A low-etching-degree glass frosting powder, a glass frosting liquid, a preparation method thereof and a frosted glass

Abstract

The application provides a low-etching-degree glass frosting powder, a glass frosting liquid, a preparation method of the glass frosting liquid and a frosting glass, and belongs to the technical field of glass surface treatment. The low-etching-degree glass frosting powder comprises a first component and a second component, and the mass ratio of the first component and the second component is 42-46:54-58. The first component comprises the following preparation raw materials in mass fraction: 24.7-27.8 parts of a fluorine-containing compound, 50-56.5 parts of an inorganic sulfate, 14-16 parts of an acidity regulator, 2.2-5.3 parts of sodium chloride and 0.25-1.5 parts of sodium dodecyl sulfonate; the fluorine-containing compound comprises at least one of a fluoride, a fluorosilicate and a hydrogen fluoride salt; and the second component is ammonium hydrogen fluoride. The low-etching-degree glass frosting powder is prepared into the glass frosting liquid to perform frosting treatment on transparent glass, and the frosting glass obtained has a low etching degree and a uniform distribution on the surface and good light transmittance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of glass surface treatment, and particularly relates to a low-etching-degree glass frosting powder, a glass frosting liquid, and a preparation method and frosted glass thereof. BACKGROUND

[0002] Frosted glass is a kind of translucent glass with uniform frosting effect on the surface, which is a new product developed on the basis of existing transparent glass. Frosted glass can be used in various occasions such as partitions, show windows, doors and windows, and wall surfaces, and has the effects of enhancing privacy protection, filtering harmful ultraviolet rays, and reducing sunlight radiation to a certain extent, and can also obtain unique artistic patterns through different processing methods.

[0003] In the prior art, fluorides and additives thereof are usually used to frosted process transparent glass to prepare frosted glass, but the frosting effect of the frosted glass prepared by the above method still needs to be improved. SUMMARY

[0004] The present application provides a low-etching-degree glass frosting powder, a glass frosting liquid, and a preparation method and frosted glass thereof. The glass frosting liquid prepared by using the low-etching-degree glass frosting powder provided by the present application is used to frosted process transparent glass, and the obtained frosted glass has a low and uniform etching degree on the surface and good light transmittance.

[0005] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] The present application provides a low-etching-degree glass frosting powder, which comprises a first component and a second component, and the mass ratio of the first component to the second component is 42-46:54-58.

[0007] In mass parts, the first component comprises the following preparation raw materials: 24.7-27.8 parts of a fluorine-containing compound, 50-56.5 parts of an inorganic sulfate, 14-16 parts of an acidity regulator, 2.2-5.3 parts of sodium chloride, and 0.25-1.5 parts of sodium dodecyl sulfonate; the fluorine-containing compound comprises at least one of a fluoride, a fluorosilicate, and a hydrogen fluoride salt.

[0008] The second component is ammonium bifluoride.

[0009] Preferably, the fluoride comprises one or more of barium fluoride, potassium fluoride, and ammonium fluoride; the fluorosilicate comprises one or more of aluminum fluorosilicate, magnesium fluorosilicate, and zinc fluorosilicate; and the hydrogen fluoride salt comprises one or more of potassium hydrogen fluoride, sodium hydrogen fluoride, and ammonium hydrogen fluoride.

[0010] Preferably, the inorganic sulfate comprises barium sulfate and / or potassium sulfate.

[0011] Preferably, the acidity regulator is an organic acid and / or an inorganic acid.

[0012] Preferably, the organic acid is oxalic acid; the inorganic acid is sulfamic acid.

[0013] The present application provides a preparation method of the low-etching-degree glass frosting powder as described in the above technical solution, comprising the following steps:

[0014] The preparation raw materials of the first component are mixed to obtain the first component; and the first component is mixed with the second component to obtain the low-etching-degree glass frosting powder.

[0015] The present application provides a glass frosting liquid, and preparation raw materials thereof comprise a low-etching-degree glass frosting powder and an acidic solvent, wherein the use amount ratio of the low-etching-degree glass frosting powder and the acidic solvent is 380-420 g: 100-140 mL; the low-etching-degree glass frosting powder is the low-etching-degree glass frosting powder as described in the above technical solution or the low-etching-degree glass frosting powder prepared by the preparation method as described in the above technical solution.

[0016] Preferably, the acidic solvent is concentrated hydrochloric acid, and the mass fraction of the concentrated hydrochloric acid is 31-36%.

[0017] The present application provides a preparation method of the glass frosting liquid as described in the above technical solution, comprising the following steps:

[0018] The low-etching-degree glass frosting powder is dissolved in the acidic solvent to obtain the glass frosting liquid.

[0019] The present application provides a frosted glass, which is obtained by performing frosting etching treatment on a transparent glass substrate by using the glass frosting liquid as described in the above technical solution or the glass frosting liquid prepared by the preparation method as described in the above technical solution.

[0020] The present application provides a low-etching degree glass frosting powder, which comprises a first component and a second component, and the mass ratio of the first component and the second component is 42-46:54-58; the first component comprises the following preparation raw materials in mass fraction: 24.7-27.8 parts of a fluorine-containing compound, 50-56.5 parts of inorganic sulfate, 14-16 parts of an acidity regulator, 2.2-5.3 parts of sodium chloride and 0.25-1.5 parts of sodium dodecyl sulfonate; the fluorine-containing compound comprises at least one of fluoride, fluorosilicate and hydrogen fluoride salt; and the second component is ammonium hydrogen fluoride. In the present application, the fluorine-containing compound in the first component and the ammonium hydrogen fluoride in the second component can improve the etching degree of the frosted glass; the acidity regulator can slowly react with the fluorine-containing compound to generate hydrofluoric acid, which is beneficial to improve the frosting effect; the inorganic sulfate can change the anisotropy of the glass lattice by uniformly rubbing the surface of the transparent glass substrate corroded by physical friction, so as to change the refractive index of the glass and improve the frosting effect; the sodium chloride serves as an auxiliary electrolyte of the inorganic sulfate; and the sodium dodecyl sulfonate serves as a dispersant, which can control the wetting degree between the liquid and the solid, so as to improve the adhesion and deposition amount of the glass frosting liquid prepared from the low-etching degree glass frosting powder on the surface of the transparent glass, accelerate the etching speed and improve the frosting effect. In the low-etching degree glass frosting powder provided by the present application, the components cooperate with each other, so that the etching degree of the glass surface after the frosting treatment is low and uniformly distributed, and the light transmittance is good. The examples show that the low-etching degree glass frosting powder provided by the present application is prepared into a glass frosting liquid to perform the frosting treatment on the transparent glass, and the etching degree of the surface of the frosted glass is low, about 0.1 μm. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description only constitute some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0022] Figure 1 SEM image of the frosted glass obtained in Example 1;

