CN115246711A

CN115246711A - Glass shell for electronic equipment, preparation method of glass shell and electronic equipment

Info

Publication number: CN115246711A
Application number: CN202110471601.0A
Authority: CN
Inventors: 杨啸; 王红卫
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Priority date: 2021-04-28
Filing date: 2021-04-28
Publication date: 2022-10-28

Abstract

The application provides a preparation method of a glass shell for electronic equipment, which comprises the following steps: carrying out sand blasting, cleaning and acid washing on the surface to be etched of the glass substrate, wherein the acid washing comprises treatment by adopting an acid solution containing hydrofluoric acid; forming a water film which completely covers the surface to be etched on the glass substrate; placing the glass substrate with the water film in a snowflake texture etching solution for etching treatment to form snowflake textures on the surface to be etched, wherein the snowflake textures consist of a plurality of snowflake patterns, and each snowflake pattern comprises a plurality of raised structures; and cleaning and processing the etched glass substrate to obtain the glass shell, wherein the surface of the glass shell is provided with snowflake textures. The preparation method can be used for preparing the glass shell with the snowflake texture, the uniformity of the snowflake texture is good, and the visual effect of the glass shell is improved. The application also provides a glass shell and an electronic device.

Description

Glass shell for electronic equipment, preparation method of glass shell and electronic equipment

Technical Field

The application belongs to the technical field of electronic equipment, and particularly relates to a glass shell for electronic equipment, a preparation method of the glass shell and the electronic equipment.

Background

Glass has the characteristics of high brightness, high transparency and high strength, and is commonly used as a shell of electronic equipment. In recent years, different appearance effects are formed by etching the surface of glass, but the problem of poor etching effect often exists in the process, the visual effect is greatly influenced, and the application of the glass in electronic equipment is restricted.

Disclosure of Invention

In view of this, the application provides a method for manufacturing a glass housing for an electronic device, which can form a snowflake texture on the surface of the glass housing, and the formed snowflake texture has good uniformity, thereby improving the appearance effect of the glass housing and being beneficial to the application thereof.

In a first aspect, the present application provides a method of making a glass housing for an electronic device, comprising:

carrying out sand blasting, cleaning and acid washing on the surface to be etched of the glass substrate, wherein the acid washing comprises treatment by using an acid solution containing hydrofluoric acid;

forming a water film which completely covers the surface to be etched on the glass substrate;

placing the glass substrate with the water film in a snowflake texture etching solution, and forming snowflake textures on the surface to be etched through etching treatment;

the etched glass substrate is cleaned and processed to obtain a glass shell, the surface of the glass shell is provided with the snowflake textures, the snowflake textures are composed of a plurality of snowflake patterns, and each snowflake pattern comprises a plurality of protruding structures.

In a second aspect, the present application provides a glass housing for an electronic device, which is obtained by the manufacturing method of the first aspect.

In a third aspect, the present application provides a glass housing for an electronic device, the surface of the glass housing having a snowflake texture, the snowflake texture consisting of a plurality of snowflake patterns, each of the snowflake patterns comprising a plurality of raised structures, the snowflake patterns having a lateral dimension of from 80 μm to 1.5mm, the raised structures having a lateral dimension of from 0.8 μm to 2 μm, and the raised structures having a height of from 2 μm to 7 μm.

In a fourth aspect, the present application provides an electronic device comprising a display screen and a housing assembly connected to the display screen, the housing assembly comprising the glass housing of the second or third aspect.

The preparation method for the glass shell for the electronic equipment can be used for preparing the glass shell with the snowflake texture, and the uniformity of the formed snowflake texture is good; the glass shell has the appearance of the snowflake textures, so that the glass shell has an anti-glare effect, meanwhile, the snowflake textures can generate a flash effect under different angles, and the visual effect of the glass shell is greatly improved; the electronic equipment with the glass shell improves appearance competitiveness and is high in product expressive force.

Drawings

In order to more clearly explain the technical solution in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.

Fig. 1 is a schematic flow chart of a method for manufacturing a glass housing for an electronic device according to an embodiment of the present disclosure.

Fig. 2 is a schematic view of a surface to be etched in an etching process according to an embodiment of the present application.

Fig. 3 is a schematic surface view of a glass substrate after etching treatment according to an embodiment of the present disclosure.

Fig. 4 is a schematic surface view of a glass housing according to an embodiment of the present disclosure.

Fig. 5 is an enlarged schematic view of a snowflake texture on the surface of a glass housing according to an embodiment of the present application, where (a) in fig. 5 is a 2D microscopic image and (b) in fig. 5 is a 3D microscopic image.

Fig. 6 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Detailed Description

The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, various modifications and embellishments can be made without departing from the principle of the present application, and these modifications and embellishments are also regarded as the scope of the present application.

The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.

Referring to fig. 1, a schematic flow chart of a method for manufacturing a glass housing for an electronic device according to an embodiment of the present disclosure includes:

operation 101: the surface to be etched of the glass substrate is subjected to sand blasting, cleaning and acid washing, wherein the acid washing comprises treatment with an acidic solution containing hydrofluoric acid.

Operation 102: a water film is formed on the glass substrate to completely cover the surface to be etched.

Operation 103: and (3) placing the glass substrate with the water film in the snowflake texture etching solution, and forming the snowflake texture on the surface to be etched through etching treatment.

Operation 104: the etched glass substrate is cleaned and processed to obtain the glass shell, the surface of the glass shell is provided with snowflake textures, each snowflake texture is composed of a plurality of snowflake patterns, and each snowflake pattern comprises a plurality of convex structures.

When the snowflake texture etching liquid is adopted to etch a glass substrate, the etching reaction is rapid, once the surface to be etched of the glass substrate is contacted with the snowflake texture etching liquid, the etching can be rapidly carried out, so that the situation that some positions form complete snowflake textures and some positions just start to react is easily generated, and further the bad conditions of sand leakage, uneven distribution of snowflake textures, large size difference of snowflake patterns and the like are caused; meanwhile, in the process of forming the snowflake texture, dendritic dendrites need to grow firstly, and then small crystal grains grow along the dendrite orientation and are distributed orderly to obtain the snowflake texture, so that the forming condition of the snowflake texture is strict, and the snowflake texture effect cannot be obtained if the conditions of no dendrite, disordered crystal grain arrangement and the like occur in the etching process.

