Glass-based structural member as well as preparation method and application thereof

Abstract

The embodiment of the invention provides a glass-based structural member as well as a preparation method and application thereof, and the preparation method comprises the following steps: carrying out at least one pre-plating cleaning selected from alkali cleaning, acid pickling and plasma treatment on a glass substrate, so that the surface water drop angle of the glass substrate is in a range of 10-30 degrees; forming a dielectric layer comprising a silicon dioxide layer on the surface of one side of the glass substrate cleaned before plating; forming an anti-fingerprint layer on the silicon dioxide layer; si-CH2 bonds are formed between the silicon dioxide layer and the anti-fingerprint layer. After the glass base material is cleaned before plating, the binding force between the SiO2 layer formed on the glass base material and the glass base material and the binding force between the anti-fingerprint layer and the SiO2 layer are both high, so that the thickness of the SiO2 layer and the anti-fingerprint layer can be large, the structure of the whole coating is stable, and the glass-based structural part can have good abrasion resistance, good scratch resistance and a lasting anti-fingerprint effect; and the application requirements in the fields of electronic equipment and the like can be well met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass, in particular to a glass-based structural member and a preparation method and application thereof. BACKGROUND

[0002] Electronic devices such as smart phones usually use a glass-based structural member as a display screen cover plate, which is usually composed of a glass substrate, a SiO2 primer layer and an anti-fingerprint layer (AF layer) arranged in layers. However, the wear resistance and scratch resistance of the existing glass-based structural member are not high, which affects the use reliability of the electronic device. In order to improve the scratch resistance of the glass member, the industry also prepares a glass-based structural member including a glass substrate, a superhard coating (such as diamond-like film, etc.) and an AF layer arranged in layers, but the superhard coating usually causes the cost of the glass-based structural member to increase and reduces the anti-fingerprint life, etc., and the application range is limited. Therefore, it is necessary to provide a glass-based structural member with good wear resistance and scratch resistance, and good anti-fingerprint effect, and a preparation method thereof. SUMMARY

[0003] In view of this, the embodiments of the present application provide a glass-based structural member and a preparation method and application thereof, which can have good wear resistance, scratch resistance and anti-fingerprint effect, and can better meet the application requirements in the field of electronic devices.

[0004] Specifically, the first aspect of the embodiments of the present application provides a glass-based structural member, which includes a glass substrate, and a dielectric layer and an anti-fingerprint layer arranged in layers on one side surface of the glass substrate; wherein the dielectric layer includes a silicon dioxide (SiO2) layer arranged close to one side of the anti-fingerprint layer, the anti-fingerprint layer contains a-CH2-structure in its composition, and a Si-CH2 bond is formed between the SiO2 layer and the anti-fingerprint layer.

[0005] In the above glass-based structural member, a Si-CH2 bond is formed between the SiO2 layer and the anti-fingerprint layer, which can ensure that the bonding force between the anti-fingerprint layer and the SiO2 layer is strong, and the thickness of the anti-fingerprint layer can be made thicker to ensure that the glass-based structural member 200 has a lasting anti-fingerprint effect, which is also beneficial to the improvement of the wear resistance of the glass-based structural member. In addition, the Si-CH2 bond formed between the SiO2 layer and the anti-fingerprint layer is also beneficial to the structural stability of the SiO2 layer, and the thickness of the SiO2 layer can be thicker, which makes the wear resistance and scratch resistance of the glass-based structural member can be improved.

[0006] In some embodiments of the present application, the thickness of the SiO2 layer is greater than or equal to 16 nm. The SiO2 layer can be thick and not easy to fall off, thereby facilitating the glass-based structural member to have good wear resistance and scratch resistance, and improving its resistance to alkali sweat.

[0007] In some embodiments of the present application, the thickness of the SiO2 layer is greater than or equal to 16 nm. The SiO2 layer can be thick and not easy to fall off, thereby facilitating the glass-based structural member to have good wear resistance and scratch resistance, and improving its resistance to alkali sweat.

[0008] In some embodiments of the present application, the thickness of the SiO2 layer is in the range of 18 nm to 50 nm. The thickness of the SiO2 layer in this range can ensure that the glass-based structural member has good wear resistance, scratch resistance, and resistance to alkali sweat, and also allows the anti-fingerprint layer disposed thereon to have a relatively thick thickness and good anti-fingerprint durability.

[0009] In some embodiments of the present application, the thickness of the SiO2 layer is in the range of 18 nm to 50 nm. The thickness of the SiO2 layer in this range can ensure that the glass-based structural member has good wear resistance, scratch resistance, and resistance to alkali sweat, and also allows the anti-fingerprint layer disposed thereon to have a relatively thick thickness and good anti-fingerprint durability.

[0010] In some embodiments of the present application, the thickness of the anti-fingerprint layer is in the range of 60 nm to 100 nm. The anti-fingerprint layer with an appropriate thickness can facilitate the glass-based structural member to have good anti-fingerprint durability and wear resistance, and also can not significantly affect the transparency of the original glass substrate.

[0011] In some embodiments of the present application, the medium layer further comprises a silicon carbide layer or an aluminum oxide layer disposed close to the glass substrate. The introduction of the silicon carbide layer or the aluminum oxide layer can improve the hardness of the glass-based structural member and help improve its scratch resistance.

[0012] In some embodiments of the present application, the thickness of the silicon carbide layer or the aluminum oxide layer is less than 3 nm. The low thickness of the silicon carbide layer or the aluminum oxide layer can avoid reducing the bonding force between the SiO2 layer formed thereon and the glass substrate.

[0013] In some embodiments of the present application, the glass-based structural member has an initial water droplet angle of the exposed surface of the anti-fingerprint layer greater than or equal to 110°, and a water droplet angle greater than 100° after 13000 times of rubber friction. The glass-based structural member provided by the present application still has a water droplet angle greater than 100° after a large number of times of rubber friction, which indicates that it has excellent wear resistance and retains good anti-fingerprint dirt resistance. The existing glass-based structural member with a SiO2 layer and an AF layer has a limit of less than 4000 times of rubber friction.

[0014] In the embodiments of the present application, the load threshold value for the glass-based structural member to produce a scratch at Mohs hardness 6 is above 750 g. This can reflect that the glass-based structural member provided by the present application has better scratch resistance. The load threshold value for the existing glass-based structural member with a SiO2 layer and an AF layer to produce a scratch is basically below 500 g.

[0015] In the embodiments of the present application, the glass-based structural member soaked in the simulated alkaline sweat with pH = 9.5 does not have a film layer falling off after being placed in a thermostat at 70°C for 24 hours. This can reflect that the medium layer and the anti-fingerprint layer of the glass-based structural member provided by the present application are more reliable, and in particular, can reflect that the film layer structure of the medium layer between the glass substrate and the anti-fingerprint layer is good in integrity and high in compactness.

[0016] In some embodiments of the present application, the average transmittance of the glass-based structural member to light with a wavelength of 400 nm-700 nm is ≥ 88%, and the Lab color chroma index b value satisfies |b value| ≤ 1.2. This indicates that the glass-based structural member with the aforementioned medium layer and anti-fingerprint layer with a relatively thick thickness can still have excellent optical transparency and low coloration.

[0017] In the embodiments of the present application, the glass substrate is strengthened microcrystalline glass or strengthened ordinary glass without a crystal phase. The selection can be made according to the application scenario of the glass-based structural member.

[0018] The second aspect of the embodiments of the present application provides a preparation method of a glass-based structural member, comprising:

[0019] performing pre-plating cleaning on the glass substrate selected from at least one of alkaline cleaning, acid cleaning and plasma treatment, so that the water drop angle of the surface of the glass substrate is in the range of 10°-30°;

[0020] forming a medium layer including a silicon dioxide layer on one side surface of the glass substrate after the pre-plating cleaning;

[0021] forming an anti-fingerprint layer on the silicon dioxide layer; wherein a Si-CH2 bond is formed between the silicon dioxide layer and the anti-fingerprint layer.

