CN111233339B - Glass etching solution, high-alumina-silica glass etching method and high-alumina-silica glass with texture on surface - Google Patents
Glass etching solution, high-alumina-silica glass etching method and high-alumina-silica glass with texture on surface Download PDFInfo
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- CN111233339B CN111233339B CN202010203992.3A CN202010203992A CN111233339B CN 111233339 B CN111233339 B CN 111233339B CN 202010203992 A CN202010203992 A CN 202010203992A CN 111233339 B CN111233339 B CN 111233339B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
- H04M1/026—Details of the structure or mounting of specific components
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Abstract
The invention belongs to the technical field of glass chemical etching, and particularly relates to a glass etching solution, a high-alumina-silica glass etching method and high-alumina-silica glass with texture on the surface. The glass etching solution comprises the following raw materials in percentage by mass: 5-15wt% of ammonium fluoride, 10-22wt% of ammonium bifluoride, 8-18wt% of potassium bifluoride, 5-15wt% of hydrochloric acid, 15-30wt% of nitric acid, 3-8 wt% of potassium chloride, 1.5-6 wt% of copper sulfate, NaNO3 3‑8wt％、NaH2PO4 3‑8wt％、FeCL32-5wt% and H210-30wt% of O; the glass etching solution can be used for etching high-alumina-silica glass to form snowflake-like concave-convex textures on the surface of the high-alumina-silica glass.
Description
Technical Field
The invention belongs to the technical field of glass chemical etching, and particularly relates to a glass etching solution, a high-alumina-silica glass etching method and high-alumina-silica glass with texture on the surface.
Background
With the coming of the 5G information era, in order to prevent the shielding and shielding of smart phone signals, the material of the mobile phone rear cover is selected and mainly concentrated on the aspects of glass and ceramics, high-alumina-silica glass is popularized and applied in the field of mobile phone 3D glass rear covers by virtue of the characteristics of high strength and high chemical stability, and if the 3D glass shell of the electronic equipment such as a mobile phone is provided with snowflakes or other patterns loved by consumers, the decoration grade and connotation of the mobile phone rear cover and other electronic equipment are greatly enriched, and the mobile phone rear cover is more easily favored by consumers.
At present, the snowflake effect is realized only on the surface of the common soda-lime glass by using an acid etching technology in China, the glass is widely applied to the fields of furniture decoration, business space partition and the like, no precedent for realizing the snowflake effect on the surface of high-alumina-silica glass exists, the requirement of a mobile phone glass rear cover for the snowflake effect decoration is severely restricted, and the requirement of mobile phone manufacturers for new products cannot be met. If the formula of the etching solution with the snowflake effect for the soda-lime glass is adopted to etch the high-alumina-silica glass, the defects of uneven snowflake effect etching, too small snowflake particles, uneven snowflake sizes, missing frosting and the like can be caused, and the application prospect of the snowflake effect product for the high-alumina-silica glass is severely restricted.
Disclosure of Invention
The invention provides a glass etching solution which can be used for etching high-alumina-silicon glass and solves the technical problems that the etching solution in the prior art has poor etching effect on the high-alumina-silicon glass and the decorative pattern on the surface of the high-alumina-silicon glass cannot meet the requirement of attractive appearance.
The second purpose of the invention is to provide an etching method of high alumina silica glass.
A third object of the present invention is to provide a high aluminosilicate glass having a texture on the surface.
The invention also aims to provide the application of the high-alumina-silica glass with the textured surface.
The glass etching solution adopts the following technical scheme: the glass etching solution comprises the following raw materials in percentage by mass: 5-15wt% of ammonium fluoride, 10-22wt% of ammonium bifluoride, 8-18wt% of potassium bifluoride, 5-15wt% of hydrochloric acid, 15-30wt% of nitric acid, 3-8 wt% of potassium chloride, 1.5-6 wt% of copper sulfate, NaNO3 3-8wt％、NaH2PO4 3-8wt％、FeCL32-5wt% and H2O10-30 wt%; the glass etching solution can be used for etching high-alumina-silica glass.
