A glass frosting liquid, a preparation method and application thereof

Abstract

The application discloses a glass frosting liquid and a preparation method and application thereof, and relates to the technical field of glass surface treatment. The glass frosting liquid comprises the following components: ammonium hydrogen fluoride, sodium chloride, hydrofluoric acid, nitric acid, hydrochloric acid and a dispersing agent; wherein the mass percentage of the nitric acid in the glass frosting liquid is 10-20%. The glass frosting liquid is prepared by compounding specific components and controlling the proportion of the nitric acid, is simple to use, and is stable in frosting, wherein the sodium chloride and the nitric acid can promote crystal nucleus growth and control crystal form, stably and uniformly frost the microcrystalline glass, and do not cause sand leakage, thereby solving the problems that ordinary glass frosting liquids cannot stably frost the microcrystalline glass or are prone to uneven frosting, which results in excessively low yield and unstable mass production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass surface treatment, in particular to a glass frosting liquid and a preparation method and application thereof. BACKGROUND

[0002] Microcrystalline glass has the dual characteristics of glass and ceramic, and the texture on the outer surface is more inclined to ceramic, and the brightness of microcrystalline glass is higher than that of ceramic, and the toughness is stronger than that of glass. The surface of natural stone such as marble and granite is rough and easy to hide dirt, while microcrystalline glass does not have this problem. In addition, the main component of marble is calcium carbonate, and it is easy to react with water and carbon dioxide in the air, so the marble building is discolored with time, while the microcrystalline glass hardly reacts with the air, so it can be new for a long time. At the same time, compared with natural stone, microcrystalline glass decorative plate also has the advantages of uniform strength, simple process and low cost.

[0003] Based on the above advantages, microcrystalline glass is gradually applied to the mobile phone cover industry, and compared with ordinary glass, microcrystalline glass has stronger acid and alkali resistance. Strong acid resistance causes great difficulty in decorating the back cover of the mobile phone. The ordinary frosting liquid often does not sand or sand unevenly, which leads to the inability to make an attractive back cover with frosting effect, and it is also difficult to achieve high flash and high transparency snowflake crystal type frosting effect. With the application of microcrystalline glass, it is urgent to develop a frosting liquid that can frost microcrystalline glass and has stable snowflake crystal type frosting effect. SUMMARY

[0004] The present application aims to solve at least one of the above technical problems in the prior art. To this end, the purpose of the present application is to provide a glass frosting liquid, by compounding specific components and controlling the proportion of nitric acid, so that the glass frosting liquid can stably and uniformly sand the microcrystalline glass, realize the snowflake frosting effect and avoid the phenomenon of sand leakage.

[0005] The second aspect of the present application provides a preparation method of a glass frosting liquid.

[0006] The third aspect of the present application provides a microcrystalline glass.

[0007] The fourth aspect of the present application provides an application of a microcrystalline glass.

[0008] In order to achieve the above purpose, the technical solution adopted by the present application is:

[0009] The first aspect of the present application provides a glass frosting liquid, which comprises the following components: ammonium hydrogen fluoride, sodium chloride, hydrofluoric acid, nitric acid, hydrochloric acid and dispersing agent.

[0010] The mass percentage of nitric acid in the glass frosting liquid is 10-20%.

[0011] Ammonium bifluoride is the main component of the glass frosting solution, which can react with acid to provide hydrofluoric acid, and can also provide the required ammonium ion for complexing with sodium ions and potassium ions, chloride ions, lithium ions and the like in the glass.

[0012] Sodium chloride can promote crystal nucleus growth, and when hydrofluoric acid reacts with glass, the sodium ions of sodium chloride in the solution also participate in the reaction to form sodium fluorosilicate, which adheres to the surface of the glass to form a crystal nucleus and protect the glass from continuous etching.

[0013] Hydrofluoric acid, nitric acid and hydrochloric acid can all provide hydrogen ions, among which hydrofluoric acid is the main acid component for etching glass. The nitrate ions in nitric acid help to regulate the shape of the crystal form, and a snowflake-like frosting effect is obtained. The higher the proportion of nitric acid, but when the proportion of nitric acid is too high, the problem of sand leakage will occur.

[0014] In some embodiments of the present application, the mass percentage of nitric acid in the glass frosting solution is 10-15%.

[0015] In some embodiments of the present application, the mass percentage of nitric acid in the glass frosting solution is 12-15%.

[0016] It should be noted that the mass percentage of nitric acid is based on the mass percentage of nitric acid solution.

