Ultrathin glass, reinforced impact-resistant ultrathin glass and preparation method and application thereof

Abstract

The invention provides ultra-thin glass and reinforced impact-resistant ultra-thin glass as well as a preparation method and application thereof, the composition of the ultra-thin glass is controlled, and the components of the ultra-thin glass are controlled to simultaneously meet the following relational expressions (1)-(3): (1) ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) is more than or equal to 11.00% and less than or equal to 20%; (2) 6% < = ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) < = 14% (3) 4.1 < = ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) < = 5.1. The ultra-thin glass provided by the invention keeps an ultra-high Young modulus under the condition that the thickness is not more than 0.40 mm, and has a relatively low thermal expansion coefficient; the reinforced impact-resistant ultrathin glass prepared by the preparation method has good impact resistance and falling resistance, and also has good bending strength and low warping performance.

Description

Technical Field

[0001] The present application relates to the technical field of glass materials, and in particular to an ultra-thin glass and a reinforced impact-resistant ultra-thin glass, and a preparation method and use thereof. Background Art

[0002] With the rapid rise of foldable devices, the application of ultra-thin glass in foldable devices has gradually become popular. However, during the use of foldable devices, due to the insufficient strength of ultra-thin glass, the glass will break when it falls or is impacted, affecting the actual user experience. After testing and analysis, the surface quality of the glass is one of the main reasons affecting the strength of ultra-thin glass, and it is closely related to its production method.

[0003] In recent years, the field of foldable devices has launched products using ultra-thin glass, including primary molded products and secondary molded (chemically thinned) ultra-thin glass products. Primary molded products refer to ultra-thin original sheets directly produced by methods such as the down-draw method, which are then cut, strengthened, coated, and processed to form ultra-thin glass cover plates. Secondary molded products are relatively thick glass original sheets that are thinned to a specific thickness through chemical technology and then post-processed. In contrast, the surface quality of secondary molded products is difficult to control, while primary molded products have better surface quality, higher strength, and lower cost, giving them an advantage in market competition.

[0004] In addition, with the continuous development of the electronic products industry, the market has higher and higher performance requirements for ultra-thin glass materials, especially in terms of taking into account the bending strength while ensuring its impact resistance and drop resistance. Increasing the Young's modulus of ultra-thin glass can prevent ultra-thin glass from deforming when subjected to force and improve its impact resistance; at the same time, reducing its thermal expansion coefficient can solve the technical problem of excessive warping. In addition, chemical strengthening can also improve the surface CS performance of ultra-thin glass, thereby improving its impact resistance and drop resistance. Therefore, ultra-thin glass with high Young's modulus, low thermal expansion coefficient and high CS has become the choice of more terminal manufacturers and is also a hot spot that urgently needs research and development. Summary of the invention

[0005] The purpose of the present application is to provide an ultra-thin glass with a high Young's modulus and a low thermal expansion coefficient, which can improve its impact resistance and reduce the warping of the prepared strengthened ultra-thin glass. In addition, after chemical strengthening, the obtained strengthened impact-resistant ultra-thin glass further has a high surface compressive stress, improves its impact resistance and drop resistance, and also has good bending strength.

[0006] In a first aspect, the present application provides an ultra-thin glass, which comprises the following components, measured by molar percentage of oxides:

[0007] SiO2: 63.50 - 66.00 mol%;

[0008] Al2O3: 10.50 - 12.50 mol%;

[0009] P2O5: 0.00 - 1.00 mol%;

[0010] Li2O: 0.00 - 3.00 mol%;

[0011] Na2O: 12.00 - 14.00 mol%;

[0012] K2O: 1.00 - 4.00 mol%;

[0013] MgO: 5.00 - 7.00 mol%;

[0014] Zr2O: 0.10 - 1.10 mol%;

[0015] B2O3: 0.20 - 1.10 mol%;

[0016] Wherein, each component simultaneously satisfies the following relationships shown in (1) to (3):

[0017] (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%;

[0018] (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14%

[0019] (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.1.

[0020] Furthermore, in some embodiments of the present application, the thickness of the ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm.

[0021] Furthermore, in some embodiments of the present application, the average linear thermal expansion coefficient of the ultra-thin glass ≤ 94×10 -7 / °C, preferably 83×10 -7 / °C - 94×10 -7 / °C.

[0022] Furthermore, in some embodiments of the present application, the Young's modulus of the ultra-thin glass is not less than 72.0 GPa; and / or

[0023] when the ultra-thin glass has a thickness of 0.70 mm, the light transmittance at 550 nm ≥ 91.0%.

[0024] In a second aspect, the present application also provides a method for preparing the ultra-thin glass described in the first aspect, including the following steps: mixing the raw materials for preparing the glass, melting them, forming them in one step, and then obtaining the ultra-thin glass through annealing.

[0025] Further, in some embodiments of the present application, the melting temperature is 1300°C - 1700°C, and the melting time is 4h - 240h.

[0026] Further, in some embodiments of the present application, the annealing temperature is 550°C - 650°C, and the annealing treatment time is 1min - 1440min.

[0027] Further, in some embodiments of the present application, the one-step forming includes any one of slot-draw, overflow down-draw, double-draw thinning method, and the float process.

[0028] In a third aspect, the present application also provides a strengthened impact-resistant ultra-thin glass with a thickness of t, which includes double-sided strengthening layers and a tensile stress layer. The strengthening layers extend from the surface of the strengthened impact-resistant ultra-thin glass towards the interior direction, wherein the double-sided strengthening layers are symmetrically distributed, and the thickness of each strengthening layer is not higher than 0.28t;

[0029] In the central region of the tensile stress layer, in terms of molar percentage of oxides, it includes the following components:

[0030] SiO2: 63.50 - 66.00 mol%;

[0031] Al2O3: 10.50 - 12.50 mol%;

[0032] P2O5: 0.00 - 1.00 mol%;

[0033] Li2O: 0.00 - 3.00 mol%;

[0034] Na2O: 12.00 - 14.00 mol%;

[0035] K2O: 1.00 - 4.00 mol%;

[0036] MgO: 5.00 - 7.00 mol%;

[0037] Zr2O: 0.10 - 1.10 mol%;

[0038] B2O3: 0.20 - 1.10 mol%;

[0039] Among them, each component simultaneously satisfies the following relationships shown in (1) - (3):

[0040] (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%;

[0041] (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14%

[0042] (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.1.

[0043] Further, in some embodiments of the present application, the thickness t of the impact-resistant ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm.

[0044] Further, in some embodiments of the present application, the chemical strengthening process of the impact-resistant ultra-thin glass includes single-step chemical strengthening.

[0045] Further, in some embodiments of the present application, in the single-step chemical strengthening, a salt bath containing KNO3 is used for chemical strengthening; preferably, in the single-step chemical strengthening, the content of KNO3 in the salt bath containing KNO3 is 100 wt%.

