A curved photosensitive glass and a method of making and using the same

Abstract

The application discloses a curved photosensitive glass, a preparation method and application thereof, and belongs to the technical field of glass materials.The application meets the specific composition of the curved photosensitive glass, in particular, the content of CeO2, Sb2O3 and Ag2O meets the specific range, so that the exposed area of the curved photosensitive glass has good shielding performance, and the curved photosensitive glass shows uniform black color after heat bending treatment; meanwhile, the non-exposed area of the curved photosensitive glass has good light transmittance; and the curved photosensitive glass can meet the requirements in the fields of mobile phone cover plates, smart watches and the like.

Description

Technical Field

[0001] This application relates to the field of glass technology, and more specifically, to a curved photosensitive glass, its preparation method, and its uses. Background Technology

[0002] After ultraviolet exposure and heat treatment, photosensitive glass forms an opaque area in the exposed region, which has low light transmittance and provides light-blocking properties compared to the unexposed glass. Therefore, applying photosensitive glass to mobile phone cover plates, smartwatch back covers, and other applications can avoid signal crosstalk between test lights of different wavelengths. However, current curved photosensitive glass, especially after heat bending, still suffers from insufficient shielding performance against visible and near-infrared light in the exposed region; consequently, its application in mobile phone cover plates, smartwatches, and other fields cannot fully meet the requirements. Summary of the Invention

[0003] The purpose of this application is to provide a curved photosensitive glass with good shielding performance in the exposure area, which can meet the requirements of mobile phone cover glass, smartwatches and other fields.

[0004] To achieve the above objectives, this application provides the following technical solution:

[0005] In a first aspect, a curved photosensitive glass is provided, comprising an exposed region and a non-exposed region, wherein the curved photosensitive glass comprises the following components by mass percentage of oxides: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Li2O: 7.00%–15.00%, Na2O: 1.00%–4.00%, K2O: 1.00%–4.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%.

[0006] As an optional implementation, the curved photosensitive glass comprises the following components, by mass percentage of oxides:

[0007] The SiO2 content is 66.00% to 74.60%, preferably 66.50% to 74.00%; and / or,

[0008] The Al2O3 content is 5.10% to 9.70%, preferably 5.20% to 9.40%; and / or,

[0009] The Li₂O content is 7.10% to 14.50%, preferably 8.00% to 14.50%; and / or,

[0010] The Na₂O content is 1.00% to 3.80%, preferably 1.00% to 3.75%; and / or,

[0011] The K₂O content is 1.40%–3.90%, preferably 1.40%–3.85%; and / or, the ZrO₂ content is 5.00%–7.50%, preferably 5.10%–7.50%; and / or,

[0012] The Ag₂O content is 0.15% to 0.60%, preferably 0.15% to 0.50%; and / or,

[0013] The CeO2 content is 0.05% to 0.14%, preferably 0.07% to 0.14%; and / or,

[0014] The Sb2O3 content is 0.20% to 0.50%, preferably 0.20% to 0.48%.

[0015] As an optional implementation, the curved photosensitive glass includes one or more of 3D photosensitive glass, 4D photosensitive glass, 5D photosensitive glass, irregularly shaped photosensitive glass, and four-curved photosensitive glass.

[0016] As an optional implementation, the curved photosensitive glass is obtained by processing a substrate glass, the processing including radiation treatment and subsequent heat treatment and hot bending treatment.

[0017] As an optional implementation, the composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass.

[0018] As an optional implementation, the thickness of the curved photosensitive glass is 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm.

[0019] As an optional implementation, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T1 of the exposure area of ​​the curved photosensitive glass at a wavelength of 550 nm is 0.00%-5.00%, preferably 0.00%-3%; and / or,

[0020] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T2 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 550 nm is above 90%; and / or,

[0021] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T3 of the exposure area of ​​the curved photosensitive glass at a wavelength of 850 nm is 0.00%-8.00%, preferably 0.00%-5%; and / or,

[0022] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T4 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 850 nm is above 90%; and / or,

[0023] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposure area of ​​the curved photosensitive glass at a wavelength of 900 nm is 0.00%-10.00%, preferably 0.00%-8%; and / or,

[0024] When the thickness of the curved photosensitive glass is 0.30-1.00mm, the transmittance T6 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 900nm is above 90%.