[0017] In some embodiments of the present application, the mass ratio of sodium chloride to nitric acid is 1:(1-2).

[0018] By further controlling the mass ratio of sodium chloride to nitric acid, the transmittance of the microcrystalline glass after frosting with the glass frosting solution can be regulated, and the frosting effect can be further improved. Among them, nitric acid is added in the form of nitric acid solution, and the mass ratio here is the mass ratio of sodium chloride to nitric acid solution, and the purity of sodium chloride is 99%.

[0019] In some embodiments of the present application, the mass percentage of sodium chloride in the glass frosting solution is 8-20%.

[0020] In some embodiments of the present application, the mass percentage of sodium chloride in the glass frosting solution is 15-20%.

[0021] In some specific embodiments of the present application, the mass percentage of sodium chloride in the glass frosting solution is 18-20%.

[0022] In some embodiments of the present application, the dispersing agent includes polyvinyl chloride powder and barium sulfate.

[0023] In some embodiments of the present application, the dispersing agent includes polyvinyl chloride powder.

[0024] The polyvinyl chloride plays a role of dispersion and suspension in the glass frosting liquid. Compared with the traditional barium sulfate, the polyvinyl chloride has better suspension, and the frosting liquid prepared by the polyvinyl chloride is more uniform, and the process yield is more stable.

[0025] In some embodiments of the present application, the polyvinyl chloride powder has a mesh number of 50-150.

[0026] In some embodiments of the present application, the polyvinyl chloride powder has a mesh number of 50-150.

[0027] In some embodiments of the present application, the polyvinyl chloride powder has a mesh number of 50-150.

[0028] The mesh number of the polyvinyl chloride powder is controlled to further improve the dispersion and suspension effect and improve the frosting uniformity of the frosting liquid.

[0029] In some embodiments of the present application, the mass concentration of the hydrofluoric acid is 40-60%.

[0030] In some embodiments of the present application, the mass concentration of the hydrofluoric acid is 40-60%.

[0031] In some embodiments of the present application, the mass concentration of the hydrofluoric acid is 40-60%.

[0032] In some embodiments of the present application, the mass concentration of the nitric acid is 55-75%.

[0033] In some embodiments of the present application, the mass concentration of the nitric acid is 55-75%.

[0034] In some embodiments of the present application, the mass concentration of the nitric acid is 55-75%.

[0035] In some embodiments of the present application, the mass concentration of the hydrochloric acid is 25-45%.

[0036] In some embodiments of the present application, the mass concentration of the hydrochloric acid is 25-45%.

[0037] In some embodiments of the present application, the mass concentration of the hydrochloric acid is 25-45%.

[0038] The concentration of the acid solution affects the roughness of the glass after frosting.

[0039] In some embodiments of the present application, the glass frosting liquid comprises the following components in percentage by mass:

[0040] Ammonium bifluoride 30-45%, sodium chloride 8-20%, hydrofluoric acid 4-8%, nitric acid 10-20%, hydrochloric acid 15-30%, dispersing agent 3-8%.

[0041] In some embodiments of the present application, the glass frosting liquid comprises the following components in percentage by mass:

[0042] Ammonium bifluoride 30-40%, sodium chloride 15-20%, hydrofluoric acid 5-7%, nitric acid 10-15%, hydrochloric acid 20-30%, dispersing agent 3-6%.

[0043] In some specific embodiments of the present application, the glass frosting liquid comprises the following components in percentage by mass:

[0044] Ammonium bifluoride 35-40%, sodium chloride 18-20%, hydrofluoric acid 6-7%, nitric acid 10-15%, hydrochloric acid 20-28%, dispersing agent 3-4%.

[0045] In some embodiments of the present application, the glass frosting liquid comprises the following components in percentage by mass:

[0046] Ammonium bifluoride 35-40%, sodium chloride 18-20%, hydrofluoric acid 6-7%, nitric acid 12-15%, hydrochloric acid 20-28%, dispersing agent 3-4%.

[0047] The second aspect of the present application provides a preparation method of the glass frosting liquid of the first aspect of the present application, comprising the following steps:

[0048] Mixing and maturing the components under heating to obtain the glass frosting liquid.

[0049] In some embodiments of the present application, the heating temperature is 45-60°C.

[0050] In some embodiments of the present application, the mixing is stirring mixing, and the stirring speed is 700-900 r / min.

[0051] In some embodiments of the present application, the maturing time is 48-60 h.

[0052] The third aspect of the present application provides a microcrystalline glass, which is obtained by frosting the glass frosting liquid of the first aspect of the present application.