[0046] Further, in some embodiments of the present application, the temperature of the single-step chemical strengthening is 380°C to 500°C, and the time of the single-step chemical strengthening is 10 min to 360 min; preferably, the temperature of the single-step chemical strengthening is 390°C to 500°C, preferably 390°C; further preferably, the time of the single-step chemical strengthening is 20 min to 360 min, more preferably 90 min.

[0047] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.10 mm - 0.40 mm, its surface compressive stress CS ≥ 1100 MPa, and preferably its surface compressive stress CS is 1100 MPa - 1300 MPa.

[0048] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, its surface compressive stress CS ≥ 1100 MPa; preferably its surface compressive stress CS is 1100 MPa - 1200 MPa.

[0049] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, its depth of the compressive stress layer Dol ≤ 11.00 μm, and preferably its depth of the compressive stress layer Dol is 8.00 μm - 11.00 μm.

[0050] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm, and preferably the depth Dol of its compressive stress layer is 8.00 μm - 11.00 μm.

[0051] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, its average drop height ≥ 60 mm, and preferably its average drop height is 60.00 mm - 250.00 mm.

[0052] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, its average drop height ≥ 200.00 mm, and preferably its average drop height is 200.00 mm - 250.00 mm.

[0053] Further, in some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its bending critical curvature radius ≤ 0.40 mm; preferably its bending critical curvature radius is 0.30 mm - 0.40 mm.

[0054] Fourthly, the present application also provides an application of the ultra-thin glass described in the first aspect or the ultra-thin glass prepared by the preparation method of the ultra-thin glass described in the second aspect or the impact-resistant ultra-thin glass described in the third aspect in the field of electronic products.

[0055] Further, in some embodiments of the present application, the application in the field of electronic products is an application on the display screen of a foldable electronic device.

[0056] Further, in some embodiments of the present application, the application in the field of electronic products is an application in a color filter, a filter printing electronic device, a sensor of a touch panel, a fingerprint sensor, a thin film battery substrate, a mobile electronic device, a semiconductor interposer, a flexible / foldable display, a solar cell or a display.

[0057] Fifthly, the present application also provides an electronic device, including the ultra-thin glass described in the first aspect or the ultra-thin glass prepared by the preparation method of the ultra-thin glass described in the second aspect or the impact-resistant ultra-thin glass described in the third aspect.

[0058] Sixthly, the present application also provides a glass product, including the ultra-thin glass described in the first aspect or the ultra-thin glass prepared by the preparation method of the ultra-thin glass described in the second aspect or the impact-resistant ultra-thin glass described in the third aspect.

[0059] Advantages of the present application:

[0060] 1. The present application provides an ultra-thin glass. By controlling its composition to conform to a specific component correlation, the prepared ultra-thin glass maintains an ultra-high Young's modulus at a thickness not exceeding 0.40 mm and has a low coefficient of thermal expansion; furthermore, it has good impact resistance and the prepared strengthened impact-resistant ultra-thin glass has low warpage performance.

[0061] 2. The present application also provides a strengthened impact-resistant ultra-thin glass. By controlling the composition of the impact-resistant ultra-thin glass to conform to a specific component correlation, when the thickness t of the prepared strengthened impact-resistant ultra-thin glass is 0.10 mm - 0.30 mm, its surface compressive stress CS ≥ 1100 MPa, the depth of the compressive stress layer Dol ≤ 11.00 μm, and it also has good drop resistance and bending resistance. Brief Description of the Drawings

[0062] To more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings required for use in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0063] Figure 1 It is a schematic diagram of the test device for the pen-drop impact height in the present application; wherein, 1 - marker pen, 2 - pen-drop impact height, 3 - coated glass sample, 3-1 - the first surface of the coated glass sample, 3-2 - the second surface of the coated glass sample, 4 - PVC board. Detailed Embodiments

[0064] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0065] In the present application, the surface compressive stress (CS) is the compressive stress value of the compressive stress layer formed on the glass surface after chemical strengthening due to ion exchange treatment. For ion exchange treatment, the surface of the glass is ion-exchanged to form a surface layer with residual compressive stress, which is the compressive stress layer.

[0066] In the present application, the depth of the compressive stress layer (DOL) is the layer thickness of the glass surface where ion exchange occurs during chemical strengthening.

[0067] In this application, the central tensile stress (CT) is the value of the stress formed at the center of the strengthened glass, which is opposite to the direction of the surface compressive stress, after the compressive stress layer is formed on the glass surface through chemical strengthening.

[0068] In this application, the transmittance refers to the ratio of the radiant energy that is projected and transmitted through an object to the total radiant energy projected onto the object during the process where the incident light flux enters from the illuminated surface or the incident surface of the medium and exits from the other side.

[0069] Test methods:

[0070] 1. Stress test

[0071] In this application, the FSM-6000 device is used to test the CS, CT, and DOL of the glass to be tested. During the test, the refractive index is set to 1.51 and the photoelastic coefficient is set to 28.6.

[0072] 2. Thickness test

[0073] In this application, a digital micrometer mitutoyo 406-250-30 or a laser thickness gauge is used to test the thickness of the glass to be tested.

[0074] 3. Optical property test

[0075] In this application, according to the national standard "GB / T 7962.12-2010 Test Methods for Colorless Optical Glass - Part 12: Spectral Transmittance within the Spectrum", a haze meter is used to test the transmittance and optical b value of the glass to be tested. Specifically, the haze meter is used to test the transmittance of the same batch of 5 glasses to be tested for light of different wavelengths and their optical b values. The average value of the transmittances measured for the 5 glasses to be tested at a wavelength of 550 nm is taken as the transmittance result of the glass to be tested at a wavelength of 550 nm. The average value of the optical b values measured for the 5 glasses to be tested is taken as the optical b value result of the glass to be tested.

[0076] The haze meter used in the test of the present invention is the Konica Minolta Spectrophotometer CM-3600A from Japan. The light-receiving optical system is transmission, the spectral splitting method is a plane diffraction grating, the wavelength range is 360 nm to 740 nm, the wavelength interval is 10 nm, the illumination light source is a pulsed xenon lamp X4, the ambient temperature where the instrument is placed is 24 °C, and the air humidity is 40%.

[0077] 4. Young's modulus test

[0078] In this application, the UMS-100 ultrasonic material characterization system is used to test the Young's modulus of the glass to be tested through acoustic waves.

[0079] 5. Density test

[0080] The density of the glass to be tested is tested using the electronic density balance SD-200L produced by Japan ALFA MIRAGE based on the principle of “Archimedes drainage method”.

[0081] 6. Refractive index test

[0082] In this application, the test was carried out according to the GB / T7962.1-2010 method.