[0023] Figure 2 SEM image of the frosted glass obtained in Example 2;

[0024] Figure 3 SEM image of the frosted glass obtained in Example 3;

[0025] Figure 4 SEM image of the frosted glass obtained in Example 4;

[0026] Figure 5SEM image of the frosted glass obtained in Example 5;

[0027] Figure 6 SEM image of the frosted glass obtained in Example 6;

[0028] Figure 7 SEM image of the frosted glass obtained in Example 7;

[0029] Figure 8 SEM image of the frosted glass obtained in Example 8;

[0030] Figure 9 SEM image of the frosted glass obtained in Example 9;

[0031] Figure 10 SEM image of the frosted glass obtained in Example 10;

[0032] Figure 11 SEM image of the frosted glass obtained in Example 11;

[0033] Figure 12 SEM image of the frosted glass obtained in Example 12 with a frosted etching treatment time of 2 minutes and 10 seconds;

[0034] Figure 13 SEM image of the frosted glass obtained in Example 12 with a frosted etching treatment time of 2 minutes and 30 seconds;

[0035] Figure 14 SEM image of the frosted glass obtained in Example 12 with a frosted etching treatment time of 2 minutes and 40 seconds;

[0036] Figure 15 SEM image of the frosted glass obtained in Example 12 with a frosted etching treatment time of 3 minutes;

[0037] Figure 16 SEM image of the frosted glass obtained in Example 13. DETAILED DESCRIPTION

[0038] The present application provides a low-etching frosted glass powder, comprising a first component and a second component, wherein the mass ratio of the first component and the second component is 42-46:54-58;

[0039] The first component comprises the following raw materials in mass fraction: 24.7-27.8 parts of a fluorine-containing compound, 50-56.5 parts of an inorganic sulfate, 14-16 parts of an acidity regulator, 2.2-5.3 parts of sodium chloride, and 0.25-1.5 parts of sodium dodecyl sulfonate; the fluorine-containing compound comprises at least one of a fluoride, a fluorosilicate, and a hydrogen fluoride salt;

[0040] The second component is ammonium hydrogen fluoride.

[0041] In the present application, the raw materials used are all commercially available goods well known to those skilled in the art, unless otherwise specified.

[0042] The low-etching glass frosting powder comprises a first component and a second component, and the mass ratio of the first component to the second component is 42-46:54-58, preferably 44:56.

[0043] In the present application, the first component comprises the following raw materials: fluorine-containing compound, inorganic sulfate, acidity regulator, sodium chloride and sodium dodecyl sulfonate.

[0044] The preparation raw material of the low-etching degree glass frosting powder according to the application comprises 24.7-27.8 parts of fluorine-containing compounds, preferably 25.3-27.3 parts. In the application, the fluorine-containing compounds preferably comprise at least one of fluoride, fluorosilicate and hydrogen fluoride salt; the fluoride preferably comprises one or more of barium fluoride, potassium fluoride and ammonium fluoride; the fluorosilicate comprises one or more of aluminum fluorosilicate, magnesium fluorosilicate and zinc fluorosilicate; and the hydrogen fluoride salt comprises one or more of potassium hydrogen fluoride, sodium hydrogen fluoride and ammonium hydrogen fluoride. In the embodiment of the application, the fluorine-containing compounds are in the following combinations: (1) the fluorine-containing compounds are aluminum fluorosilicate, potassium hydrogen fluoride, magnesium fluorosilicate, sodium hydrogen fluoride, barium fluoride and potassium fluoride, and the mass ratio is preferably 10-12.6:1.5-3.5:1-2.5:1-2:3-5:3-5, more preferably 11.9:1.5-3.1:1-2.5:1.5:4.3:4.5; (2) the fluorine-containing compounds are aluminum fluorosilicate, potassium hydrogen fluoride, sodium hydrogen fluoride, barium fluoride and potassium fluoride, and the mass ratio is preferably 10-12.6:1.5-3.5:1-2:3-5:3-5, more preferably 11.9:3.1:1.5:4.3:4.5; (3) the fluorine-containing compounds are aluminum fluorosilicate, potassium hydrogen fluoride, magnesium fluorosilicate, sodium hydrogen fluoride, barium fluoride, potassium fluoride and ammonium fluoride, and the mass ratio is preferably 5.5-6.4:1.5-3.5:1-2.5:1-2:3-5:3-5:3-5, more preferably 5.9:3.1:2.25:1.5:4.3:4.5:4; (4) the fluorine-containing compounds are aluminum fluorosilicate, potassium hydrogen fluoride, magnesium fluorosilicate, sodium hydrogen fluoride, barium fluoride, potassium fluoride, ammonium hydrogen fluoride and ammonium fluoride, and the mass ratio is preferably 5.5-6.4:1.5-3.5:1-2.5:1-2:3-5:3-5:0.5-1.5:3-5, more preferably 5.9:3.1:2.25:1.5:4.3:4.5:1:4; (5) the fluorine-containing compounds are potassium hydrogen fluoride, magnesium fluorosilicate, sodium hydrogen fluoride, barium fluoride, potassium fluoride, zinc fluorosilicate, ammonium hydrogen fluoride and ammonium fluoride, and the mass ratio is preferably 1.5-3.5:1-2.5:1-2:3-5:3-5:5.5-7:0.5-1.5:3-5, more preferably 3.1:2.25:1.5:4.3:4.5:5.9-6.4:1:4. In the application, when the silicic acid in the transparent glass substrate is dissolved, the aluminum fluorosilicate serves as a silicic acid gel accelerator to accelerate the polymerization of the silicic acid on the surface of the transparent glass substrate dissolved by the ammonium hydrogen fluoride to form uniform gel particles; the potassium hydrogen fluoride (KHF2) provides hydrogen fluoride to increase the corrosion degree of the transparent glass substrate; the magnesium fluorosilicate serves as a rapid-setting agent to promote the rapid setting of the silicic acid sol and significantly increase the apparent roughness; the sodium hydrogen fluoride (NaHF2) provides hydrogen fluoride to increase the corrosion degree of the transparent glass substrate; the barium fluoride increases the surface roughness of the frosted glass; and the potassium fluoride provides F- The ion, forming ammonium hydrogen fluoride, reduces the corrosion of low-etching degree glass frosting powder, adjusts the frosting etching process of transparent glass substrate; the function of zinc fluorosilicate is to improve the etching degree of frosting glass, and simultaneously acts as a rapid hardening agent; the function of ammonium hydrogen fluoride is to reduce the frosting phenomenon of frosting glass, to make the surface of frosting glass more smooth during the frosting process, to reduce the number of small holes and recesses on the surface of frosting glass, and to reduce the size of small holes and recesses; the partial function of ammonium fluoride is consistent with the function of potassium fluoride, wherein the ammonium ion has a buffering effect on acidity.