[0025] As an optional implementation, the crystal phase of the exposure region of the curved photosensitive glass includes one or more of lithium metasilicate, lithium disilicate, lepidolite, quartz, spodumene, nepheline, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, and Bi nanocrystals.

[0026] As an optional implementation, the non-exposed area of ​​the curved photosensitive glass is substantially free of crystalline phases or includes one or more of lithium metasilicate, lithium disilicate, lepidolite, quartz, spodumene, nepheline, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, and Bi nanocrystals.

[0027] As an optional implementation, the exposed and unexposed areas of the curved photosensitive glass have the same crystal phase.

[0028] Secondly, a method for preparing the above-mentioned curved photosensitive glass is provided, the method comprising:

[0029] Obtain the substrate glass;

[0030] The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain a masked substrate glass.

[0031] After processing the masked substrate glass, a curved photosensitive glass with a non-exposed area and an exposed area is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area; the processing includes radiation treatment and subsequent heat treatment and hot bending treatment.

[0032] As an optional implementation, the composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass.

[0033] As an optional implementation, the thickness of the substrate glass is 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm.

[0034] As an alternative implementation, radiation treatment methods include ultraviolet irradiation.

[0035] As an optional implementation, the wavelength of the ultraviolet irradiation treatment is 300nm-320nm, and the intensity of the ultraviolet irradiation treatment is 20mw / cm². 2 -360mw / cm 2 The ultraviolet irradiation treatment time is 5 min-60 min.

[0036] As an alternative implementation, the masking process includes masking using masking inks and / or photomasks.

[0037] As an alternative implementation, heat treatment includes nucleation and crystallization.

[0038] As an optional implementation, the heating rate of the nucleation treatment is 1℃ / min-10℃ / min; and / or,

[0039] The nucleation treatment temperature is 430℃-500℃; and / or,

[0040] The nucleation treatment time is 30 min-360 min; and / or,

[0041] The heating rate for crystallization treatment is 1℃ / min-10℃ / min; and / or,

[0042] The crystallization treatment temperature is higher than the nucleation treatment temperature, and the crystallization treatment temperature is 500℃-800℃; and / or,

[0043] The crystallization treatment time is 30 min to 480 min.

[0044] Thirdly, a reinforced curved photosensitive glass with a thickness of t is provided, comprising a reinforcing layer extending inward from the surface of the curved photosensitive glass body. The thickness of the reinforcing layer is 0–0.22t. The reinforcing layer, by mass percentage of oxides, comprises the following components: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Na2O: 5.00%–20.00%, K2O: 2.00%–6.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%. The Li2O content is lower than the Li2O content at the center.

[0045] The center of the reinforced curved photosensitive glass contains the following components by mass percentage of oxides: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Li2O: 7.00%–15.00%, Na2O: 1.00%–4.00%, K2O: 1.00%–4.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%.

[0046] The reinforced curved photosensitive glass includes a non-exposed area and an exposed area.

[0047] As an alternative implementation method, chemical fortification includes single-step chemical fortification or multi-step chemical fortification.

[0048] As an optional implementation, the single-step chemical enhancement uses a salt bath containing NaNO3; preferably, the content of NaNO3 is 30-100 wt%; more preferably, the single-step chemical enhancement uses a mixed salt bath containing NaNO3 and KNO3, preferably, the content of KNO3 in the mixed salt bath is 80-100 wt%, and the content of NaNO3 is 0-20 wt%.

[0049] As an optional implementation, the temperature of the single-step chemical enhancement is 380-480℃, and preferably, the ion exchange time of the single-step chemical enhancement is 1-10h.

[0050] As an optional implementation, the multi-step chemical strengthening includes two chemical strengthening steps, wherein the first chemical strengthening step uses a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%; and the second chemical strengthening step uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%.

[0051] As an optional implementation, the temperature of the first step of chemical strengthening is 380-480℃, and the time of the first step of chemical strengthening is preferably 1-10h; preferably, the temperature of the second step of chemical strengthening is 380-480℃, and the time of the second step of chemical strengthening is preferably 5-120min.