[0022] In the preparation method of the glass-based structural member, the pre-plating cleaning is performed on the glass substrate to achieve a specific surface state that the water drop angle of the surface of the glass substrate is 10°-30°, and then the medium layer containing SiO2 is plated and the anti-fingerprint layer is plated. The bonding force between the SiO2 layer and the glass substrate formed on such a glass substrate is strong, the bonding force between the anti-fingerprint layer and the SiO2 layer is also strong and a Si-CH2 bond is formed, so that the thickness of the SiO2 layer and the anti-fingerprint layer can be relatively thick and the structure of the overall coating is stable, which is beneficial to the glass-based structural member prepared to have good wear resistance, better scratch resistance and long-lasting anti-fingerprint effect.

[0023] In some embodiments, the plasma treatment is performed in a chamber, a flame, or a glow discharge. The plasma treatment is performed at a power in a range from 500 W to 1500 W and a time in a range from 30 s to 1200 s. The plasma treatment is not performed in a coating device. The power and time of the plasma treatment are controlled in a proper range, so that the desired surface state can be achieved without damaging the surface of the glass substrate and deteriorating the scratch resistance and abrasion resistance of the glass substrate.

[0024] In some embodiments, the medium layer and the anti-fingerprint layer are formed by vacuum coating. The vacuum degree during the coating of the medium layer is ≤5×10 -3 Pa, and the coating rate is ≤2 nm / min. The vacuum degree during the coating of the anti-fingerprint layer is ≤5×10 -3 Pa, and the coating rate is ≤10 nm / min. The protective gas during the coating is argon or nitrogen. The vacuum coating parameters can ensure that the medium layer and the anti-fingerprint layer have high purity, uniform thickness, good structural integrity, and high density.

[0025] In some embodiments, the plasma cleaning is performed during or after the formation of the medium layer. The plasma cleaning is performed in a coating device used for forming the medium layer. The plasma cleaning can help to construct a surface of the medium layer suitable for combining with the anti-fingerprint layer to be formed.

[0026] The third aspect of the embodiments of the present application provides a housing assembly, which comprises the glass-based structural member of the first aspect of the embodiments of the present application or the glass-based structural member prepared by the preparation method of the second aspect of the embodiments of the present application.

[0027] The housing assembly comprises the glass-based structural member of the present application, which also has good abrasion resistance, scratch resistance, and anti-fingerprint effect. In some embodiments, the housing assembly can further comprise other layer structures. In addition, the housing assembly can further comprise other film layer structures.

[0028] The fourth aspect of the embodiments of the present application provides an electronic device, which comprises a housing assembled on the outside of the electronic device and a circuit board located inside the housing. The housing comprises the glass-based structural member of the first aspect of the embodiments of the present application or the housing assembly of the third aspect of the embodiments of the present application.

[0029] In some embodiments of the present application, the shell comprises a display screen cover plate assembled on the front side of the electronic device, and the display screen cover plate comprises the glass-based structural member or the shell assembly. In some other embodiments of the present application, the shell comprises a back cover assembled on the back side of the electronic device, and the back cover comprises the glass-based structural member or the shell assembly. In some other embodiments of the present application, the electronic device further comprises a camera assembly located inside the shell, and the shell comprises a camera protection cover plate covering the camera assembly, and the camera protection cover plate comprises the glass-based structural member or the shell assembly. In the electronic device of the present application, one or more of the display screen cover plate, the back cover, and the camera protection cover plate can comprise the glass-based structural member or the shell assembly.

[0030] Due to the good wear resistance, scratch resistance, and anti-fingerprint effect of the glass-based structural member or the shell assembly, the shell of the electronic device using the same has a long service life, good appearance retention, and is not easy to adhere to dirt, thereby improving the market competitiveness of the electronic device. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 A front side structure schematic diagram of an electronic device provided by an embodiment of the present application.

[0032] Figure 2 A back side structure schematic diagram of an electronic device provided by an embodiment of the present application.

[0033] Figure 3 A preparation flowchart of a glass-based structural member provided by an embodiment of the present application.

[0034] Figure 4 A structure schematic diagram of a glass-based structural member provided by an embodiment of the present application.

[0035] Figure 5 Surface state diagrams of the glass-based structural members of Example 1 and Comparative Example 1 under the action of a metal pen with a Mohs hardness of 6 under different loads are shown.

[0036] Figure 6 FTIR spectra of glass-based structural members with the same SiO2 layer and AF layer prepared by using the same plating process on glass-based substrates with different water drop angles are summarized; wherein the wave number corresponding to the dashed line is the infrared absorption peak position of the Si-CH2 bond. DETAILED DESCRIPTION

[0037] The embodiments of the present application will be described below with reference to the drawings of the embodiments of the present application.

[0038] Reference is made to Figure 1 and Figure 2The electronic device 100 can be a mobile phone, a tablet computer, a smart wearable device, or the like. The electronic device 100 includes an outer shell assembled on the outside of the electronic device, and a circuit board located inside the outer shell. The outer shell includes a display screen cover plate 101 assembled on the front side of the electronic device 100 and a back cover 102 assembled on the back side of the electronic device 100. The display screen cover plate 101 is arranged on a display module. The back cover 102 can cover only the back side of the electronic device 100 (and the side away from the display screen), or can cover the back side and the side frame of the electronic device 100. Alternatively, the back cover 102 can cover all side frames of the electronic device, or can cover part of the side frames. The display screen cover plate 101 and / or the back cover 102 are made of a glass-based structural member. Specifically, the display screen cover plate 101 can be made of a glass-based structural member entirely or partially; and the back cover 102 can be made of a glass-based structural member entirely or partially.

[0039] In some embodiments of the present application, as shown in Figure 2 The electronic device 100 further includes a camera assembly 2 located inside the outer shell. The outer shell can include a camera protective cover plate 103 arranged on the camera assembly 2 to protect the camera assembly 2. The camera protective cover plate 103 is made of a glass-based structural member. Similarly, the camera protective cover plate 103 can be made of a glass-based structural member partially or entirely. In embodiments of the present application, the camera protective cover plate 103 can be arranged on the front side of the electronic device 100 or on the back side of the electronic device 100, depending on the arrangement position of the camera assembly 2. In some embodiments of the present application, the camera protective cover plate 103 can be a separate structure from the display screen cover plate 101 or the back cover 102. In other embodiments of the present application, the camera protective cover plate 103 can be an integral structure with the display screen cover plate 101 or the back cover 102.

[0040] In embodiments of the present application, the display screen cover plate 101, the back cover 102, and the camera protective cover plate 103 of the electronic device 100 can be made of a glass-based structural member partially or entirely.

[0041] The glass-based structural member used in the electronic device 100 can be a glass-based structural member prepared by the preparation method provided in embodiments of the present application. The glass-based structural member and the preparation method thereof provided in embodiments of the present application are described below.

[0042] Specifically, the present application provides a preparation method of a glass-based structural member, including the following steps S01, S02 and S03. Figure 3A preparation flow chart of the glass-based structural member is shown.

[0043] In step S01, the pre-plating cleaning is performed on at least one side surface of the glass substrate 21 to be formed with the medium layer 22, for example, only on the side surface of the glass substrate 21 to be formed with the medium layer 22, or on all exposed surfaces of the glass substrate 21. In addition, the pre-plating cleaning can not only achieve the effect of "making the water drop angle of the surface of the glass substrate 21 in the range of 10°-30°", but also remove dirt on the surface of the glass substrate. In some embodiments of the present application, before or after the pre-plating cleaning of the glass substrate 21 selected from at least one of alkali cleaning, acid cleaning and plasma treatment, alcohol wiping can also be performed to achieve the effect of removing dirt on the surface of the glass substrate before or after the pre-plating cleaning. Figure 3

[0044] In step S02, a medium layer 22 including a silicon dioxide layer (i.e., a SiO2 layer) is formed on one side surface of the glass substrate 21 after the pre-plating cleaning.

[0045] In step S03, a fingerprint-resistant layer 23 is formed on the silicon dioxide layer to obtain the glass-based structural member; and a Si-CH2 bond is formed between the silicon dioxide layer and the fingerprint-resistant layer 23.