In the application, the surface to be etched on the glass substrate is subjected to sand blasting and acid pickling, so that the surface roughness of the glass substrate is high, a water film is favorably covered on the surface to be etched, the acid pickling has the effect of activating the glass, more reaction sites are exposed, and the forming of snowflake textures is ensured; through treating the sculpture surface to cover the one deck water film, treat the sculpture surface and play the guard action, make the glass substrate when getting into snowflake texture etching liquid, treat the sculpture surface can not contact and react with the etching liquid at once, the water film has played the prevention effect to a certain extent, be favorable to treating the whole snowflake texture etching liquid that dip in sculpture surface after, the etching reaction begins to take place, guarantee to treat that the reaction of the different positions in sculpture surface is close to going on simultaneously, the homogeneity of the homogeneity that has promoted the snowflake pattern distribution and the homogeneity of size, the sand leakage phenomenon has been avoided, and simultaneously and guaranteed the formation of dendritic crystal and the orderly orientation of crystalline grain, be favorable to the formation of snowflake texture. The method provided by the application can ensure that the snowflake textures can be formed on the surface of the glass shell, and the uniformity of the snowflake textures is very excellent, so that the appearance effect and the flash effect of the surface of the glass shell are improved, the uniformity of the integral strength of the glass shell is also improved, and the mechanical property is good.

In operation 101, a plurality of pits are formed on a surface to be etched by sandblasting the surface to be etched of a glass substrate, so as to improve roughness of the surface to be etched; meanwhile, the acid cleaning can further improve the roughness of the surface to be etched, which is beneficial to the subsequent covering of a water film on the surface to be etched and the uniformity of the covering of the water film, and when the acid solution containing hydrofluoric acid is used for acid cleaning, the hydrofluoric acid plays a role in activating glass, and the hydrofluoric acid can react with silicon elements on the surface to be etched, so that the content of alkali metal on the surface to be etched is improved, and more sites which can react with the snowflake texture etching solution are exposed. The inventor of the application discovers that the texture of the surface of the glass shell obtained without pickling is not a snowflake texture, the roughness of the surface to be etched is improved through the pickling process, the content of alkali metal on the surface to be etched is also improved, and the pickling process is favorable for forming dendrite on the surface to be etched during etching and is favorable for the oriented growth of crystal grains, so that the snowflake texture is formed.

In the application, when the first surface and the second surface which are oppositely arranged on the glass substrate are provided with the snowflake textures, the protective layer can be formed on the second surface to prevent the second surface from being etched. In particular, but not limited to, the protective ink may be formed on the second surface. It is understood that after the etching is finished, the protective layer on the second surface is removed. In the present application, any known glass material for the electronic housing may be selected as the glass substrate, and specifically, but not limited to, aluminosilicate glass. In one embodiment, the glass substrate is high alumina glass. The high-alumina glass is Al ₂ O ₃ The content of glass is more than 12%, the high-alumina glass is high in hardness, good in chemical stability, high in mechanical strength and high-temperature resistant, the application in electronic equipment is facilitated, meanwhile, the etching stability of the snowflake texture etching liquid on the surface of the high-alumina glass in the related technology is poor, the production yield is low, the method provided by the application is suitable for glass substrates including the high-alumina glass, the snowflake texture is formed on the surface of the glass substrates, and the uniformity of the snowflake texture is excellent. In the present application, the thickness of the glass substrate may be selected according to the use requirements. In one embodiment, the glass substrate has a thickness of 0.4mm to 1.2mm. Furthermore, the thickness of the glass substrate is 0.5mm-1mm. Specifically, the thickness of the glass substrate may be, but is not limited to, 0.4mm, 0.6mm, 0.9mm, 1mm, 1.1mm, or the like.

In the application, the snowflake texture comprises a plurality of snowflake patterns, and the uniformity of the snowflake texture is high, namely the uniformity of the sizes of the snowflake patterns is high, and the uniformity of the distribution of the snowflake patterns is good.

In this application, can improve the surface roughness who treats the sculpture surface through the sandblast, be favorable to the cover of follow-up water film. In the embodiment of the present application, the particle size of the blasting material in the blasting is 40 μm to 70 μm. Therefore, the micro pits can be formed on the surface to be etched, the roughness of the surface to be etched is improved, and the uniformity of subsequent water film coverage is improved. Specifically, the particle size of the blasting material in the blasting may be, but not limited to, 43 μm, 46 μm, 48 μm, 50 μm, 53 μm, 55 μm, 58 μm, 60 μm, 61 μm, 63 μm, or the like. In one embodiment, the grit size of the blasting material is 45 μm to 65 μm. In another embodiment, the grit size of the blasting is from 52 μm to 63 μm. In yet another embodiment, the grit blasting is 240 mesh silicon carbide.

In the embodiment of the application, the height of the spray gun in the sand blasting is 25cm-35cm, the swing speed of the spray gun is 30Hz-40Hz, the conveying speed of the glass substrate is 10Hz-20Hz, the time of the sand blasting is 4s-10s, and the frequency of the sand blasting is 1-2 times. By adopting the sand blasting process, the distribution density of pits on the surface to be etched is improved, so that the crystal growth and the size of a formed snowflake pattern in the etching process are favorably controlled, the fineness of snowflake textures is ensured, and the mechanical property of the surface of the glass shell with the snowflake textures is favorably improved. Specifically, the height of the spray gun in the sand blasting may be, but is not limited to, 27cm, 29cm, 30cm, 32cm, 33cm, 35cm, etc., the swing speed of the spray gun may be, but is not limited to, 32Hz, 35Hz, 38Hz, 39Hz, etc., the transport speed of the glass substrate may be, but is not limited to, 10Hz, 13Hz, 15Hz, 16Hz, 18Hz, 19Hz, etc., and the time of the sand blasting may be, but is not limited to, 4s, 5s, 7s, 9s, 10s, etc. In one embodiment, the height of the spray gun in the sand blasting is 27cm-32cm, the swing speed of the spray gun is 31Hz-38Hz, the transmission speed of the glass substrate is 12Hz-18Hz, the sand blasting time is 5s-9s, and the sand blasting times are 1-2 times. In another embodiment, the height of the spray gun in the sand blasting is 28cm-31cm, the swing speed of the spray gun is 33Hz-35Hz, the conveying speed of the glass substrate is 14Hz-16Hz, the sand blasting time is 6s-8s, and the sand blasting times are 1-2.