[0053] In some embodiments of the present application, the temperature of the glass frosting liquid during the frosting of the microcrystalline glass is 15-25°C.

[0054] In some embodiments of the present application, the treatment time of the glass frosting liquid on the microcrystalline glass is 120-180 s.

[0055] The fourth aspect of the present application provides application of the microcrystalline glass of the third aspect of the present application in preparation of a mobile phone back cover or a mobile phone cover plate.

[0056] Compared with the prior art, the present application has the following beneficial effects:

[0057] (1) The glass frosting liquid of the present application is simple to use and stable in frosting, and can obtain a high-shine high-transparency snowflake-like frosting effect. The sodium chloride and nitric acid contained therein can promote crystal nucleus growth and control crystal form, stably and uniformly frosted on the microcrystalline glass, and no sand leakage phenomenon occurs, solving the problem that ordinary glass frosting liquid cannot stably frosted on microcrystalline glass, or easily appears uneven sanding, resulting in too low yield and cannot stably produce.

[0058] (2) The microcrystalline glass obtained after frosting of the glass frosting liquid of the present application has improved surface roughness and haze, while the transmittance is controlled, so that the frosted microcrystalline glass surface presents a shiny effect, which can be applied to the mobile phone cover plate industry to make a beautiful mobile phone back cover with frosting effect. BRIEF DESCRIPTION OF DRAWINGS

[0059] Figure 1 The crystal form diagram of the microcrystalline glass frosted by the glass frosting liquid obtained in Example 1 of the present application. DETAILED DESCRIPTION

[0060] The content of the present application will be further described in detail through specific examples. The raw materials, reagents or devices used in the examples and comparative examples are commercially available or can be obtained by existing technical methods unless otherwise specified. Unless otherwise specified, the test or test method is a conventional method in the art.

[0061] Some raw materials in the following examples and comparative examples of the present application are described as follows:

[0062] Hydrofluoric acid is an aqueous solution with a mass concentration of 50%;

[0063] Nitric acid is an aqueous solution with a mass concentration of 68%;

[0064] Hydrochloric acid is an aqueous solution with a mass concentration of 36%;

[0065] Ammonium bifluoride and sodium chloride are both solid with a purity of 99%;

[0066] Polyvinyl chloride powder: Shanghai Jinshu Yushu Plastic Raw Material Co., Ltd., mesh size 100 mesh.

[0067] Example 1

[0068] The present embodiment provides a glass frosting liquid, which comprises the following components by mass fraction:

[0069] Ammonium bifluoride 38 parts,

[0070] Sodium chloride 20 parts,

[0071] Polyvinyl chloride powder 3 parts,

[0072] Hydrofluoric acid 6 parts,

[0073] Nitric acid 12 parts,

[0074] Hydrochloric acid 21 parts.

[0075] The preparation method of the glass frosting liquid of the present embodiment can refer to the following steps:

[0076] The production of the glass frosting liquid is prepared by mixing powder with liquid and curing: the raw materials are put into the stirring tank according to the proportion, after all the raw materials are added, the stirrer is started to continuously stir, the stirring speed is 750 r / min, the curing heating temperature is set to 50℃, and the curing time is 48h; after curing, the glass frosting liquid is taken from the bottom while stirring and is packed as 25kg per barrel.

[0077] The stirring tank used in the production of the glass frosting liquid is a 1000L capacity round stirring tank, the bottom of the stirring tank is funnel-shaped, provided with a liquid outlet valve, and the material of the stirring tank is polytetrafluoroethylene; the stirrer is made of stainless steel 304, and the stirrer is wrapped with polytetrafluoroethylene to prevent the glass frosting liquid from directly contacting with stainless steel; the stirring fan blade is a high-speed dispersion disc; the heating mode of the stirring tank is coil circulation heating.

[0078] Example 2

[0079] The present embodiment provides a kind of glass frosting liquid, by mass fraction, including the following components:

[0080] Ammonium hydrogen fluoride 35 parts,

[0081] Sodium chloride 18 parts,

[0082] Polyvinyl chloride powder 3 parts,

[0083] Hydrofluoric acid 6 parts,

[0084] Nitric acid 12 parts,

[0085] Hydrochloric acid 26 parts.

[0086] The preparation method of the glass frosting liquid of the present embodiment is same as example 1.

[0087] Example 3

[0088] The present embodiment provides a kind of glass frosting liquid, by mass fraction, including the following components:

[0089] Ammonium hydrogen fluoride 35 parts,

[0090] Sodium chloride 18 parts,

[0091] Polyvinyl chloride powder 3 parts,

[0092] Hydrofluoric acid 6 parts,

[0093] Nitric acid 15 parts,

[0094] Hydrochloric acid 23 parts.