Preferably, after the high-alumina-silica glass is etched by using the etching solution, the surface of the glass has concave-convex textures.
Preferably, the uneven texture is uniformly distributed and has a snowflake-like shape.
The etching method of the high-alumina-silica glass adopts the following technical scheme: a method for etching high alumina silicate glass, which comprises etching with the etching solution for high alumina silicate glass as defined in any one of the above.
Preferably, the method comprises the following steps: (1) protecting the surface of the high-alumina-silica glass which does not need to be etched; (2) cleaning the surface of the high-alumina-silica glass to be etched with deionized water; (3) immersing the high-alumina-silica glass treated in the steps (1) and (2) into the etching solution for etching; the etching temperature in the step (3) is 20-25 ℃.
Preferably, the etching time in the step (3) is 10-15 min.
Preferably, the method further comprises the steps of taking the high alumina silica glass out of the etching solution, washing with deionized water and drying.
The high-alumina-silica glass with the texture on the surface adopts the following technical scheme: the high alumina-silica glass with the texture on the surface is obtained by the etching method of the high alumina-silica glass.
Preferably, the high-alumina-silica glass has the light transmittance of 55-65%, the glossiness of 60-65%, the haze of 35-38%, the roughness of 2.5-3.2% and the reflectivity of 6.8-7.5%.
The application of the high-alumina-silica glass with the texture on the surface adopts the following technical scheme: use of a high alumina silica glass having a textured surface as defined in any one of the preceding claims in the manufacture of a housing for an electronic device.
The invention has the beneficial effects that: the glass etching solution can etch high-alumina-silicon glass and can prepare high-alumina-silicon glass products with textures on the surfaces. The invention optimizes the components and content of the formula of the high-alumina-silicon glass etching solution, and selects NH4F、NH4HF2、KHF2、HCL、HNO3、KCL、CuSO4、NaNO3、NaH2PO4、FeCL3The combination of the components optimizes the proportion of the raw materials, and the soaking type acid etching technology is adopted, so that the growth, enlargement and connection of snowflake crystal forms on the surface of the high-alumina-silicon glass can be realized, and the purposes of uniform snowflake effect and uniform snowflake crystal form size on the surface of the high-alumina-silicon glass are realized.
After the high-alumina-silica glass is etched by the glass etching solution, the obtained pattern with a snowflake-like effect is exquisite (better in ornamental value compared with the snowflake-effect glass in the prior art), can meet the requirements of the field of electronic products such as smart phones and the like on appearance, and has good photoelectric property.
The etching method of the high-alumina-silica glass has the advantages of simple and practical process, easy operation and low cost.
The high-alumina-silica glass with the texture on the surface has good decorative performance, and can meet the specific technical index of the electronic equipment field for the snow covering effect of the high-alumina-silica 3D glass.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram illustrating the effect of frosting ordinary glass (soda-lime glass) in the prior art;
FIG. 2 is a diagram showing the effect of etching surfaces obtained by etching high alumina silica glass using the glass etching solution of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation (wt%) of the special etching solution for the high-aluminum-silicon glass snowflake effect is carried out according to the following proportion: NH (NH)4F 10.8％、NH4HF2 21.5％、KHF2 11.6％、HCL 5.8％、HNO3 23.5％、KCL 3.8％、CuSO4 1.7％、NaNO33.5％、NaH2PO4 3.8％、FeCL3 2.2％、H2And O11.8 percent, fully and uniformly stirring until the liquid medicine is in a transparent state of complete dissolution, thus obtaining the glass etching solution.
And secondly, covering and protecting the surface (the tin surface) of the high-alumina silicon glass original sheet which does not need to be etched with a sticky protective film.
And thirdly, cleaning the surface of the high-alumina-silica glass raw sheet to be etched with deionized water, and soaking and etching the high-alumina-silica glass raw sheet in an etching solution in a wet state.
And fourthly, controlling the temperature of the etching solution to be 20-25 ℃. The etching time is controlled to be 10-15 minutes.
And fifthly, taking out the etched glass from the etching solution in time after the etching time requirement is met, cleaning the etched glass with deionized water, and drying the glass to obtain the high-alumina-silica glass with the texture on the surface.