In the present embodiment, 70 to 90 pits are distributed per 1mm diameter circle on the surface to be etched after the sandblasting. Make after handling through the sandblast and treat that the sculpture surface forms the pit that distributes densely to guarantee the even cover of follow-up water film, further improve the homogeneity of snowflake pattern distribution and size, be favorable to the snowflake pattern of shaping suitable size, promote holistic mechanical strength. Specifically, after sandblasting, 73, 75, 78, 80, 82, 85, or 88 pits are distributed per 1mm diameter circle on the surface to be etched. In one embodiment, 75-88 pits are distributed per 1mm diameter circle on the surface to be etched after sandblasting. In a specific embodiment, the transverse size of the pits formed on the surface to be etched is 20-35 μm by using the sand blasting process and the blasting material with the particle size of 40-70 μm.

In one embodiment of the application, the grain size of the spray material in the sand blasting is 40-70 μm, the height of the spray gun in the sand blasting is 25-35 cm, the swing speed of the spray gun is 30-40 Hz, the transmission speed of the glass substrate is 10-20 Hz, the sand blasting time is 4-10 s, and the sand blasting frequency is 1-2 times, so that 70-90 pits are distributed in each circle with the diameter of 1mm on the surface to be etched after the sand blasting. The roughness of waiting to etch the surface after the sandblast is high, is favorable to the even cover of follow-up water film, and the big pit of distribution density that forms simultaneously is favorable to restricting the size of the snowflake pattern that forms among the follow-up etching process, and the snowflake pattern of shaping suitable size promotes holistic mechanical strength.

In the application, the sand-blasting material and the grease, dirt and the like on the surface of the glass substrate are removed through cleaning, so that the follow-up operation is ensured.

In one embodiment of the present application, the cleaning includes a pretreatment process and a cleaning process, wherein the pretreatment process includes removing the sandblasted spray material on the surface to be etched of the glass substrate with water, and the cleaning process includes first acid cleaning, first alkali cleaning and first water cleaning, and removing grease, dirt and the like on the surface to be etched of the glass substrate. In an embodiment of the present application, the cleaning process includes sequentially performing a first acid cleaning, a first alkali cleaning, and a first water cleaning on the pretreated glass substrate. In another embodiment of the present application, the cleaning process includes sequentially performing a first alkali cleaning, a first acid cleaning, and a first water cleaning on the pretreated glass substrate. The inventor finds that the first acid washing and then the first alkali washing are more beneficial to improving the production yield of the formed snowflake textures. In one embodiment, the solution of the first acid washing is 1% -2% of citric acid, the temperature of the first acid washing is 50-60 ℃, and the time of the first acid washing is 2-4 min; the solution of the first alkali washing is 2-5% of an alkali cleaning agent, the temperature of the first alkali washing is 50-60 ℃, and the time of the first alkali washing is 4-8 min; the time of the first water washing is 12min-24min. Specifically, the glass substrate may be, but not limited to, placed in a first acid washing tank, then placed in a first alkali washing tank, then subjected to pure water cleaning and bubbling, then subjected to pure water spray cleaning, and finally subjected to slow pull cleaning in pure water. In another embodiment, the cleaning process may be performed in an ultrasonic cleaning apparatus, and the specific ultrasonic current may be, but is not limited to, 2.5A to 3.5A.

In another embodiment of the present application, the cleaning includes a pretreatment process, a cleaning process, a second alkaline wash, and a second aqueous wash. Through the second alkali washing and the second water washing, the cleaning effect is further enhanced, impurity residues on the surface to be etched are removed, and the problem of generating different colors on the surface of the formed glass shell is avoided. The pretreatment process and the cleaning process are as described above and will not be described in detail herein. In one embodiment of the present application, the solution of the second alkali washing comprises at least one of a 10% -20% sodium hydroxide solution and a 10% -20% potassium hydroxide solution, the temperature of the second alkali washing is 10 ℃ to 20 ℃, and the time of the second alkali washing is 2min to 4min. Impurities on the surface to be etched can be further removed by carrying out second alkali washing with a strong alkaline solution; and the second water washing comprises soaking the glass substrate in water, and removing glass powder and residual alkali liquor formed on the surface to be etched after the second alkali washing treatment.

In the application, the acid washing can improve the surface roughness of the surface to be etched, is beneficial to the covering of a water film and plays a role in activating glass; the acid washing ensures the forming of the snowflake texture. In one embodiment of the present application, the mass ratio of hydrofluoric acid in the acidic solution is greater than or equal to 5%. Therefore, in the acid washing process, the acid solution can react with silicon on the surface to be etched more, the content of alkali metal on the surface is improved, and the subsequent etching and the uniform coverage of a water film are facilitated. In another embodiment of the present application, the acidic solution further comprises a strong acid. Thereby being beneficial to further improving the surface roughness of the surface to be etched. Specifically, the strong acid may be, but is not limited to, at least one of sulfuric acid, nitric acid, and hydrochloric acid. In one embodiment, the acidic solution includes 5% -20% hydrofluoric acid, 10% -15% strong acid, and the balance water. Thereby being beneficial to improving the surface roughness of the surface to be etched and ensuring the uniform coverage of the water film. In one embodiment, the acidic solution includes 6 parts by weight of sulfuric acid, 6 parts by weight of nitric acid, 15 parts by weight of hydrofluoric acid, and 78 parts by weight of water. In another embodiment of the present application, the pH of the acidic solution is less than or equal to 1. Thereby ensuring that the pH of the acid solution is low and improving the surface roughness of the surface to be etched. In another embodiment of the present application, the time for pickling is 1min to 3min, and the temperature for pickling is 10 ℃ to 20 ℃. Thereby being beneficial to improving the efficiency of activating the glass, improving the content of alkali metal on the surface to be etched and being beneficial to the etching. It is understood that the acid cleaning is followed by a third water cleaning to remove residual acid and glass frit from the surface to be etched. In one embodiment, the pickled glass substrate is placed in water and bubbled, and the treatment is carried out for 2min to 3min.