[0045] The preparation raw material of the low-etching degree glass frosting powder in the present application includes inorganic sulfate 50-56.5 parts by mass, preferably 54.5 parts. The inorganic sulfate preferably includes barium sulfate and / or potassium sulfate, more preferably barium sulfate and potassium sulfate; the mass ratio of the barium sulfate and potassium sulfate is preferably 27.2:24.7-28.7, more preferably 27.2:27.3. In the present application, the potassium sulfate acts as an electrolyte dispersant in the low-etching degree glass frosting powder, and the barium sulfate has a physical friction effect, which uniformly rubs the surface of transparent glass substrate corroded, changes the anisotropy of glass lattice, thereby changing the refractive index of glass and improving the frosting effect.

[0046] The preparation raw material of the low-etching degree glass frosting powder in the present application includes acidity regulator 14-16 parts by mass, preferably 15 parts. In the present application, the acidity regulator preferably includes organic acid and / or inorganic acid, more preferably organic acid and inorganic acid. The organic acid in the present application is preferably oxalic acid, and the inorganic acid is preferably sulfamic acid; the mass ratio of the oxalic acid and sulfamic acid is preferably 4-9:7-10, more preferably 6:9. In the present application, the function of the acidity regulator is to act as a buffer in the frosting etching process, so that the surface of the obtained frosting glass reaches a balanced state that is neither too rough nor too smooth, and the gloss of the surface of the frosting glass is improved; wherein the oxalic acid has a corrosion-inhibiting effect on transparent glass; the sulfamic acid provides acidity, acts as a strong organic acid, and has a corrosion effect on transparent glass together with ammonium hydrogen fluoride.

[0047] The preparation raw material of the low-etching degree glass frosting powder in the present application includes sodium chloride 2.2-5.3 parts by mass, preferably 2.7-4.7 parts. In the present application, the function of sodium chloride is to act as an electrolyte.

[0048] The preparation raw material of the low-etching degree glass frosting powder in the present application includes sodium dodecyl sulfonate 0.25-1.5 parts by mass, preferably 0.5 parts. In the present application, the sodium dodecyl sulfonate acts as a dispersant, which can control the wetting degree between liquid and solid, thereby adjusting the adhesion and deposition amount of the glass frosting liquid prepared from the low-etching degree glass frosting powder on the surface of transparent glass, improving the frosting effect, and accelerating the etching speed.

[0049] In the present application, the second component is ammonium bifluoride. In the present application, ammonium bifluoride can improve the etching degree of the frosted glass.

[0050] The present application also provides a preparation method of the low-etching-degree glass frosted powder, comprising the following steps:

[0051] The preparation raw materials of the first component are mixed to obtain the first component; and the first component is mixed with the second component to obtain the low-etching-degree glass frosted powder.

[0052] The present application does not have special limitations on the mixing method, and the mixing method known to those skilled in the art can be used.

[0053] The present application also provides a glass frosted liquid, and the preparation raw materials comprise the low-etching-degree glass frosted powder and an acidic solvent. The amount ratio of the low-etching-degree glass frosted powder to the acidic solvent is preferably 380-420 g:100-140 mL, and more preferably 400 g:120 mL. The low-etching-degree glass frosted powder is the low-etching-degree glass frosted powder described in the above technical solution or the low-etching-degree glass frosted powder prepared by the preparation method described in the above technical solution.

[0054] In the present application, the acidic solvent is preferably concentrated hydrochloric acid, and the mass fraction of the concentrated hydrochloric acid is preferably 31-36%, and specifically can be 31%, 32%, 33%, 34%, 35% or 36%.

[0055] The present application also provides a preparation method of the glass frosted liquid described in the above technical solution, comprising the following steps:

[0056] The low-etching-degree glass frosted powder is dissolved in the acidic solvent to obtain the glass frosted liquid.

[0057] In the present application, the dissolution preferably comprises first dissolution and second dissolution performed in sequence. The temperature of the first dissolution is preferably 30-45℃, and more preferably 40℃. The time of the first dissolution is preferably 35-50 min, and more preferably 40 min. The first dissolution is preferably water bath dissolution. The temperature of the second dissolution is preferably 20-30℃, and more preferably 22-25℃. The time of the second dissolution is 18-48 h, and more preferably 20-30 h. The second dissolution is preferably water bath dissolution. The present application preferably performs dissolution under stirring. The present application does not have special limitations on the stirring method and conditions, and the stirring method known to those skilled in the art can be used.

[0058] The application further provides a frosted glass, which is obtained by subjecting a transparent glass substrate to frosted etching treatment by using the glass frosting liquid or the glass frosting liquid prepared by the preparation method.

[0059] In the application, the preparation method of the transparent glass substrate preferably comprises the following steps: sequentially subjecting the transparent glass to acid washing, first alcohol washing, water washing and second alcohol washing to obtain the transparent glass substrate. The acid washing method is preferably immersion washing; the acid washing reagent is preferably hydrochloric acid; the mass fraction of the hydrochloric acid is preferably 30-36%, more preferably 31%; the acid washing time is preferably 2-5 min, more preferably 3 min. The first alcohol washing method is immersion washing; the first alcohol washing reagent is preferably anhydrous ethanol; the first alcohol washing time is preferably 2-5 min, more preferably 3 min. The water washing method is flushing; the number of times of the flushing is preferably 3-5 times. The second alcohol washing method is immersion washing; the second alcohol washing reagent is preferably anhydrous ethanol; the second alcohol washing time is preferably 2-5 min, more preferably 3 min. In the application, the water washing is preferably followed by drying, and the application does not have special limitations on the drying method and conditions, and any drying method known to those skilled in the art can be used. In the application, the second alcohol washing is preferably followed by drying. The application does not have special limitations on the drying method and conditions, and any drying method known to those skilled in the art can be used. In the embodiments of the application, in order to facilitate the frosted etching treatment, a protective layer is arranged on any surface of the transparent glass; the protective layer is an adhesive tape.

