阅读说明：本技术 一种用于玻璃渐变蒙砂的蚀刻液及其制备方法和应用 (Etching solution for glass gradual-change frosting and preparation method and application thereof ) 是由 杨国威 马兰 于 2019-11-28 设计创作，主要内容包括：本发明提供了一种用于玻璃渐变蒙砂的蚀刻液,包括如下质量百分含量的各组分：氟化氢铵：20％～25％；有机酸：2％～5％；氟硅酸：1％～2％；分散剂：0.1％～0.5％；表面活性剂：0.001％～0.005％；余量为水；其中,所述蚀刻液中不含固体颗粒。所述蚀刻液的配方简单、成分安全、稳定性高,酸度合适,不含固体颗粒,适合在玻璃上形成雾度渐变的渐变蒙砂效果。本发明还提供了用于玻璃渐变蒙砂的蚀刻液的制备方法,以及渐变蒙砂玻璃的生产方法。(The invention provides an etching solution for glass gradual-change frosting, which comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; wherein the etching solution does not contain solid particles. The etching solution has the advantages of simple formula, safe components, high stability, proper acidity and no solid particles, and is suitable for forming the haze-gradient gradual-change frosting effect on glass. The invention also provides a preparation method of the etching solution for glass gradual change frosting and a production method of the gradual change frosting glass.)

1. The etching solution for glass gradual-change frosting is characterized by comprising the following components in percentage by mass:

ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; wherein the etching solution does not contain solid particles.

2. The etching solution for glass graded frosting as claimed in claim 1, wherein said organic acid is selected from one or more of citric acid, oxalic acid, sulfamic acid, sorbic acid, tartaric acid and maleic acid.

3. The etching solution for glass graded frosting according to claim 2, wherein the organic acid is citric acid.

4. The etching solution for glass graded frosting according to claim 1, wherein the dispersant is selected from one or more of sodium gluconate, glucose, guar gum and gum arabic; the surfactant is a water-soluble anionic surfactant.

5. The etching solution for glass graded frosting according to claim 4, wherein the etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; citric acid: 2% -5%; fluosilicic acid: 1% -2%; sodium gluconate: 0.1 to 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 to 0.005 percent; water: 68 to 75 percent.

6. The etching solution for glass graded frosting as claimed in any one of claims 1 to 5, wherein the fluorine ion content of the etching solution is in the range of 8 to 12 mol/L.

7. The preparation method of the etching solution for glass gradual-change frosting is characterized by comprising the following steps of:

dissolving ammonium bifluoride and organic acid in water, uniformly mixing, adding fluosilicic acid, a dispersing agent and a surfactant, and uniformly stirring to obtain an etching solution for glass gradual-change frosting;

the etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; the etching solution does not contain solid particles.

8. The method according to claim 7, wherein the water is hot water heated to 40 to 80 ℃ when dissolving the ammonium bifluoride and the organic acid in the water.

9. The production method of the gradually-changed frosted glass is characterized by comprising the following steps:

providing an etching solution according to any one of claims 1 to 6;

and immersing one end of the glass to be processed into the etching solution, gradually immersing the rest glass to be frosted into the etching solution, and taking out the processed glass after reaction to obtain the gradually-changed frosted glass.

10. The production method according to claim 9, wherein the reaction time of the glass to be processed with the etching solution is 1 to 3 min.

Technical Field

The invention relates to the technical field of glass processing, in particular to an etching solution for glass gradual-change frosting and a preparation method and application thereof.

Background

The glass frosting is a process for forming irregular pits on the surface of glass by utilizing the chemical reaction between etching solution and the glass. The frosted glass can form diffuse reflection to light and is often applied to a glass back shell of a high-end mobile phone. The general frosting etching solution is composed of ammonium bifluoride, potassium fluoride, sodium fluoride, hydrofluoric acid, barium sulfate and fluosilicate, and the processing technology mostly adopts a spraying method or a soaking method. With the diversification of the decoration of the mobile phone glass back shell, the gradual frosting process is becoming the current mainstream trend. The gradual frosting refers to that one end of the glass has high haze, the haze is slowly reduced and transited to the other end, and the other end has low haze or the haze is 0. The main process is to immerse the glass into the etching solution gradually and control the reaction time of the glass and the etching solution to form a gradual change effect.

