Glass etching liquid capable of etching out fish scale three-dimensional texture and preparation method and application thereof

Abstract

The application provides a glass etching liquid capable of etching a fish scale three-dimensional texture, and a preparation method and application thereof. The glass etching liquid comprises the following components in percentage by mass: 17-35% of a fluorinated salt, 3-10% of a crystal grain regulator, 0.5-5% of a gemini surfactant, 10-25% of a strong acid, 3-10% of a weak acid, 1-2% of a siloxane compound, 0.2-3% of a fluorine-containing heterochain acid, 0.1-2% of a beta type cyclodextrin, and the balance of water. The glass etching liquid and the etching method of the application process the aluminum-silicon glass, the surface crystal distribution of which is regularly goose feather-shaped microcrystal particles; the corresponding macroscopic morphology also shows different visual effects, which are fish scale texture effects. In addition, the glass etching liquid composition and the etching method of the application process the AG glass which has the characteristics of low roughness, soft hand feeling, high scratch resistance and good anti-fingerprint effect.

Description

Technical Field

[0001] This invention relates to the field of glass etching technology, and in particular to a glass etching solution capable of etching fish-scale-like three-dimensional textures, its preparation method, and its application. Background Technology

[0002] With the progress and development of society, consumers' consumption concepts and aesthetic levels are constantly improving, and therefore the demand for diversified smartphones is becoming increasingly prominent. Currently, most mid-to-high-end mobile phones on the market use glass back covers, and consumers especially value personalized back cover customization. Therefore, the etching and frosting decoration of mobile phone glass back covers is becoming increasingly popular. However, existing traditional glass etching solutions still have the following shortcomings: (1) Although it can etch a glittering sand effect to improve anti-glare, anti-fingerprint, and anti-scratch, the feel is slightly inferior; (2) The etching effect is relatively simple, and it is difficult to process special patterns. It can only adjust the size of the particles, but cannot control the shape and distribution pattern, lacking novelty and failing to meet the increasingly higher requirements of modern consumers; (3) After a period of use, the etching solution is prone to sand leakage and reduced etching efficiency.

[0003] For example, CN104761150A discloses a glass etching solution, which includes: ammonium fluoride, a surfactant, an alkali metal hydrochloride, an acid, and water; wherein, the molar number 'a' of fluoride ions that can be ionized in the ammonium fluoride and the molar number 'b' of hydrogen ions that can be ionized in the acid satisfy the following formula: a:b=(0.2~3):1. This etching solution can effectively etch glass, and various glass products can be effectively etched according to actual needs, so that the cover glass forms an uneven, rough surface, thereby giving it an anti-glare function. However, the etching effect is relatively simple, and the feel is slightly inferior.

[0004] For example, CN116217085A discloses a glass etching solution and a method for creating a starlight effect on the surface of lithium aluminum silicon glass. The glass etching solution comprises the following raw materials in weight percentages (Wt%): sulfuric acid 12-20%, nitric acid 15-25%, ammonium fluoride 20-30%, ammonium fluoroborate 5-15%, copper sulfate 2-8%, ammonium nitrate 3-10%, polyethylene glycol 0.3-1.5%, resin 1-3%, and water 20-35%. This glass etching solution can form a micron-sized, irregularly and loosely arranged crystal diamond particle structure layer on the surface of lithium aluminum silicon glass, but its ability to control the etching rate, crystal growth rate, and crystal morphology of aluminum silicon glass remains limited.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] One objective of this invention is to provide a glass etching solution capable of etching a fish-scale-like three-dimensional texture. This glass etching solution overcomes the shortcomings of existing etching solutions, such as ineffective adjustment of glass feel, limited etching effects, and decreased stability after a period of use. By adjusting the proportions and amounts of components such as fluoride salts, grain control agents, twin surfactants, strong acids, weak acids, and siloxane compounds, the etching rate, crystal growth rate, and crystal morphology of the etching solution system on aluminosilicate glass can be controlled. Ultimately, AG glass with a fish-scale-like macroscopic three-dimensional texture effect, characterized by low surface roughness and high haze, is obtained, enriching the etching effects of mobile phone back cover glass.

[0007] A second objective of this invention is to provide a method for preparing the glass etching solution capable of etching a fish-scale-like three-dimensional texture. The preparation method includes the following steps: mixing fluoride salts, grain size regulators, gemini surfactants, strong acids, weak acids, siloxane compounds, fluorinated heterochain acids, and β-cyclodextrin in a specified ratio, followed by standing and aging to obtain the glass etching solution capable of etching a fish-scale-like three-dimensional texture.

[0008] The third objective of this invention is to provide an application of the glass etching solution capable of etching fish-scale three-dimensional textures in etching aluminosilicate glass.

[0009] The fourth objective of this invention is to provide an etching method for an electronic glass substrate, the etching method comprising the following steps: immersing and oscillating the side of the electronic glass substrate to be etched in the glass etching solution that can etch a fish-scale three-dimensional texture, so that the etched side of the electronic glass substrate exhibits a fish-scale three-dimensional texture.

[0010] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0011] In a first aspect, the present invention provides a glass etching solution capable of etching out a fish-scale-like three-dimensional texture, the glass etching solution comprising the following components by mass percentage:

[0012] Fluoride salts 17–35%, grain size regulators 3–10%, gemini surfactants 0.5–5%, strong acids 10–25%, weak acids 3–10%, siloxane compounds 1–2%, fluorinated heterochain acids 0.2–3%, β-cyclodextrins 0.1–2%, with the balance being water.

[0013] Based on the total mass of the glass etching solution as 100%, the amount of fluoride added is 17% to 35%, for example, it can be 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc.