[0083] 7. Average pen impact height test

[0084] In this application, a marker pen is used to test the pen impact, and the pen impact height is obtained by referring to the method in the group standard T / CSTM 00409-2021. Before testing the pen impact height, a 50 μm PE film is coated on the first surface and the second surface of the glass to be tested using a roller press, and the average of the pen impact heights measured on 5 pieces of the coated glass to be tested is taken as the average pen impact height of the glass to be tested, refer to Figure 1 .

[0085] 8. Bending critical curvature radius test

[0086] In this application, the national standard GB / T 38686-2020 "Ultra-thin glass flexibility test method two-point bending method" was used for testing.

[0087] 9. Thermal expansion test

[0088] The present application tests the average linear thermal expansion coefficient of the glass to be tested in the range of 25 to 300° C. in accordance with the GB / T7962.16-2010 test method.

[0089] 10. Warpage value test

[0090] The present application uses a two-dimensional measuring instrument to test the warpage value of the glass to be tested.

[0091] Foldable devices, especially foldable screens, require the cover and substrate of the display screen to be flexible so that they can be bent and rolled up without obvious creases when unfolded. They also have high service life requirements and extremely high light transmittance requirements. However, the existing ultra-thin glass used for foldable screens cannot have good bending strength while ensuring its impact resistance and drop resistance, and low warping performance.

[0092] Based on this, the present application proposes an ultra-thin glass, which can achieve high Young's modulus, low expansion coefficient, and high impact resistance by controlling its composition to meet specific component correlations. The prepared reinforced ultra-thin glass has high surface compressive stress, and has high impact resistance and drop resistance, bending strength, and low warping performance.

[0093] In a first aspect, the present application provides an ultra-thin glass, comprising the following components:

[0094] SiO2: 63.50 - 66.00 mol%;

[0095] Al2O3: 10.50 - 12.50 mol%;

[0096] P2O5: 0.00 - 1.00 mol%;

[0097] Li2O: 0.00 - 3.00 mol%;

[0098] Na2O: 12.00 - 14.00 mol%;

[0099] K2O: 1.00 - 4.00 mol%;

[0100] MgO: 5.00 - 7.00 mol%;

[0101] Zr2O: 0.10 - 1.10 mol%;

[0102] B2O3: 0.20 - 1.10 mol%;

[0103] Wherein, each component simultaneously satisfies the following relationships shown in (1) to (3):

[0104] (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%;

[0105] (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14%

[0106] (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.1.

[0107] In the ultra-thin glass of the present application, SiO2 is an oxide that forms the glass network skeleton and is used to stabilize the network structure of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of SiO2 is 63.50 mol% to 66.00 mol%, preferably 64.00 mol% to 66.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of SiO2 can be: 63.50 mol%, 63.60 mol%, 63.70 mol%, 63.80 mol%, 63.90 mol%, 64.00 mol%, 64.10 mol%, 64.20 mol%, 64.30 mol%, 64.40 mol%, 64.50 mol%, 64.60 mol%, 64.70 mol%, 64.80 mol%, 64.90 mol%, 65.00 mol%, 65.10 mol%, 65.20 mol%, 65.30 mol%, 65.40 mol%, 65.50 mol%, 65.60 mol%, 65.70 mol%, 65.80 mol%, 65.90 mol% or 66.00 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0108] In the glass system of the present application, Al2O3 is used to construct the glass skeleton and plays a role in supplementing the network; it can also adjust the ion exchange rate by changing the spatial dimensions for ion exchange within the glass network. Since the application of the ultra-thin glass in the present application has extremely high requirements for the flexural strength, the dosage of Al2O3 also needs to be limited within a specific range; too high an Al2O3 content will result in very high melting temperature and working temperature of the glass, which is prone to crystallization and poor transparency and flexibility of the glass, while too low an Al2O3 content will lead to poor chemical stability of the glass. In some embodiments of the present application, calculated in terms of the molar percentage of oxides, the content of Al2O3 is 10.50 mol% - 12.50 mol%, preferably 11.00 mol% - 12.50 mol%. In some embodiments of the present application, calculated in terms of the molar percentage of oxides, the content of Al2O3 can be: 10.50 mol%, 10.60 mol%, 10.70 mol%, 10.80 mol%, 10.90 mol%, 11.00 mol%, 11.10 mol%, 11.20 mol%, 11.30 mol%, 11.40 mol%, 11.50 mol%, 11.60 mol%, 11.70 mol%, 11.80 mol%, 11.90 mol%, 12.00 mol%, 12.10 mol%, 12.20 mol%, 12.30 mol%, 12.40 mol% or 12.50 mol% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0109] In the glass system of the present application, P2O5 is a glass-forming oxide, and it exists in the network structure in the form of phospho-oxygen tetrahedron [PO4], playing a role in forming the glass network structure. In some embodiments of the present application, calculated in terms of the molar percentage of oxides, the content of P2O5 is 0.00 mol% - 1.00 mol%, preferably 0.10 mol% - 1.00 mol%. In some embodiments of the present application, calculated in terms of the molar percentage of oxides, the content of P2O5 can be 0.00 mol%, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.60 mol%, 0.70 mol%, 0.80 mol%, 0.90 mol% or 1.00 mol% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0110] In the glass system of the present application, ZrO₂ acts as a network intermediate. An appropriate amount of ZrO₂ can increase the viscosity, Young's modulus, refractive index, chemical stability of the glass and reduce the thermal expansion coefficient of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of ZrO₂ is 0.10 mol% - 1.10 mol%, preferably 0.20 mol% - 1.10 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of ZrO₂ can be 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.60 mol%, 0.70 mol%, 0.80 mol%, 0.90 mol%, 1.00 mol% or 1.10 mol% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0111] In the glass system of the present application, Na₂O is an external glass network oxide, which can provide free oxygen to increase the oxygen-silicon ratio in the glass structure, facilitate the improvement of the viscosity of the glass, promote the melting and clarification of the glass melt, increase the Na-K exchange in the glass, and achieve high CS. However, too high a content of Na₂O will affect the network structure of the glass, thereby affecting the stability of the glass, increasing the thermal expansion coefficient of the glass, and thus increasing the warping of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of Na₂O is 12.00 mol% - 14.00 mol%, preferably 12.10 mol% - 14.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of Na₂O can be 12.00 mol%, 12.10 mol%, 12.20 mol%, 12.30 mol%, 12.40 mol%, 12.50 mol%, 12.60 mol%, 12.70 mol%, 12.80 mol%, 12.90 mol%, 13.00 mol%, 13.10 mol%, 13.30 mol%, 13.40 mol%, 13.50 mol%, 13.60 mol%, 13.70 mol%, 13.80 mol%, 13.90 mol% or 14.00 mol% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0112] In the glass system of the present application, K2O is an external oxide of the glass network and can affect the chemical strengthening effect in the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of K2O is 1.00 mol% - 4.00 mol%, preferably 1.10 mol% - 4.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of K2O can be 1.00 mol%, 1.10 mol%, 1.20 mol%, 1.60 mol%, 1.80 mol%, 2.00 mol%, 2.20 mol%, 2.40 mol%, 2.60 mol%, 2.80 mol%, 3.00 mol%, 3.20 mol%, 3.40 mol%, 3.60 mol%, 3.80 mol% or 4.00 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0113] In the glass system of the present application, Li2O is an external oxide of the glass network, which is beneficial to improving the melting and forming effect of ultra-thin glass. Replacing Na2O with Li2O can reduce the thermal expansion coefficient of the glass and ensure the warpage of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of Li2O is 0.00 mol% - 3.00 mol%, preferably 0.10 mol% - 3.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of Li2O can be: 0.00 mol%, 0.10 mol%, 0.30 mol%, 0.50 mol%, 0.70 mol%, 0.90 mol%, 1.10 mol%, 1.30 mol%, 1.50 mol%, 1.70 mol%, 1.90 mol%, 2.10 mol%, 2.30 mol%, 2.50 mol%, 2.70 mol%, 2.90 mol% or 3.00 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0114] In the glass system of the present application, MgO can reduce the forming temperature of the glass and improve the Young's modulus of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of MgO is 5.00 mol% - 7.00 mol%, preferably 5.10 mol% - 7.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of MgO can be: 5.00 mol%, 5.10 mol%, 5.20 mol%, 5.30 mol%, 5.40 mol%, 5.50 mol%, 5.60 mol%, 5.70 mol%, 5.90 mol%, 6.00 mol%, 6.10 mol%, 6.20 mol%, 6.30 mol%, 6.40 mol%, 6.50 mol%, 6.70 mol%, 6.80 mol%, 6.90 mol% or 7.00 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0115] In the glass system of the present application, B2O3 helps to reduce the melting temperature of the substrate glass and improve the properties such as the light transmittance and overall uniformity of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of B2O3 is 0.20 mol% - 1.10 mol%, preferably 0.25 mol% - 1.10 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of B2O3 can be: 0.20 mol%, 0.25 mol%, 0.30 mol%, 0.35 mol%, 0.40 mol%, 0.45 mol%, 0.50 mol%, 0.55 mol%, 0.60 mol%, 0.65 mol%, 0.70 mol%, 0.75 mol%, 0.80 mol%, 0.85 mol%, 0.90 mol%, 0.95 mol%, 1.00 mol%, 1.05 mol% or 1.10 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0116] In the glass system of the present application, Y2O3 can improve the Young's modulus and chemical stability of the glass. In some embodiments of the present application, based on the molar percentage of oxides, the content of Y2O3 is 0.00 mol% - 1.00 mol%, preferably 0.10 mol% - 1.00 mol%. In some embodiments of the present application, based on the molar percentage of oxides, the content of Y2O3 can be: 0.00 mol%, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.60 mol%, 0.70 mol%, 0.80 mol%, 0.90 mol% or 1.00 mol%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0117] In the present application, the thickness of the ultra-thin glass does not exceed 0.70 mm. In some embodiments of the present application, the thickness of the ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm. In some embodiments of the present application, the thickness of the ultra-thin glass can be 0.40 mm, 0.30 mm, 0.20 mm, 0.10 mm, 0.09 mm, 0.08 mm, 0.07 mm, 0.06 mm, 0.05 mm, 0.04 mm, 0.03 mm or 0.02 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0118] In the present application, based on the ultra-thin glass, its coefficient of thermal expansion is reduced through its own composition and structure, thereby reducing the warpage of the strengthened anti-impact ultra-thin glass prepared therefrom. In some embodiments of the present application, the average linear thermal expansion coefficient of the ultra-thin glass ≤ 94×10 -7 / ℃, preferably 83×10 -7 / ℃ - 94×10 -7 / ℃. In some embodiments of the present application, the average linear thermal expansion coefficient of the ultra-thin glass can be 83×10 -7 / ℃, 85×10 -7 / ℃, 87×10 -7 / ℃, 88×10 -7 / ℃, 89×10 -7 / ℃, 90×10 -7 / ℃, 91×10 -7 / ℃, 92×10 -7 / ℃, 93×10 -7 / ℃ or 94×10 -7 / °C, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in an embodiment, any of the above ranges can be combined with any other range.