[0052] As an optional implementation, the surface pressure (CS) of the non-exposed area of ​​the reinforced curved photosensitive glass is above 300 MPa, preferably above 350 MPa, and more preferably between 350 MPa and 600 MPa.

[0053] As an optional implementation, the single bar static compressive strength of the reinforced curved photosensitive glass is above 100N, preferably 100N to 400N, and more preferably 200N to 400N.

[0054] Fourthly, a cover glass is provided, the cover glass being a curved photosensitive glass prepared by a method for preparing curved photosensitive glass as described in any embodiment of the first aspect, or a curved photosensitive glass prepared by a method for preparing curved photosensitive glass as described in any embodiment of the second aspect, or a reinforced curved photosensitive glass as described in any embodiment of the third aspect.

[0055] Fifthly, an electronic device is provided, the electronic device comprising curved photosensitive glass as described in any embodiment of the first aspect, or curved photosensitive glass prepared by a method for preparing curved photosensitive glass as described in any embodiment of the second aspect, or reinforced curved photosensitive glass as described in any embodiment of the third aspect.

[0056] As an alternative embodiment, the electronic device includes a smart wearable device worn on the body, comprising a housing having a top and a bottom, the bottom being designed to contact the user's skin when worn, the bottom housing comprising curved photosensitive glass as described in any embodiment of the first aspect, or curved photosensitive glass prepared by a method for preparing curved photosensitive glass as described in any embodiment of the second aspect, or reinforced curved photosensitive glass as described in any embodiment of the third aspect.

[0057] As an optional embodiment, the electronic device further includes a camera assembly located inside a housing, the housing including a camera protective cover covering the camera assembly, the camera protective cover comprising curved photosensitive glass as described in any embodiment of the first aspect, or curved photosensitive glass prepared by a method for preparing curved photosensitive glass as described in any embodiment of the second aspect, or reinforced curved photosensitive glass as described in any embodiment of the third aspect.

[0058] Sixthly, the invention provides the use of the above-described curved photosensitive glass or the curved photosensitive glass prepared by the above-described method for use in components in mobile phones, wearable devices, camera modules or vehicles.

[0059] One or more of the technical solutions provided in this application have the following advantages compared with the prior art:

[0060] This application achieves this by controlling the content of CeO2, Sb2O3 and Ag2O in curved photosensitive glass to meet specific composition requirements, particularly by controlling the content of CeO2, Sb2O3 and Ag2O to meet specific ranges. This results in the exposed area of ​​the curved photosensitive glass having good shielding performance and displaying a uniform black color after hot bending, while its non-exposed area has good light transmittance. This meets the requirements of fields such as mobile phone cover glass and smartwatches. Attached Figure Description

[0061] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0062] Figure 1 A schematic diagram of the structure of the substrate glass after being masked with masking ink, provided for an embodiment of this application.

[0063] Figure 2 A schematic diagram of the structure of the photosensitive glass provided in the embodiments of this application.

[0064] Figure 3 The morphological photographs of the photosensitive glass provided for the embodiments of this application are shown, where a is the morphology from a first viewpoint and b is the morphology from a second viewpoint.

[0065] Figure 4 This is a schematic diagram of the rear structure of an electronic device provided in an embodiment of this application.

[0066] Figure 5 A schematic diagram of the structure of a smartwatch provided in an embodiment of this application.

[0067] Figure 6 This is a comparison of the transmittance curves of the substrate glass provided in Example 4 and Comparative Example 2 of this application in the range of 240nm-360nm.

[0068] Reference numerals: 11-Light-transmitting area; 12-Light-blocking area; 21-Exposure area; 22-Non-exposure area; 31-Camera protective cover; 32-Camera assembly; 33-Back cover; 41-Back cover of smartwatch. Detailed Implementation

[0069] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0070] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The terms "optional" and "optional" mean that they may or may not be included (or may or may not be present). The term "and / or" as used herein is inclusive; for example, "A and / or B" means only A, or only B, or both A and B.

[0071] Terminology and testing methods:

[0072] In this application, the main surface refers to the surface with the largest surface area, such as the upper or lower surface of a horizontally placed photosensitive glass sheet.