[0095] The preparation method of the glass frosting liquid of this example is the same as that of Example 1.

[0096] Example 4

[0097] This example provides a glass frosting liquid, which comprises the following components in parts by mass:

[0098] Ammonium hydrogen fluoride 35 parts,

[0099] Sodium chloride 18 parts,

[0100] Polyvinyl chloride powder 3 parts,

[0101] Hydrofluoric acid 6 parts,

[0102] Nitric acid 10 parts,

[0103] Hydrochloric acid 28 parts.

[0104] The preparation method of the glass frosting liquid of this example is the same as that of Example 1.

[0105] Example 5

[0106] This example provides a glass frosting liquid, which comprises the following components in parts by mass: Ammonium hydrogen fluoride 38 parts, Sodium chloride 20 parts,

[0107] Barium sulfate (mesh 3000) 3 parts,

[0108] Hydrofluoric acid 6 parts,

[0109] Nitric acid 12 parts,

[0110] Hydrochloric acid 21 parts.

[0111] The preparation method of the glass frosting liquid of this example is the same as that of Example 1.

[0112] Comparative Example 1

[0113] This comparative example provides a glass frosting liquid, which comprises the following components in parts by mass: Ammonium hydrogen fluoride 35 parts,

[0114] Sodium chloride 18 parts,

[0115] Polyvinyl chloride powder 3 parts,

[0116] hydrofluoric acid 6 parts,

[0117] nitric acid 30 parts,

[0118] hydrochloric acid 8 parts.

[0119] The glass frosting solution of the present comparative example was prepared in the same manner as in Example 1.

[0120] Comparative Example 2

[0121] The present comparative example provides a glass frosting solution comprising the following components by mass parts: ammonium hydrogen fluoride 35 parts,

[0122] sodium chloride 18 parts,

[0123] polyvinyl chloride powder 3 parts,

[0124] hydrofluoric acid 6 parts,

[0125] hydrochloric acid 38 parts.

[0126] The glass frosting solution of the present comparative example was prepared in the same manner as in Example 1.

[0127] Comparative Example 3

[0128] The present comparative example provides a glass frosting solution comprising the following components by mass parts: ammonium hydrogen fluoride 53 parts,

[0129] polyvinyl chloride powder 3 parts,

[0130] hydrofluoric acid 6 parts,

[0131] nitric acid 12 parts,

[0132] hydrochloric acid 26 parts.

[0133] The glass frosting solution of the present comparative example was prepared in the same manner as in Example 1.

[0134] Test Example

[0135] The glass frosting solutions obtained in the above examples and comparative examples were used to frosted microcrystalline glass, respectively, in the following steps:

[0136] 1. Loading: one side of the glass was fastened by suction using a suction disc after spraying a protective oil;

[0137] 2. Pretreatment: the pretreatment temperature was 30°C, and the glass to be frosted was soaked in a pretreatment tank for 120s;

[0138] 3. Pure water rinsing: the pure water rinsing temperature was 18°C, and the glass after pretreatment was washed in a pure water tank by swinging up and down or left and right for 120s;

[0139] 4. The glass frosting liquid medicine water temperature is 18℃, the microcrystalline glass to be frosted is vertically entered into the glass frosting liquid medicine water at a speed of 1000mm / s, and is circularly swung at a speed of 800mm / s for about 120s, and then taken out after the swinging is completed;

[0140] 5. The frosted product is soaked into the cleaning liquid for 2min for cleaning, and the frosting is completed.

[0141] Result detection

[0142] The roughness is tested by using a Japanese Sanfeng measuring instrument SJ210 handheld tester 178-560-11DC;

[0143] The haze and transmittance data are tested by using a WGT-S transmittance haze tester. The higher the transmittance is, the more transparent the frosted glass is, and the more the color texture of the film itself appears; when the transmittance decreases, the frosted glass for the film color presents distortion, and the snowflake-like frosting effect of high flash and high transmittance is reduced.

[0144] The performance test results of the frosted microcrystalline glass after the glass frosting liquid of the above examples and comparative examples are shown in Table 1.