[0014] In this invention, fluoride salts are used as the main raw material for etching, providing sufficient fluoride ions to the etching solution composition to etch the glass skeleton. Under acidic conditions, they can erode the glass surface, soften the glass surface, and the reaction product fluorosilicates will form a precipitate and deposit on the glass surface, playing a role in forming nano- and micron-sized crystalline particles on the glass surface.

[0015] Based on the total mass of the glass etching solution as 100%, the amount of the grain control agent added is 3% to 10%, for example, it can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0016] In this invention, the grain size regulator can control the structure and shape of the microcrystalline particles, thereby achieving the goal of composition determining structure and structure determining performance. The ratio of raw materials in the grain size regulator also directly affects the effect of the etching solution, so there are certain limitations on the ratio of raw materials.

[0017] Based on the total mass of the glass etching solution as 100%, the amount of Gemini surfactant added is 0.5% to 5%, for example, it can be 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.

[0018] In this invention, the Gemini surfactant reduces the surface tension of the etching solution on the glass, increases the wettability of the etching solution composition on the glass substrate, and works synergistically with β-cyclodextrin to inhibit sand leakage, while also inhibiting the escape of acid gas.

[0019] Based on the total mass of the glass etching solution as 100%, the amount of strong acid added is 10-25%, for example, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, etc.

[0020] In this invention, strong acid provides an acidic environment and sufficient hydrogen ions for the etching solution, which makes the etching performance of the etching solution last longer and causes the fluoride salt etchant to destroy the glass surface structure in a short time. Controlling the combined strong acid content in the etching solution composition within a suitable range is beneficial to balancing etching and frosting.

[0021] Based on the total mass of the glass etching solution as 100%, the amount of the weak acid added is 3% to 10%, for example, it can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0022] In this invention, the weak acid mainly acts as a buffer, timely ionizing and replenishing the hydrogen ions consumed in the etching solution system, thereby maintaining etching stability and preserving etching life.

[0023] Based on the total mass of the glass etching solution being 100%, the amount of the added siloxane compound is 1-2%, for example, it can be 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc.

[0024] In this invention, siloxane compounds play a role in promoting the rapid crystallization and precipitation of fluorosilicates generated in the initial stage of etching.

[0025] Based on the total mass of the glass etching solution as 100%, the amount of fluorinated heterochain acid added is 0.2% to 3%, for example, it can be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 3%, etc.

[0026] In this invention, fluorinated heterochain acids act as etchant stabilizers and, in conjunction with Gemini surfactants, improve the wettability of the etchant on the etched glass substrate, thereby improving the uniformity of etching in both the longitudinal and transverse directions and playing a positive regulatory role in the formation of ordered microcrystals on the glass surface.

[0027] Based on the total mass of the glass etching solution as 100%, the amount of β-cyclodextrin added is 0.1% to 2%, for example, it can be 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.8%, 2%, etc.

[0028] In this invention, β-cyclodextrin can effectively adjust the viscosity of the etching solution system to improve the etching uniformity and reduce the etching leakage effect, so that the generated nano-scale microcrystalline snowflake sand can be evenly and orderly distributed and grown on the glass surface, thereby achieving a uniform micromorphological effect.

[0029] In this invention, the glass etching solution achieves the etching effect of fish-scale three-dimensional textured patterns through the synergistic combination of multiple components and specific etching process conditions. It can meet the etching needs of different types of aluminosilicate glass and can simultaneously manufacture fish-scale textured effects of aluminosilicate glass from different brands, effectively improving etching efficiency.

[0030] Furthermore, the balance being water means that the balance of the etching solution composition of the present invention, excluding fluoride salts, grain control agents, gemini surfactants, strong acids, weak acids, siloxane compounds, fluorinated heterochain acids, β-cyclodextrins, and optionally other raw materials, is water; the sum of the mass percentages of water and other raw materials is 100%.

[0031] Preferably, the glass etching solution comprises the following components by mass percentage:

[0032] Fluoride salts 17-30%, grain size regulators 5-10%, gemini surfactants 0.8-4%, strong acids 10-20%, organic weak acids 3-8%, siloxane compounds 1-1.5%, fluorinated heterochain acids 0.5-2.5%, β-cyclodextrins 0.1-1.5%, with the balance being water.

[0033] This invention provides a specialized glass etching solution composition capable of etching a fish-scale-like macroscopic three-dimensional texture effect. It primarily comprises specific amounts of fluorinated salts, grain regulators, Gemini surfactants, inorganic combined acids, organic acids, siloxane compounds, fluorinated heterochain acids, and β-cyclodextrin, with the remainder being water. Through the synergistic effect of these raw materials and the etching method provided by this invention, the resulting glass etching solution composition can be used to etch aluminosilicate glass. The surface crystal distribution is regular, and the microstructure is characterized by goose-feather-like microcrystalline particles, significantly different from the microcrystalline forms of other similar products on the market. Correspondingly, the macroscopic morphology also exhibits a unique visual effect, resembling a fish-scale texture. This is significantly different from the microscopic polyhedral morphology of frosted glass produced by commercially available frosted glass etching solutions. This invention improves upon the technical problems of existing glass etching solutions, such as limited etching effects, poor tactile experience of etched glass, and the tendency for sand leakage after a period of use. Furthermore, the AG glass processed by the glass etching solution composition and etching method of this invention features low roughness, high scratch resistance, and good fingerprint resistance.

[0034] Preferably, the fluoride salt includes fluorides and hydrogen fluoride compounds.

[0035] Preferably, the mass ratio of the fluoride to the hydrogen fluoride compound is 1:(1-3), for example, it can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, etc.