In operation 102 and operation 103, a water film completely covering the surface to be etched is formed on the glass substrate, so that during etching, it can be ensured that etching reaction can occur at each position on the surface to be etched, thereby avoiding sand leakage, and meanwhile, the etching start time and the etching degree at different positions have little difference, thereby ensuring the uniformity of etching and further improving the uniformity of the formed snowflake texture. Through research, the inventor of the application finds that when no water film or water film completely covers the surface to be etched, the poor conditions of sand leakage, uneven etching, large size difference of snowflake patterns, uneven distribution and the like can occur, even the primary crystals are too much, the growth is too fast, and the snowflake textures cannot be generated; the inventor of the application completely covers the water film of the surface to be etched through forming on the glass substrate, so that when the surface to be etched enters the snowflake texture etching liquid, the water film prevents the etching reaction from being carried out at once, thereby avoiding the conditions of excessive primary crystallization, too fast growth and incapability of growing up, ensuring the formation of snowflake textures, being beneficial to the etching of all positions of the surface to be etched to occur nearly simultaneously, and improving the uniformity of the distribution and the size of the formed snowflake patterns.

In an embodiment of the present application, forming a water film on a glass substrate to completely cover a surface to be etched includes: soaking the glass substrate in water, inclining the surface to be etched by 15-30 degrees, and removing the glass substrate from the water, wherein the surface to be etched faces to the direction away from the water; and (4) after the glass substrate is moved out of the water, the glass substrate is flatly placed, and a water film is formed on the surface to be etched. That is, after the glass substrate is completely immersed in water, the glass substrate is moved out of the water, and the surfaces to be etched face to the direction away from the water surface in the moving-out process, that is, the direction of the surfaces to be etched is opposite to the direction of gravity, so that when the glass substrate is moved out of the water surface, water remains on the surfaces to be etched, and meanwhile, after the glass substrate is straightened, the remaining water moves to completely cover the surfaces to be etched; meanwhile, the inclination angle of the surface to be etched is 15-30 degrees, which is the included angle between the surface to be etched and the horizontal plane, and the horizontal plane is a plane vertical to the plane of the gravity direction. In the application, the glass substrate is moved out of water by inclining 15-30 degrees, if the inclination angle is too large, the amount of water remained on the surface to be etched is too small, the surface to be etched cannot be completely covered after being flatly placed, and if the inclination angle is too small, the acting force between the glass substrate and the water surface is large when the glass substrate is moved out of the water surface, so that the remained water is easily dispersed and distributed on the surface to be etched; by adopting the method, the water film can be completely covered on the surface to be etched, and simultaneously, the water film can be uniformly covered on the surface to be etched, so that the etching is more favorably carried out, the snowflake patterns with high size uniformity and good distribution uniformity are formed, and the generation of the heterochrosis phenomenon is avoided. In one embodiment, the soaking temperature is 0.3-9 deg.C, and the soaking time is 30-60 s. The soaking temperature is low, the temperature of the water film is low, the etching reaction can be further slowed down, the size of the snowflake patterns can be controlled, the distribution density of the snowflake patterns can be improved, and therefore the mechanical performance and the flashing effect of the glass shell can be improved. Further, the soaking temperature is 0.5-8.5 ℃, 1-8 ℃, 1.5-7 ℃ or 2-5 ℃. Specifically, the soaking temperature may be, but not limited to, 0.3 ℃, 0.4 ℃, 0.8 ℃, 1.2 ℃, 1.7 ℃,2.5 ℃ or 4 ℃, and the soaking time may be, but not limited to, 30s, 40s, 50s or 60s. In a specific embodiment, the glass substrate is placed in water with the temperature of 0.3-9 ℃ for soaking for 30s, then the glass substrate is inclined by 30 degrees by a mechanical arm and is removed from the water, the glass substrate is straightened, the water flow is leveled to the surface to be etched, and the water film is uniformly distributed and completely covers the surface to be etched.

In the application, the glass substrate is placed in the snowflake texture etching liquid so as to form the snowflake texture on the surface to be etched. It can be understood that the snowflake texture etching solution can be but is not limited to a commercially available snowflake texture etching solution, and the method can ensure the formation of snowflake textures, and meanwhile, the snowflake patterns are uniformly distributed and have good size uniformity.