The etching solution used by the traditional glass frosting contains a large amount of solid particles (such as barium sulfate and the like), when the glass is immersed in the etching solution, the solid particles of the etching solution can generate relative motion with the glass, a large amount of flow marks are generated on the surface of the glass, and the requirements of the glass gradual-change frosting process cannot be met.

Disclosure of Invention

In view of the above, the invention provides an etching solution suitable for glass gradual change frosting, which is clear and transparent, does not contain solid particles, and when the etching solution is applied to a glass gradual change frosting process, a uniform gradual change effect of glass from high haze to low haze can be realized, and no flow mark is generated on the surface of the glass.

Specifically, the invention provides an etching solution for glass gradual-change frosting, which comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; wherein the etching solution does not contain solid particles.

In the etching solution, ammonium bifluoride and fluosilicic acid can react with glass to etch the surface of the glass to form a matte effect; the organic acid can be used as a pH buffering agent to stabilize the acidity of the etching solution, the dispersing agent and the surfactant are favorable for improving the stability of each component in the etching solution, and the obtained etching solution has proper acidity and fluorine content and does not contain solid particles through the synergistic effect of the components with the specific mass percentage (particularly, the ammonium bifluoride content is controlled to be 20-25%), so that the effect of uniform and gradual change of the haze on the surface of the glass can be generated.

Optionally, the etching solution uniformly transitions the haze of the glass from 70-90 to 0-20. Namely, the etching solution can produce a gradual frosting effect on the glass. For example, the haze at one end of the glass is in the range of 70 to 90, the haze at a distance from that end is in the range of 0 to 20, and the haze in the middle section is uniformly transitioning.

In the invention, the content of the ammonium bifluoride is controlled to be in a proper range, and if the content is too high, the ammonium bifluoride is not completely dissolved, solid particles are separated out from the etching solution, and further more flow marks are generated on the surface of the glass. If the ammonium bifluoride content is too low, the frosting effect is not significant. Optionally, in the etching solution, the mass percentage of ammonium bifluoride is 21% to 25%.

In one embodiment of the present invention, the etching solution comprises the following components by mass: ammonium acid fluoride: 21% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; water: 68% -75%; the etching solution does not contain solid particles.

In the invention, the mass ratio of the ammonium bifluoride to the organic acid is (4-12.5): 1. preferably (4-10): 1. more preferably (4-8): 1.

the ammonium bifluoride is very easy to dissolve in water, has high solubility in water, has strong acidity in water solution, can free fluorine ions, and reacts with silicon atoms in a glass structure to form an etching effect.

Optionally, the fluorine ion content of the etching solution is in the range of 8-12 mol/L. Further preferably 10 to 12 mol/L.

Optionally, the pH of the etching solution is 2-3.5. The etching solution has low acidity, the fluorine content is lower than that of the common etching solution, and under the mild regulation of the use amount of each material, the etching solution can be ensured to have no solid particles and can generate uniform gradual frosting effect on glass.

Wherein the organic acid is selected from one or more of citric acid, oxalic acid, sulfamic acid, sorbic acid, tartaric acid and maleic acid. The existence of the organic acid can better stabilize the acidity of the etching solution and ensure that the etching solution can still generate the effect of gradual frosting after being placed for a long time.

Preferably, the organic acid is citric acid. Citric acid is used as a solubilizer and a pH buffer, can promote the dissolution of each component in the solution, and also plays a role in stabilizing the acidity of the etching solution.

Wherein the surfactant is a water-soluble anionic surfactant. Specifically, the surfactant can be one or more selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, anionic polyacrylamide, sodium polyacrylate, carboxymethyl cellulose and sodium carboxymethyl cellulose.

Wherein the dispersant is selected from one or more of sodium gluconate, glucose, guar gum and gum arabic.

In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: ammonium acid fluoride: 20% -25%; citric acid: 2% -5%; fluosilicic acid: 1% -2%; sodium gluconate: 0.1 to 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 to 0.005 percent; water: 68% -75%; wherein the etching solution does not contain solid particles.

In another embodiment of the present invention, the etching solution comprises the following components by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; hydrofluoric acid: 0-2%; the balance of water; wherein the etching solution does not contain solid particles. A small amount of hydrofluoric acid can improve the content of fluorine ions in the etching solution and accelerate the etching rate of the glass.