Example 2
The preparation method comprises the following steps of preparing the glass etching solution according to the following proportion (wt%): NH (NH)4F 13.6％、NH4HF2 16.5％、KHF215.8％、HCL 7.6％、HNO3 20.5％、KCL 4.6％、CuSO4 2.8％、NaNO3 8％、NaH2PO4 3.0％、FeCL3 2.7％、H2O10.4 percent, fully and uniformly stirring until the liquid medicine is in a transparent state of complete dissolution, thus obtaining the special etching liquid for the high-aluminum-silicon glass snowflake effect.
And secondly, covering and protecting the surface (the tin surface) of the high-alumina silicon glass original sheet which does not need to be etched with a sticky protective film.
And thirdly, cleaning the surface of the high-alumina-silica glass raw sheet to be etched with deionized water, and soaking and etching the high-alumina-silica glass raw sheet in an etching solution in a wet state.
And fourthly, controlling the temperature of the etching solution to be 20-25 ℃. The etching time is controlled to be 10-15 minutes.
And fifthly, taking out the etched glass from the etching solution in time after the etching time requirement is met, cleaning the etched glass with deionized water, and drying the glass to obtain the high-alumina-silica glass with the texture on the surface.
Example 3
The preparation (wt%) of the special etching solution for the high-aluminum-silicon glass snowflake effect is carried out according to the following proportion: NH (NH)4F 15％、NH4HF210％、KHF2 8％、HCL 15％、HNO3 15％、KCL 5％、CuSO4 6％、NaNO3 8％、NaH2PO43％、FeCL3 5％、H2O10 percent, fully and uniformly stirring until the liquid medicine is in a transparent state of complete dissolution, thus obtaining the special etching liquid with high aluminum-silicon glass snowflake effect.
And secondly, covering and protecting the surface (tin surface) of the high-alumina-silica glass which does not need to be etched with a sticky protective film.
And thirdly, cleaning the surface of the high-alumina-silica glass raw sheet to be etched with deionized water, and soaking and etching the high-alumina-silica glass raw sheet in an etching solution in a wet state.
And fourthly, controlling the temperature of the etching solution to be 20-25 ℃. The etching time is controlled to be 10-15 minutes.
And fifthly, taking out the etched glass from the etching solution in time after the etching time requirement is met, cleaning the etched glass with deionized water, and drying the glass to obtain the high-alumina-silica glass product with the texture on the surface.
Example 4
The preparation method comprises the following steps of preparing the glass etching solution according to the following proportion (wt%): NH (NH)4F 5％、NH4HF2 11％、KHF218％、HCL 10％、HNO3 16％、KCL 8％、CuSO4 3％、NaNO3 3％、NaH2PO4 8％、FeCL3 3％、H2O15 percent, fully and uniformly stirring until the liquid medicine is in a transparent state of complete dissolution, thus obtaining the special etching liquid with high aluminum-silicon glass snowflake effect.
And secondly, covering and protecting the surface (the tin surface) of the high-alumina silicon glass original sheet which does not need to be etched with a sticky protective film.
And thirdly, cleaning the surface of the high-alumina-silica glass raw sheet to be etched with deionized water, and soaking and etching the high-alumina-silica glass raw sheet in an etching solution in a wet state.
And fourthly, controlling the temperature of the etching solution to be 20-25 ℃. The etching time is controlled to be 10-15 minutes.
And fifthly, taking out the etched glass from the etching solution in time after the etching time requirement is met, cleaning the etched glass with deionized water, and drying the glass to obtain the high-alumina-silica glass product with the texture on the surface.
Example 5
The preparation method comprises the following steps of preparing the glass etching solution according to the following proportion (wt%): NH (NH)4F 5.5％、NH4HF2 10％、KHF28％、HCL 5％、HNO3 30％、KCL 3.9％、CuSO4 1.5％、NaNO3 3.1％、NaH2PO4 3.5％、FeCL32％、H2O27.5 percent, fully and uniformly stirring until the liquid medicine is in a transparent state of complete dissolution, thus obtaining the special etching liquid for the high-aluminum-silicon glass snowflake effect.
