] The inorganic acid in the first type of solution serves to stabilize the inorganic fluoride, ensuring the stability of the etched glass surface. The oxidant in the first type of solution selectively breaks down the film on the glass surface, creating channels for the first type of etching solution to etch the glass surface and form an anti-glare surface structure. The surfactant in the solution increases the wettability between the etching solution and the glass surface.

[0031] In the first type of solution processing, the coated glass is generally immersed in the first type of etching solution for 3-5 minutes. Longer immersion time will result in greater surface roughness.

[0032] The second type of solution is used to remove the residual crystal barrier layer on the surface of aluminosilicate glass and cannot react with the glass.

[0033] The third type of solution is a glass etching solution. In order to accelerate the etching rate of glass, the solution itself can be heated when reacting with glass, which can more effectively control the roughness of the AG structure.

[0034] The etching time for AG with the third type of solution is generally controlled within 5-15 minutes. A longer etching time will result in a smoother AG glass surface with lower roughness.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] 1. The method described in this invention only requires depositing a film layer on the glass surface, and then placing the glass with the film deposited in a specific solution formula to etch and form an AG structure on the glass surface, thereby achieving an anti-glare effect. It is low in cost, and the opening diameter is controlled between 4-6 μm, which can ensure the uniformity of the AG structure size.

[0037] 2. This invention uses a wet multi-stage chemical etching process to obtain fine AG microstructures, eliminating the need for complex exposure, development, and pattern transfer equipment in photolithography AG processes. This reduces process complexity and production costs while ensuring AG effects. Attached Figure Description

[0038] Figure 1 This is a process flow diagram of the method described in this invention;

[0039] Figure 2 This is a schematic diagram of the cross-section of the AG glass prepared by the method described in this invention;

[0040] Figure 3 The SEM characterization of the AG glass described in Example 1, wherein Figure 3 (a) shows the SEM characterization on a 40µm scale. Figure 3 (b) shows the SEM characterization on a 20µm scale;

[0041] Figure 4 This is a 3D topography scan of the AG glass described in Example 1;

[0042] Figure 5 SEM characterization of the cross-section of the AG glass described in Example 1;

[0043] Figure 6 The surface roughness characterization diagram of the AG glass described in Example 1 is obtained using a 3D topology analyzer.

[0044] Figure 7 This is a surface profile undulation characterization diagram of the AG glass described in Example 1, obtained using a 3D topology analyzer. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, 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.

[0046] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0047] Example 1

[0048] A wet etching method for AG glass specifically includes the following steps:

[0049] 1) Glass substrate processing; 2) Coating layer; 3) Etching process;

[0050] 1) Rinse the high-alumina glass with deionized water and use a soft brush to remove dust and organic impurities from the substrate surface. The treatment temperature is 100℃ and the treatment time is 10 minutes to prepare for the glass surface coating.

[0051] 2) A layer of Nb2O5 with a thickness of 800 Å was deposited on the surface of the high-alumina glass by physical vapor deposition for later use;

[0052] 3) Immerse the glass obtained in step 2) into the first type of solution, control the reaction temperature at 30°C and the reaction time at 6 minutes. Remove the glass, clean the glass surface to ensure that the residual solution on the glass surface is completely cleaned. Immerse the glass etched by the first type of solution into the second type of solution, control the reaction temperature at 35°C and the reaction time at 10 minutes. After the reaction is completed, remove the glass, clean the glass surface to ensure that the residual solution on the glass surface is completely cleaned. Immerse the glass treated by the first and second types of solutions into the prepared third type of solution, control the reaction temperature at 30°C and the reaction time at 5 minutes. Remove and clean the glass surface to ensure that the residual solution on the glass surface is completely cleaned to obtain the AG glass.

[0053] The first type of solution is composed of the following raw materials by mass percentage:

[0054] H2SO4 25wt%;

[0055] HF 5wt%

[0056] NH4HF2 8wt%

[0057] HNO3 2wt%

[0058] Alkyl glycoside (APG) 0.2wt %

[0059] The remainder is water.

[0060] The second type of solution is composed of the following raw materials by mass percentage:

[0061] H2SO4 25wt%;

[0062] The remainder is water.

[0063] The third type of solution is composed of the following raw materials by mass percentage:

[0064] HF 10wt%

[0065] NH4F 5wt%

[0066] H2SO4 15wt%;

[0067] The remainder is water.