In the etching solution provided by the first aspect of the present invention, the main components are ammonium bifluoride, organic acid, fluorosilicic acid, dispersant, surfactant and water, and the etching solution does not contain solid particles (such as calcium fluoride, aluminum fluoride, barium sulfate, barium carbonate, kaolin, bentonite, and fluorosilicates (such as sodium fluorosilicate, potassium fluorosilicate, aluminum fluorosilicate) with low solubility at room temperature), and the prepared etching solution is clear and transparent, and does not have solid precipitation even after being placed for a long time. When the etching solution is applied to the glass gradual-change frosting process, the uniform gradual-change effect of the glass from high haze to low haze can be realized, and no flow mark is generated on the surface of the glass.

In a second aspect, the invention provides a preparation method of an etching solution for glass gradual-change frosting, which comprises the following steps:

dissolving ammonium bifluoride and organic acid in water, uniformly mixing, adding fluosilicic acid, a dispersing agent and a surfactant, and uniformly stirring to obtain an etching solution for glass gradual-change frosting;

the etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; wherein the etching solution does not contain solid particles.

Wherein, when the ammonium bifluoride and the organic acid are dissolved in water, the water is hot water heated to 40-80 ℃. Therefore, the dissolution of the dissolved ammonium bifluoride and the organic acid can be accelerated, and the configuration time is saved.

The components of the etching solution are as described in the first aspect of the present invention, and are not described herein again.

The preparation method provided by the second aspect of the invention has a simple process, and the prepared etching solution is clear and transparent, does not contain solid particles, can generate a frosting gradual change effect on the surface of glass, and does not generate bad flow marks.

In a third aspect, the invention provides a method for producing frosted graded glass, which comprises the following steps:

providing an etching solution for glass gradual-change frosting, wherein the etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 20% -25%; organic acid: 2% -5%; fluosilicic acid: 1% -2%; dispersing agent: 0.1 to 0.5 percent; surfactant (b): 0.001 to 0.005 percent; the balance of water; wherein the etching solution does not contain solid particles;

and immersing one end of the glass to be processed into the etching solution, gradually immersing the rest glass to be frosted into the etching solution at a preset speed, and taking out the processed glass after reaction to obtain the frosted gradient glass.

In the invention, the speed of immersing the glass into the etching solution from one end is not fixed, but different speeds can be selected, such as slow speed increasing or fast speed decreasing, and a mode of uniform speed, uniform speed changing or speed changing and uniform speed changing can be adopted.

In one embodiment of the invention, the glass to be processed is uniformly immersed in the etching solution at a speed of 1 to 3 mm/s.

Optionally, the reaction time of the glass to be processed and the etching solution is 1-3 min. The reaction time refers to the contact time of the glass to be processed and the etching solution.

According to the production method of frosting gradual change glass provided by the third aspect of the invention, the specific etching solution is adopted, and the reaction time of different parts of the glass to be processed in contact with the etching solution is different, so that different frosting effects are generated on different parts. And because the difference of the reaction time is relatively uniformly changed, the frosted area of the glass to be processed has uniform gradual change effect.

Advantages of embodiments of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.

Detailed Description

While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise specified, reagents used in the embodiments of the present invention are commercially available.

Example 1

An etching solution for glass gradual-change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 25 percent; citric acid: 3.5 percent; fluosilicic acid: 1 percent; sodium gluconate: 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 percent; water: 69.999 percent; the etching solution does not contain solid particles.

The preparation process of the etching solution is as follows: adding weighed ammonium bifluoride and citric acid into a beaker, adding water of 40 ℃ and fully stirring, adding sodium gluconate, sodium dodecyl benzene sulfonate and fluosilicic acid after complete dissolution, and uniformly stirring for later use.

The application mode of the etching solution is as follows: and taking the cleaned mobile phone rear cover glass, immersing the mobile phone rear cover glass into the etching solution at a constant speed of 2mm/s along a direction vertical to the liquid level of the etching solution, quickly pulling out the glass after the mobile phone rear cover glass is completely immersed, washing away the attached residual liquid by using pure water, and drying to obtain the processed glass. Wherein, the action time of the glass to be processed and the etching solution is 2 min.

In order to highlight the beneficial effects of the invention, the following comparative examples are set:

comparative example 1 (equal amount of hydrochloric acid instead of citric acid in example 1)

The glass etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 25 percent; hydrochloric acid: 3.5 percent; fluosilicic acid: 1 percent; sodium gluconate: 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 percent; water: 69.999 percent; the etching solution does not contain solid particles.