[0060] The frosted etching treatment preferably comprises the following steps: up-and-down pulling of the transparent glass substrate in the prepared glass frosting liquid, stopping the pulling after the frosted etching treatment is completed, water washing of the obtained glass substrate, and drying to obtain the frosted glass. In the application, the frosted etching treatment temperature is preferably 18-50℃, further preferably 20-45℃, more preferably 22-40℃; the frosted etching treatment time is preferably 1-5 min, more preferably 2-3 min. The number of times of the water washing is preferably 3-5 times. The application does not have special limitations on the drying method and conditions, and any drying method known to those skilled in the art can be used.

[0061] The technical solutions in the application will be described clearly and completely in combination with the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative efforts fall within the protection scope of the application.

[0062] The reagents used in the embodiments are commercially available.

[0063] The transparent glass used in the examples is float glass (formula: Na2O-CaO-SiO2, CAS NO: 1344-09-8, 65997-17-3) with a size of 55 mm x 55 mm x 3 mm, which is purchased from Taibo Qingdao Glass Co., Ltd.

[0064] Example 1

[0065] (1) Preparation of low-etching-degree glass frosting powder

[0066] The raw materials for the first component are prepared according to the following mass parts:

[0067] The fluorine-containing compound is 24.7 parts, specifically: aluminum fluorosilicate 11.9 parts, potassium bifluoride 1.5 parts, magnesium fluorosilicate 1 part, sodium bifluoride 1.5 parts, barium fluoride 4.3 parts, potassium fluoride 4.5 parts;

[0068] The inorganic sulfate is 54.5 parts, specifically: barium sulfate 27.2 parts, potassium sulfate 27.3 parts;

[0069] The acidity regulator is 15 parts, specifically: sulfamic acid 9 parts, oxalic acid 6 parts;

[0070] The potassium chloride is 5.3 parts;

[0071] The sodium dodecyl sulfonate is 0.5 parts.

[0072] The second component is ammonium bifluoride.

[0073] Preparation method: aluminum fluorosilicate 20.944 g, potassium bifluoride 2.64 g, magnesium fluorosilicate 1.76 g, sodium bifluoride 2.64 g, barium fluoride 7.568 g, potassium fluoride 7.92 g, barium sulfate 47.872 g, potassium sulfate 48.048 g, sulfamic acid 15.84 g, oxalic acid 10.56 g, potassium chloride 9.328 g, and sodium dodecyl sulfonate 0.88 g are mixed to obtain the first component; the first component is mixed with the second component 224 g to obtain the low-etching-degree glass frosting powder.

[0074] (2) Preparation of glass frosting solution

[0075] 120 mL of concentrated hydrochloric acid with a mass fraction of 31% is mixed with the low-etching-degree glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating is stopped, and the stirring is continued at 22°C for 18-48 h to obtain the glass frosting solution.

[0076] (3) Preparation of frosted glass

[0077] A transparent glass with a size of 55mm x 55mm x 3mm is provided, the transparent glass has a first surface and a second surface opposite to the first surface, a protective layer is arranged on the second surface of the transparent glass by sticking a tape thereon, the transparent glass is immersed in 31% hydrochloric acid for 3 minutes, then immersed in anhydrous ethanol for 3 minutes, then washed with water for 3-5 times, after the washing, the water on the surface of the transparent glass is wiped dry with non-woven fabric, and finally the transparent glass is washed with anhydrous ethanol and dried on the non-woven fabric. In order to facilitate operation, a longer tape is additionally arranged on the surface of the transparent glass as a handle for lifting and pulling, and a transparent glass substrate is obtained.

[0078] The first surface of the transparent glass substrate is subjected to frosting etching treatment by the glass frosting solution obtained in step (2) at 22°C: the transparent glass substrate is suspended above the glass frosting solution, timing is started, the transparent glass substrate is lifted up and down in the glass frosting solution by the left hand, and a plastic stirring rod is stirred in the glass frosting solution by the right hand, until 2 minutes and 30 seconds are reached, and then the lifting and pulling is stopped. The obtained glass substrate is washed with running water for 3-5 times to remove the residual glass frosting solution on the surface of the glass substrate, then the water on the surface is absorbed dry with non-woven fabric, and the glass substrate is naturally dried to obtain a frosted glass.

[0079] Example 2

[0080] (1) Preparation of low-etching-degree glass frosting powder

[0081] The raw materials for the first component are prepared according to the following mass fractions:

[0082] 26.02 parts of fluorine-containing compounds, specifically: 11.9 parts of aluminum fluorosilicate, 2.82 parts of potassium bifluoride, 1 part of magnesium fluorosilicate, 1.5 parts of sodium bifluoride, 4.3 parts of barium fluoride, and 4.5 parts of potassium fluoride;

[0083] 54.5 parts of inorganic sulfate, specifically: 27.2 parts of barium sulfate and 27.3 parts of potassium sulfate;

[0084] 15 parts of an acidity regulator, specifically: 9 parts of sulfamic acid and 6 parts of oxalic acid;

[0085] 3.98 parts of potassium chloride;

[0086] 0.5 parts of sodium dodecyl sulfonate.

[0087] The second component is ammonium bifluoride.

[0088] Preparation method: 20.944 g of aluminum fluosilicate, 4.9632 g of potassium hydrogen fluoride, 1.76 g of magnesium fluosilicate, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 7.0048 g of potassium chloride and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with 224 g of a second component to obtain a low-etching glass frosting powder.

[0089] (2) Preparation of glass frosting liquid

[0090] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain a glass frosting liquid.

[0091] (3) Preparation of frosted glass

[0092] A transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) was used to frosted etch the first surface of the transparent glass substrate at 22°C. The other frosted etching conditions were the same as those in Example 1 to obtain frosted glass.

[0093] Example 3

[0094] (1) Preparation of low-etching glass frosting powder

[0095] The preparation raw materials of the first component were prepared according to the following mass parts:

[0096] 26.3 parts of fluorine-containing compounds, specifically: 11.9 parts of aluminum fluosilicate, 3.1 parts of potassium hydrogen fluoride, 1 part of magnesium fluosilicate, 1.5 parts of sodium hydrogen fluoride, 4.3 parts of barium fluoride, 4.5 parts of potassium fluoride;

[0097] 54.5 parts of inorganic sulfate, specifically: 27.2 parts of barium sulfate, 27.3 parts of potassium sulfate;

[0098] 15 parts of acidity regulator, specifically: 9 parts of sulfamic acid, 6 parts of oxalic acid;

[0099] 3.7 parts of potassium chloride;

[0100] 0.5 parts of sodium dodecyl sulfonate.

[0101] Preparation method: 20.944 g of aluminum fluosilicate, 5.456 g of potassium hydrogen fluoride, 1.76 g of magnesium fluosilicate, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 6.512 g of potassium chloride and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with 224 g of ammonium hydrogen fluoride to obtain a low-etching glass frosting powder.