[0068] Example 2

[0069] A wet etching method for AG glass specifically includes the following steps:

[0070] The difference between this embodiment and Embodiment 1 is that in step 3), the nitric acid (HNO3) in the first type of solution is replaced with potassium permanganate (KMnO4), while the other reaction conditions remain unchanged.

[0071] The first type of solution is composed of the following raw materials by mass percentage:

[0072] H2SO4 25wt%;

[0073] HF 5wt%

[0074] NH4HF2 8wt%

[0075] KMnO4 2wt%

[0076] Alkyl glycoside (APG) 0.2wt %

[0077] The remainder is water.

[0078] The second type of solution is composed of the following raw materials by mass percentage:

[0079] H2SO4 25wt%;

[0080] The remainder is water.

[0081] The third type of solution is composed of the following raw materials by mass percentage:

[0082] HF 10wt%

[0083] NH4F 5wt%

[0084] H2SO4 15wt%;

[0085] The remainder is water.

[0086] Example 3

[0087] A wet etching method for AG glass specifically includes the following steps:

[0088] The difference between this embodiment and Example 1 is that in step 3), the alkyl glycoside (APG) in the first type of solution is replaced with polyethylene glycol with a molecular weight of 2000, while the other reaction conditions remain unchanged.

[0089] The first type of solution is composed of the following raw materials by mass percentage:

[0090] H2SO4 25wt%;

[0091] HF 5wt%

[0092] NH4HF2 8wt%

[0093] HNO3 2wt%

[0094] PEG-2000 0.5wt %

[0095] The remainder is water.

[0096] The second type of solution is composed of the following raw materials by mass percentage:

[0097] H2SO4 25wt%;

[0098] The remainder is water.

[0099] The third type of solution is composed of the following raw materials by mass percentage:

[0100] HF 10wt%

[0101] NH4F 5wt%

[0102] H2SO4 15wt%;

[0103] The remainder is water.

[0104] Example 4

[0105] A wet etching method for AG glass specifically includes the following steps:

[0106] The difference between this embodiment and Embodiment 1 is that in step 1), high-alumina glass is replaced with soda-lime glass; otherwise, they are the same as in Embodiment 1.

[0107] Test Example 1

[0108] Morphological characteristics:

[0109] Characterization of Example 1 using scanning electron microscopy and a 3D topology analyzer is as follows: Figure 3 and Figure 5 As shown, Figure 3 The method described in Example 1 illustrates how the method etches a uniform AG structure with an opening size of 4-6 μm onto a glass surface; from Figure 5 The cross-sectional characterization of the AG structure shows that the Rz value of this AG structure is between 0.7 and 1.5 μm.

[0110] The surface roughness Sa value and maximum fluctuation value of the AG glass described in Example 1 were characterized by 3D morphology analysis, and the results are as follows: Figure 6 and Figure 7 As shown, the surface roughness Sa value of the obtained AG glass is between 0.2 and 0.3 μm, and the profile undulation of the AG glass has a maximum undulation value of less than 3.0 μm.

[0111] Haze meter and gloss meter tests:

[0112] The AG glass described in Example 1 was characterized using a haze meter. Even with a high haze of 90%, the transmittance of this AG glass was still 91.5%.

[0113] The DOI value at 60° was characterized using a gloss meter. For the AG glass with a haze of 90 as described in Example 1, the DOI value at 60° can be controlled within the range of 0-2. This low DOI value indicates good anti-glare performance. Polishing the AG glass with a third-class solution resulted in the DOI value at 60° increasing to 40 when the haze was polished to 80. Further polishing reduced the haze to 50, increasing the DOI value at 60° to 80.

[0114] Meanwhile, directly extending the reaction time of the first type of solution reduces the haze of the AG glass. The trend of DOI value change at 60° under different haze conditions is similar to that of the DOI value change at 60° of the AG glass polished with the third type of solution. The test results are shown in Table 1 below:

[0115] Table 1. Variation of DOI values ​​of the AG glass described in Example 1 at different haze levels (60°).