[0145] Table 1. Performance test data of the frosted microcrystalline glass after the glass frosting liquid of the examples and comparative examples

[0146] Roughness / μm Haze / % Transmittance / % Remarks Example 1 2.5 54.1 45.6 - Example 2 3.0 53.2 46.1 Total proportion of acid solution increased, roughness increased Example 3 2.8 48.3 51.2 Proportion of nitric acid increased, transmittance increased Example 4 3.1 56.2 43.5 Proportion of nitric acid decreased, transmittance decreased Example 5 2.5 54.3 45.4 Frit after frosting, frit arc edge position sand leakage Comparative Example 1 - - - Sand leakage Comparative Example 2 3.2 77.1 22.3 Light sand leakage, frosting crystal shape is quadrilateral pyramid Comparative Example 3 - - - No sanding

[0147] It should be noted that the frosting is that part of the glass area does not form a granular frosting effect, and is relatively flat and has no granular feeling.

[0148] From Table 1, it can be seen that the glass frosting liquid obtained by the application can stably sand the microcrystalline glass, the roughness of the frosted microcrystalline glass is not less than 2.5μm, the haze is not less than 48%, and the transmittance is between 40-55%, which improves the frosting effect while ensuring the transmittance of the glass. In Examples 3 and 4, when the proportion of nitric acid changes while the total proportion of the acid solution remains unchanged compared with Example 2, the roughness, haze and transmittance of the frosted microcrystalline glass all change, that is, the frosting effect changes; in Comparative Example 1, the amount of nitric acid is high, and the frosting phenomenon occurs; in Comparative Example 2, no nitric acid is added, and the frosting phenomenon also occurs, and the crystal type after frosting cannot be controlled, and the frosting effect of the four-edge conical crystal type has low transmittance, generally below 30%, and in Comparative Example 2, it is only 22.3%, the transmittance is low, and when used as a mobile phone back cover or cover plate, the original color of the film attached to the mobile phone cover plate cannot be presented, and the color of the film will be distorted; in Comparative Example 3, no sodium chloride is added, and the microcrystalline glass cannot be sanded.

[0149] Figure 1The crystal pattern of the glass frosting liquid obtained in Embodiment 1 on the frosted glass-ceramics is obtained by a mirror microscope, and it can be seen from the figure that the crystal pattern of the glass-ceramics frosted by the glass frosting liquid obtained in the application is snowflake-shaped, has excellent frosting effect, and can provide a beautiful appearance for the glass-ceramics.

[0150] In summary, the glass frosting liquid obtained in the application contains sodium chloride and nitric acid, can promote crystal nucleus growth and control crystal pattern, stably and uniformly frosts the glass-ceramics, improves the roughness and haze of the glass-ceramics surface after frosting, controls the transmittance, can make the glass-ceramics surface after frosting present a sparkling effect, and will not appear the frosting leakage phenomenon. Therefore, the glass-ceramics frosted by the glass frosting liquid of the application can be applied to the mobile phone cover industry, and a beautiful mobile phone back cover with frosting effect can be made.

[0151] The above embodiment is a preferred embodiment of the application, but the embodiment of the application is not limited by the above embodiment, and any change, modification, substitution, combination, simplification made without departing from the spirit and principle of the application should be an equivalent replacement mode, and all are included in the protection scope of the application.

Claims

1. A glass frosting liquid, characterized by, According to the mass percentage, the components include: Ammonium bifluoride 30~45%, sodium chloride 8~20%, hydrofluoric acid 4~8%, nitric acid 10~20%, hydrochloric acid 15~30%, dispersant 3~8%; The dispersant includes polyvinyl chloride powder; The mass concentration of the nitric acid is 55~75%.

2. The glass frosting solution of claim 1, wherein The mass ratio of the sodium chloride to the nitric acid is 1: (1~2).

3. The glass frosting solution of claim 1, wherein The mesh number of the polyvinyl chloride powder is 50~150.

4. The glass frosting solution of claim 1, wherein The mass concentration of the hydrofluoric acid is 45~55%; And / or, the mass concentration of the hydrochloric acid is 30~40%.

5. A method of preparing the glass frosting solution according to any one of claims 1 to 4, characterized in that, The steps include: Mixing and aging the components under heating to obtain a glass frosting liquid.

6. A microcrystalline glass characterized by, The microcrystalline glass is frosted by the glass frosting liquid according to any one of claims 1~4.

7. The glass-ceramic according to claim 6, characterized in that, During the frosting of the microcrystalline glass, the temperature of the glass frosting liquid is 15~25℃; And / or, the treatment time of the glass frosting liquid on the microcrystalline glass is 120~180s.

8. Use of the microcrystalline glass according to claim 6 or 7 in the preparation of a mobile phone back cover or a mobile phone cover plate.

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