[0073] In this application, the infrared wavelength range refers to 750nm to 1000nm.

[0074] In this application, the thickness of the glass was obtained by micrometer measurement.

[0075] In this application, the dimensions of the glass slides were measured using a two-dimensional measuring machine (instrument model: MiyuMY-YXCL-4030).

[0076] Surface compressive stress (CS) was measured using an Orihara FSM-6000 from Japan. Test conditions: light source wavelength 596 nm, SOC = 28.6 (nm / cm) / MPa, refractive index = 1.52. In this application, the surface compressive stress of the glass is measured in the non-exposed area (CS). The exposed area cannot be tested because light cannot penetrate the glass.

[0077] In this application, the crystal phase and crystal content of the glass were confirmed by XRD testing as follows:

[0078] (1) XRD test: The photosensitive glass of this application was crushed and ground into samples with a particle size of less than 75 μm. The ground samples were tested using an X-ray diffractometer to obtain XRD diffraction peak curves and XRD diffraction data. The X-ray diffractometer used in this application was a Shimadzu XRD-6100, the target material was copper, 2θ=10°-50°, the scanning speed was 6° / min, the working voltage was 40kV, and the working current was 30mA.

[0079] (2) Determination of crystal phase: The crystal phase in the sample was determined by analyzing the XRD diffraction data using Jade software (JADEStandard8.6).

[0080] (3) Determination of crystal content (also known as crystallinity): The crystallinity of the sample can be determined by importing the XRD test results (RAW format) into the Rietveld X-ray diffraction data refinement software Jade for fitting and calculation. Specifically, the ratio of the fitted crystal phase peak area to the fitted total peak area is recorded as the crystal content of the sample. In this application, the average crystal content is taken after testing the crystal content at different locations on the same glass piece.

[0081] In this application, a UV-Vis spectrophotometer is used to test the transmittance of the exposed and unexposed areas of the glass under test. The UV-Vis spectrophotometer used in this application is the Shimadzu UV-2000 UV-Vis spectrophotometer.

[0082] The specific method for testing the exposure area of ​​the glass under test is as follows: First, a blank sample is used as a fixture with the same shape and size as the glass under test, where the area corresponding to the exposure area is a cutout area and the area corresponding to the non-exposure area is an opaque area. The connection point between the cutout area and the opaque area is also opaque. This fixture is then used for test calibration. Next, a sample with the exposure area of ​​the glass under test cut out to match the shape of the cutout area of ​​the fixture is placed into the cutout area of ​​the fixture and the transmittance is tested. The transmittance of the exposure area of ​​five pieces of glass under test from the same batch to different wavelengths of light is measured using a UV-Vis spectrophotometer. The average value is then recorded as the transmittance result of the exposure area of ​​the glass under test at that wavelength.

[0083] In addition, the transmittance of the unexposed areas of five glass samples from the same batch to different wavelengths of light was measured using a UV-Vis spectrophotometer. The average transmittance of the unexposed areas of the five glass samples under different wavelengths of light was taken as the transmittance result of the unexposed area of ​​the glass sample under that wavelength of light.

[0084] In this application, the single-bar static compressive strength test can be performed as follows: Place the glass sample to be tested on the bottom ring of a tensile testing machine (LT-850A), start the testing software, and set the moving speed of the compression bar (8mm diameter, 10mm indenter radius) to 50mm / min. Click "Start Test." The compression bar will apply force to the center of the glass sample at the set moving speed until the glass sample cracks and breaks. The testing software will automatically read the force (N) at the time of glass sample breakage as the test result. Ten glass samples in the same condition are tested, and the average value of the test results is taken as the single-bar static compressive strength of the glass sample under test.

[0085] In some embodiments of this application, a curved photosensitive glass is provided, comprising an exposed area and a non-exposed area. The curved photosensitive glass comprises the following components by mass percentage of oxides: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Li2O: 7.00%–15.00%, Na2O: 1.00%–4.00%, K2O: 1.00%–4.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%.