[0119] In some embodiments of the present application, the Young's modulus of the ultra-thin glass is not less than 72.0 GPa, preferably not less than 73.0 GPa. In some embodiments of the present application, the Young's modulus of the ultra-thin glass is 72.0 GPa - 85.0 GPa. In some embodiments of the present application, the Young's modulus of the ultra-thin glass can be 72.0 GPa, 73.0 GPa, 74.0 GPa, 75.0 GPa, 76.0 GPa, 77.0 GPa, 78.0 GPa, 78.6 GPa, 79.0 GPa, 79.5 GPa, 80.0 GPa, 81.0 GPa, 82.0 GPa, 83.0 GPa, 84.0 GPa or 85.0 GPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in an embodiment, any of the above ranges can be combined with any other range.

[0120] In some embodiments of the present application, when the thickness of the ultra-thin glass is 0.70 mm, the light transmittance at 550 nm is ≥ 91.0%. In some embodiments of the present application, when the thickness of the ultra-thin glass is 0.70 mm, the light transmittance at 550 nm is 91.0% - 93.0%.

[0121] In a second aspect, the present application provides a method for preparing the ultra-thin glass as described above, comprising the following steps:

[0122] Mix the raw materials for preparing the glass, melt them, form them in one step, and then anneal to obtain the ultra-thin glass.

[0123] Among them, the mixing process is to mix the raw materials for preparing the glass in a container by using an existing mixing method, such as stirring. The stirring speed, the temperature and the atmosphere environment during the stirring process are the temperature and the atmosphere environment in the existing glass preparation process, such as room temperature and air environment. It is also possible to appropriately increase the temperature during the mixing process.

[0124] In the preparation method of the present application, the melting temperature is 1300°C - 1700°C, and the melting time is 4h - 240h. In some embodiments of the present application, the melting temperature can be 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C, 1600°C, 1650°C or 1700°C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the melting time can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 23h, 24h, 28h, 30h, 35h, 40h, 43h, 48h, 50h, 55h, 58h, 60h, 65h, 68h, 70h, 75h, 80h, 85h, 88h, 90h, 95h, 98h, 100h, 105h, 110h, 115h, 120h, 125h, 130h, 135h, 140h, 145h, 150h, 155h, 160h, 165h, 170h, 175h, 180h, 185h, 190h, 195h, 200h, 205h, 210h, 215h, 220h, 225h, 230h, 235h or 240h, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0125] In the preparation method of the present application, the annealing temperature is 550°C - 650°C, and the annealing time is 1 min - 1440 min. In some embodiments of the present application, the annealing temperature can be 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the annealing time can be 1 min, 10 min, 20 min, 30 min, 50 min, 80 min, 100 min, 150 min, 180 min, 200 min, 250 min, 280 min, 300 min, 350 min, 380 min, 400 min, 450 min, 480 min, 500 min, 550 min, 600 min, 650 min, 700 min, 750 min, 800 min, 850 min, 900 min, 950 min, 980 min, 1000 min, 1050 min, 1100 min, 1150 min, 1200 min, 1250 min, 1300 min, 1350 min, 1400 min, 1420 min, 1440 min, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0126] In the preparation method of the present application, any one of the existing glass primary forming processes can be selected for the primary forming, such as any one of slot-draw, overflow-down, double-draw thinning method, and float process. In some embodiments of the present application, the primary forming includes any one of slot-draw, overflow-down, double-draw thinning method, and float process.