[0046] In the preparation method of the glass-based structural member, the pre-plating cleaning of the glass substrate is controlled to achieve a specific surface state of "the water drop angle of the surface of the glass substrate being 10°-30°", and then the plating of the medium layer containing SiO2 and the plating of the fingerprint-resistant layer are performed, which can help to ensure that the bonding force between the SiO2 layer formed on the glass substrate and the glass substrate is strong, the thickness of the SiO2 layer is thick, and then the fingerprint-resistant layer formed on the SiO2 layer can form a Si-CH2 bond with the SiO2 layer, the bonding force between the two is good, and the thickness of the fingerprint-resistant layer can be at a relatively thick level, so that the coating structure of the prepared glass-based structural member is stable, and the wear resistance, scratch resistance and fingerprint resistance of the glass-based structural member can be good for a long time. In addition, the thickness of the formed SiO2 layer is thick, which can also improve the resistance of the glass-based structural member to alkali sweat and reduce the probability of film peeling.

[0047] Therefore, the preparation method of the glass-based structural member provided by the present application is simple, convenient to operate, low in manufacturing cost, and can prepare a glass-based structural member with good wear resistance, scratch resistance and long-lasting fingerprint resistance, so as to better meet the application requirements in the field of electronic equipment.

[0048] In step S01, the pre-plating cleaning is performed on at least one side surface of the glass substrate 21 to be formed with the medium layer 22, for example, only on the side surface of the glass substrate 21 to be formed with the medium layer 22, or on all exposed surfaces of the glass substrate 21. In addition, the pre-plating cleaning can not only achieve the effect of "making the water drop angle of the surface of the glass substrate 21 in the range of 10°-30°", but also remove dirt on the surface of the glass substrate. In some embodiments of the present application, before or after the pre-plating cleaning of the glass substrate 21 selected from at least one of alkali cleaning, acid cleaning and plasma treatment, alcohol wiping can also be performed to achieve the effect of removing dirt on the surface of the glass substrate before or after the pre-plating cleaning. ​

[0049] In the embodiments of the present application, the pH of the alkali solution used in the alkali cleaning is between 9 and 11. The solutes in the alkali solution can include one or more of sodium metasilicate, NaOH, Na2CO3, and NaHCO3. Specifically, the pH of the alkali solution can be 9.2, 9.5, 9.8, 10.0, 10.2, 10.5, or 10.8, etc. In the embodiments of the present application, the alkali cleaning is performed at a temperature in the range of 20°C to 95°C, for example, specifically 25°C, 30°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C, etc. In some embodiments, the alkali cleaning is performed at a temperature in the range of 20°C to 60°C. The alkali cleaning is performed at an appropriate temperature, which can ensure good alkali cleaning efficiency and cleaning effect, and also ensure high feasibility for industrial mass production. In addition, the duration of the alkali cleaning can be adjusted according to the surface area of the glass substrate 21 to be treated. For example, the duration of the alkali cleaning can be 120s to 600s, for example, specifically 150s, 180s, 210s, 240s, 270s, 300s, 360s, 420s, 480s, or 540s, etc. If the pre-plating cleaning is alkali cleaning, the parameters including the pH / concentration of the alkali solution, the alkali cleaning temperature, and the duration of the alkali cleaning can be adjusted to achieve the effect that the water droplet angle of the glass substrate surface after alkali cleaning is in the range of 10° to 30°.

[0050] In addition, the alkali solution can be applied by immersion or spraying. If the alkali solution is applied by immersion, all the exposed surfaces of the glass substrate 21 after the alkali cleaning achieve a surface state with a water droplet angle of 10° to 30°. If the alkali solution is applied by spraying, only the side surface of the glass substrate 21 sprayed with the alkali solution after the alkali cleaning achieves a surface state with a water droplet angle of 10° to 30°.

[0051] In the embodiments of the present application, the pH of the acid solution used in the acid cleaning is between 2 and 4, the solutes in the acid solution include one or more of sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid (HNO3), and oxalic acid (H2C2O4), and the acid solution does not contain hydrofluoric acid (HF). The absence of HF in the acid solution can avoid etching of the SiO2 component in the glass substrate by the acid solution, thereby significantly reducing the surface roughness of the glass substrate and deteriorating the scratch resistance. Controlling the pH of the acid solution in an appropriate range can ensure that the acid solution can effectively clean the surface of the glass substrate without significantly reducing the surface roughness of the glass substrate.

[0052] In some embodiments, the acid washing is performed at a temperature in the range of 20-95°C, such as 25°C, 30°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C. In some embodiments, the acid washing is performed at a temperature in the range of 20-60°C. The acid washing is performed at a suitable temperature to ensure good acid washing efficiency and cleaning effect, and to ensure high controllability of the acid washing. In addition, the acid washing time can be adjusted according to the surface area of the glass substrate 21 to be treated. For example, the acid washing time can be in the range of 120-600s, such as 150s, 180s, 240s, 270s, 300s, 330s, 360s, 390s, 420s, 450s, 480s, 540s, or 570s. In some embodiments, the acid washing time is in the range of 300-600s. Similarly, if the pre-coating cleaning is acid washing, the parameters including the pH value / concentration of the acid solution, the acid washing temperature, the acid washing time, etc. can be adjusted to achieve the effect that the water droplet angle of the glass substrate surface after acid washing is in the range of 10-30°.

[0053] In some embodiments, if the pre-coating cleaning includes plasma treatment, the equipment used for the plasma treatment can include one or more of a box type, a flame type, and a glow type. The power of the plasma treatment can be in the range of 500-1500W, and the treatment time can be in the range of 30-1200s. Controlling the power and time of the plasma treatment in a suitable range can achieve sufficient cleaning intensity to achieve the desired surface treatment effect, while avoiding excessive damage to the surface of the glass substrate and deterioration of its scratch resistance and friction resistance due to too high power or too long treatment time.

[0054] In some embodiments, the plasma used for the plasma treatment is N2 plasma. Using N2 plasma for pre-coating cleaning can avoid oxidation of the surface of the glass substrate and ensure that the surface structure of the glass substrate is not excessively damaged, which is easy to achieve the effect that the target water droplet angle is in the range of 10-30°, and is beneficial to improving the wear resistance of the glass product in the later stage.

[0055] In the present application, the above-mentioned pre-coating cleaning can be only alkaline cleaning, or acid cleaning, or plasma treatment, or two or three of them. For example, in some embodiments, the above-mentioned pre-coating cleaning is alkaline cleaning and acid cleaning; in this case, the acid cleaning can be performed first, followed by alkaline cleaning. In some other embodiments, the above-mentioned pre-coating cleaning is plasma treatment followed by alkaline cleaning.

[0056] In step S01 of the present application, the glass substrate 21 is cleaned before plating, and the water droplet angle of the surface of the glass substrate 21 can be 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 21°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, or 29°, etc.

[0057] In the embodiments of the present application, the medium layer 22 in step S02 and the anti-fingerprint layer 23 in step S03 can be formed by vacuum plating. The medium layer 22 and the anti-fingerprint layer 23 can be deposited in a deposition cavity of a plating device (such as an evaporation machine or a sputtering machine, etc.). Generally, the deposition cavity of the plating device is first evacuated to a predetermined vacuum degree, and then the evaporation or sputtering of raw materials is started to start the plating. The evacuation can be completed within 5-30 minutes.

[0058] In the embodiments of the present application, the vacuum degree during the plating process of the medium layer 22 is ≤5×10 -3 Pa, the plating rate is ≤2 nm / min, and the protective gas during the plating process is argon or nitrogen. The vacuum degree during the plating process of the anti-fingerprint layer 23 is ≤5×10 - 3 Pa, the plating rate is ≤10 nm / min, and the protective gas during the plating process is argon or nitrogen. The lower vacuum degree can ensure the purity of the plated film, and the appropriate plating rate can ensure the uniform thickness and good structural integrity of the plated film. By adjusting the plating parameters and plating time, etc., the medium layer 22 and the anti-fingerprint layer 23 with different thicknesses and different densities can be formed. In some embodiments of the present application, the vacuum degree during the plating process of the medium layer 22 and the anti-fingerprint layer 23 is 1×10 -3 Pa.

[0059] In some embodiments of the present application, during the formation of the medium layer 22 or after the formation of the medium layer 22, plasma cleaning can also be performed. The plasma cleaning can help to construct a medium layer surface suitable for combining with the anti-fingerprint layer 23. The plasma cleaning is performed in the deposition cavity of the plating device, and can also be referred to as “in-cavity plasma cleaning”. Generally, the plasma cleaning is performed after the deposition cavity of the plating device reaches a predetermined vacuum degree. For example, when the vacuum degree in the deposition cavity of the plating device is ≤5×10 -3 Pa, the ion source is turned on and inert gas is introduced. In the embodiments of the present application, the plasma used in the plasma cleaning is Ar plasma. The use of Ar plasma for cleaning can ensure the construction of a medium layer surface suitable for combining with the anti-fingerprint layer 23, and at the same time, the purity of the medium layer 22 is not affected.