[0036] Preferably, the fluoride is selected from alkali metal fluorides and / or ammonium fluorides, and is preferably any one or a combination of at least two of potassium fluoride, sodium fluoride or ammonium fluoride.

[0037] Preferably, the hydrogen fluoride compound is selected from any one or a combination of at least two of sodium hydrogen fluoride, potassium hydrogen fluoride, or ammonium hydrogen fluoride.

[0038] Preferably, the fluoride salt further includes fluorosilicate.

[0039] Preferably, the amount of fluorosilicate added accounts for 1 to 5% of the total mass of the fluoride salt, for example, it can be 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, etc.

[0040] Preferably, the fluorosilicate is ammonium fluorosilicate.

[0041] As some preferred embodiments of the present invention, the fluoride salt is selected from any one of potassium fluoride / sodium hydrogen fluoride, sodium fluoride / ammonium hydrogen fluoride, and ammonium fluoride / potassium hydrogen fluoride / ammonium fluorosilicate.

[0042] It should be noted that the " / " in the above fluoride salts represents "and". For example, potassium fluoride / sodium hydrogen fluoride means that the fluoride salt is a combination of potassium fluoride and sodium hydrogen fluoride. Similarly, ammonium fluoride / potassium hydrogen fluoride / ammonium fluorosilicate means that the fluoride salt is a combination of three raw materials: ammonium fluoride, potassium hydrogen fluoride and ammonium fluorosilicate.

[0043] Furthermore, when the fluoride salt is a combination of potassium fluoride and sodium hydrogen fluoride, the mass ratio of potassium fluoride to sodium hydrogen fluoride is 1:(1.2 to 2.5), for example, it can be 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.5, etc.

[0044] Furthermore, when the fluoride salt is a combination of sodium fluoride and ammonium bifluoride, the mass ratio of sodium fluoride to ammonium bifluoride is 1:(1.2 to 2.5), for example, it can be 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.5, etc.

[0045] Furthermore, when the fluoride salt is a combination of ammonium fluoride, potassium hydrogen fluoride, and ammonium fluorosilicate, the mass ratio of the ammonium fluoride, potassium hydrogen fluoride, and ammonium fluorosilicate is 1:(1.5-2):(0.05-0.1), for example, 1:1.5:0.05, 1:1.6:0.06, 1:1.7:0.07, 1:1.8:0.08, 1:1.9:0.09, 1:2:0.1, etc.

[0046] Preferably, the grain control agent comprises chloride and sulfate; wherein the mass ratio of the chloride to sulfate must satisfy the following formula I:

[0047] (M a / M b ) 2 +(M b / M a ) 2 ≤3 Formula I

[0048] Among them, M a M represents the mass of the chloride salt. b This represents the mass of sulfate.

[0049] Preferably, the chloride salt is selected from any one or a combination of at least two of potassium chloride, ferric chloride, zinc chloride, copper chloride, or nickel chloride, and more preferably from any one of potassium chloride, ferric chloride, or zinc chloride.

[0050] Preferably, the sulfate is selected from any one or a combination of at least two of ferric sulfate, potassium sulfate, cobalt sulfate, nickel sulfate, or copper sulfate, and is preferably any one of ferric sulfate, potassium sulfate, or cobalt sulfate.

[0051] As some preferred embodiments of the present invention, the grain regulator is composed of chloride salt and sulfate salt, such as any one of potassium chloride / ferric sulfate, ferric chloride / potassium sulfate, and zinc chloride / cobalt sulfate.

[0052] It should be noted that the " / " in the above grain control agent means "and". For example, potassium chloride / ferric sulfate means that the grain control agent is a combination of potassium chloride and ferric sulfate, and so on.

[0053] Preferably, the grain control agent comprises chloride, sulfate, and acetate, wherein the mass ratio of the chloride, sulfate, and acetate must satisfy the following formula II:

[0054] [(M c +M d ) / M e ] 2 +[(M c +M e ) / M d ] 2 +[(M d +M e ) / M c ] 2 ≤15FormulaⅡ

[0055] Among them, M c M represents the mass of the chloride salt. d M represents the mass of sulfate. e This represents the mass of acetate.

[0056] Preferably, the chloride salt is selected from any one or a combination of at least two of potassium chloride, ferric chloride, zinc chloride, copper chloride, or nickel chloride, and is preferably copper chloride or nickel chloride.

[0057] Preferably, the sulfate is selected from any one or a combination of at least two of ferric sulfate, potassium sulfate, cobalt sulfate, nickel sulfate, or copper sulfate, and is preferably nickel sulfate or copper sulfate.

[0058] Preferably, the acetate is selected from sodium acetate or zinc acetate.

[0059] In some preferred embodiments of the present invention, the grain regulator is composed of chloride salt, sulfate and acetate, such as any one of copper chloride / nickel sulfate / sodium acetate or nickel chloride / copper sulfate / zinc acetate.

[0060] It should be noted that the " / " in the above grain control agents represents the meaning of "and". For example, copper chloride / nickel sulfate / sodium acetate refers to a combination of copper chloride, nickel sulfate and sodium acetate as grain control agents, and so on.

[0061] The above-mentioned grain control agent can only make the etched glass surface exhibit a stable goose feather-like microcrystalline structure when a specific combination of raw materials is selected and a specific ratio between the raw materials is maintained.

[0062] Preferably, the gemini surfactant is selected from any one or a combination of at least two of sodium tetradecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether diamide, or sodium dodecyloxy diphosphate.

[0063] Preferably, the strong acid is composed of inorganic strong acid and organic strong acid.