[0086] In this application, SiO2 is a glass-forming oxide that forms an irregular, continuous network of silicon-oxygen tetrahedral structural units, serving as the framework for glass formation. In some embodiments of this application, the SiO2 content in the curved photosensitive glass, based on the mass percentage of the oxide, is 65.00% to 75.00%, preferably 66.00% to 74.60%, and more preferably 66.50% to 74.00%.

[0087] In some embodiments of this application, the SiO2 content in the curved photosensitive glass, by mass percentage of oxides, can be 65.00%, 66.00%, 67.00%, 68.00%, 69.00%, 70.00%, 71.00%, 72.00%, 73.00%, 74.00%, 75.00%, 67.20%, 74.60%, 68.26%, 70.28%, 70.01%, 69.05%, or 65.30%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0088] In this application, Al2O3 serves as an intermediate in the glass network, entering the glass network structure as [AlO4] tetrahedra. Increasing the amount of Al2O3 can improve the glass's temperature (T). gTemperature and thermal stability are enhanced, and it is beneficial to suppress phase separation during glass heat treatment; however, excessive amounts will increase the melting temperature of the glass. In some embodiments of this application, the Al2O3 content in the curved photosensitive glass is 5.00% to 10.00% by mass percentage of oxides, preferably 5.10% to 9.70%, and more preferably 5.20% to 9.40%.

[0089] In some embodiments of this application, the Al2O3 content in the curved photosensitive glass, by mass percentage of oxides, can be 5.00%, 5.50%, 6.00%, 6.50%, 7.00%, 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 7.25%, 5.83%, 8.76%, 7.62%, 7.89%, 6.47%, or 8.96%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0090] In some embodiments of this application, the content of Li2O in the curved photosensitive glass is 7.00% to 15.00% by mass percentage of oxides, preferably 7.10% to 14.50%, and more preferably 8.00% to 14.50%.

[0091] In some embodiments of this application, the Li₂O content in the curved photosensitive glass, by mass percentage of oxides, can be 7.00%, 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 10.50%, 11.00%, 11.50%, 12.00%, 12.50%, 13.00%, 13.50%, 14.00%, 14.50%, 15.00%, 12.30%, 8.02%, 12.26%, 9.81%, 9.48%, 11.05%, or 14.37%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0092] In some embodiments of this application, the Na₂O content in the curved photosensitive glass, based on the mass percentage of oxides, is 1.00% to 4.00%, preferably 1.00% to 3.80%, and more preferably 1.00% to 3.75%. In some embodiments of this application, the Na₂O content in the curved photosensitive glass, based on the mass percentage of oxides, can be 1.00%, 1.10%, 1.20%, 1.30%, 1.40%, 1.50%, 1.60%, 1.70%, 1.80%, 1.90%, 2.00%, 2.10%, 2.20%, 2.30%, 2.40%, 2.50%, 2.60%, or 2.70%. The values ​​may be 2.80%, 2.90%, 3.00%, 3.10%, 3.20%, 3.30%, 3.40%, 3.50%, 3.60%, 3.70%, 3.80%, 3.90%, 4.00%, 3.22%, 3.71%, 2.08%, 2.42%, 2.40%, 2.50%, or 1.02%, or values ​​within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in the implementation scheme, any of the above ranges may be combined with any other range.