[0060] In some embodiments of the present application, after the coating of the medium layer 22 is completed, plasma cleaning is performed in the deposition cavity of the coating equipment. Specifically, after the coating of the medium layer 22 is completed, the deposition cavity of the coating equipment reaches a predetermined vacuum degree, the ion source is turned on, inert gas (such as Ar) is introduced to generate inert gas plasma for cleaning. After the formation of the medium layer 22, the surface of the medium layer 22 is plasma cleaned, which not only removes stains, but also ensures that the surface of the medium layer has sufficient activity, thereby helping to improve the bonding force between the subsequently formed anti-fingerprint layer 23 and the medium layer. In the deposition cavity of the coating equipment, the vacuum degree is ≤5×10 -3 Pa, the ion source is turned on, inert gas is introduced, and the surface of the medium layer is inert gas plasma cleaned. The voltage and / or current of the ion source, the cavity pressure during plasma cleaning, the flow rate of the inert gas, the plasma cleaning time, etc. can be adjusted to control the effect of plasma cleaning. In some embodiments of the present application, the voltage of the ion source during plasma cleaning is 50-100V, the Ar flow rate is 50-300sccm, the cavity pressure is 1×10 - 2 Pa to 5×10 -1 Pa, and the plasma cleaning time can be 10-30min.

[0061] In some embodiments of the present application, after the deposition cavity of the coating equipment reaches a predetermined vacuum degree, the coating of the medium layer 22 is started or a period of time after the coating of the medium layer 22 is started, the ion source is turned on, and inert gas is introduced to generate inert gas plasma. In this way, the surface of the deposited medium layer and the anti-fingerprint layer 233 can also have good bonding force.

[0062] In some embodiments of the present application, in step S02, the formed medium layer 22 is only a SiO2 layer. In some other embodiments of the present application, the medium layer 22 includes a SiO2 layer and other medium layers stacked. The other medium layer is arranged close to the glass substrate 21, and the SiO2 layer is arranged close to the anti-fingerprint layer 23. That is, on the glass substrate 21 after the pre-coating cleaning in step S01, the other medium layer is formed first, and then the SiO2 layer is formed. In embodiments of the present application, the other medium layer includes a silicon carbide (SiC) layer or an aluminum oxide (Al2O3) layer. The introduction of the SiC layer or the Al2O3 layer can improve the hardness of the finally prepared glass-based structural member, and help to improve its scratch resistance. In embodiments of the present application, the thickness of the silicon carbide layer or the aluminum oxide layer is less than 3nm. In this way, an excessively thick SiC layer or Al2O3 layer can reduce the bonding force between the SiO2 layer formed thereon and the glass substrate.

[0063] In the step S02, the thickness of the SiO2layer formed can be greater than or equal to 16 nm. Thanks to the above-mentioned specific surface state of the glass substrate after the pre-plating cleaning, the thickness of the SiO2layer formed on the glass substrate is strong in bonding force with the glass substrate, and the SiO2layer is less likely to fall off, thereby improving the wear resistance and scratch resistance of the glass-based structural member prepared, and improving the resistance of the glass-based structural member to alkali sweat.

[0064] In some embodiments of the present application, the thickness of the SiO2layer can be greater than or equal to 18 nm, greater than or equal to 20 nm, greater than or equal to 22 nm, greater than or equal to 25 nm, greater than or equal to 30 nm, greater than or equal to 40 nm, etc. The thickness of the SiO2layer in a higher range is conducive to improving the wear resistance and scratch resistance of the glass-based structural member prepared, and improving the resistance of the glass-based structural member to alkali sweat. In some embodiments, the thickness of the SiO2layer can be in a range of 18 nm to 50 nm. The thickness of the SiO2layer in this range can not only make the wear resistance, scratch resistance, and alkali sweat resistance of the glass-based structural member prepared better, but also ensure that the SiO2layer is less likely to fall off from the glass substrate 21, and the thickness of the anti-fingerprint layer provided thereon can be thicker, and the anti-fingerprint durability is good. Further, the thickness of the SiO2layer can be in a range of 18 nm to 25 nm.

[0065] In the embodiments of the present application, the sum of the thicknesses of the medium layer 22 and the anti-fingerprint layer 23 can be greater than or equal to 70 nm. Thanks to the above-mentioned specific surface state of the glass substrate after the pre-plating cleaning when preparing the glass-based structural member, the thicknesses of the SiO2layer and the AF layer formed on the glass substrate can be thicker, and the sum of the thicknesses of the SiO2layer and the AF layer is also thicker, thereby making the glass-based structural member prepared have wear resistance, scratch resistance, and anti-fingerprint effect. In some embodiments of the present application, the sum of the thicknesses of the medium layer 22 and the anti-fingerprint layer 23 is in a range of 70 nm to 150 nm, for example, specifically 75 nm, 80 nm, 90 nm, 100 nm, 110 nm, 112 nm, 115 nm, 118 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, or 145 nm, etc. In this case, the laminated structure of the medium layer 22 and the anti-fingerprint layer 23 is less likely to fall off from the glass substrate, and the transparency of the original glass substrate is not significantly reduced.

[0066] In the step S03, the anti-fingerprint layer 23 comprises a perfluoroalkyl compound or a polyfluoroalkyl compound containing the -CH2- structure. The compound containing the fluorine-containing group has good hydrophobic and oleophobic properties, and the coating containing the compound has good anti-fingerprint effect. In addition, the compound containing the fluorine-containing group contains the -CH2- structure, and the Si-CH2 bond can be formed between the anti-fingerprint layer 23 and the SiO2 layer formed on the surface of the glass substrate after the pre-plating cleaning.

[0067] In the step S03, the thickness of the anti-fingerprint layer 23 is greater than or equal to 50 nm, and can be greater than or equal to 60 nm. As described above, the Si-CH2 bond is formed between the anti-fingerprint layer 23 and the SiO2 layer, and the thickness of the anti-fingerprint layer 23 can be in a relatively thick range and is not easy to fall off. In some embodiments of the present application, the thickness of the anti-fingerprint layer 23 can be in the range of 60 nm to 100 nm. The AF layer with an appropriate thickness can not only improve the anti-fingerprint durability and wear resistance of the glass-based structure, but also will not significantly affect the transparency of the original glass substrate. For example, the thickness of the anti-fingerprint layer 23 can be 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, or 100 nm, etc.

[0068] In some embodiments of the present application, after the anti-fingerprint layer 23 is formed, the obtained glass-based structure can be cleaned to ensure the cleanliness.

[0069] In the step S03, the Si-CH2 bond formed between the SiO2 layer and the anti-fingerprint layer 23 can be obtained by Fourier Transform Infrared Spectroscopy (FTIR) test of the obtained glass-based structure. Specifically, in the obtained FTIR graph, the infrared characteristic absorption peak at the wave number of 600-700 cm -1 The Si-CH2 bond formed between the SiO2 layer and the anti-fingerprint layer 23 can be obtained by the infrared characteristic absorption peak at the wave number of 600-700 cm

[0070] The embodiments of the present application also provide a glass-based structure. A schematic structural diagram of the glass-based structure can be shown in FIG. 2. Figure 4 The glass-based structure 200 comprises a glass substrate 21, and a medium layer 22 and an anti-fingerprint layer 23 (i.e., an AF layer 23) sequentially arranged on one side of the glass substrate 21. The medium layer 22 comprises a silicon dioxide layer (i.e., a SiO2 layer) arranged on the side close to the anti-fingerprint layer 23. The anti-fingerprint layer 23 comprises a perfluoroalkyl compound or a polyfluoroalkyl compound containing the -CH2- structure, and the Si-CH2 bond is formed between the SiO2 layer and the anti-fingerprint layer 23.