In the embodiment of the application, the method for forming the snowflake texture on the surface to be etched by etching treatment by placing the glass substrate with the water film in the snowflake texture etching solution comprises the following steps: the glass substrate is inclined by 10 degrees to 20 degrees and moves into the snowflake texture etching liquid, the water film covers the surface to be etched, and the moving speed of the glass substrate is 15mm/s to 20mm/s; and (3) flatly placing the glass substrate in the snowflake texture etching liquid so as to horizontally place the surface to be etched for etching treatment. The glass substrate is inclined by 10-20 degrees, so that a water film is kept on the whole surface to be etched, the problem that the edge of the glass substrate is subjected to overlarge impact force is solved, the etching of different positions of the surface to be etched can be guaranteed, the etching time difference is small, the etching uniformity is further improved, and the forming of snowflake textures is guaranteed; the moving speed of the glass substrate effectively reduces the impact of the snowflake texture etching liquid on the glass substrate. Specifically, the glass substrate is inclined and then vertically and downwards immersed into the snowflake texture etching liquid along the gravity direction. Furthermore, the inclination angle of the glass substrate is 10-18 degrees, and the moving speed of the glass substrate is 16-19 mm/s. Specifically, the tilt angle of the glass substrate may be, but not limited to, 10 °, 12 °, 14 °,15 °,16 °,18 °, etc., and the moving speed of the glass substrate may be, but not limited to, 16mm/s, 17mm/s, 18mm/s, 18.5mm/s, etc. In one embodiment, the glass substrate in the snowflake texture etching liquid is swung, the swinging speed is 10mm/s-20mm/s, the swinging amplitude is 3cm-5cm, and the swinging times are 3-5 times. By swinging the glass substrate, the full contact between the surface to be etched and the snowflake texture etching liquid is facilitated, and the uniformity of the snowflake texture is ensured. Furthermore, the surface to be etched of the glass substrate is vertical to the gravity direction during swinging. In the embodiment of the application, the temperature of the etching treatment is 10-15 ℃, and the time of the etching treatment is 4-6 min. The temperature of the etching treatment is too low, which is not beneficial to controlling the size of the snowflake pattern, and the temperature of the etching treatment is too high, which is easy to dissolve part of the crystal, thus causing poor texture effect. Specifically, the temperature of the etching process may be, but is not limited to, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, or 15 ℃.

In the embodiment of the application, the snowflake texture etching solution comprises, by weight, 28 to 30 parts of an acid solution, 15 to 18 parts of ammonium fluoride, 24 to 27 parts of ammonium bifluoride, 2 to 3 parts of ferric trichloride, 0.9 to 1.3 parts of sodium dihydrogen phosphate, 0.5 to 0.7 parts of polyacrylamide, 5 to 15 parts of sodium sulfamate, 6 to 10 parts of sodium cellulose, 1 to 1.3 parts of polyvinyl alcohol, and 32 to 40 parts of water, wherein the acid solution comprises at least 20 parts of nitric acid. The ammonium fluoride salt and the inorganic acid in the snowflake texture etching liquid generate hydrofluoric acid, the hydrofluoric acid reacts with silicon dioxide in the glass to generate fluosilicic acid, and the fluosilicic acid reacts with sodium salt to generate sodium fluosilicate which is adsorbed on the surface of the glass to serve as a primary crystal nucleus; fluosilicic acid reacts with fluorine ammonium salt to generate ammonium fluosilicate, reacts with salt on the surface to be etched of the glass substrate to generate fluosilicate, is adsorbed on a primary crystal nucleus, and is subjected to crystal growth and expansion, dendritic crystals are generated firstly, and then crystal grains grow along the dendritic crystal orientation and are distributed orderly, so that snowflake textures are formed. In this application, can make the protruding structure of square crystal form through above-mentioned snowflake texture etching liquid, the protruding structure of square crystal form promptly, protruding structure has many edges, and area of contact during the friction is little, and the wearing and tearing that receive are little, is favorable to promoting the wear resistance of glass casing, and simultaneously at the rotation in-process, the protruding structure of many edges has a plurality of faceted pebbles, and the light intensity of reflection is bigger, and the produced protruding structure of productionThe flashing effect is more obvious. Polyvinyl alcohol in the snowflake texture etching liquid plays a role in thickening, and meanwhile, a polymer chain of the polyvinyl alcohol can adsorb ions, so that the snowflake texture etching liquid has a function of adsorbing nucleation, the uniformity of the etching effect of a surface to be etched is ensured, and heterochrosis is effectively prevented. Furthermore, when the glass substrate is high-alumina glass, the content of sodium salt is low, and the content of sodium salt in the system can be increased by adopting the snowflake texture etching liquid, so that more dendritic crystals can be formed, and the formation of snowflake textures is ensured. Specifically, the acid solution may include, but is not limited to, at least one of hydrochloric acid and citric acid, and nitric acid. Further, the snowflake texture etching liquid comprises 28-30 parts by weight of acid liquid, 16-17 parts by weight of ammonium fluoride, 25-26 parts by weight of ammonium bifluoride, 2.5-3 parts by weight of ferric trichloride, 1-1.2 parts by weight of sodium dihydrogen phosphate, 0.55-0.6 part by weight of polyacrylamide, 8-13 parts by weight of sodium sulfamate, 7-8.5 parts by weight of sodium cellulose, 1-1.2 parts by weight of polyvinyl alcohol and 34-38 parts by weight of water, wherein the acid liquid comprises at least 20 parts by weight of nitric acid. In one embodiment, H in the etching of the snowflake texture ⁺ The molar concentration of (b) is 15.3mol/L-18.5mol/L. Thereby being beneficial to the production of hydrofluoric acid in the etching process, ensuring the etching and being more beneficial to the formation of snowflake textures. Further, H in etching of snowflake texture ⁺ The molar concentration of (b) is 15.8mol/L to 18mol/L. Further, H in the etching of the snowflake texture ⁺ The molar concentration of (b) is 16mol/L to 17.7mol/L. Specifically, H in the etching of snowflake texture ⁺ The molar concentration of (A) may be, but is not limited to, 15.5mol/L, 16mol/L, 16.5mol/L, 17mol/L, 17.5mol/L, or 18.2mol/L, etc.

Referring to fig. 2, which is a schematic diagram of a surface to be etched in an etching process according to an embodiment of the present application, in the etching process using the snowflake texture etching solution, a dendrite is formed on the surface to be etched first, then a crystal grain grows along the dendrite orientation, and finally the growth of the crystal grain is completed to form a snowflake texture.

In operation 104, the etched glass substrate is cleaned and processed to obtain the glass housing.