[0127] In a third aspect, the present application provides a toughened impact-resistant ultra-thin glass with a thickness of t, which includes a double-sided toughened layer and a tensile stress layer. The toughened layer extends from the surface of the toughened impact-resistant ultra-thin glass towards the interior direction, wherein the double-sided toughened layer is symmetrically distributed, and the thickness of each toughened layer is not higher than 0.28t;

[0128] In the central region of the tensile stress layer, in terms of mole percentage of oxides, it includes the following components:

[0129] SiO2: 63.50 - 66.00 mol%;

[0130] Al2O3: 10.50 - 12.50 mol%;

[0131] P2O5: 0.00 - 1.00 mol%;

[0132] Li2O: 0.00 - 3.00 mol%;

[0133] Na2O: 12.00 - 14.00 mol%;

[0134] K2O: 1.00 - 4.00 mol%;

[0135] MgO: 5.00 - 7.00 mol%;

[0136] Zr2O: 0.10 - 1.10 mol%;

[0137] B2O3: 0.20 - 1.10 mol%;

[0138] Among them, each component simultaneously satisfies the following relationships shown in (1) to (3):

[0139] (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%;

[0140] (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14%

[0141] (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.1.

[0142] In this application, the impact-resistant reinforced ultra-thin glass is obtained by chemically strengthening the aforementioned ultra-thin glass. Since chemical strengthening only occurs on the surface of the ultra-thin glass body, and the thickness of the strengthened layer formed after chemical strengthening is much smaller than the thickness of the ultra-thin glass; therefore, the central region of the tensile stress layer of the impact-resistant reinforced ultra-thin glass is almost completely the same or completely the same as the glass composition of the ultra-thin glass.

[0143] In some embodiments of this application, the chemical strengthening process of the impact-resistant reinforced ultra-thin glass includes single-step chemical strengthening.

[0144] In some embodiments of this application, in the single-step chemical strengthening, a salt bath containing KNO3 is used for chemical strengthening; preferably, in the single-step chemical strengthening, the content of KNO3 in the salt bath containing KNO3 is 100 wt%.

[0145] In some embodiments of this application, the temperature of the single-step chemical strengthening is 380°C to 500°C, and the time of the single-step chemical strengthening is 10 min to 360 min; preferably, the temperature of the single-step chemical strengthening is 390°C to 500°C, preferably 390°C; further preferably, the time of the single-step chemical strengthening is 20 min to 360 min, more preferably 90 min.

[0146] In some embodiments of the present application, after chemical strengthening, surface strengthening treatment is performed on the strengthened impact-resistant ultra-thin glass. In some embodiments of the present application, the strengthened impact-resistant ultra-thin glass is placed in an etching solution for surface strengthening treatment. Preferably, the etching solution contains one or more of hydrofluoric acid, nitric acid, hydrochloric acid, and sulfuric acid. In some embodiments of the present application, by mass percentage, the composition of the etching solution includes 0.1% - 2% hydrofluoric acid, 0.5 - 2% nitric acid, 0% - 1% hydrochloric acid, 0 - 1% sulfuric acid, and water. Preferably, the etching time is 60s - 1200s, and the etching temperature is 20°C - 50°C.