And secondly, covering and protecting the surface (the tin surface) of the high-alumina silicon glass original sheet which does not need to be etched with a sticky protective film.
And thirdly, cleaning the surface of the high-alumina-silica glass raw sheet to be etched with deionized water, and soaking and etching the high-alumina-silica glass raw sheet in an etching solution in a wet state.
And fourthly, controlling the temperature of the etching solution to be 20-25 ℃. The etching time is controlled to be 10-15 minutes.
And fifthly, taking out the etched glass from the etching solution in time after the etching time requirement is met, cleaning the etched glass with deionized water, and drying the glass to obtain the high-alumina-silica glass product with the texture on the surface.
Example 6 the high alumina-silica glass master and the high alumina-silica glass with a textured surface prepared in examples 1-5 were tested for gloss, light transmittance, haze, roughness and reflectance and the results are shown in table 1 below:
TABLE 1
| Sample (I) | Gloss (%) | Light transmittance (%) | Haze (%) | Roughness (μm) | Reflectance (%) |
| High alumina silica glassOriginal sheet | 110.8 | 95.6 | 0.08 | 0 | 8.8 |
| Example 1 | 63.8 | 60.3 | 36.2 | 2.8 | 7.3 |
| Example 2 | 64.5 | 59.8 | 35.5 | 3.0 | 7.0 |
| Example 3 | 63.9 | 60.0 | 35.8 | 2.8 | 7.2 |
| Example 4 | 64.8 | 59.9 | 35.5 | 2.9 | 7.2 |
| Example 5 | 64.1 | 60.5 | 36.1 | 2.9 | 7.1 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The glass etching solution is characterized by comprising the following raw materials in percentage by mass: 5-15wt% of ammonium fluoride, 10-22wt% of ammonium bifluoride, 8-18wt% of potassium bifluoride, 5-15wt% of hydrochloric acid, 15-30wt% of nitric acid, 3-8 wt% of potassium chloride, 1.5-6 wt% of copper sulfate, NaNO3 3-8wt%、NaH2PO4 3-8 wt%、FeCl32-5wt% and H210-30wt% of O; the glass etching solution can be used for etching high-alumina-silica glass.
2. The glass etching solution according to claim 1, wherein after the high alumina silica glass is etched by using the etching solution, the surface of the glass has a concave-convex texture.
3. The glass etching solution of claim 2, wherein the uneven texture is uniformly distributed and has a snowflake-like shape.
4. A method for etching a high alumina silicate glass, characterized in that the etching is carried out using the high alumina silicate glass etching solution according to any one of claims 1 to 3.
5. The etching method according to claim 4, comprising the steps of: (1) protecting the surface of the high-alumina-silica glass which does not need to be etched; (2) cleaning the surface of the high-alumina-silica glass to be etched with deionized water; (3) immersing the high-alumina-silica glass treated in the steps (1) and (2) into the etching solution for etching; the etching temperature in the step (3) is 20-25 ℃.
6. The etching method according to claim 5, wherein the etching time in the step (3) is 10-15 min.
7. The etching method according to claim 5, further comprising a step of removing the high alumina silica glass from the etching solution, washing with deionized water, and drying.
8. A high aluminosilicate glass having a texture on the surface, characterized in that the high aluminosilicate glass having a texture on the surface is obtained by the etching method of the high aluminosilicate glass according to any one of claims 4 to 7.
9. The high aluminosilicate glass having a textured surface according to claim 8, wherein the high aluminosilicate glass has a light transmittance of 55 to 65%, a gloss of 60 to 65%, a haze of 35 to 38%, a roughness of 2.5 to 3.2 μm, and a reflectance of 6.8 to 7.5%.
10. Use of a high alumina silica glass with a textured surface according to claim 8 or 9 for the manufacture of a housing for an electronic device.
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| WO2022051281A1 (en) | 2020-09-04 | 2022-03-10 | Corning Incorporated | Textured glass articles and methods of making same |
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| CN104724936A (en) * | 2013-12-23 | 2015-06-24 | 黄淼 | Decorative glass making technology |
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