In an embodiment of the present application, the cleaning comprises a fourth water wash. And removing the residual etching solution and part of crystals on the glass substrate by fourth washing. In another embodiment of the present application, the cleaning further comprises a second acid wash and a fifth water wash. Crystals on the surface of the glass substrate can be dissolved through the second acid washing, the stability of snowflake textures is improved, and acid liquor is removed through the fifth water washing. In one embodiment, the second acid wash is treated with 3% to 5% sulfuric or hydrochloric acid. Further, the time of the second acid washing is 3min-5min. In one embodiment, the second acid wash is treated with 5% sulfuric acid for 3min.

In the present application, the etched glass substrate may be made into a glass housing by, but not limited to, CNC machining. The shape of the glass shell can be selected according to actual needs.

In this application, through adopting foretell method, finally make the glass casing, the surface of glass casing has the snowflake texture to the outward appearance effect of glass casing has been promoted, and the snowflake texture comprises a plurality of snowflake patterns, and each snowflake pattern includes a plurality of protruding structures, and the glass casing is at the rotation in-process, and light is at the structural reflection light direction of protruding and change, thereby realizes the flash of light effect. In the application, the distribution of the raised structures has certain orientation, so that a snowflake texture with ordered distribution is formed.

In the application, during the process of forming the snowflake texture, dendritic dendrites need to grow firstly, and then small crystal grains grow along the dendrite orientation and are distributed orderly, so that the snowflake texture is obtained; the snowflake texture comprises a plurality of snowflake patterns, and each snowflake pattern comprises a plurality of raised structures. In one embodiment, the protrusion structure includes at least one of linear protrusions and dot-shaped protrusions. It is understood that the linear protrusion is a protrusion structure extending linearly, and may be, but not limited to, extending linearly, extending in a curve, etc.; the dot-shaped bulges are convex dot-shaped bulge structures. In one embodiment, the snowflake pattern includes a plurality of linear raised structures, and a plurality of dotted raised structures are distributed among the linear raised structures. Furthermore, at least two of the linear convex structures intersect. Specifically, the plurality of linear protrusion structures may, but are not limited to, exhibit at least one of a shape of a Chinese character mi, a shape of a Chinese character jing, a shape of a star, and the like. It is understood that the snowflake pattern may be snowflake-like or snowflake-like. In one embodiment, the snowflake shape may be, but is not limited to, hexagonal. Furthermore, the snowflake shape is a hexagonal prism shape. In another embodiment, the snowflake-like shape may be, but is not limited to, a polygon, such as a quadrangle, a pentagon, a heptagon, and the like. Specifically, the snowflake-like shape may be, but is not limited to, a regular polygon or an irregular polygon. In the application, the snowflake patterns are regularly or irregularly arranged to form snowflake textures, the snowflake patterns can also be arranged in a staggered mode to form snowflake textures, and the snowflake patterns can also be arranged at intervals to form snowflake textures. It should be understood that the above description is merely illustrative of the texture shapes formed on the glass shell and should not be construed as limiting the texture of the snowflakes.

In an embodiment of the application, the snowflake pattern has a lateral dimension of 80 μm to 1.5mm. Therefore, the surface of the glass shell has clear texture patterns, and the texture is improved. Further, the snowflake pattern has a lateral dimension of 150 μm to 1.2mm. Further, the snowflake pattern has a lateral dimension of 300 μm to 1mm. So that a more uniform snowflake pattern can be obtained. Specifically, the lateral dimension of the snowflake pattern may be, but is not limited to, 80 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 800 μm, 950 μm, 1050 μm, 1300 μm, or the like. In the embodiment of the present application, the lateral dimension of the bump structure is 0.8 μm to 2 μm, and the height of the bump structure is 2 μm to 7 μm. The raised structures in the same direction are combined to form a snowflake pattern, and the sizes of the raised structures are not greatly different, so that the snowflake pattern with high uniformity is formed. Further, the lateral dimension of the convex structure is 1 μm to 1.8 μm, and the height of the convex structure is 2.5 μm to 6 μm. Further, the lateral dimension of the bump structure is 1.2 μm to 1.5 μm, and the height of the bump structure is 3 μm to 5 μm. Specifically, the lateral dimension of the bump structure may be, but is not limited to, 0.8 μm, 0.9 μm, 1 μm, 1.2 μm, 1.5 μm, 1.7 μm, or 1.9 μm, etc., and the height of the bump structure may be, but is not limited to, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, or 7 μm, etc. In a specific example, by using the etching solution for the snowflake texture in the above embodiment, the snowflake pattern with a lateral dimension of 80 μm to 1.5mm, a lateral dimension of the bump structure with a lateral dimension of 0.8 μm to 2 μm, and a height of the bump structure with a height of 2 μm to 7 μm is obtained.

In an embodiment of the present application, the roughness of the surface having the snowflake texture in the glass housing is 0.4 μm to 0.8. Mu.m. Therefore, the glass shell has the frosting effect and the flashing effect, and has silky touch, and the texture of the glass shell is improved. Further, the roughness of the surface having the snowflake texture in the glass housing is 0.5 μm to 0.7. Mu.m. Specifically, the roughness of the surface having the snowflake texture in the glass housing may be, but is not limited to, 0.4 μm, 0.45 μm, 0.5 μm, 0.6 μm, 0.65 μm, 0.7 μm, or the like.

In the application, the snowflake textures are formed on the surface of the glass shell, so that the surface of the glass shell has an anti-glare effect, and the texture of the glass shell is changed. In an embodiment of the present application, the glass housing has a transmittance of 22% to 30%, a haze of 70% to 80%, and a gloss of 8 ° to 13 °. The above is the result in the visible range. Furthermore, the transmittance of the glass shell is 25-28%, the haze is 72-77%, and the glossiness is 10-12 degrees. Specifically, the transmittance of the glass housing may be, but is not limited to, 25%, 26%, 27%, 28%, etc., the haze may be, but is not limited to, 72%, 74%, 75%, 76%, 77%, etc., and the gloss may be, but is not limited to, 10 °, 11 °, 12 °, etc.