[0147] In some embodiments of the present application, the thickness t of the strengthened impact-resistant ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm. In some embodiments of the present application, the thickness t of the strengthened impact-resistant ultra-thin glass can be 0.40 mm, 0.30 mm, 0.20 mm, 0.10 mm, 0.09 mm, 0.08 mm, 0.07 mm, 0.06 mm, 0.05 mm, 0.04 mm, 0.03 mm, or 0.02 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0148] In some embodiments of the present application, when the thickness t of the strengthened impact-resistant ultra-thin glass is 0.10 mm - 0.40 mm, its surface compressive stress CS ≥ 1100 MPa, preferably its surface compressive stress CS is 1100 MPa - 1300 MPa. In some embodiments of the present application, when the thickness t of the strengthened impact-resistant ultra-thin glass is 0.10 mm - 0.40 mm, its surface compressive stress CS can be 1100 MPa, 1150 MPa, 1200 MPa, 1250 MPa, or 1300 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0149] In some embodiments of the present application, when the thickness t of the strengthened impact-resistant ultra-thin glass is 0.10 mm - 0.30 mm, its surface compressive stress CS ≥ 1100 MPa, preferably its surface compressive stress CS is 1100 MPa - 1200 MPa. In some embodiments of the present application, when the thickness t of the strengthened impact-resistant ultra-thin glass is 0.10 mm - 0.30 mm, its surface compressive stress CS can be 1100 MPa, 1150 MPa, or 1200 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0150] In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.40 mm, its surface compressive stress CS ≥ 1200 MPa; preferably, its surface compressive stress CS is 1200 MPa to 1300 MPa. In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.40 mm, its surface compressive stress CS can be 1200 MPa, 1210 MPa, 1230 MPa, 1250 MPa, 1270 MPa, 1290 MPa, 1300 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0151] In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.30 mm, its surface compressive stress CS ≥ 1100 MPa; preferably, its surface compressive stress CS is 1100 MPa to 1200 MPa. In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.30 mm, its surface compressive stress CS can be 1100 MPa, 1130 MPa, 1150 MPa, 1170 MPa, 1190 MPa, 1200 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0152] In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.10 mm, its surface compressive stress CS ≥ 1100 MPa; preferably, its surface compressive stress CS is 1100 MPa to 1200 MPa. In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.10 mm, its surface compressive stress CS can be 1100 MPa, 1130 MPa, 1150 MPa, 1170 MPa, 1190 MPa, 1200 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0153] In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.07 mm, its surface compressive stress CS ≥ 960 MPa; preferably, its surface compressive stress CS is 960 MPa to 1010 MPa. In some embodiments of the present application, when the thickness t of the impact-resistant strengthened ultra-thin glass is 0.07 mm, its surface compressive stress CS can be 960 MPa, 980 MPa, 990 MPa, 1000 MPa, 1010 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0154] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its surface compressive stress CS ≥ 920 MPa; preferably, its surface compressive stress CS is 920 MPa to 960 MPa. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its surface compressive stress CS can be 920 MPa, 930 MPa, 940 MPa, 950 MPa, 960 MPa, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0155] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm; preferably, the depth Dol of its compressive stress layer is 8.00 μm to 11.00 μm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, the depth Dol of its compressive stress layer can be 8.00 μm, 8.20 μm, 8.50 μm, 8.70 μm, 8.90 μm, 9.00 μm, 9.20 μm, 9.40 μm, 9.60 μm, 9.80 μm, 10.00 μm, 10.10 μm, 10.30 μm, 10.50 μm, 10.70 μm, 10.90 μm, 11.00 μm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0156] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.10 mm - 0.30 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm; preferably, the depth Dol of its compressive stress layer is 8.00 μm to 11.00 μm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.10 mm - 0.30 mm, the depth Dol of its compressive stress layer can be 8.00 μm, 8.20 μm, 8.50 μm, 8.70 μm, 8.90 μm, 9.00 μm, 9.20 μm, 9.40 μm, 9.60 μm, 9.80 μm, 10.00 μm, 10.10 μm, 10.30 μm, 10.50 μm, 10.70 μm, 10.90 μm, 11.00 μm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0157] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm, preferably the depth Dol of its compressive stress layer is 8.00 μm to 11.00 μm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, the depth Dol of its compressive stress layer can be 8.00 μm, 8.20 μm, 8.50 μm, 8.70 μm, 8.90 μm, 9.00 μm, 9.20 μm, 9.40 μm, 9.60 μm, 9.80 μm, 10.00 μm, 10.10 μm, 10.30 μm, 10.50 μm, 10.70 μm, 10.90 μm or 11.00 μm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0158] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, its average drop height ≥ 60 mm, preferably its average drop height is 60.00 mm to 250.00 mm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.10 mm - 0.40 mm, its average drop height can be 60.00 mm, 64.00 mm, 68.00 mm, 70.00 mm, 73.00 mm, 75.00 mm, 78.00 mm, 80.00 mm, 82.00 mm, 84.00 mm, 88.00 mm, 90.00 mm, 93.00 mm, 95.00 mm, 97.00 mm, 99.00 mm, 100.00 mm, 120.00 mm, 140.00 mm, 160.00 mm, 180.00 mm, 190.00 mm, 200.00 mm, 210.00 mm, 220.00 mm, 230.00 mm, 240.00 mm or 250.00 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0159] In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.30 mm, its average dropping height ≥ 200.00 mm, and preferably its average dropping height is 200.00 mm to 250.00 mm. In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.30 mm, its average dropping height can be 200.00 mm, 210.00 mm, 220.00 mm, 230.00 mm, 240.00 mm, 250.00 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0160] In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.10 mm, its average dropping height ≥ 74.00 mm, and preferably its average dropping height is 74.00 mm to 92.00 mm. In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.10 mm, its average dropping height can be 74.00 mm, 78.00 mm, 80.00 mm, 82.00 mm, 84.00 mm, 88.00 mm, 90.00 mm, 91.00 mm, 92.00 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0161] In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.07 mm, its average dropping height ≥ 74.00 mm, and preferably its average dropping height is 74.00 mm to 84.00 mm. In some embodiments of the present application, when the thickness t of the impact-resistant reinforced ultra-thin glass is 0.07 mm, its average dropping height can be 74.00 mm, 75.00 mm, 77.00 mm, 79.00 mm, 80.00 mm, 81.00 mm, 82.00 mm, 83.00 mm, 84.00 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0162] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its average drop height ≥ 60.00 mm, and preferably its average drop height is 60.00 mm to 71.00 mm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its average drop height can be 60.00 mm, 62.00 mm, 64.00 mm, 66.00 mm, 68.00 mm, 70.00 mm, 71.00 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0163] In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its critical bending radius of curvature ≤ 0.40 mm; preferably its critical bending radius of curvature is 0.30 mm to 0.40 mm. In some embodiments of the present application, when the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its critical bending radius of curvature can be 0.30 mm, 0.32 mm, 0.35 mm, 0.37 mm, 0.39 mm, 0.40 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0164] In some embodiments of the present application, the warpage value of the impact-resistant ultra-thin glass does not exceed 0.08 mm, preferably 0.01 mm - 0.08 mm. In some embodiments of the present application, the warpage value of the impact-resistant ultra-thin glass can be 0.01 mm, 0.02 mm, 0.03 mm, 0.04 mm, 0.05 mm, 0.06 mm, 0.08 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0165] Fourthly, the present application provides an application of the above ultra-thin glass or the ultra-thin glass prepared by the above preparation method or the above impact-resistant ultra-thin glass in the field of electronic products; in particular, its application on the display screen of foldable electronic devices, such as in color filters, printed electronic devices for filtration, sensors of touch panels, fingerprint sensors, thin-film battery substrates, mobile electronic devices, semiconductor interposers, flexible / foldable displays, solar cells or displays.

[0166] In a fifth aspect, the present application further provides an electronic device; the electronic device comprises the ultra-thin glass as described above, or the ultra-thin glass prepared by the preparation method as described above, or the reinforced impact-resistant ultra-thin glass as described above. The impact-resistant ultra-thin glass can be applied to its display screen or glass cover, and the electronic device can be at least one of a mobile phone, a tablet computer, a handheld game console, a portable digital device (such as a digital camera), a vehicle-mounted central control, an electronic whiteboard glass, a smart home, and a smart wearable (such as a smart bracelet, a smart watch, and smart glasses).

[0167] In a sixth aspect, the present application also provides a glass product; the glass product comprises the ultra-thin glass as described above, or the ultra-thin glass prepared by the preparation method as described above, or the strengthened impact-resistant ultra-thin glass as described above.

[0168] In order to facilitate those skilled in the art to better understand the innovative features of the present application, the technical solution of the present application is further described in detail below in conjunction with the embodiments. The embodiments of the present application described in detail below are exemplary and are only used to explain the present application, and cannot be understood as limiting the present application.

[0169] Example 1

[0170] This embodiment provides a method for preparing ultra-thin glass, which specifically includes the following steps:

[0171] According to the formula of Example 1 in Table 1, each raw material component was accurately weighed according to the proportion, and was fully mixed to obtain a mixture, which was melted at 1500° C. for 8 h, and then a glass substrate with a size of 440×360 mm was formed by a down-drawing method, and then annealed at 550° C. for 600 min to obtain an ultra-thin glass substrate, which was then cut into ultra-thin glass samples of 50×50×0.70 mm, ultra-thin glass samples of 50×150×0.30 mm, ultra-thin glass samples of 50×150×0.10 mm, ultra-thin glass samples of 50×150×0.07 mm, ultra-thin glass samples of 50×150×0.03 mm, and ultra-thin glass samples of 120×35×0.03 mm according to actual needs.