[0071] The Si-CH2 bond formed between the SiO2 layer and the anti-fingerprint layer 23 can obviously improve the bonding force between the anti-fingerprint layer 23 and the SiO2 layer serving as a primer, so that the thickness of the anti-fingerprint layer 23 can be made thicker to ensure that the glass-based structural member 200 has a long-lasting anti-fingerprint effect and is also beneficial to the improvement of the wear resistance. In addition, as can be seen from the preparation method of the glass-based structural member described in the foregoing, the Si-CH2 bond formed between the SiO2 layer and the anti-fingerprint layer 23 can also reflect that the bonding force between the SiO2 layer and the glass substrate is strong, and the thickness of the SiO2 layer can be thicker, which makes the wear resistance and scratch resistance of the glass-based structural member 200 both improved.

[0072] In the existing glass-based structural member, no Si-CH2 bond is formed between the SiO2 layer and the anti-fingerprint layer (AF layer), the thickness of the SiO2 layer provided on the glass substrate is usually less than 10 nm, and the thickness of the AF layer is also low, so the wear resistance and scratch resistance are not good. Although the industry also has a glass-based structural member prepared to include a glass substrate, a superhard coating (such as diamond-like film, etc.) and an AF layer stacked to improve the scratch resistance, the superhard coating usually causes the cost of the glass-based structural member to increase sharply and reduces the anti-fingerprint life, etc., so the application range is limited. Therefore, as can be seen from the above, the glass-based structural member 200 provided by the present application can have excellent wear resistance and scratch resistance and a longer anti-fingerprint effect, and the manufacturing cost is lower.

[0073] The thickness of the SiO2 layer, the thickness of the anti-fingerprint layer 23, and the sum of the thicknesses of the two can be referred to the description in the foregoing.

[0074] As described in the foregoing, in some embodiments of the present application, the medium layer 22 is a SiO2 layer; in some other embodiments of the present application, the medium layer 22 includes a SiO2 layer provided close to the anti-fingerprint layer 23 and a SiC layer or an Al2O3 layer provided close to the glass substrate 21. That is, the SiC layer or the Al2O3 layer is provided with the SiO2 layer on the side away from the glass substrate 21. The introduction of the SiC layer or the Al2O3 layer can improve the hardness of the glass-based structural member 200 and help to improve the scratch resistance. Further, the thickness of the SiC layer or the Al2O3 layer is less than 3 nm. In this way, the excessively thick SiC layer or Al2O3 layer can avoid reducing the bonding force between the SiO2 layer formed thereon and the glass substrate and reducing the thickness of the SiO2 layer.

[0075] In the glass-based structural member 200, the initial water drop angle of the exposed surface of the anti-fingerprint layer 23 is above 110°, and the water drop angle after 13000 times of rubber friction is greater than 100°.

[0076] The initial water drop angle of the glass-based structure 200 is high, which can reflect that the surface provided with the AF layer has excellent anti-fouling performance. The wear resistance of the film layer provided on the glass substrate 21 can be represented by the limit number of times of rubber friction (Time to Failure, TTF) when the water drop angle is greater than 100°. Generally, the surface of the glass sample will gradually decrease in water drop angle after the rubber friction test. The surface of the glass-based structure 200 provided with the AF layer in the present application still has a water drop angle greater than 100° after 13000 times of rubber friction (i.e., the rubber friction TTF of the glass-based structure 200 is greater than or equal to 13000), which indicates that the wear resistance is good and the anti-fingerprint fouling ability is reserved. However, the limit number of times of rubber friction of the glass-based structure with a SiO2 layer and an AF layer in the prior art is generally less than 4000 times. That is, the water drop angle of the glass-based structure in the prior art is less than 100° after 4000 times of rubber friction. In the present application, the rubber friction test is carried out by using a rubber to rub the surface of the glass-based structure at a speed of 40 circles / min under a load of 1 kg, and the single stroke is 40 mm.

[0077] In some embodiments of the present application, the water drop angle of the glass-based structure 200 is greater than 100° after 14000 times of rubber friction, that is, the rubber friction TTF of the glass-based structure 200 is greater than or equal to 14000. Further, the rubber friction TTF of the glass-based structure 200 is greater than or equal to 18000. In some embodiments, the rubber friction TTF of the glass-based structure 200 is greater than or equal to 20000.

[0078] In the embodiments of the present application, the load threshold value for producing a scratch on the glass-based structure 200 under Mohs hardness 6 is greater than or equal to 750 g. The scratch resistance of the film layer provided on the glass substrate can be represented by Mohs hardness. A metal pen with Mohs hardness of 6 is used to scratch the surface of the glass-based structure sample (the surface provided with the AF layer) under different loads, and whether the sample has a scratch is observed under an optical microscope, and the corresponding load value when the sample surface has a scratch (i.e., the load threshold value for producing a scratch) is recorded. The glass-based structure 200 in the embodiments of the present application has a high load threshold value for producing a scratch under the metal pen with Mohs hardness of 6, which can reflect that the scratch resistance is good. In some embodiments of the present application, the load threshold value for producing a scratch on the glass-based structure 200 under Mohs hardness 6 can be greater than or equal to 800 g, or greater than or equal to 1000 g, or greater than or equal to 1200 g, or even greater than or equal to 1400 g, etc.

[0079] In the embodiments of the present application, the glass-based structural member 200 soaked by the simulated alkaline sweat solution with pH = 9.5 does not have film layer peeling after being placed in a constant temperature oven at 70°C for 24 hours. This phenomenon can reflect that the film layers (medium layer 22, anti-fingerprint layer 23) of the glass-based structural member 200 provided by the present application are reliable, have good alkali sweat resistance, and in particular, can reflect that the film layer structure of the SiO2-containing medium layer 22 is good in integrity and high in density. In order to avoid the volatilization of the alkaline sweat solution when the glass-based structural member soaked by the simulated alkaline sweat solution is placed in a constant temperature oven at 70°C, the glass-based structural member soaked by the simulated alkaline sweat solution can be placed in a high-temperature-resistant and moisture-retaining bag, and then placed in a constant temperature oven at 70°C, and whether there is film layer peeling phenomenon after being placed for 24 hours is observed.

[0080] In some embodiments of the present application, the average transmittance of the glass-based structural member 200 to light with a wavelength of 400 nm-700 nm is ≥ 88%, and the Lab color chromaticity index b value satisfies: |b value| ≤ 1.2. Even if the aforementioned SiO2 medium layer and AF layer with a relatively large thickness are arranged on the glass substrate 21, the glass-based structural member 200 still has excellent optical performance, high light transmittance, and low coloration, and is particularly suitable for display screen cover plates 101, camera protective cover plates 103, etc. that require high transparency. In particular, |b value| ≤ 1.2 reflects that the glass-based structural member 200 does not yellow or blue, and has high transparency. In some embodiments, the aforementioned |b value| ≤ 1.0, further ≤ 0.9, ≤ 0.8, ≤ 0.7, ≤ 0.5, etc.

[0081] In the embodiments of the present application, the aforementioned glass substrate 21 can be strengthened microcrystalline glass or strengthened ordinary glass without crystal phase. The main difference between microcrystalline glass and ordinary glass is whether it contains a crystal phase. Generally, the drop resistance of strengthened microcrystalline glass is better than that of strengthened ordinary glass. After being chemically strengthened, the microcrystalline glass or ordinary glass can have residual stress, specifically, the surface of the strengthened microcrystalline glass or ordinary glass has a compressive stress layer.

[0082] In some embodiments of the present application, the glass substrate 21 is strengthened microcrystalline glass. The strengthened microcrystalline glass can include the following components in terms of mole percentage: Li2O: 10%-25%, SiO2: 58%-72%, Na2O and K2O: 3%-7%, Al2O3: 2%-8%, P2O5+ZrO2+TiO2: 2%-13%, MgO+CaO+ZnO: 0-3%, B2O3: 0-5%. The strengthened microcrystalline glass satisfying the component requirements can have the characteristics of high transmittance, low coloration, high crystallinity, and high Young's modulus, thereby better meeting the application requirements in the field of electronic devices, etc.

[0083] In some embodiments of the present application, the strengthened microcrystalline glass can include a glass phase and a crystal phase, and the crystal phase can include at least one of quartz, spodumene, petalite, lithium silicate, lithium disilicate, and spinel. The presence of these crystal phases can help improve the drop resistance, wear resistance, and scratch resistance of the microcrystalline glass. In some embodiments of the present application, the crystal phase in the strengthened microcrystalline glass includes lithium silicate, lithium disilicate, and petalite. Further, the total mass content of the crystal phase in the strengthened microcrystalline glass is greater than or equal to 20%. The high total content of the crystal phase in the strengthened microcrystalline glass can further improve the drop resistance, wear resistance, and scratch resistance of the strengthened microcrystalline glass.