[0116]

[0117] The performance comparison of each embodiment is shown in Table 2 below:

[0118] Table 2 Performance Comparison of Various Embodiments

[0119]

[0120] As shown in Table 2, the samples prepared in Examples 1-4 all exhibit low surface roughness, with the roughness controlled within the range of 0.2-0.3 μm. Based on this, each example demonstrates excellent optical performance, with haze ranging from 88.78% to 90.45% and transmittance from 91.48% to 91.74%, indicating that the present invention achieves high haze diffuse reflection while maintaining high light transmittance. Furthermore, the 60° DOI values ​​of each example are low, ranging from 0.3 to 1.0, indicating that the obtained sample surfaces have excellent extinction effects and low specular reflection.

[0121] In summary, the product prepared by this invention can simultaneously achieve high haze, high transmittance, and low DOI value while maintaining similar surface roughness, thus exhibiting excellent overall optical performance.

[0122] It should be noted that the above embodiments are merely some preferred embodiments of the present invention, and not all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0123] The above description of the embodiments is intended to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A wet etching method for AG glass, characterized in that, The wet etching method specifically includes the following steps: 1) Glass substrate processing; 2) Coating layer; 3) Etching process; In step 3), the etching process refers to sequentially performing solution etching, barrier layer removal, and polishing using a first type of solution, a second type of solution, and a third type of solution, respectively; wherein the first type of solution is prepared from inorganic fluorides, oxidants, inorganic acids, and surfactants.

2. The wet etching method for AG glass according to claim 1, characterized in that, In step 1), the substrate is first rinsed with deionized water, and dust and organic impurities are removed from the substrate surface by means of a soft brush or ultrasonic waves. The temperature range of the treatment is 20-100℃ and the treatment time is 1-10 minutes.

3. The wet etching method for AG glass according to claim 1, characterized in that, In step 1), the glass substrate is one of soda-lime glass, aluminosilicate glass, lithium aluminosilicate glass, or high-alumina glass.

4. The wet etching method for AG glass according to claim 1, characterized in that, In step 2), the material of the film layer includes one of a metal film layer or a metal compound film layer, wherein the metal film layer is one or more of Al, Cr, Ni, Mo or Cu; the metal compound film layer is one or more of Nb2O5, CrNO, Cr2O3, MgF2 or ITO; the film layer is prepared by one of physical vapor deposition, chemical vapor deposition or sputtering deposition; and the thickness of the film layer is 600 Å-2000 Å.

5. The wet etching method for AG glass according to claim 1, characterized in that, In step 3), the inorganic fluoride is one or more of NH4F, HF, NaF, or NH4HF2, and the amount used is 5wt%-20wt%; the oxidant is one or more of K2Cr2O7, H2O2, FeCl3, HNO3, KMnO4, or HClO2, and the amount used is 0.5-2wt%; the inorganic acid is one or more of HCl, H2SO4, or H3PO4, and the amount used is 20wt%-40wt%; the surfactant is one or more of ethanol, propanol, glycerol, sodium dodecyl sulfate, PEG, alkyl glycoside, or polyoxyethylene lauryl ether, and the amount used is 0.1wt%-1.0wt%.

6. The wet etching method for AG glass according to claim 1, characterized in that, In step 3), the second type of solution is an inorganic strong acid with a mass fraction of 15-25%, wherein the inorganic strong acid is one or more of H2SO4, H3PO4 or HCl.

7. The wet etching method for AG glass according to claim 1, characterized in that, In step 3), the third type of solution is a mixed solution of HF, NH4F and H2SO4, wherein the total mass fraction of HF and NH4F is 10-20 wt% and the mass fraction of H2SO4 is 5-15 wt%.

8. The wet etching method for AG glass according to any one of claims 1, 5, 6 or 7, characterized in that, In step 3), the etching time of the first type of solution used in the solution etching is 3-10 min and the etching temperature is 25-35℃; the removal of the barrier layer using the second type of solution is 5-15 min and the etching temperature is 25-35℃; and the etching time of the third type of solution used in the polishing is 3-20 min and the etching temperature is 25-35℃.

9. An AG glass prepared by the wet etching method as described in claim 1, wherein the AG glass has an opening size of 4-6 μm; a surface roughness Sa value of 0.20-0.35 μm; and a maximum profile undulation value of less than 3.0 μm.

10. An application of the AG glass as described in claim 9 in a cover screen of consumer electronics products, characterized in that, The consumer electronics products include mobile phones, tablets, or computers.

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