[0064] Preferably, the mass ratio of the inorganic strong acid to the organic strong acid is 1:(0.1 to 0.8), for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, etc.

[0065] Preferably, the inorganic strong acid is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid, or perchloric acid.

[0066] In this invention, the concentration of sulfuric acid can be around 98%; the concentration of hydrochloric acid can be 35-38%; and the concentration of perchloric acid can be 85-86%.

[0067] Preferably, the strong organic acid is selected from organic sulfonic acid compounds, and more preferably any one or a combination of at least two of benzosulfonic acid, methanesulfonic acid, or aminosulfonic acid.

[0068] As some preferred embodiments of the present invention, the strong acid is composed of inorganic strong acid and organic strong acid, such as any one of sulfuric acid / parabensulfonic acid, hydrochloric acid / methanesulfonic acid, and perchloric acid / aminosulfonic acid.

[0069] It should be noted that the " / " in the above strong acid refers to the combination of sulfuric acid and p-benzenesulfonic acid. For example, sulfuric acid / p-benzenesulfonic acid means that the strong acid is a combination of sulfuric acid and p-benzenesulfonic acid, and so on.

[0070] Furthermore, when the strong acid is a combination of sulfuric acid and p-benzylsulfonic acid, the mass ratio of sulfuric acid to p-benzylsulfonic acid is 1:(0.1 to 0.5), for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, etc.

[0071] Furthermore, when the strong acid is a combination of hydrochloric acid and methanesulfonic acid, the mass ratio of the hydrochloric acid to the methanesulfonic acid is 1:(0.3 to 0.8), for example, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, etc.

[0072] Furthermore, when the strong acid is a combination of perchloric acid and aminosulfonic acid, the mass ratio of the perchloric acid to the aminosulfonic acid is 1:(0.1 to 0.5), for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, etc.

[0073] Preferably, the weak acid is an organic weak acid.

[0074] Preferably, the organic weak acid is selected from any one or a combination of at least two of maleic acid, methylene succinic acid, or 2,3-dihydroxysuccinic acid.

[0075] Preferably, the siloxane compound is selected from any one or a combination of at least two of γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, or γ-methacryloyloxypropyltrimethoxysilane.

[0076] Preferably, the fluorinated heterochain acid is selected from any one or a combination of at least two of perfluoro-2,5-dimethyl-3,6-dioxaheptanoic acid, perfluoro-2,5-dimethyl-3,6-dioxaoctanoic acid, or perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid.

[0077] Preferably, the β-cyclodextrin is selected from any one or a combination of at least two of the following: sodium sulfonyl-β-cyclodextrin, heptasubstituted sulfonyl ether-β-cyclodextrin, sodium carboxymethyl-β-cyclodextrin, mono(6-amino-6-deoxy)-β-cyclodextrin, and hepta(6-amino-6-deoxy)-β-cyclodextrin.

[0078] Secondly, the present invention provides a method for preparing a glass etching solution capable of etching a fish-scale-like three-dimensional texture as described in the first aspect, the preparation method comprising the following steps:

[0079] Fluoride salts, grain regulators, gemini surfactants, strong acids, weak acids, siloxane compounds, fluorinated heterochain acids, and β-cyclodextrins are mixed in a specific ratio and allowed to stand for aging to obtain the glass etching solution capable of etching fish-scale three-dimensional textures.

[0080] Preferably, the curing time is 36 to 72 hours, for example, 36 hours, 42 hours, 48 ​​hours, 54 hours, 60 hours, 66 hours, 72 hours, etc.

[0081] More specifically, the weighed raw materials are placed in a mixing tank and stirred thoroughly until the solution is a uniform supersaturated solution. The solution is then allowed to stand for 36–72 hours to obtain a special glass etching solution composition that can etch a fish-scale three-dimensional texture effect.

[0082] Thirdly, the present invention provides an application of a glass etching solution capable of etching fish-scale three-dimensional textures as described in the first aspect in etching aluminosilicate glass.

[0083] Fourthly, the present invention provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0084] The side of the electronic glass substrate that needs to be etched is immersed and agitated in a glass etching solution that can etch a fish-scale three-dimensional texture as described in the first aspect, so that the etched side of the electronic glass substrate presents a fish-scale three-dimensional texture.

[0085] Preferably, a protective treatment is required before immersion: the side of the electronic glass substrate that does not need to be etched is covered with an acid-resistant film to prevent it from being corroded by the etching solution composition.

[0086] Preferably, the soaking temperature is 16-23°C, for example, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, etc.

[0087] Preferably, the trajectory of the swing is in the shape of an "8".

[0088] Preferably, the oscillation frequency is 20 to 30 revolutions / min, for example, it can be 20 revolutions / min, 21 revolutions / min, 22 revolutions / min, 23 revolutions / min, 24 revolutions / min, 25 revolutions / min, 26 revolutions / min, 27 revolutions / min, 28 revolutions / min, 29 revolutions / min, 30 revolutions / min, etc.

[0089] Preferably, the swing time is controlled between 4 and 6 minutes, for example, it can be 4 minutes, 4.2 minutes, 4.4 minutes, 4.6 minutes, 4.8 minutes, 5 minutes, 5.2 minutes, 5.4 minutes, 5.6 minutes, 5.8 minutes, 6 minutes, etc.

[0090] Compared with the prior art, the present invention has the following beneficial effects:

[0091] (1) The glass etching solution composition provided by the present invention achieves the etching effect of fish scale three-dimensional texture pattern through the synergistic combination of multiple components and specific etching process conditions. It can meet the etching needs of different types of aluminosilicate glass and can simultaneously manufacture fish scale texture effect of different brands of aluminosilicate glass, effectively improving etching efficiency.