In the embodiment of the present application, the four-point bending strength of the glass housing is 597MPa to 732MPa. In the present application, the bending strength test is performed according to GB/T37781-2019. The glass shell has high strength and strong bending resistance, and is beneficial to the application. In one embodiment, the glass housing has a four-point bending strength of 597MPa to 720MPa. Specifically, the four-point bending strength of the glass case may be, but not limited to, 597MPa, 600MPa, 620MPa, 658MPa, 682MPa, 703MPa, 725MPa, 732MPa, or the like.

In the embodiment of the application, in the ball drop impact performance test, the weight of the steel ball is 32g, the steel ball is not broken when falling to the central point of the surface of the glass shell at the maximum of 80cm-110cm, and the steel ball is not broken when falling to the peripheral edge of the surface of the glass shell at the maximum of 50cm-55 cm. The glass shell has high mechanical strength and good shock resistance. In one embodiment, the steel ball does not break when 110cm drops to the center point of the glass housing surface and the steel ball does not break when 55cm drops to the peripheral edge of the glass housing surface. In another embodiment, the steel ball does not break when 90cm drops to the center point of the glass housing surface and the steel ball does not break when 52cm drops to the peripheral edge of the glass housing surface.

In the embodiment of the application, the surface of the glass shell is not scratched when the 0000# steel wire ball is rubbed more than 3000 times. In the snowflake texture of the glass shell, the snowflake pattern comprises a plurality of protruding structures, so that the wear-resistant effect can be achieved, the wear-resistant performance of the glass shell is improved, the service life is prolonged, and the application of the glass shell in electronic equipment is facilitated.

In a specific embodiment of the application, high-alumina glass is adopted, the high-alumina glass comprises a first surface and a second surface which are oppositely arranged, the second surface is coated with protective printing ink to form a protective layer, and the first surface is a surface to be etched; carrying out sand blasting treatment on the first surface by adopting 240-mesh green silicon carbide, wherein the height of a spray gun is 30cm, the swing speed is 30Hz, and the transmission speed of the high-alumina glass is 20Hz; showering the high-alumina glass by water; sequentially placing high-alumina glass in a tank containing 1% citric acid and a tank containing 2% alkaline cleaning agent for 3min respectively, bubbling in pure water and ultrasonically treating for 9min, then spraying and cleaning with water, and finally pulling and cleaning in water; soaking the cleaned high-alumina glass in 10% sodium hydroxide solution for 2min at 10 ℃, and then washing with water; soaking the washed high-alumina glass in an acid solution for 3min at the temperature of 10 ℃, wherein the acid solution comprises 6 parts by weight of sulfuric acid, 6 parts by weight of nitric acid, 15 parts by weight of hydrofluoric acid and 78 parts by weight of water, and then washing with water; after soaking the high-alumina glass in water at 0.5 ℃ for 30s, inclining the high-alumina glass by 15 degrees and removing the high-alumina glass from the water, wherein the first surface faces to the direction away from the water surface; after the glass is moved out of the water, the high-alumina glass is leveled, and a water film which uniformly covers the whole first surface is formed on the first surface; moving high-alumina glass with a water film into the snowflake texture etching liquid in an inclined manner of 10 degrees, wherein the water film covers the first surface, the moving speed of the high-alumina glass is 15mm/s, the high-alumina glass is flatly placed in the snowflake texture etching liquid, and then the high-alumina glass swings back and forth for 3 times at the swinging speed of 10mm/s, the swinging range is 3cm-5cm, the etching treatment temperature is 10 ℃, and the etching treatment time is 4min, wherein the snowflake texture etching liquid comprises, by weight, 22 parts of nitric acid, 2 parts of hydrochloric acid, 5 parts of citric acid, 18 parts of ammonium fluoride, 24 parts of ammonium bifluoride, 2 parts of ferric trichloride, 1 part of sodium dihydrogen phosphate, 0.5 parts of polyacrylamide, 5 parts of sodium sulfamate, 7 parts of sodium cellulose, 1.3 parts of polyvinyl alcohol and 35 parts of water; washing the etched high-alumina glass with water, then washing with 5% sulfuric acid, and then washing with water and processing to obtain a glass shell with the thickness of 0.7mm, wherein the surface of the glass shell has snowflake textures. Referring to fig. 3, a schematic view of the surface of the etched glass substrate shows that the method provided by the present application can form uniformly distributed snowflake patterns with proper sizes, thereby improving the anti-glare effect and having the glittering effect. Referring to fig. 4, a schematic surface view of a glass housing is shown, in which the glass substrate is processed into the glass housing, and the surface of the glass housing has snowflake texture, so as to improve the appearance quality of the glass housing. Please refer to fig. 5, which is an enlarged schematic view of a snowflake texture on the surface of a glass housing, wherein (a) in fig. 5 is a 2D microscopic image, and (b) in fig. 5 is a 3D microscopic image, it can be seen that the snowflake texture is composed of a plurality of snowflake patterns under 400 times of magnification, each snowflake pattern includes a plurality of raised structures, the raised structures are square crystal forms, and have orientation and uniform size, thereby improving the dimensional uniformity of the snowflake patterns. The transmittance of the prepared glass shell is 25%, the haze is 75%, the glossiness is 11 degrees, and the roughness of the surface with the snowflake texture is 0.7 mu m. Meanwhile, the performance of the prepared glass shell is detected, the bending strength is detected according to GB/T37781-2019, and the minimum bending strength of four points is 597MPa; in a ball drop impact performance test, the weight of the steel ball is 32g, the steel ball is not broken when falling to the central point of the surface of the glass shell at a position of 110cm, and the steel ball is not broken when falling to the peripheral edge of the surface of the glass shell at a position of 55 cm; no mark is left on the surface of the glass shell after the No. 0000 steel wire ball is rubbed for more than 3000 times.

The application also provides a glass shell for electronic equipment, which is prepared by adopting the preparation method provided by any one of the above embodiments. The properties of the glass housing are as described above and will not be described in detail here.