[0084] In some embodiments of the present application, the glass substrate 21 is a strengthened general glass, which can be a typical lithium-aluminum-silicon system glass. In some embodiments, the strengthened general glass includes the following components in terms of mole percentage: SiO2: 45%-59.5%, Al2O3: 9%-30%, MgO: 7%-30%, ZnO: 0-5%, ZrO2: 0-10%, La2O3: 0-10%, Li2O: 5.5%-15%, Na2O: 1%-5%, and K2O: 2%-5%.

[0085] In some embodiments of the present application, the glass substrate structure includes the strengthened general glass described above, or is prepared by the preparation method described above.

[0086] In addition, the shell assembly can further include one or more of a UV texture layer, a color layer, a film coating layer, and a cover bottom oil film layer on the side of the glass substrate 21 away from the anti-fingerprint layer 23, according to the actual needs of the shell assembly.

[0087] In some embodiments of the present application, the electronic device includes the shell assembly or the glass substrate structure described above.

[0088] As described above, at least one of the display screen cover plate 101, the back cover 102, and the camera protection cover plate 103 of the electronic device 100 can include the glass substrate structure 200 or the shell assembly provided by the embodiments of the present application. In addition, when the user uses the electronic device, the user's fingers can directly contact the anti-fingerprint layer 23 in the glass substrate structure 200.

[0089] The shell of the electronic device 100 uses the shell assembly or the glass substrate structure 200 provided by the embodiments of the present application, which has good wear resistance, scratch resistance, and anti-fingerprint effect. The service life of the shell of the electronic device is long, the appearance retention is good, and the shell is not easy to stick dirt, thereby improving the comprehensive performance and market competitiveness of the electronic device 100.

[0090] The application is further described in the following embodiments.

[0091] Embodiment 1

[0092] A method for preparing a glass-based structure, comprising the following steps:

[0093] (1) Taking a microcrystalline glass comprising the following components in mole percentage: 20% of Li2O, 60% of SiO2, 3% of Na2O, 1% of K2O, 3% of Al2O3, 3% of P2O5, 6% of ZrO2, 1% of TiO2, 1% of MgO, 1% of CaO, and 1% of ZnO, wherein the crystal phase in the raw material of the microcrystalline glass comprises petalite and lithium disilicate, and the total content of the crystal phase is 90wt%; the microcrystalline glass is chemically strengthened to obtain a strengthened microcrystalline glass as a glass-based substrate to be used;

[0094] The glass-based substrate is subjected to pre-plating cleaning, specifically alkaline cleaning, so that the water drop angle of the surface thereof reaches 14°, wherein the process parameters of the alkaline cleaning include: the alkaline solution is an aqueous solution containing NaOH and KOH with pH=10.5, the alkaline cleaning temperature is 55°C, and the alkaline cleaning time is 120s.

[0095] (2) A 18nm-thick SiO2 layer is formed on one side surface of the glass-based substrate after the pre-plating cleaning as a medium layer between the glass-based substrate and an AF layer to be formed; wherein the forming process of the SiO2 layer includes: placing the glass-based substrate after the pre-plating cleaning in a sputtering cavity of a sputtering machine, placing a Si target in the sputtering cavity, setting the deposition temperature and the sputtering power of the Si target, after vacuumizing the sputtering cavity to a vacuum degree of 1×10 -3 Pa, turning on the Si target, introducing O2, and forming a 18nm-thick SiO2 layer on one side of the glass-based substrate at a coating rate of 1nm / min. After the coating of the SiO2 layer is completed, the vacuum degree in the sputtering cavity is controlled to be 1×10 -3 Pa, the ion source is turned on again, the voltage thereof is controlled to be 80V, argon (Ar) is introduced at a flow rate of 200sccm so that the cavity gas pressure is 10 -1 Pa, and the surface of the SiO2 layer is subjected to Ar plasma cleaning for 10min.

[0096] (3) A 100nm-thick AF layer is formed on the SiO2 layer by vacuum coating, and a Si-CH2 bond is formed between the AF layer and the SiO2 layer; wherein the vacuum degree during the coating of the AF layer is 1×10 -3 Pa, and the coating rate is ≤10nm / min; the protective gas during the coating is Ar.

[0097] Embodiment 2

[0098] The method for preparing the glass-based structure of Example 2 is different from that of Example 1 in that a 25 nm-thick SiO2layer is formed in step (2).

[0099] Example 3

[0100] The method for preparing the glass-based structure of Example 3 is different from that of Example 1 in that a 50 nm-thick SiO2layer is formed in step (2).

[0101] Example 4

[0102] The method for preparing the glass-based structure of Example 4 is different from that of Example 1 in that the SiO2layer formed in step (2) is 16 nm thick, and two plasma treatments are applied; the specific process is as follows: ① After the sputtering chamber is evacuated to a vacuum degree of 1 x 10 -3 Pa, the Si target is turned on, O2is introduced, and a 8 nm-thick SiO2layer is formed on one side of the glass substrate at a coating rate of 1 nm / min; ② The ion source is turned on, and the voltage is controlled at 80 V. Ar is introduced as a protective gas at a flow rate of 200 sccm to make the gas pressure in the chamber 10 -1 Pa, and the surface of the SiO2layer is cleaned by Ar plasma for 10 min; then, a 8 nm-thick SiO2layer is regrown according to step ①, and the Ar plasma cleaning according to step ① is performed again.

[0103] Example 5

[0104] The method for preparing the glass-based structure of Example 5 is different from that of Example 4 in that the AF layer formed in step (3) is 60 nm thick.

[0105] Comparative Example 1

[0106] A glass-based structure is prepared, which is different from Example 1 in that the pre-coating cleaning process is different, and the thickness of the SiO2layer is different.

[0107] Specifically, the preparation of the glass-based structure of Comparative Example 1 comprises:

[0108] (1) The same glass substrate as in Example 1 is pre-coated and cleaned to make the water drop angle of the surface reach 36°; wherein the pre-coating cleaning is neutral cleaning, and the process parameters include: the neutral cleaning solution is a water solution with pH = 7, the cleaning temperature is 55°C, and the cleaning time is 400 s;

[0109] (2) A 10 nm-thick SiO2layer is formed on one side of the glass substrate after the pre-coating cleaning according to the method of Example 1 above;

[0110] (3) The method of Example 1 above was imitated to form an AF layer with a thickness of 50 nm on the SiO2 layer by vacuum plating.

[0111] Comparative Example 2

[0112] A glass-based structure was prepared, which was different from Example 1 in that: 1) the pre-plating cleaning process was different: the same glass substrate as in Example 1 was subjected to a pre-plating cleaning, specifically an alkali cleaning, to make the water drop angle of its surface reach 8°; wherein the process parameters of the alkali cleaning included: the alkali solution was an aqueous solution containing NaOH with pH = 11.5, the alkali cleaning temperature was 55°C, and the time was 600s; 2) the thickness of the SiO2 layer in Comparative Example 2 was 10 nm, and the thickness of the AF layer was 50 nm.

[0113] The glass-based structures prepared in Examples 1-5 and Comparative Examples 1-2 above were subjected to a rubber friction test, a 24-hour alkali sweat resistance test, and a Mohs hardness scratch resistance test, and the results are summarized in Table 1 below.

[0114] Among them, the rubber friction test is to rub the surface of the glass-based structure provided with the AF layer with a rubber under a load of 1 kg at a speed of 40 circles / min, with a single stroke of 40 mm, and the limit number of times of rubber friction (Time to Failure, abbreviated as TTF) experienced when the water drop angle of the AF layer surface is greater than 100° is recorded. That is, after the number of times of rubber friction exceeds the limit number of times, the water drop angle of the AF layer surface is less than 100°.

[0115] Among them, the 24-hour alkali sweat resistance test is to place each glass-based structure immersed in a simulated alkali sweat solution with pH = 9.5 in a heat-resistant moisture-retaining bag and then in a constant temperature oven at 70°C, and observe whether there is a film layer peeling phenomenon after 24 hours; if not, it is considered to pass the alkali sweat resistance test.