[0092] In this process, fluoride salts serve as the main material for etching glass, providing sufficient fluoride ions to the etching solution composition to etch the glass skeleton. The reaction product, fluorosilicate, forms a precipitate and deposits on the glass surface, playing a role in forming nano- and micron-sized crystalline particles on the glass surface.

[0093] Among them, the combination of strong acids provides an acidic environment and sufficient hydrogen ions, which promotes the destruction of the surface structure of the glass by the fluoride salt to achieve the purpose of etching, while also maintaining the service life of the etching solution. Controlling the proportion and content of the combination of strong acids in the etching solution composition within a suitable range is beneficial to etching balance.

[0094] Among them, siloxane compounds make it easier for fluorosilicates to form in the initial etching of glass. Under the catalytic action of metal ions of grain control agent, the etching solution will quickly etch down a part of the glass to form a three-dimensional etching effect.

[0095] Among them, the metal ions in the grain regulator will form different fluorosilicates. Due to their differences in solubility and the different dominant crystal faces of crystal growth, they will eventually form a special goose feather-like microscopic effect and a corresponding fish scale-like three-dimensional macroscopic texture effect, thereby achieving the purpose of composition determining structure and structure determining appearance.

[0096] Among them, the organic weak acid mainly acts as a buffer, timely ionizing and replenishing the hydrogen ions consumed in the etching solution system, thus maintaining etching stability and synergistically combining with strong acids to maintain etching life.

[0097] Among them, β-cyclodextrin can effectively adjust the viscosity of the etching solution to facilitate uniform etching and reduce sand leakage, so as to make the nano-scale microcrystalline particles grow evenly on the glass surface, thereby achieving a uniform micro-morphological effect.

[0098] Among them, Gemini surfactant reduces the effect of the etching solution on the etched glass and increases the wettability of the etching solution composition on the glass substrate. It can also work synergistically with β-cyclodextrin to suppress sand leakage. In addition, since Gemini surfactant contains two hydrophobic chains and two hydrophilic chains, the two hydrophobic chains will transfer from the aqueous phase to the micelle phase with a large change in free energy, which is conducive to the formation of micelles. The two hydrophilic groups tend to be arranged in an orderly manner at the air / etching solution interface, forming an orderly aggregate of hydrophobic chains facing outward from the etching solution. This forms foam on the surface of the etching solution and helps to suppress the escape of acid gas.

[0099] Fluorinated heterochain acids act as stabilizers and dispersants in the etching solution, and work synergistically with Gemini surfactants and β-cyclodextrins to improve the wettability of the etching solution on the etched glass substrate, thereby improving the uniformity of etching in both the longitudinal and transverse directions and playing a positive regulatory role in the formation of ordered microcrystals on the glass surface.

[0100] (2) The AG glass treated by the glass etching solution composition and etching method of the present invention has a regular surface crystal distribution and a microscopic morphology of goose feather-shaped microcrystalline particles, which is significantly different from the microscopic crystal type of other similar products on the market; the corresponding macroscopic morphology also shows a different visual effect, showing a fish scale texture effect; which is significantly different from the ordinary sand and flash sand effects produced by glass etching solutions on the market.

[0101] (3) The roughness of the AG glass surface obtained by the glass etching solution composition of the present invention is 0.8 to 1.3 μm, the haze is >70%, and the surface crystals are regularly distributed and uniform in size, exhibiting better touch feel and appearance, while also having good scratch resistance and fingerprint resistance. Attached Figure Description

[0102] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0103] Figure 1 The image shows the distribution of microcrystalline particles on the glass surface under a 200x magnifying glass, as provided in Example 1.

[0104] Figure 2 The image shows the appearance features of the glass surface under macroscopic conditions as provided in Example 1.

[0105] Figure 3 The distribution of microcrystalline particles on the glass surface under a 200x magnifying glass is provided for Comparative Example 1.

[0106] Figure 4 A photograph showing the appearance of the glass surface under macroscopic conditions, provided for Comparative Example 1.

[0107] Figure 5 The distribution of microcrystalline particles on the glass surface under a 200x magnifying glass is provided for Comparative Example 2.

[0108] Figure 6 A photograph showing the appearance of the glass surface under macroscopic conditions, provided for Comparative Example 2. Detailed Implementation

[0109] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or". Furthermore, the use of the term "comprising" and other forms is non-limiting.

[0110] It should be noted that specific details are set forth in the following description to provide a full understanding of the invention. However, the invention can be practiced in many ways other than those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0111] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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.

[0112] The present invention will be further illustrated below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0113] Example 1

[0114] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0115] Potassium fluoride 10%, sodium hydrogen fluoride 15%, potassium chloride 3%, ferric sulfate 2%, sodium tetradecyl diphenyl ether disulfonate 2%, hydrochloric acid 15%, methanesulfonic acid 5%, maleic acid 5%, γ-methacryloyloxypropyltrimethoxysilane 0.5%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 0.2%, sodium sulfobutyl-β-cyclodextrin 0.5%, with the balance being water.

[0116] The glass etching solution is prepared by the following steps:

[0117] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 48 hours to obtain the glass etching solution.

[0118] Example 2

[0119] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0120] Potassium fluoride 8%, sodium hydrogen fluoride 17%, ferric chloride 5%, potassium sulfate 5%, sodium tetradecyl diphenyl ether disulfonate 2%, hydrochloric acid 12%, methanesulfonic acid 8%, methylene succinic acid 8%, γ-methacryloyloxypropyltrimethoxysilane 1%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 0.5%, sodium sulfobutyl-β-cyclodextrin 0.5%, with the balance being water.