The application also provides a glass shell for an electronic device, the surface of the glass shell is provided with a snowflake texture, the snowflake texture is composed of a plurality of snowflake patterns, each snowflake pattern comprises a plurality of raised structures, the transverse dimension of the snowflake pattern is 80-1.5 mm, the transverse dimension of each raised structure is 0.8-2 μm, and the height of each raised structure is 2-7 μm. The glass shell has snowflake textures, can improve the appearance effect and is beneficial to application in electronic equipment. In the embodiment of the present application, the protruding structure has a square crystal form. That is to say, protruding structure is square crystal form, and protruding structure has many edges, and area of contact during the friction is little, and the wearing and tearing that receive are little, are favorable to promoting the wear resistance of glass casing, and simultaneously at the rotation in-process, the protruding structure of many edges has a plurality of facets, and the light intensity of reflection is bigger, and the flash of light effect of production is more obvious. In the embodiments of the present application, the glass housing may be manufactured by using the manufacturing method provided in any of the above embodiments. The nature of the glass shell is as above, and will not be described in detail here.

The present application further provides an electronic device, which includes a display screen and a housing assembly 100 connected to the display screen, wherein the housing assembly 100 includes the glass housing in any of the above embodiments. It is understood that the electronic device may be, but is not limited to, a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, etc. The following description will be given taking a mobile phone as an example. Referring to fig. 6, a schematic structural diagram of an electronic device according to an embodiment of the present disclosure is shown, where the electronic device includes a housing assembly 100. It can be understood that when the glass shell is applied to the electronic device, the glass shell has an appearance surface and an inner surface which are oppositely arranged, and the surface with the snowflake texture is used as the appearance surface, so that the anti-glare effect and the flashing effect of the star points are more obvious. In one embodiment of the present application, the housing assembly 100 further includes a color layer disposed on the inner surface of the glass housing. Thereby improving the color of the housing assembly 100 and the electronic device and enriching the visual effect. In another embodiment of the present application, the housing assembly 100 further comprises a transparent protective layer disposed on the outer surface of the glass housing. Therefore, the snow pattern effect can be protected, the snow pattern can be kept for a long time, meanwhile, the glass shell is protected, and the service life is further prolonged.

The foregoing detailed description has provided for the embodiments of the present application, and the principles and embodiments of the present application have been presented herein for purposes of illustration and description only and to facilitate understanding of the methods and their core concepts; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims

1. A method of making a glass housing for an electronic device, comprising:

2. The method according to claim 1, wherein the etching solution for the snowflake texture comprises, by weight, 28 to 30 parts of acid solution, 15 to 18 parts of ammonium fluoride, 24 to 27 parts of ammonium bifluoride, 2 to 3 parts of ferric chloride, 0.9 to 1.3 parts of sodium dihydrogen phosphate, 0.5 to 0.7 parts of polyacrylamide, 5 to 15 parts of sodium sulfamate, 6 to 10 parts of sodium cellulose, 1 to 1.3 parts of polyvinyl alcohol, and 32 to 40 parts of water, wherein the acid solution comprises at least 20 parts of nitric acid.

3. The method of claim 2, wherein H is in the snowflake texture etching ⁺ The molar concentration of (b) is 15.3mol/L to 18.5mol/L.

4. The preparation method according to claim 1, wherein the mass ratio of the hydrofluoric acid in the acidic solution is greater than or equal to 5%, the pH of the acidic solution is less than or equal to 1, the pickling time is 1min to 3min, and the pickling temperature is 10 ℃ to 20 ℃.

5. The method according to claim 1, wherein forming a water film on the glass substrate that completely covers the surface to be etched comprises:

soaking the glass substrate in water, inclining the surface to be etched by 15-30 degrees, and removing the glass substrate from the water, wherein the surface to be etched faces to the direction back to the water;

and after the glass substrate is moved out of the water, the glass substrate is leveled, and the water film is formed on the surface to be etched.

6. The preparation method according to claim 1, wherein the glass substrate having the water film is placed in a snowflake texture etching solution, and a snowflake texture is formed on the surface to be etched by an etching treatment, comprising:

the glass substrate is inclined by 10-20 degrees and moves into the snowflake texture etching liquid, the water film covers the surface to be etched, and the moving speed of the glass substrate is 15-20 mm/s;

and flatting the glass substrate in the snowflake texture etching liquid so as to enable the surface to be etched to be horizontally placed, wherein the etching treatment temperature is 10-15 ℃, and the etching treatment time is 4-6 min.

7. The method of claim 1, wherein the snowflake pattern has a lateral dimension of 80 μm to 1.5mm, the raised structures have a lateral dimension of 0.8 μm to 2 μm, and the raised structures have a height of 2 μm to 7 μm.

8. A glass housing for an electronic device, characterized by being produced by the production method according to any one of claims 1 to 7.

9. The glass housing for an electronic device according to claim 8, wherein the surface of the glass housing having the snowflake texture has a roughness of 0.4 μ ι η to 0.8 μ ι η.

10. The glass enclosure according to claim 8, wherein the glass enclosure has a transmittance of 22% to 30%, a haze of 70% to 80%, and a gloss of 8 ° to 13 °.

11. A glass housing for an electronic device, characterized in that the surface of the glass housing has a snowflake texture consisting of a plurality of snowflake patterns, each of the snowflake patterns comprising a plurality of raised structures, the snowflake patterns having a lateral dimension of from 80 μm to 1.5mm, the raised structures having a lateral dimension of from 0.8 μm to 2 μm, the raised structures having a height of from 2 μm to 7 μm.

12. The glass enclosure for an electronic device of claim 11, wherein the raised structure is in a square crystal form.

13. The glass housing for an electronic device according to claim 11, wherein the surface of the glass housing having the snowflake texture has a roughness of 0.4 μm to 0.8 μm, a transmittance of 22% to 30%, a haze of 70% to 80%, and a gloss of 8 ° to 13 °.

14. An electronic device comprising a display screen and a housing assembly connected to the display screen, the housing assembly comprising the glass housing for an electronic device of any of claims 8-10 or any of claims 11-13.