[0116] Among them, the Mohs hardness scratch resistance test is to test the scratch on the surface of each glass-based structure sample provided with the AF layer with a metal pen with a Mohs hardness of 6 under different loads, and observe whether there is a scratch on the sample under an optical microscope, and record the load value corresponding to the appearance of the scratch on the surface of the sample (i.e. the load threshold value that produces the scratch).

[0117] Table 1

[0118]

[0119] From Table 1, it can be seen that the glass substrate of Comparative Example 1 has a water drop angle of 36° after pre-plating cleaning, which is not within the range of 10°-30° required by the present application. The glass-based structure prepared by forming a SiO2layer and an AF layer on the glass substrate of Comparative Example 1 can pass the 24h alkali sweat resistance test, but the limit number of rubber friction resistance is low, indicating that the wear resistance is poor. The load threshold value of the surface scratch caused by a metal pen with a Mohs hardness of 6 is only 500g, and the scratch resistance is poor. In Example 1-5, the glass substrate is treated to the same water drop angle of 14° by using the same pre-plating cleaning process, and then glass-based structures with different thicknesses of SiO2layer and AF layer are prepared. The thickness of the SiO2layer can be more than 16nm, and the thickness of the AF layer can be more than 100nm. The glass-based structures of Examples 1-5 can all pass the 24h alkali sweat resistance test, and the wear resistance and scratch resistance are improved. The limit number of rubber friction resistance is more than 3.5 times that of Comparative Example 1, and the load threshold value of the surface scratch is more than 3.5 times that of Comparative Example 1. Among them, the wear resistance and scratch resistance of the glass-based structure of Example 1 are improved more obviously than those of Comparative Example 1.

[0120] Figure 5 The surface state diagrams of the glass-based structures of Example 1 and Comparative Example 1 under the action of a metal pen with a Mohs hardness of 6 under different loads are also shown. From the diagrams, it can be seen that Figure 5 the surface of the glass-based structure of Comparative Example 1 under the action of a metal pen with a Mohs hardness of 6 at a load of 750g has obvious scratches (see the white dotted box), indicating that the load threshold value of the surface scratch is less than 750g. However, the surface of the glass-based structure of Example 1 under the action of a metal pen with a Mohs hardness of 6 at a load of 1400g has no obvious scratches (it should be noted that Figure 5 the right diagram in the rectangular box shows one of the areas subjected to the metal pen friction).

[0121] In addition, the surface of the glass substrate of Comparative Example 2 after pre-plating cleaning has a water drop angle of 8°, which is lower than the lower limit value of 10° required by the present application. The glass-based structure prepared by forming a SiO2layer and an AF layer on the glass substrate of Comparative Example 2 not only has poor wear resistance and scratch resistance, but also cannot pass the 24h alkali sweat resistance test. This may be due to the fact that the surface of the glass substrate of Comparative Example 2 becomes too rough after pre-plating cleaning, and the SiO2layer formed thereon is not enough to completely cover the surface.

[0122] To explore the influence of the water drop angle state achieved by different pre-plating processes on the coating structure characteristics and performance of the final glass product, the present application also provides the following Examples 6-10 and Comparative Examples 3-4.

[0123] Example 6

[0124] Preparation of a glass-based structure, which is different from example 1 in that: 1) the pre-plating cleaning process is different: the same glass substrate as example 1 is subjected to a pre-plating cleaning, specifically an alkali cleaning, so that the surface water drop angle reaches 20°; wherein the process parameters of the alkali cleaning include: the alkali solution is an aqueous NaOH solution with pH = 13, the alkali cleaning temperature is 55°C, and the alkali cleaning time is 120s; 2) the thickness of the SiO2layer is different, specifically 20nm; 3) the thickness of the AF layer is different, specifically 60nm.

[0125] Example 7

[0126] Preparation of a glass-based structure, which is different from example 1 in that: 1) the pre-plating cleaning process is different: the same glass substrate as example 1 is subjected to a pre-plating cleaning, specifically an acid cleaning, so that the surface water drop angle reaches 13°; the process parameters of the acid cleaning include: the acid solution is an aqueous dilute sulfuric acid solution with pH = 2.3, the acid cleaning temperature is 20°C, and the acid cleaning time is 300s; 2) the thickness of the AF layer is different, specifically 80nm.

[0127] Example 8

[0128] Preparation of a glass-based structure, which is different from example 1 in that: the pre-plating cleaning process is different: the same glass substrate as example 1 is subjected to a pre-plating cleaning, so that the surface water drop angle reaches 10°; wherein the pre-plating cleaning includes acid cleaning first and then alkali cleaning, the process parameters of the acid cleaning are the same as example 3, and the process parameters of the alkali cleaning are the same as example 1.

[0129] Example 9

[0130] Preparation of a glass-based structure, which is different from example 1 in that: the pre-plating cleaning process is different: the same glass substrate as example 1 is subjected to a pre-plating cleaning, so that the surface water drop angle reaches 22°; wherein the pre-plating cleaning includes box-type plasma cleaning first and then alkali cleaning, the power of the box-type plasma cleaning is 800W, and the cleaning time is 180s, and the process parameters of the alkali cleaning are the same as example 1.

[0131] Example 10

[0132] Preparation of a glass-based structure, which is different from example 1 in that: the pre-plating cleaning process is different: the same glass substrate as example 1 is subjected to a pre-plating cleaning, so that the surface water drop angle reaches 25°; wherein the pre-plating cleaning includes flame-type plasma cleaning first and then alkali cleaning, the power of the flame-type plasma cleaning is 800W, and the cleaning time is 120s, and the process parameters of the alkali cleaning are the same as example 1.

[0133] Comparative example 3

[0134] A glass-based structure was prepared, which was different from Example 1 in that: 1) the pre-plating cleaning process was different: the same glass substrate as in Example 1 was pre-plated and cleaned to make the surface water drop angle reach 5°; wherein the pre-plating cleaning included acid pickling and alkali washing, the process parameters of the acid pickling included: the acid solution was a dilute sulfuric acid aqueous solution with pH = 2.0, the acid pickling was carried out at a temperature of 20℃ for 600s; the process parameters of the alkali washing were the same as in Example 1; 2) the thickness of the SiO2 layer in Comparative Example 3 was 8nm, and the thickness of the AF layer was 12nm.

[0135] Comparative Example 4

[0136] A glass-based structure was prepared, which was different from Example 1 in that: 1) the pre-plating cleaning process was different: the same glass substrate as in Example 1 was pre-plated and cleaned to make the surface water drop angle reach 40°; the pre-plating cleaning was specifically water washing using water with a temperature of 55℃ for 400s. 2) the thickness of the SiO2 layer in Comparative Example 4 was 8nm, and the thickness of the AF layer was 12nm.

[0137] Figure 6 The FTIR spectra of the glass-based structures containing the same SiO2 layer and AF layer prepared by using the same plating process for the glass substrates with different water drop angles were also summarized; wherein the wave number corresponding to the dashed line is the infrared absorption peak position of the Si-CH2 bond. Figure 6 In the above embodiments and comparative examples, the implementation of the different water drop angles of each glass substrate to be plated can be referred to.

[0138] From Figure 6 It can be known that when the surface water drop angle of the glass substrate to be plated is in the range of 10°-30°, the Si-CH2 bond is formed between the AF layer and the SiO2 layer located thereunder in the obtained glass-based structure (in the infrared spectrum of Figure 6 , the characteristic absorption peak is reflected at a wave number of 645cm -1 ), which increases the adhesion of the AF layer on the SiO2 layer, thereby facilitating the improvement of the rubber friction resistance of the glass-based structure. When the surface water drop angle of the glass substrate to be plated is less than 10° (for example, 5°) or greater than 30° (for example, 40°), no Si-CH2 bond is formed between the AF layer and the SiO2 layer located thereunder in the obtained glass-based structure.

[0139] Table 2 below summarizes the different water drop angles reached after pre-plating cleaning of the glass substrates of Examples 6-10 and Comparative Examples 3-4, the limiting number of rubber friction resistance after plating and cleaning, and the test results of the glass-based structures prepared by using the plating process.