[0172] Embodiments 2 to 7

[0173] Examples 2 to 7 are carried out under the same conditions as Example 1, except that an ultra-thin glass substrate is prepared according to the formula shown in Examples 2 to 7 in Table 1, and then cut into ultra-thin glass samples of 50×50×0.70 mm, ultra-thin glass samples of 50×150×0.30 mm, ultra-thin glass samples of 50×150×0.10 mm, ultra-thin glass samples of 50×150×0.07 mm, ultra-thin glass samples of 50×150×0.03 mm, and ultra-thin glass samples of 120×35×0.03 mm according to actual needs.

[0174] Comparative Examples 1 to 10

[0175] Comparative Examples 1 to 10 were operated under the same conditions as Example 1, except that ultra-thin glass substrates were prepared according to the formulations shown in Table 2, and then cut into comparative ultra-thin glass samples of 50×50×0.70 mm, comparative ultra-thin glass samples of 50×150×0.30 mm, comparative ultra-thin glass samples of 50×150×0.10 mm, comparative ultra-thin glass samples of 50×150×0.07 mm, comparative ultra-thin glass samples of 50×150×0.03 mm, and comparative ultra-thin glass samples of 120×35×0.03 mm according to actual needs.

[0176] The performance tests were respectively carried out on the 50×50×0.70 mm ultra-thin glass samples of Examples 1 to 7 and the 50×50×0.70 mm comparative ultra-thin glass samples of Comparative Examples 1 to 10, and the result data are shown in Table 1 and Table 2 respectively.

[0177] The 50×150×0.30 mm ultra-thin glass samples of Examples 1 to 7 and the 50×150×0.30 mm comparative ultra-thin glass samples of Comparative Examples 1 to 10 were respectively trimmed to eliminate edge microcracks; then chemically strengthened in 100% KNO3 at 390°C for 120 min, and the performance tests were carried out on the strengthened ultra-thin glass samples after strengthening as shown in Tables 3 - 4.

[0178] The 50×150×0.10 mm ultra-thin glass samples of Examples 1 to 7 and the 50×150×0.10 mm comparative ultra-thin glass samples of Comparative Examples 1 to 10 were respectively trimmed to eliminate edge microcracks; then chemically strengthened in 100% KNO3 at 390°C for 120 min, and the performance tests were carried out on the strengthened ultra-thin glass samples after strengthening as shown in Tables 5 - 6.

[0179] The 50×150×0.07 mm ultra-thin glass samples, 50×150×0.03 mm ultra-thin glass samples and the 50×150×0.07 mm comparative ultra-thin glass samples, 50×150×0.03 mm comparative ultra-thin glass samples of Comparative Examples 1 to 10 were respectively trimmed to eliminate edge microcracks; then chemically strengthened in 100% KNO3 at 390°C for 90 min, and the performance tests were carried out on the strengthened ultra-thin glass samples after strengthening as shown in Tables 5 - 6.

[0180] The 120×35×0.03 mm ultra-thin glass samples obtained in Examples 1-7 and the 120×35×0.03 mm comparative ultra-thin glass samples in Comparative Examples 1-10 were trimmed to eliminate microcracks at the edges; then they were chemically strengthened in 100% KNO3 at 390 °C for 90 min. Then, the above-mentioned strengthened ultra-thin glass samples and comparative ultra-thin glass samples were placed in an etching solution for surface strengthening treatment; the etching solution for this surface strengthening treatment, by mass percentage, includes 0.7% HF, 0.8% HNO3, and water; the etching time is 100 s, and the etching temperature is 24 °C. Subsequently, the above-mentioned surface-strengthened ultra-thin glass samples were ultrasonically cleaned to obtain the required ultra-thin glass samples for testing, and the performance of the above-mentioned ultra-thin glass samples for testing was tested as shown in Tables 7-8.

[0181] As can be seen from Table 1 and Table 2, the Young's modulus of the ultra-thin glass prepared in the examples of the present application is very high, at least reaching 73.50 GPa, and even reaching 81.9 GPa.

[0182] As can be seen from Table 3 and Table 4, after the ultra-thin glass samples provided in the examples of the present application were chemically strengthened, compared with the comparative ultra-thin glass samples that were also strengthened, the depth Dol of the compressive stress layer was lower, at 8-10 μm, and the surface compressive stress CS was higher. The surface compressive stress CS of the strengthened ultra-thin glass sample with a thickness of 0.3 mm in the example could reach more than 1140 MPa, and the average pen-down height increased extremely significantly, at least 40% higher than that in the comparative example, reaching more than 220 mm. It can be seen that the strengthened ultra-thin glass provided in the examples of the present application has better impact resistance.

[0183] As can be seen from Table 5 and Table 6, the strengthened ultra-thin glass provided in the examples of the present application still shows extremely good surface compressive stress even at extremely low thicknesses, such as 0.10 mm, 0.07 mm, and 0.03 mm. Even the surface compressive stress of the strengthened ultra-thin glass with a thickness of 0.03 mm is not lower than that of the comparative strengthened ultra-thin glass sample with a thickness of 0.07 mm. Similarly, the strengthened ultra-thin glass provided in the examples of the present application still shows extremely good impact resistance even at extremely low thicknesses, such as 0.10 mm, 0.07 mm, and 0.03 mm. The impact resistance of the strengthened ultra-thin glass with a thickness of 0.07 mm is already close to that of the comparative strengthened ultra-thin glass sample with a thickness of 0.10 mm, providing great material support for the thinning of electronic devices.

[0184] As can be seen from Table 7 and Table 8, the flexural strength of the strengthened ultra-thin glass provided by this application has also been significantly improved. Even at extremely low thicknesses, such as at a thickness of 0.03 mm, its critical bending radius of curvature can be as low as below 0.40 mm, providing great material support for the service life of electronic devices with frequent display folding.

[0185] The above is only the specific implementation manner of this application, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by this invention should be covered within the protection scope of this application. Therefore, the protection scope of this application should be subject to the protection scope of the claims.

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Claims

1. An ultra-thin glass, characterized in that, Comprising the following components in terms of molar percentage of oxides: SiO2: 63.50 - 66.00 mol%; Al2O3: 10.50 - 12.50 mol%; P2O5: 0.00 - 1.00 mol%; Li2O: 0.00 - 3.00 mol%; Na2O: 12.00 - 14.00 mol%; K2O: 1.00 - 4.00 mol%; MgO: 5.00 - 7.00 mol%; Zr2O: 0.10 - 1.10 mol%; B2O3: 0.20 - 1.10 mol%; Wherein, each component simultaneously satisfies the following relationships (1) - (3): (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%; (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14% (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.

1.