[0093] In some embodiments of this application, the K2O content in the curved photosensitive glass, based on the mass percentage of oxides, is 1.00% to 4.00%, preferably 1.40% to 3.90%, and more preferably 1.40% to 3.85%. In some embodiments of this application, the K2O content in the curved photosensitive glass, based on the mass percentage of oxides, can be 1.00%, 1.10%, 1.20%, 1.30%, 1.40%, 1.50%, 1.60%, 1.70%, 1.80%, 1.90%, 2.00%, 2.10%, 2.20%, 2.30%, 2.40%, 2.50%, 2.60%, 2.70%, etc. 2.80%, 2.90%, 3.00%, 3.10%, 3.20%, 3.30%, 3.40%, 3.50%, 3.60%, 3.70%, 3.80%, 3.90%, 4.00%, 3.83%, 1.42%, 3.02%, 3.41%, 3.52%, 2.58%, or 2.87%, or values ​​within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0094] In some embodiments of this application, the ZrO2 content in the curved photosensitive glass, based on the mass percentage of oxides, is 5.00% to 8.00%, preferably 5.00% to 7.50%, and more preferably 5.10% to 7.50%. In some embodiments of this application, the ZrO2 content in the curved photosensitive glass, based on the mass percentage of oxides, can be 5.00%, 5.10%, 5.20%, 5.30%, 5.40%, 5.50%, 5.60%, 5.70%, 5.80%, 5.90%, 6.00%, 6.10%, 6.20%, 6.30%, 6.40%, 6.50%, 6.60%, or 6.70%. The values ​​may be 6.80%, 6.90%, 7.00%, 7.10%, 7.20%, 7.30%, 7.40%, 7.50%, 7.60%, 7.70%, 7.80%, 7.90%, 8.00%, 5.56%, 5.72%, 5.12%, 5.58%, 5.63%, 7.50%, or 6.98%, or values ​​within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in the implementation scheme, any of the above ranges may be combined with any other range.

[0095] In some embodiments of this application, the Ag2O content in the curved photosensitive glass is 0.15% to 0.80% by mass percentage of oxides, preferably 0.15% to 0.60%, and more preferably 0.15% to 0.50%. In some embodiments of this application, the Ag₂O content in the curved photosensitive glass, by mass percentage of oxides, can be 0.15%, 0.20%, 0.22%, 0.24%, 0.26%, 0.28%, 0.30%, 0.32%, 0.34%, 0.36%, 0.38%, 0.40%, 0.42%, 0.44%, 0.46%, 0.48%, 0.50%, 0.23%, 0.27%, 0.15%, 0.36%, 0.45%, 0.31%, 0.21%, 0.60%, 0.70%, or 0.80%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0096] In this application, CeO2 is a photosensitizer, and Ag is used. + When the CeO2 content is below 0.05%, it cannot provide enough electrons to reduce Ag. + Silver atoms Ag 0This reduces the light-shielding performance of the exposure area; when the CeO2 content is higher than 0.15%, the penetration depth of ultraviolet light into the exposure area of ​​the glass decreases, resulting in a reduction in the light-shielding performance of the exposure area. In some embodiments of this application, the mass percentage of CeO2 in the curved photosensitive glass, based on the mass percentage of oxides, is 0.05% to 0.15%, preferably 0.05% to 0.14%, and more preferably 0.07% to 0.14%.

[0097] In some embodiments of this application, the CeO2 content in the curved photosensitive glass, by mass percentage of oxide, can be 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, or 0.15%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0098] In this application, Sb₂O₃ is a weak reducing agent and also acts as a clarifying agent. 3+ During the glass melting process, it will react with Ce. 4+ A redox reaction occurs, maintaining Ce 3+ The effective content. In some embodiments of this application, the mass percentage of Sb2O3 in the curved photosensitive glass, based on the mass percentage of oxides, is 0.05% to 0.15%, preferably 0.05% to 0.14%, and more preferably 0.07% to 0.14%.

[0099] In some embodiments of this application, the Sb₂O₃ content in the curved photosensitive glass, based on the mass percentage of oxides, can be 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, or 0.15%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0100] In some embodiments of this application, the curved photosensitive glass includes one or more of 3D photosensitive glass, 4D photosensitive glass, 5D photosensitive glass, irregularly shaped photosensitive glass, and four-curved photosensitive glass.

[0101] The curved photosensitive glass is obtained by processing a substrate glass, including radiation treatment and subsequent heat treatment and hot bending. In some embodiments of this application, the preferred hot bending temperature is 560°C to 630°C. In some embodiments of this application, the hot bending temperature can be 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, or 630°C, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0102] In some embodiments of this application, the composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass, as specifically described above.

[0103] In some embodiments of this application, the thickness of the curved photosensitive glass and / or photosensitive glass described in this application is not particularly limited, for example, it can be 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm. In some embodiments of this application, the thickness of the curved photosensitive glass and / or photosensitive glass described in this application can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, or 2.0 mm, or a value within the range formed by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0104] In some embodiments of this application, the exposed area has low transmittance in the visible and infrared wavelength ranges, while the non-exposed area has high transmittance in the visible and infrared wavelength ranges. Curved photosensitive glass that meets these transmittance requirements ensures good light transmission and transparency in the non-exposed area, while the exposed area has low transmittance and good shielding effect, making it suitable for use in cover glass where light sources need to be shielded. Here, "infrared wavelength range" refers to light with wavelengths from 750nm to 1000nm.