Comparative example 2 (weight percent of ammonium bifluoride different from example 1)

The glass etching solution comprises the following components in percentage by mass: ammonium acid fluoride: 55 percent; citric acid: 3.5 percent; fluosilicic acid: 1 percent; sodium gluconate: 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 percent; water: 39.999 percent. The prepared etching solution contains precipitated ammonium bifluoride particles.

The above comparative examples 1 to 2 were applied to surface processing of a mobile phone rear cover glass in the same manner as in example 1, and then appearance test and haze test were performed on the processed glass. In the haze test, measurement was performed once every 20mm from high haze to low haze using a BYK haze tester, and the measurement was repeated three times at the same position.

The appearance test result of the embodiment 1 of the invention is as follows: the haze is uniform and transitional, and no flow mark exists. While the test results for comparative example 1 were: the frosting effect is not obvious; the test results for comparative example 2 were: more flow marks and uneven frosting.

The haze test result of the embodiment 1 of the invention is as follows: the haze of one side is 89, the haze of the other side is 0.1, and the haze of the middle section is uniformly transitional. While the test results for comparative example 1 were: the haze of one side is 5, the haze of the other side is 0.2, and no obvious frosting effect exists; the test results for comparative example 2 were: the haze on one side was 95 and the haze on the other side was 10, and the high haze region was large.

From the above results, it can be seen that the content of ammonium bifluoride in the etching solution provided by the embodiment of the present invention should be controlled within a suitable range, and if the content is too high (as in comparative example 2), the ammonium bifluoride may not be completely dissolved, solid particles may be precipitated in the etching solution, and further, more flow marks may be generated on the glass surface, and the frosting may not be uniform. If the content of ammonium bifluoride is too low, the fluorine ions in the solution are less, and the frosting effect is not obvious. If an inorganic acid such as hydrochloric acid is used instead of an organic acid such as citric acid in the present invention (as in comparative example 1), the gradual frosting effect cannot be obtained because of the excessive acidity and no buffering effect.

Example 2

An etching solution for glass gradual change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 20 percent; citric acid: 4 percent; fluosilicic acid: 2 percent; guar gum: 0.4 percent; sodium dodecylbenzenesulfonate: 0.002%; the balance of water; wherein the etching solution does not contain solid particles.

The etching solution of the embodiment 2 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 78, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and the surface of the glass has no flow mark.

Example 3

An etching solution for glass gradual change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 21 percent; citric acid: 3 percent; fluosilicic acid: 1.5 percent; sodium gluconate: 0.45 percent; sodium dodecyl sulfate: 0.003%; the balance of water; wherein the etching solution does not contain solid particles.

The etching solution of the embodiment 3 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 80, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and the surface of the glass has no flow mark.

Example 4

An etching solution for glass gradual-change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 25 percent; tartaric acid: 3.5 percent; fluosilicic acid: 1 percent; sodium gluconate: 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 percent; water: 69.999 percent; the etching solution does not contain solid particles.

The etching solution of the embodiment 4 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 81, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and the surface of the glass has no flow mark.

Example 5

An etching solution for glass gradual change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 25 percent; sulfamic acid: 5 percent; fluosilicic acid: 1 percent; sodium gluconate: 0.5 percent; sodium dodecylbenzenesulfonate: 0.001 percent; the balance of water; wherein the etching solution does not contain solid particles.

The etching solution of the embodiment 5 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 82.5, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and no flow mark exists on the surface of the glass.

Example 6

An etching solution for glass gradual change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 23 percent; maleic acid: 2 percent; fluosilicic acid: 2 percent; gum arabic: 0.3 percent; sodium polyacrylate: 0.0015 percent; the balance of water; wherein the etching solution does not contain solid particles.

The etching solution of the embodiment 6 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 81, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and the surface of the glass has no flow mark.

Example 7

An etching solution for glass gradual change frosting comprises the following components in percentage by mass: ammonium acid fluoride: 25 percent; tartaric acid: 5 percent; fluosilicic acid: 1 percent; guar gum: 0.2 percent; sodium carboxymethylcellulose: 0.002%; the balance of water; wherein the etching solution does not contain solid particles.

The etching solution of the embodiment 7 is applied to the surface processing of the mobile phone rear cover glass in the same way as the embodiment 1, the haze of one side of the processed glass is 82, the haze of the other side of the processed glass is 0.1, the haze of the middle section is uniform and transitional, and the surface of the glass has no flow mark.

The foregoing is illustrative of the present invention and it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and are intended to be within the scope of the invention.