[0121] The glass etching solution is prepared by the following steps:

[0122] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 48 hours to obtain the glass etching solution.

[0123] Example 3

[0124] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0125] Sodium fluoride 10%, ammonium bifluoride 18%, copper chloride 5%, cobalt sulfate 5%, sodium tetradecyl diphenyl ether disulfonate 2%, sulfuric acid 15%, p-toluenesulfonic acid 5%, maleic acid 3%, γ-methacryloyloxypropyltrimethoxysilane 1%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 0.2%, sodium sulfobutyl-β-cyclodextrin 0.5%, with the balance being water.

[0126] The glass etching solution is prepared by the following steps:

[0127] First, prepare and weigh each raw material of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 72 hours to obtain the glass etching solution.

[0128] Example 4

[0129] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0130] Sodium fluoride 10%, ammonium bifluoride 25%, ferric chloride 3%, potassium sulfate 2%, sodium dodecyl diphenyl ether sulfonate diamide 1%, hydrochloric acid 12%, methanesulfonic acid 8%, methylene succinic acid 3%, γ-aminopropyltriethoxysilane 1%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 0.5%, sodium sulfobutyl-β-cyclodextrin 1%, with the balance being water.

[0131] The glass etching solution is prepared by the following steps:

[0132] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 32 hours to obtain the glass etching solution.

[0133] Example 5

[0134] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0135] Ammonium fluoride 10%, potassium hydrogen fluoride 15%, ammonium fluorosilicate 0.5%, ferric chloride 3%, potassium sulfate 2%, sodium dodecyl diphenyl ether sulfonate diamide 2%, sulfuric acid 16.5%, p-toluenesulfonic acid 3.5%, dihydroxysuccinic acid 8%, γ-methacryloyloxypropyltrimethoxysilane 1%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 1%, sodium sulfobutyl-β-cyclodextrin 1%, with the balance being water.

[0136] The glass etching solution is prepared by the following steps:

[0137] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 48 hours to obtain the glass etching solution.

[0138] Example 6

[0139] This embodiment provides a glass etching solution capable of etching out fish-scale-like three-dimensional textures. The glass etching solution comprises the following components by mass percentage:

[0140] Ammonium fluoride 10%, potassium hydrogen fluoride 15%, ammonium fluorosilicate 1%, nickel chloride 2%, copper sulfate 2%, zinc acetate 2%, sodium dodecyloxybisphosphate 3%, hydrochloric acid 15%, methanesulfonic acid 5%, dihydroxysuccinic acid 8%, γ-aminopropyltriethoxysilane 1%, perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid 2%, mono(6-amino-6-deoxy)-β-cyclodextrin 2%, balance being water.

[0141] The glass etching solution is prepared by the following steps:

[0142] First, prepare and weigh each raw material of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 72 hours to obtain the glass etching solution.

[0143] Comparative Example 1

[0144] This comparative example provides a glass etching solution, which comprises the following components by mass percentage:

[0145] Potassium fluoride 10%, sodium hydrogen fluoride 15%, potassium chloride 5%, sodium tetradecyl diphenyl ether disulfonate 2%, hydrochloric acid 20%, maleic acid 5%, perfluoro-2,5-dimethyl-3,6-dioxanoic acid 0.2%, sodium sulfobutyl-β-cyclodextrin 0.5%, balance water.

[0146] The glass etching solution is prepared by the following steps:

[0147] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 48 hours to obtain the glass etching solution.

[0148] Comparative Example 2

[0149] This comparative example provides a glass etching solution, which comprises the following components by mass percentage:

[0150] Potassium fluoride 8%, sodium hydrogen fluoride 17%, ferric chloride 3%, potassium sulfate 2%, sodium dodecyl sulfonate 2%, hydrochloric acid 15%, sulfuric acid 5%, maleic acid 5%, and the balance is water.

[0151] The glass etching solution is prepared by the following steps:

[0152] First, prepare and weigh the raw materials of the glass etching solution according to the above ratio. Then, place the weighed raw materials in the mixing tank and stir them thoroughly until the solution presents a uniform supersaturated solution state. Let it stand and mature for 48 hours to obtain the glass etching solution.

[0153] Comparative Example 3

[0154] This comparative example provides a glass etching solution, which differs from Example 1 only in that sodium tetradecyl diphenyl ether disulfonate is replaced with an equal mass of the anionic surfactant sodium dodecylbenzene sulfonate. The content of other components and the preparation method are completely consistent with Example 1.

[0155] Comparative Example 4

[0156] This comparative example provides a glass etching solution, which differs from Example 1 only in that γ-methacryloyloxypropyltrimethoxysilane is replaced with an equal mass of ammonium fluorosilicate, while the content of other components and the preparation method are completely consistent with Example 1.

[0157] Comparative Example 5

[0158] This comparative example provides a glass etching solution, which differs from Example 1 only in that perfluoro-2,5-dimethyl-3,6-dioxanoic acid is replaced with an equal mass of polyethylene glycol monooctylphenyl ether as a dispersant. The content of other components and the preparation method are completely consistent with Example 1.

[0159] Comparative Example 6

[0160] This comparative example provides a glass etching solution, which differs from Example 1 only in that sodium sulfonyl-β-cyclodextrin is replaced with an equal mass of α-cyclodextrin. The content of other components and the preparation method are completely consistent with Example 1.

[0161] Application Example 1

[0162] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0163] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0164] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Example 1 at 16-18°C and swish it for 4 minutes.

[0165] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0166] Application Example 2

[0167] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0168] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0169] S2. The side of the electronic glass substrate that needs to be etched is washed with deionized water, and then immersed and swirled in the glass etching solution provided in Example 2 at 16-18°C for 4 minutes.