[0105] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T1 of the exposure area of ​​the curved photosensitive glass at a wavelength of 550 nm is 0.00%-5.00%, preferably 0.00%-3%.

[0106] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T1 of the exposure area of ​​the curved photosensitive glass at a wavelength of 550 nm can be 0%, 1.00%, 2.00%, 3.00%, 4.00%, or 5.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0107] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T2 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 550 nm is above 90%. In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T2 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 550 nm can be 90.00%, 90.10%, 90.50%, 91.20%, 92.00%, 93.50%, 94.00%, 94.80%, or 95.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0108] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T3 of the exposure area of ​​the curved photosensitive glass at a wavelength of 850 nm is 0.00%-10.00%, preferably 0.00%-8%.

[0109] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T3 of the exposure area of ​​the curved photosensitive glass at a wavelength of 850 nm can be 0%, 1.00%, 2.00%, 3.00%, 4.00%, 5.00%, 6.00%, 7.00%, 8.00%, 9.00%, or 10.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0110] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T4 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 850 nm is above 90%. In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T4 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 850 nm can be 90.00%, 90.10%, 90.50%, 91.20%, 92.00%, 93.50%, 94.00%, 94.80%, or 95.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0111] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposure area of ​​the curved photosensitive glass at a wavelength of 900 nm is 0.00%-10.00%, preferably the transmittance T3 is 0.00%-8%.

[0112] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposure area of ​​the curved photosensitive glass at a wavelength of 900 nm can be 0%, 1.00%, 2.00%, 3.00%, 4.00%, 5.00%, 6.00%, 7.00%, 8.00%, 9.00%, or 10.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0113] In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T6 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 900 nm is above 90%. In some embodiments of this application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T6 of the non-exposed area of ​​the curved photosensitive glass at a wavelength of 900 nm can be 90.00%, 90.10%, 90.50%, 91.20%, 92.00%, 93.50%, 94.00%, 94.80%, or 95.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0114] In some embodiments of this application, the crystal phase of the exposure area of ​​the curved photosensitive glass includes one or more of lithium metasilicate, lithium disilicate, lithium feldspar, quartz, spodumene, nepheline, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, and Bi nanocrystals.

[0115] In some embodiments of this application, the non-exposed area of ​​the curved photosensitive glass is substantially free of crystalline phases or includes one or more of lithium metasilicate, lithium disilicate, lithium feldspar, quartz, spodumene, nepheline, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, and Bi nanocrystals.

[0116] In some embodiments of this application, the exposed and unexposed areas of the curved photosensitive glass have the same crystal phase.

[0117] In some embodiments of this application, a method for preparing the above-mentioned curved photosensitive glass is provided, which includes:

[0118] Obtain the substrate glass;

[0119] The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain a masked substrate glass.

[0120] After processing the masked substrate glass, curved photosensitive glass with non-exposed areas and exposed areas is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area; the processing includes radiation treatment and subsequent heat treatment and hot bending treatment.

[0121] In some embodiments of this application, the composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass; the specific composition is as described above.

[0122] In this application, the substrate glass can be prepared using existing forming methods, and this application has no limitations on this. For example, the forming method of the substrate glass may include, but is not limited to, float glass, overflow glass, calendering, or casting processes. For instance, by uniformly mixing the components according to the formula, melting and forming the substrate glass, and then cooling and annealing it, the substrate glass can be obtained.