[0102] (2) Preparation of glass frosting liquid

[0103] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain the frosting liquid.

[0104] (3) Preparation of frosted glass

[0105] The transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in (2) was used to frosted etch the first surface of the transparent glass substrate at 22°C. The other frosting etching conditions were the same as those in Example 1 to obtain the frosted glass.

[0106] Example 4

[0107] (1) Preparation of low-etching glass frosting powder

[0108] The preparation raw materials of the first component were prepared according to the following mass parts:

[0109] 25.3 parts of fluorine-containing compounds, specifically: 11.9 parts of aluminum fluosilicate, 3.1 parts of potassium hydrogen fluoride, 1.5 parts of sodium hydrogen fluoride, 4.3 parts of barium fluoride, and 4.5 parts of potassium fluoride;

[0110] 54.5 parts of inorganic sulfate, specifically: 27.2 parts of barium sulfate and 27.3 parts of potassium sulfate;

[0111] 15 parts of acidity regulator, specifically: 9 parts of sulfamic acid and 6 parts of oxalic acid;

[0112] 4.7 parts of potassium chloride;

[0113] 0.5 parts of sodium dodecyl sulfonate.

[0114] The second component is ammonium hydrogen fluoride.

[0115] Preparation method: 20.944 g of aluminum fluosilicate, 5.456 g of potassium hydrogen fluoride, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 8.272 g of potassium chloride and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with 224 g of a second component to obtain a low-etching glass frosting powder.

[0116] (2) Preparation of glass frosting liquid

[0117] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain a glass frosting liquid.

[0118] (3) Preparation of frosted glass

[0119] A transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) was used to frosted etch the first surface of the transparent glass substrate at 22°C. The other frosted etching conditions were the same as those in Example 1 to obtain frosted glass.

[0120] Example 5

[0121] (1) Preparation of low-etching glass frosting powder

[0122] The preparation raw materials of the first component were prepared according to the following mass parts:

[0123] 27.3 parts of fluorine-containing compounds, specifically: 11.9 parts of aluminum fluosilicate, 3.1 parts of potassium hydrogen fluoride, 2 parts of magnesium fluosilicate, 1.5 parts of sodium hydrogen fluoride, 4.3 parts of barium fluoride, 4.5 parts of potassium fluoride;

[0124] 54.5 parts of inorganic sulfate, specifically: 27.2 parts of barium sulfate, 27.3 parts of potassium sulfate;

[0125] 15 parts of acidity regulator, specifically: 9 parts of sulfamic acid, 6 parts of oxalic acid;

[0126] 2.7 parts of potassium chloride;

[0127] 0.5 parts of sodium dodecyl sulfonate.

[0128] The second component is ammonium hydrogen fluoride.

[0129] Preparation method: 20.944 g of aluminum fluosilicate, 5.456 g of potassium hydrogen fluoride, 3.52 g of magnesium fluosilicate, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 4.752 g of potassium chloride, and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with a second component of 224 g to obtain a low-etching glass frosting powder.

[0130] (2) Preparation of the glass frosting liquid

[0131] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain a glass frosting liquid.

[0132] (3) Preparation of the frosted glass

[0133] The transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) was used to perform frosting etching treatment on the first surface of the transparent glass substrate at 22°C. The other frosting etching treatment conditions were the same as those in Example 1 to obtain a frosted glass.

[0134] Example 6

[0135] (1) Preparation of the low-etching glass frosting powder

[0136] The preparation raw materials of the first component were prepared according to the following mass parts:

[0137] The fluorine-containing compounds were 27.8 parts, specifically: 11.9 parts of aluminum fluosilicate, 3.1 parts of potassium hydrogen fluoride, 2.5 parts of magnesium fluosilicate, 1.5 parts of sodium hydrogen fluoride, 4.3 parts of barium fluoride, and 4.5 parts of potassium fluoride;

[0138] The inorganic sulfate was 54.5 parts, specifically: 27.2 parts of barium sulfate and 27.3 parts of potassium sulfate;

[0139] The acidity regulator was 15 parts, specifically: 9 parts of sulfamic acid and 6 parts of oxalic acid;

[0140] The potassium chloride was 2.2 parts;

[0141] The sodium dodecyl sulfonate was 0.5 parts.

[0142] The second component was ammonium hydrogen fluoride.

[0143] Preparation method: 20.944 g of aluminum fluosilicate, 5.456 g of potassium hydrogen fluoride, 4.4 g of magnesium fluosilicate, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 3.872 g of potassium chloride, 0.88 g of sodium dodecyl sulfonate, and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with 224 g of a second component to obtain a low-etching glass frosting powder.

[0144] (2) Preparation of glass frosting liquid

[0145] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain a glass frosting liquid.

[0146] (3) Preparation of frosted glass

[0147] A transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) was used to frosted etch the first surface of the transparent glass substrate at 22°C. The other frosted etching conditions were the same as those in Example 1 to obtain frosted glass.

[0148] Example 7

[0149] (1) Preparation of low-etching glass frosting powder

[0150] The raw materials for the preparation of the first component were prepared according to the following mass parts:

[0151] 25.55 parts of fluorine-containing compounds, specifically: 5.9 parts of aluminum fluosilicate, 3.1 parts of potassium hydrogen fluoride, 2.25 parts of magnesium fluosilicate, 1.5 parts of sodium hydrogen fluoride, 4.3 parts of barium fluoride, 4.5 parts of potassium fluoride, and 4 parts of ammonium fluoride;

[0152] 54.5 parts of inorganic sulfate, specifically: 27.2 parts of barium sulfate and 27.3 parts of potassium sulfate;

[0153] 15 parts of acidity regulator, specifically: 9 parts of sulfamic acid and 6 parts of oxalic acid;

[0154] 4.45 parts of potassium chloride;

[0155] 0.5 parts of sodium dodecyl sulfonate.

[0156] The second component was ammonium hydrogen fluoride.

[0157] Preparation method: 10.384g of aluminum fluorosilicate, 5.456g of potassium hydrogen fluoride, 3.96g of magnesium fluorosilicate, 2.64g of sodium hydrogen fluoride, 7.568g of barium fluoride, 7.92g of potassium fluoride, 7.04g of ammonium fluoride, 47.872g of barium sulfate, 48.048g of potassium sulfate, 15.84g of aminosulfonic acid, 10.56g of oxalic acid, 7.832g of potassium chloride, and 0.88g of sodium dodecyl sulfate were mixed to obtain the first component; the first component was mixed with 224g of the second component to obtain low-etching glass frosting powder.