2. The ultra-thin glass according to claim 1, characterized in that, The content of SiO2 is 64.00 mol% - 66.00 mol%; and / or, the content of Al2O3 is 11.00 mol% - 12.50 mol%; and / or, the content of P2O5 is 0.10 mol% - 1.00 mol%; and / or, the content of Li2O is 0.10 mol% - 3.00 mol%; and / or, the content of Na2O is 12.10 mol% - 14.00 mol%; and / or, the content of K2O is 1.10 mol% - 4.00 mol%; and / or, the content of MgO is 5.10 mol% - 7.00 mol%; and / or, the content of ZrO2 is 0.20 mol% - 1.10 mol%; and / or, the content of B2O3 is 0.25 mol% - 1.10 mol%.

3. The ultra-thin glass according to claim 1 or 2, characterized in that, The thickness of the ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm.

4. The ultra-thin glass according to any one of claims 1 to 3, characterized in that The average linear thermal expansion coefficient of the ultra-thin glass ≤ 94×10 -7 / °C, preferably 83×10 -7 / °C - 94×10 -7 / °C.

5. The ultra-thin glass according to any one of claims 1 to 4, characterized in that The Young's modulus of the ultra-thin glass is not less than 72.0 GPa; and / or When the thickness of the ultra-thin glass is 0.70 mm, the light transmittance at 550 nm ≥ 91.0%.

6. The preparation method of the ultra-thin glass according to any one of claims 1 to 5, characterized in that: Mix the raw materials for preparing the glass, melt them, form them in one step, and then anneal to obtain the ultra-thin glass.

7. The method for preparing the ultra-thin glass according to claim 6, characterized in that The melting temperature is 1300°C - 1700°C, and the melting time is 4 h - 240 h; and / or The annealing temperature is 550°C - 650°C, and the annealing treatment time is 1 min - 1440 min; and / or The one-step forming is selected from any one of narrow slit down-drawing, overflow down-drawing, secondary thinning method, and float method.

8. A reinforced impact-resistant ultra-thin glass with a thickness of t, which comprises double-sided reinforcement layers and a tensile stress layer. The reinforcement layers extend from the surface of the reinforced impact-resistant ultra-thin glass towards the interior direction, wherein the double-sided reinforcement layers are symmetrically distributed, and the thickness of each reinforcement layer is not higher than 0.28t; The central region of the said tensile stress layer, in terms of mol percentage of oxides, comprises the following components: SiO2: 63.50 - 66.00 mol%; Al2O3: 10.50 - 12.50 mol%; P2O5: 0.00 - 1.00 mol%; Li2O: 0.00 - 3.00 mol%; Na2O: 12.00 - 14.00 mol%; K2O: 1.00 - 4.00 mol%; MgO: 5.00 - 7.00 mol%; Zr2O: 0.10 - 1.10 mol%; B2O3: 0.20 - 1.10 mol%; Among them, Each component simultaneously satisfies the following relationships shown in (1) to (3): (1) 11.00% ≤ ((Li2O) + (K2O)) / ((Al2O3) + (Na2O)) ≤ 20%; (2) 6% ≤ ((ZrO2) + (Li2O) + (MgO)) / ((Na2O) + (K2O) + (SiO2)) ≤ 14% (3) 4.1 ≤ ((B2O3) + (SiO2) + (ZrO2)) / ((K2O) + (Na2O)) ≤ 5.

1.

9. The reinforced impact-resistant ultra-thin glass according to claim 8, wherein, The thickness t of the said impact-resistant ultra-thin glass is 0.02 - 0.40 mm, preferably 0.03 - 0.30 mm.

10. The enhanced impact-resistant ultra-thin glass according to any one of claims 8 to 9, characterized in that, The chemical strengthening process of the said impact-resistant ultra-thin glass includes single-step chemical strengthening.

11. The toughened impact-resistant ultra-thin glass according to claim 10, characterized in that, In the said single-step chemical strengthening, a salt bath containing KNO3 is used for chemical strengthening; preferably, in the said single-step chemical strengthening, the content of KNO3 in the salt bath containing KNO3 is 100 wt%.

12. The toughened impact-resistant ultra-thin glass according to any one of claims 10-11, characterized in that, The temperature of the single-step chemical strengthening is 380°C to 500°C, and the time of the single-step chemical strengthening is 10 min to 360 min; preferably, the temperature of the single-step chemical strengthening is 390°C to 500°C, preferably 390°C; further preferably, the time of the single-step chemical strengthening is 20 min to 360 min, more preferably 90 min.

13. The reinforced impact-resistant ultra-thin glass according to any one of claims 8 to 12, characterized in that When the thickness t of the said impact-resistant ultra-thin glass is 0.10 - 0.40 mm, the surface compressive stress CS ≥ 1100 MPa; preferably, its surface compressive stress CS is 1100 MPa to 1300 MPa; Further preferably, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, its surface compressive stress CS ≥ 1100 MPa; preferably, its surface compressive stress CS is 1100 MPa to 1200 MPa.

14. The toughened impact-resistant ultra-thin glass according to any one of claims 8 to 12, characterized in that, When the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm, preferably, the depth Dol of its compressive stress layer is 8.00 μm to 11.00 μm; Further preferably, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, the depth Dol of its compressive stress layer ≤ 11.00 μm, preferably, the depth Dol of its compressive stress layer is 8.00 μm to 11.00 μm.

15. The strengthened impact-resistant ultra-thin glass according to any one of claims 8 to 13, characterized in that, When the thickness t of the impact-resistant ultra-thin glass is 0.03 mm - 0.40 mm, its average pen-down height ≥ 60 mm, preferably, its average pen-down height is 60.00 mm to 250.00 mm; More preferably, when the thickness t of the impact-resistant ultra-thin glass is 0.30 mm, its average pen-drop height ≥ 200.00 mm, and preferably its average pen-drop height is 200.00 mm - 250.00 mm.

16. The strengthened impact-resistant ultra-thin glass according to any one of claims 8 to 15, characterized in that When the thickness t of the impact-resistant ultra-thin glass is 0.03 mm, its bending critical curvature radius ≤ 0.40 mm; preferably its bending critical curvature radius is 0.30 mm - 0.40 mm.

17. Application of the ultra-thin glass according to any one of claims 1 to 5, or the ultra-thin glass prepared by the preparation method of the ultra-thin glass according to any one of claims 6 to 7, or the impact-resistant ultra-thin glass according to any one of claims 8 to 16 in the field of electronic products.

18. An electronic device, characterized in that, Comprising the ultra-thin glass according to any one of claims 1 to 5, or the ultra-thin glass prepared by the preparation method of the ultra-thin glass according to any one of claims 6 to 7, or the impact-resistant ultra-thin glass according to any one of claims 8 to 16.

19. A glass product, characterized in that, Comprising the ultra-thin glass according to any one of claims 1 to 5, or the ultra-thin glass prepared by the preparation method of the ultra-thin glass according to any one of claims 6 to 7, or the impact-resistant ultra-thin glass according to any one of claims 8 to 16.

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