[0170] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0171] Application Example 3

[0172] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0173] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0174] S2. The side of the electronic glass substrate that needs to be etched is washed with deionized water, and then immersed and swirled in the glass etching solution provided in Example 3 at 20-22°C for 5 minutes.

[0175] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0176] Application Example 4

[0177] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0178] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0179] S2. The side of the electronic glass substrate that needs to be etched is cleaned with deionized water, and then immersed and swirled in the glass etching solution provided in Example 4 at 20-22°C for 4 minutes.

[0180] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0181] Application Example 5

[0182] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0183] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0184] S2. The side of the electronic glass substrate that needs to be etched is washed with deionized water, and then immersed and swirled in the glass etching solution provided in Example 5 at 16-18°C for 6 minutes.

[0185] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0186] Application Example 6

[0187] This application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0188] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0189] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Example 6 at 16-18°C and swish it for 5 minutes.

[0190] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0191] Comparative Application Example 1

[0192] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0193] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0194] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 1 at 16-18°C and swish it for 4 minutes.

[0195] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0196] Comparative Application Example 2

[0197] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0198] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0199] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 2 at 16-18°C and swish it for 4 minutes.

[0200] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0201] Comparative Application Example 3

[0202] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0203] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0204] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 3 at 16-18°C and swish it for 4 minutes.

[0205] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0206] Comparative Application Example 4

[0207] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0208] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0209] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 4 at 16-18°C and swish it for 4 minutes.

[0210] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0211] Comparative Application Example 5

[0212] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0213] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0214] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 5 at 16-18°C and swish it for 4 minutes.

[0215] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0216] Comparative Application Example 6

[0217] This comparative application example provides an etching method for an electronic glass substrate, the etching method comprising the following steps:

[0218] S1. Cover the side of the electronic glass substrate that does not need to be etched with an acid-resistant film to protect it from corrosion by the etching solution composition;

[0219] S2. Clean the side of the electronic glass substrate that needs to be etched with deionized water, and then immerse it in the glass etching solution provided in Comparative Example 6 at 16-18°C and swish it for 4 minutes.

[0220] S3. Remove the etched electronic glass from the etching solution composition, rinse it with deionized water, and then dry it further.

[0221] Performance testing

[0222] Test samples: Electronic glass substrates obtained by etching in Examples 1-6, and electronic glass substrates obtained by etching in comparison Examples 1-6;

[0223] Test methods: (1) Roughness: Measured according to national standard GB / T 32642 2016;

[0224] (2) Haze and transmittance: Measured in accordance with national standard GB / T 2410 2008;

[0225] (3) Gloss: The gloss of the etched or original glass was tested using a WGG-60 gloss meter;

[0226] (4) Reflectivity: The reflectivity of etched or original glass was detected using a DS-700 portable spectrophotometer;

[0227] Specific results are shown in Table 1 and Figures 1-6 .

[0228] Table 1

[0229]

[0230] As shown in Table 1 and the accompanying drawings, the aluminosilicate glass treated by the glass etching solution composition and etching method of Examples 1-6 of the present invention exhibits a regular surface crystal distribution and a microscopic morphology of goose feather-like microcrystalline particles; the corresponding macroscopic morphology also shows a different visual effect, resembling a fish scale texture; clearly different from the microscopic and macroscopic morphologies shown in Comparative Examples 1-2, the AG glass obtained by the glass etching solution composition and etching method of the present invention has the characteristics of low roughness, high scratch resistance, and good anti-fingerprint effect.

[0231] In summary, this invention, through the synergistic effect of the aforementioned raw materials and specific etching process conditions, can meet the needs of novel abrasive-effect etching for different types of aluminosilicate glass. The aluminosilicate glass treated with the glass etching solution composition and etching method of this invention exhibits a regular surface crystal distribution and a microscopic morphology of goose-feather-shaped microcrystalline particles, significantly different from the microscopic crystal forms of other similar products on the market. Correspondingly, the macroscopic morphology also displays a different visual effect, exhibiting a fish-scale-like texture, clearly distinguishing it from ordinary abrasive and glittery abrasive effects on the market. Furthermore, the AG glass obtained by the glass etching solution composition and etching method of this invention has the characteristics of low roughness, smooth feel, high scratch resistance, and good fingerprint resistance.

[0232] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention 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; and these 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 the present invention.

Claims

1. A glass etching solution capable of etching a fish-scale-like three-dimensional texture, characterized in that, The glass etching solution comprises the following components by mass percentage: Fluoride salts 17-35%, grain size regulators 3-10%, gemini surfactants 0.5-5%, strong acids 10-25%, weak acids 3-10%, siloxane compounds 1-2%, fluorinated heterochain acids 0.2-3%. β Cyclodextrin 0.1-2%, balance water; The grain control agent comprises chloride and sulfate; wherein the mass ratio of the chloride and sulfate must satisfy the following formula I: (M a / M b ) 2 +(M b / M a ) 2 ≤3 Formula I; Among them, M a M represents the mass of the chloride salt. b The mass of sulfate; Alternatively, the grain control agent may comprise chloride, sulfate, and acetate, wherein the mass ratio of the chloride, sulfate, and acetate must satisfy the following formula II: [(M c +M d ) / M e 2 +[(M c +M e ) / M d 2 +[(M d +M e ) / M c 2 ≤15 Formula II;​​​ Among them, M c M represents the mass of the chloride salt. d M represents the mass of sulfate. e The mass of acetate; The fluorinated heterochain acid is selected from any one or a combination of at least two of perfluoro-2,5-dimethyl-3,6-dioxaheptanoic acid, perfluoro-2,5-dimethyl-3,6-dioxaoctanoic acid, or perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid.

2. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The fluorinated salts include fluorides and hydrogen fluoride compounds.

3. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 2, characterized in that, The mass ratio of the fluoride to the hydrogen fluoride compound is 1:(1~3).

4. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 2 or 3, characterized in that, The fluoride is selected from alkali metal fluorides and / or ammonium fluorides.

5. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 4, characterized in that, The fluoride is any one or a combination of at least two of potassium fluoride, sodium fluoride, or ammonium fluoride.

6. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 2 or 3, characterized in that, The hydrogen fluoride compounds are selected from any one or a combination of at least two of sodium hydrogen fluoride, potassium hydrogen fluoride, or ammonium hydrogen fluoride.

7. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 2, characterized in that, The fluoride salt also includes fluorosilicates.

8. The glass etching solution according to claim 7, capable of etching a fish-scale-like three-dimensional texture, is characterized in that... The amount of fluorosilicate added accounts for 1 to 5% of the total mass of the fluoride.

9. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 7 or 8, characterized in that, The fluorosilicate is ammonium fluorosilicate.

10. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The chloride salt is selected from any one or a combination of at least two of potassium chloride, ferric chloride, zinc chloride, copper chloride, or nickel chloride.

11. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 1 or 10, characterized in that, When the grain regulator includes chloride and sulfate, the chloride is any one of potassium chloride, ferric chloride, or zinc chloride; Alternatively, when the grain regulator includes chloride, sulfate and acetate, the chloride is copper chloride or nickel chloride.

12. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The sulfate is selected from any one or a combination of at least two of ferric sulfate, potassium sulfate, cobalt sulfate, nickel sulfate, or copper sulfate.

13. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 1 or 12, characterized in that, When the grain regulator includes chloride and sulfate, the sulfate is any one of ferric sulfate, potassium sulfate or cobalt sulfate; Alternatively, when the grain regulator includes chloride, sulfate and acetate, the sulfate is nickel sulfate or copper sulfate.

14. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The acetate is selected from sodium acetate or zinc acetate.

15. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 1, characterized in that, The gemini surfactant is selected from any one or a combination of at least two of sodium tetradecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether diamide, or sodium dodecyloxy diphosphate.

16. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 1, characterized in that, The strong acid is composed of inorganic strong acid and organic strong acid.

17. The glass etching solution according to claim 16, capable of etching a fish-scale-like three-dimensional texture, is characterized in that, The mass ratio of the inorganic strong acid to the organic strong acid is 1:(0.1~0.8).

18. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 16 or 17, characterized in that, The inorganic strong acid is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid, or perchloric acid.

19. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 16 or 17, characterized in that, The strong organic acid is selected from organic sulfonic acid compounds.

20. The glass etching solution according to claim 19, capable of etching a fish-scale-like three-dimensional texture, is characterized in that, The strong organic acid is any one or a combination of at least two of benzosulfonic acid, methanesulfonic acid, or aminosulfonic acid.

21. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The weak acid is an organic weak acid.

22. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 21, characterized in that, The organic weak acid is selected from any one or a combination of at least two of maleic acid, methylene succinic acid, or 2,3-dihydroxysuccinic acid.

23. The glass etching solution capable of etching fish-scale-like three-dimensional textures according to claim 1, characterized in that, The siloxane compound is selected from... γ -aminopropyltriethoxysilane, γ -(2,3-epoxypropoxy)propyltrimethoxysilane or γ Any one or a combination of at least two of the following: -methacryloyloxypropyltrimethoxysilane.

24. The glass etching solution capable of etching a fish-scale-like three-dimensional texture according to claim 1, characterized in that, The β Cyclic paste is selected from sulfobutyl- β -Cyclodextrin sodium salt, heptasubstituted sulfobutyl ether- β -Cyclodextrin, carboxymethyl- β -Cyclodextrin sodium salt, mono(6-amino-6-deoxy)- β -Cyclodextrin, hepta(6-amino-6-deoxy)- β - Any one or at least two of the cyclodextrins.

25. A method for preparing a glass etching solution capable of etching a fish-scale-like three-dimensional texture according to any one of claims 1 to 24, characterized in that, The preparation method includes the following steps: Fluoride salts, grain regulators, gemini surfactants, strong acids, weak acids, siloxane compounds, and fluorinated heterochain acids are included. β After the cyclodextrins are mixed in the specified proportions, they are allowed to stand and mature to obtain the glass etching solution that can etch out fish-scale-like three-dimensional textures.

26. The preparation method according to claim 25, characterized in that, The ripening time is 36-72 hours.

27. The application of a glass etching solution capable of etching a fish-scale three-dimensional texture according to any one of claims 1 to 24 in etching aluminosilicate glass.

28. An etching method for an electronic glass substrate, characterized in that, The etching method includes the following steps: The side of the electronic glass substrate that needs to be etched is immersed and agitated in the glass etching solution that can etch a fish-scale three-dimensional texture as described in any one of claims 1 to 24, so that the etched side of the electronic glass substrate presents a fish-scale three-dimensional texture.

29. The etching method for an electronic glass substrate according to claim 28, characterized in that, The soaking temperature is 16~23℃.

30. The etching method for an electronic glass substrate according to claim 28, characterized in that, The trajectory of the swing is in the shape of an "8".

31. The etching method for an electronic glass substrate according to claim 28, characterized in that, The frequency of the oscillation is 20-30 revolutions / min.

32. The etching method for an electronic glass substrate according to claim 28, characterized in that, The swinging time is controlled between 4 and 6 minutes.

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