[0158] (2) Preparation of glass frosting solution

[0159] Mix 120 mL of concentrated hydrochloric acid with a mass fraction of 31% with the low etching degree glass frosting powder obtained in step (1), stir evenly, and heat in a water bath at 40°C. After stirring and dissolving for 40 min, stop heating and continue stirring at 22°C for 25 h to obtain glass frosting solution.

[0160] (3) Preparation of frosted glass

[0161] A transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the first surface of the transparent glass substrate was frosted and etched with the glass frosting liquid obtained in step (2) at 22°C. Other frosting and etching conditions were the same as in Example 1, and frosted glass was obtained.

[0162] Example 8

[0163] (1) Preparation of low etching glass frosting powder

[0164] The raw materials for the preparation of the first component are prepared according to the following mass proportions:

[0165] The fluorine-containing compound contains 26.55 parts, specifically: 5.9 parts aluminum fluorosilicate, 3.1 parts potassium hydrogen fluoride, 2.25 parts magnesium fluorosilicate, 1.5 parts sodium hydrogen fluoride, 4.3 parts barium fluoride, 4.5 parts potassium fluoride, 1 part ammonium hydrogen fluoride, and 4 parts ammonium fluoride.

[0166] Inorganic sulfates: 54.5 parts, specifically: barium sulfate 27.2 parts and potassium sulfate 27.3 parts;

[0167] 15 parts of acidity regulator, specifically: 9 parts aminosulfonic acid and 6 parts oxalic acid;

[0168] 3.45 parts potassium chloride;

[0169] Sodium dodecyl sulfonate 0.5 parts.

[0170] The second component is ammonium hydrogen fluoride.

[0171] Preparation method: 10.384 g of aluminum fluosilicate, 5.456 g of potassium hydrogen fluoride, 3.96 g of magnesium fluosilicate, 2.64 g of sodium hydrogen fluoride, 7.568 g of barium fluoride, 7.92 g of potassium fluoride, 1.76 g of ammonium hydrogen fluoride, 7.04 g of ammonium fluoride, 47.872 g of barium sulfate, 48.048 g of potassium sulfate, 15.84 g of sulfamic acid, 10.56 g of oxalic acid, 6.072 g of potassium chloride and 0.88 g of sodium dodecyl sulfonate were mixed to obtain a first component; the first component was mixed with 224 g of a second component to obtain a low-etching glass frosting powder.

[0172] (2) Preparation of glass frosting liquid

[0173] 120 mL of 31% concentrated hydrochloric acid was mixed with the low-etching glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain a glass frosting liquid.

[0174] (3) Preparation of frosted glass

[0175] A transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) was used to frosted etch the first surface of the transparent glass substrate at 22°C. The other frosted etching conditions were the same as those in Example 1 to obtain frosted glass.

[0176] Example 9

[0177] (1) Preparation of low-etching glass frosting powder

[0178] The preparation raw materials of the first component were prepared according to the following mass parts:

[0179] The fluorine-containing compounds were 26.55 parts, specifically: potassium hydrogen fluoride 3.1 parts, magnesium fluosilicate 2.25 parts, sodium hydrogen fluoride 1.5 parts, barium fluoride 4.3 parts, potassium fluoride 4.5 parts, zinc fluosilicate 5.9 parts, ammonium hydrogen fluoride 1 part, and ammonium fluoride 4 parts;

[0180] The inorganic sulfate was 54.5 parts, specifically: barium sulfate 27.2 parts, potassium sulfate 27.3 parts;

[0181] The acidity regulator was 15 parts, specifically: sulfamic acid 9 parts, oxalic acid 6 parts;

[0182] Potassium chloride was 3.45 parts;

[0183] Sodium dodecyl sulfonate was 0.5 parts.

[0184] The second component was ammonium hydrogen fluoride.

[0185] Preparation method: the first component is obtained by mixing potassium fluoride 5.456 g, magnesium fluosilicate 3.96 g, sodium fluoride 2.64 g, barium fluoride 7.568 g, potassium fluoride 7.92 g, zinc fluosilicate 10.384 g, ammonium hydrogen fluoride 1.76 g, ammonium fluoride 7.04 g, barium sulfate 47.872 g, potassium sulfate 48.048 g, sulfamic acid 15.84 g, oxalic acid 10.56 g, potassium chloride 6.072 g and sodium dodecyl sulfate 0.88 g; the first component is mixed with the second component 224 g to obtain a low-etching glass frosting powder.

[0186] (2) Preparation of glass frosting liquid

[0187] The low-etching glass frosting powder obtained in step (1) is mixed with 120 mL of concentrated hydrochloric acid with a mass fraction of 31%, stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating is stopped, and the stirring is continued at 22°C for 25 h to obtain a glass frosting liquid.

[0188] (3) Preparation of frosted glass

[0189] The transparent glass substrate is prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) is used to perform frosting etching treatment on the first surface of the transparent glass substrate at 40°C. The other frosting etching treatment conditions are the same as those in Example 1 to obtain frosted glass.

[0190] Example 10

[0191] (1) Preparation of low-etching glass frosting powder

[0192] The low-etching glass frosting powder is prepared according to the method and parameters of Example 9.

[0193] (2) Preparation of glass frosting liquid

[0194] The low-etching glass frosting powder obtained in step (1) is mixed with 120 mL of concentrated hydrochloric acid with a mass fraction of 31%, stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating is stopped, and the stirring is continued at 22°C for 25 h to obtain a glass frosting liquid.

[0195] (3) Preparation of frosted glass

[0196] The transparent glass substrate is prepared according to the experimental conditions described in Example 1, and the glass frosting liquid obtained in step (2) is used to perform frosting etching treatment on the first surface of the transparent glass substrate at 40°C. The other frosting etching treatment conditions are the same as those in Example 1 to obtain frosted glass.

[0197] Example 11

[0198] (1) Preparation of low-etching degree glass frosting powder

[0199] The preparation raw materials of the first component are prepared according to the following mass parts:

[0200] The fluorine-containing compound is 27.05 parts, specifically: potassium hydrogen fluoride 3.1 parts, magnesium fluorosilicate 2.25 parts, sodium hydrogen fluoride 1.5 parts, barium fluoride 4.3 parts, potassium fluoride 4.5 parts, zinc fluorosilicate 6.4 parts, ammonium hydrogen fluoride 1 part, and ammonium fluoride 4 parts;

[0201] The inorganic sulfate is 54.5 parts, specifically: barium sulfate 27.2 parts, potassium sulfate 27.3 parts;

[0202] The acidity regulator is 15 parts, specifically: sulfamic acid 9 parts, oxalic acid 6 parts;

[0203] The potassium chloride is 2.95 parts;

[0204] The sodium dodecyl sulfonate is 0.5 parts.