[0140] Table 2

[0141]

[0142] From Table 2, it can be seen that the surface water drop angles of the glass substrates of Examples 6-10 of the present application after pre-plating cleaning are different from those of Examples 1-5, but are all in the range of 10°-30°, and the glass-based structures formed on the basis of the glass substrates all pass the 24h alkali sweat resistance test, and have good resistance to rubber friction and good Mohs hardness scratch resistance, which are better than those of the glass-based structures formed on the glass substrates whose water drop angles are not in the range of 10°-30° (Comparative Examples 3-4).

[0143] The above merely expresses exemplary embodiments of the present application, which are described in detail, but should not be construed as limiting the scope of the patent of the present application. It should be noted that, for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the scope of protection of the present application. Therefore, the scope of protection of the patent of the present application should be subject to the appended claims.

[0144] In the present application, "and / or" describes the association relationship of associated objects, which means that there can be three kinds of relationships, for example, A and / or B, which can mean that A exists alone, A and B exist together, and B exists alone, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0145] In the description of the present application, unless otherwise specified, "a plurality of" means more than or equal to two. "At least one" means one or more. "At least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0146] In addition, in the present application, the numerical range indicated by "-" means a range including the minimum value and the maximum value indicated by the numbers before and after "-" respectively. In the present application, the expressions related to the range of parameters, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above", "below", all include the number. The values and value ranges involved in the embodiments of the present application are approximate values, which may have a certain range of error due to the influence of manufacturing process / testing method, etc., which can be considered negligible by those skilled in the art.

Claims

1. A glass-based structural component, characterized in that, The glass-based structural component includes a glass substrate, and a dielectric layer and an anti-fingerprint layer sequentially stacked on one side surface of the glass substrate; wherein, the dielectric layer includes a silicon dioxide layer disposed near the anti-fingerprint layer, the anti-fingerprint layer contains a -CH2- structure, and a Si-CH2 bond is formed between the silicon dioxide layer and the anti-fingerprint layer.

2. The glass-based structural component as described in claim 1, characterized in that, The combined thickness of the dielectric layer and the anti-fingerprint layer is greater than 70 nm.

3. The glass-based structural component as described in claim 1 or 2, characterized in that, The thickness of the silicon dioxide layer is greater than 16 nm.

4. The glass-based structural component as described in claim 3, characterized in that, The thickness of the silicon dioxide layer is in the range of 18nm-50nm.

5. The glass-based structural member as described in any one of claims 1-4, characterized in that, The thickness of the anti-fingerprint layer is above 50 nm.

6. The glass-based structural component as described in claim 5, characterized in that, The thickness of the anti-fingerprint layer is in the range of 60nm-100nm.

7. The glass-based structural component according to any one of claims 1-6, wherein the anti-fingerprint layer comprises a perfluoroalkyl compound or a polyfluoroalkyl compound containing the -CH2- structure.

8. The glass-based structural member according to any one of claims 1-7, characterized in that, The dielectric layer also includes a silicon carbide layer or an aluminum oxide layer disposed near the side of the glass substrate.

9. The glass-based structural component as described in claim 8, characterized in that, The thickness of the silicon carbide layer or the aluminum oxide layer is less than 3 nm.

10. The glass-based structural member according to any one of claims 1-9, characterized in that, In the glass-based structural component, the initial water droplet angle of the exposed surface of the anti-fingerprint layer is above 110°, and the water droplet angle after 13,000 rubber rubbings is greater than 100°.

11. The glass-based structural member according to any one of claims 1-10, characterized in that, The load threshold for scratching the glass-based structural component at a Mohs hardness of 6 is above 750g.

12. The glass-based structural member according to any one of claims 1-11, characterized in that, The glass-based structural component, after being soaked in simulated alkaline sweat at pH 9.5, did not show any film peeling after being kept in a constant temperature chamber at 70°C for 24 hours.

13. The glass-based structural member according to any one of claims 1-12, characterized in that, The glass-based structural component has an average transmittance of ≥88% for light with wavelengths between 400nm and 700nm; the Lab color chromaticity index b value satisfies: |b value|≤1.

2.

14. The glass-based structural member according to any one of claims 1-13, characterized in that, The glass substrate is reinforced microcrystalline glass or reinforced ordinary glass without crystalline phase.

15. The glass-based structural member according to any one of claims 1-14, characterized in that, The glass substrate is a reinforced microcrystalline glass, which, by molar percentage, comprises the following components: Li2O: 10%-25%, SiO2: 58%-72%, Na2O and K2O: 3%-7%, Al2O3: 2%-8%, P2O5+ZrO2+TiO2: 2%-13%, MgO+CaO+ZnO: 0-3%, B2O3: 0-5%.

16. The glass-based structural member as described in claim 14 or 15, characterized in that, The reinforced glass-ceramic comprises a glass phase and a crystalline phase, wherein the crystalline phase comprises at least one of quartz, spodumene, petalite, lithium silicate, lithium disilicate, and spinel; and the total mass content of the crystalline phase in the reinforced glass-ceramic is greater than or equal to 20%.

17. The glass-based structural member as described in claim 14, characterized in that, According to molar percentages, the strengthened ordinary glass comprises the following components: SiO2: 45%-59.5%, Al2O3: 9%-30%, MgO: 7%-30%, ZnO: 0-5%, ZrO2: 0-10%, La2O3: 0-10%, Li2O: 5.5%-15%, Na2O: 1%-5%, K2O: 2%-5%.

18. A method for preparing a glass-based structural component, characterized in that, include: The glass substrate is subjected to a pre-plating cleaning process selected from at least one of alkaline washing, acid washing, and plasma treatment, so that the water droplet angle on the surface of the glass substrate is in the range of 10°-30°. A dielectric layer including a silicon dioxide layer is formed on one side surface of the glass substrate after pre-plating cleaning; An anti-fingerprint layer is formed on the silicon dioxide layer; wherein, Si-CH2 bonds are formed between the silicon dioxide layer and the anti-fingerprint layer.

19. The preparation method according to claim 18, characterized in that, The alkaline solution used for the alkaline washing has a pH between 9 and 11, and the solute in the alkaline solution includes one or more of sodium metasilicate, NaOH, Na2CO3, and NaHCO3; the temperature of the alkaline washing is in the range of 20-95℃.

20. The preparation method according to claim 18 or 19, characterized in that, The acid solution used for pickling has a pH between 2 and 4, and the solute in the acid solution includes one or more of sulfuric acid, hydrochloric acid, nitric acid, and oxalic acid, but does not contain hydrofluoric acid; the pickling temperature is in the range of 20-95℃.

21. The preparation method according to any one of claims 18-20, characterized in that, The plasma treatment equipment includes one or more types such as box-type, flame-type, and glow discharge-type; the power of the plasma treatment is in the range of 500W-1500W, and the treatment time is in the range of 30s-1200s.

22. The preparation method according to any one of claims 18-21, characterized in that, Both the dielectric layer and the anti-fingerprint layer are formed by vacuum deposition; wherein, the vacuum degree during the deposition process of the dielectric layer is ≤5×10⁻⁶. -3 Pa, coating rate ≤ 2 nm / min; vacuum degree during the coating process of the anti-fingerprint layer ≤ 5 × 10 -3 Pa, coating rate ≤10nm / min; the protective gas during the coating process is argon or nitrogen.

23. The preparation method according to any one of claims 18-22, characterized in that, During or after the formation of the dielectric layer, plasma cleaning is also performed; wherein the plasma cleaning is performed in a coating apparatus used to form the dielectric layer.

24. A housing assembly, characterized in that, This includes glass-based structural components as described in any one of claims 1-17, or glass-based structural components prepared by the preparation method described in any one of claims 18-23.

25. An electronic device, characterized in that, It includes a housing assembled on the outside of the electronic device and a circuit board located inside the housing, the housing including the housing assembly as claimed in claim 24 or the glass-based structural member as claimed in any one of claims 1-17.

26. The electronic device as claimed in claim 25, characterized in that, The housing includes a display cover assembled on the front side of the electronic device, the display cover being either the housing assembly or the glass-based structural member.

27. The electronic device as claimed in claim 25 or 26, characterized in that, The housing includes a rear cover assembled on the rear side of the electronic device, the rear cover being either the housing assembly or the glass-based structural member.

28. The electronic device according to any one of claims 25-27, characterized in that, The electronic device also includes a camera assembly located inside the housing, the housing including a camera protective cover, the camera protective cover covering the camera assembly, the camera protective cover being either the housing assembly or the glass-based structural component.

Images