[0205] The second component is ammonium hydrogen fluoride.

[0206] Preparation method: mix potassium hydrogen fluoride 5.456 g, magnesium fluorosilicate 3.96 g, sodium hydrogen fluoride 2.64 g, barium fluoride 7.568 g, potassium fluoride 7.92 g, zinc fluorosilicate 11.264 g, ammonium hydrogen fluoride 1.76 g, ammonium fluoride 7.04 g, barium sulfate 47.872 g, potassium sulfate 48.048 g, sulfamic acid 15.84 g, oxalic acid 10.56 g, potassium chloride 5.192 g, and sodium dodecyl sulfonate 0.88 g to obtain the first component; mix the first component with the second component 224 g to obtain the low-etching degree glass frosting powder.

[0207] (2) Preparation of glass frosting liquid

[0208] Mix 120 mL of concentrated hydrochloric acid with a mass fraction of 31% with the low-etching degree glass frosting powder obtained in step (1), stir uniformly, and heat in a water bath at 40°C. After stirring and dissolving for 40 min, stop heating and continue stirring at 22°C for 25 h to obtain the glass frosting liquid.

[0209] (3) Preparation of frosted glass

[0210] Prepare the transparent glass substrate according to the experimental conditions described in Example 1, and perform frosting etching treatment on the first surface of the transparent glass substrate with the glass frosting liquid obtained in step (2) at 22°C. The other frosting etching treatment conditions are the same as those in Example 1 to obtain the frosted glass.

[0211] Example 12

[0212] (1) Preparation of low-etching degree glass frosting powder

[0213] The low-etching degree glass frosting powder was prepared according to the method and parameters of Example 11.

[0214] (2) Preparation of glass frosting liquid

[0215] The 120 mL of concentrated hydrochloric acid with a mass fraction of 31% was mixed with the low-etching degree glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain the glass frosting liquid.

[0216] (3) Preparation of frosted glass

[0217] The transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the first surface of the transparent glass substrate was subjected to frosting etching treatment with the glass frosting liquid obtained in step (2) at 22°C. The frosting etching treatment time was adjusted to 2 min 10 s, 2 min 30 s, 2 min 40 s, and 3 min, respectively, and the frosting etching treatment conditions were the same as those of Example 1 to obtain frosted glass with different frosting etching treatment times.

[0218] Example 13

[0219] (1) Preparation of low-etching degree glass frosting powder

[0220] The low-etching degree glass frosting powder was prepared according to the method and parameters of Example 11.

[0221] (2) Preparation of glass frosting liquid

[0222] The 120 mL of concentrated hydrochloric acid with a mass fraction of 36% was mixed with the low-etching degree glass frosting powder obtained in step (1), stirred uniformly, and heated in a water bath at 40°C. After stirring and dissolving for 40 min, the heating was stopped, and the stirring was continued at 22°C for 25 h to obtain the glass frosting liquid.

[0223] (3) Preparation of frosted glass

[0224] The transparent glass substrate was prepared according to the experimental conditions described in Example 1, and the first surface of the transparent glass substrate was subjected to frosting etching treatment with the glass frosting liquid obtained in step (2) at 22°C. The frosting etching treatment time was adjusted to 2 min 40 s, and the other frosting etching treatment conditions were the same as those of Example 1 to obtain frosted glass.

[0225] The compositions and preparation conditions of the low-etching degree glass frosting powder and the glass frosting liquid, and the frosting etching treatment conditions of the frosted glass in Examples 1-13 are shown in Table 1:

[0226] Table 1. Composition and preparation conditions of low-etching-degree glass frosting powder and glass frosting solution in Examples 1-13, and frosting etching treatment conditions of frosted glass.

[0227]

[0228]

[0229]

[0230]

[0231] Etching test on frosted glass surface:

[0232] The surface etching of the frosted glass obtained in Examples 1-11 was tested using an SJ-210 surface roughness measuring instrument, and the surface etching degree of the frosted glass was recorded. Three repeated experiments were performed, and the average surface etching degree of the frosted glass was calculated. The surface etching degree test results of the frosted glass obtained in Examples 1-11 are shown in Table 2, and the scanning electron microscope images of the frosted glass obtained in Examples 1-11 are shown in... Figures 1-11 As shown.

[0233] Table 2. Surface etching test results of the frosted glass obtained in Examples 1-11

[0234]

[0235] As shown in Table 1, in Examples 1-3, in Example 1, only 2.64g of potassium hydrogen fluoride was added to the glass frosting solution, resulting in an average surface etching degree of only 0.034μm for the frosted glass; in Example 2, the potassium hydrogen fluoride content was increased to 4.9632g, resulting in an average surface etching degree of 0.056μm for the frosted glass; and in Example 3, the potassium hydrogen fluoride content was increased to 5.456g, resulting in an average surface etching degree of 0.087μm for the frosted glass. Based on the test results of Examples 1-3, it can be concluded that increasing the potassium hydrogen fluoride content in the glass frosting solution can increase the etching degree of the resulting frosted glass, thus effectively improving the frosting effect.

[0236] In Examples 4-6, the content of magnesium fluorosilicate in the glass frosting solution was adjusted from 0 to 4.4 g. The surface etching test results of the resulting frosted glass showed that as the magnesium fluorosilicate content increased, the etching degree of the frosted glass also gradually increased, with the average surface etching increasing from 0.025 μm to 0.102 μm. Furthermore, increasing the magnesium fluorosilicate content in the glass frosting solution also improved the smoothness of the resulting frosted glass. It is speculated that this may be because the addition of magnesium fluorosilicate to the glass frosting solution has a slowing effect on gelation. However, during the frosting process, it was found that when the magnesium fluorosilicate content in the glass frosting solution exceeded 4.4 g, the resulting frosted glass exhibited a mottled appearance.

[0237] The content of aluminum fluosilicate in the glass frosting solution of Example 7 is reduced, and the average surface etching degree of the frosted glass is also reduced to 0.089 μm. Apparently, the content of aluminum fluosilicate in the glass frosting solution has certain influence on the etching degree of the frosted glass. Moreover, the aluminum fluosilicate in the glass frosting solution can increase the etching degree of the frosted glass within a certain content, and if the content exceeds a certain range, the etching degree of the frosted glass will be reduced.

[0238] The glass frosting solution of Example 8 is added with 1.76 g of ammonium bifluoride, and the frosted glass does not have the phenomenon of frosting. The glass frosting solution of Example 7 is not added with ammonium bifluoride, and part of the frosted glass has a small amount of frosting phenomenon. This is because the frosting phenomenon on the surface of the frosted glass is usually caused by the small holes and recesses on the surface of the glass substrate, and the use of ammonium bifluoride can reduce the frosting phenomenon of the frosted glass, make the surface of the frosted glass smoother during the frosting process, reduce the number of small holes and recesses, and reduce the size of the small holes and recesses. At the same time, the fluoride ions can also form a stable film structure with the ammonium ions, further reducing the defects and holes on the surface of the glass substrate, thereby protecting the surface of the glass substrate and making it less prone to frosting phenomenon.

[0239] Compared with Example 8, Examples 9 and 10 replace aluminum fluosilicate with zinc fluosilicate to prepare the glass frosting solution, and the content of zinc fluosilicate is adjusted to 10.384 g. Example 9 is frosted at 22 °C after adding zinc fluosilicate in the system, and the average surface etching degree of the frosted glass is 0.052 μm, which is small. Unlike Example 9 which is different from the frosting etching treatment at room temperature, Example 10 is frosted at 40 °C, and the average surface etching degree of the frosted glass reaches 0.103 μm, and the frosting effect is improved. This shows that the addition of zinc fluosilicate can improve the etching degree of the frosted glass, and when the content of zinc fluosilicate is low, the etching degree can be improved by increasing the frosting etching treatment temperature. The content of zinc fluosilicate in Example 11 is increased to 11.264 g. According to the test results of the surface etching degree of the frosted glass obtained in Examples 9-11, it can be seen that the surface etching degree of the frosted glass increases with the increase of the content of zinc fluosilicate, that is, the content of zinc fluosilicate in the glass frosting solution and the surface etching degree of the frosted glass have a positive correlation, which shows that the addition of zinc fluosilicate is beneficial to the improvement of the etching degree.

[0240] The surface roughness tester of SJ-210 model was used to test the etching degree of the frosted glass with different frosted etching treatment time obtained in Example 12, and the surface etching degree of the frosted glass was recorded. Three repeated experiments were performed, and the average value of the surface etching degree of the frosted glass was calculated. The surface etching degree test results of the frosted glass with different frosted etching treatment time obtained in Example 12 are shown in Table 3, and the scanning electron microscope images of the frosted glass with different frosted etching treatment time obtained in Example 12 are shown in Figures 12-15 .

[0241] Table 3 Surface etching degree test results of the frosted glass with different frosted etching treatment time obtained in Example 12

[0242]

[0243] As can be seen from Table 2, with the increase of the frosted etching treatment time, the etching degree of the obtained frosted glass also increases, so it can be seen that the frosted etching treatment time and the etching degree of the obtained frosted glass present a positive correlation. But with the increase of the frosted etching time, the probability of the appearance of the frosted glass also gradually increases, and it is the most serious when the frosted etching treatment time is 3 minutes. When the frosted etching treatment time is 2 minutes and 40 seconds, the etching degree of the obtained frosted glass is uniform, and the frosted glass has less frosted phenomenon, and the frosted effect is the best, and the average surface etching degree of the obtained frosted glass is 0.138 μm. The reason is that when the frosted etching time is short, the frosted degree is low, and then with the increase of the frosted etching time, the transparent glass surface produces frosted phenomenon, and the etching degree continues to increase, and the frosted etching is basically completed at 2 minutes and 40 seconds, so that the surface etching of the obtained frosted glass is uniform and the etching degree is high; when the frosted etching time continues to increase, the fluorosilicate crystal grains on the surface of the obtained frosted glass continue to expand and deposit, which makes the glass surface appear frosted phenomenon.

[0244] The surface roughness tester of SJ-210 model was used to test the etching degree of the frosted glass obtained in Example 13, and the surface etching degree of the frosted glass was recorded. Three repeated experiments were performed, and the average value of the surface etching degree of the frosted glass was calculated. The scanning electron microscope images of the frosted glass with different frosted etching treatment time obtained in Example 13 are shown in Figure 16 .

[0245] The average value of the three test etching degrees of Example 13 is 0.166 μm. The test results show that, under the same conditions, the fritting effect of the concentrated hydrochloric acid with a mass fraction of 36% is better than that of the concentrated hydrochloric acid with a mass fraction of 31%, and the fritted glass obtained by using the concentrated hydrochloric acid with a mass fraction of 36% has a higher etching degree and no flower phenomenon, which proves that the increase of the acidity of the glass fritting solution has a positive promoting effect on the fritting etching effect of the fritted glass. The reason may be that the increase of the acidity causes more substances on the surface of the transparent glass to be corroded in the local area, forming larger depressions and protrusions, and improving the etching degree of the surface of the obtained fritted glass.

[0246] Although the above embodiments have been described in detail, they are only part of the embodiments of the present application, not all the embodiments, and other embodiments can be obtained according to the embodiments without creativity, which all belong to the protection scope of the present application.

Claims

1. A glass frosting liquid, characterized in that, It includes low-etchability glass frosting powder and acidic solvent, wherein the low-etchability glass frosting powder is composed of a first component and a second component; The first component, by mass, consists of the following raw materials: 5.456g potassium hydrogen fluoride; 3.96g magnesium fluorosilicate; 2.64g sodium hydrogen fluoride; 7.568g barium fluoride; 7.92g potassium fluoride; 11.264g zinc fluorosilicate; 1.76g ammonium hydrogen fluoride; 7.04g ammonium fluoride; 47.872g barium sulfate; 48.048g potassium sulfate; 10.56g oxalic acid; 15.84g aminosulfonic acid; 5.192g potassium chloride and 0.88g sodium dodecyl sulfonate; The second component is 224g of ammonium bifluoride; The acidic solvent is concentrated hydrochloric acid, and the mass fraction of the concentrated hydrochloric acid is 31%. The ratio of the low etching glass frosting powder to the acidic solvent is 400g:120mL.

2. The method for preparing the glass frosting liquid according to claim 1, comprising the following steps: The raw materials for preparing the first component are mixed to obtain the first component; The first component and the second component are mixed to obtain a low-etching glass frosting powder; Low etching glass frosting powder is dissolved in an acidic solvent to obtain glass frosting solution.

3. A frosted glass, obtained by frosting and etching a transparent glass substrate with a glass frosting liquid prepared by the glass frosting liquid of claim 1 or the preparation method of claim 2; wherein the etching time is 2 minutes and 40 seconds.

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