[0123] For example, raw materials are prepared according to the formula ratio, a clarifying agent is added, and then mixed for a period of time to obtain a uniformly mixed raw material mixture. The raw material mixture is placed in a platinum crucible and heated to 1250℃~1680℃, preferably a melting temperature of 1480℃~1680℃, and preferably held at this temperature for 3~12 hours. Then, it is poured into a molding die for cooling and shaping, preferably cooled to 750℃~1000℃, and then placed in an annealing furnace for annealing treatment, preferably at an annealing temperature of 400℃~650℃, and preferably for an annealing time of 10~48 hours. Afterward, it is cooled to room temperature in the furnace to obtain the substrate glass. Those skilled in the art can select the type and amount of clarifying agent according to their needs without any inventive effort. Furthermore, the clarifying agent may include, but is not limited to, one or more of sodium chloride, tin oxide, antimony oxide, or arsenic oxide, and the amount of clarifying agent added may be 0wt%-1wt% of the total amount of each raw material.

[0124] In some embodiments of this application, the thickness of the substrate glass is not particularly limited, for example, it can be 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm. In some embodiments of this application, the thickness of the substrate glass can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, or 2.0 mm, or a value within the range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0125] In some embodiments of this application, the masking process includes masking using masking ink and / or a mask plate.

[0126] For example, a schematic diagram of the structure of the substrate glass after being masked with masking ink is shown below. Figure 1 The composite circular hole has a light-transmitting area 11 with an inner diameter and a light-blocking area 12 excluding the inner diameter; the corresponding structural schematic diagram of the photosensitive glass is shown below. Figure 2 The position corresponding to the light-transmitting area 11 forms the exposure area 21, and the position corresponding to the light-blocking area 12 forms the non-exposure area 22.

[0127] In some embodiments of this application, the radiation treatment includes ultraviolet irradiation treatment, wherein the wavelength of the ultraviolet irradiation treatment is 300 nm to 320 nm, and the intensity of the ultraviolet irradiation treatment is 20 mW / cm². 2 ~360mw / cm 2 The ultraviolet irradiation treatment time is 5 min-60 min.

[0128] In some embodiments of this application, the wavelength of the ultraviolet irradiation treatment is 300nm, 302nm, 305nm, 308nm, 310nm, 312nm, 315nm, 317nm, or 320nm, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the intensity of the ultraviolet irradiation treatment is 20mw / cm². 2 40mw / cm 2 60mw / cm 2 80mw / cm 2 100mw / cm 2 120mw / cm 2 140mw / cm 2 160mw / cm 2 180mw / cm 2 200mw / cm 2 210mw / cm 2 220mw / cm 2 230mw / cm 2 240mw / cm 2 250mw / cm 2 260mw / cm 2 270mw / cm 2 280mw / cm 2 290mw / cm 2 300mw / cm 2 310mw / cm 2 320mw / cm 2 330mw / cm 2 340mw / cm 2 350mw / cm 2 Or 360mw / cm 2 The time for ultraviolet irradiation treatment is 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min, or a value within the range defined by any two of the above specific values; as long as the photosensitive glass with the desired performance of this application is obtained, it is acceptable. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the desired performance of this application is obtained.

[0129] In some embodiments of this application, the heat treatment includes nucleation and crystallization. Nucleation and crystallization are common processes in the art.

[0130] In some embodiments of this application, the heating rate of the nucleation treatment is 1℃ / min-10℃ / min. In some embodiments of this application, the nucleation treatment time can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, or 10℃ / min, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the nucleation treatment temperature can be 430℃-500℃. In some embodiments of this application, the nucleation treatment temperature can be 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, or 500℃, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the nucleation treatment time is 30min-360min. In some embodiments of this application, the nucleation treatment time can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, 240 min, 280 min, 300 min, 320 min, 340 min, or 360 min, or a value within a range of any two of the above specific values ​​as endpoints.

[0131] In this application, the crystallization process includes one-step crystallization and multi-step crystallization. In some embodiments of this application, the heating rate of the crystallization process is 1℃ / min-10℃ / min. In some embodiments of this application, the crystallization time can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, or 10℃ / min, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0132] In some embodiments of this application, the temperature for the one-step crystallization process can be 500℃-800℃. In some embodiments of this application, the temperature for the one-step crystallization process can be 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 600℃, 650℃, 700℃, 750℃, or 800℃, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the time for the one-step crystallization process is 30 min-480 min. In some embodiments of this application, the crystallization treatment time can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, 240 min, 280 min, 300 min, 340 min, 380 min, 400 min, 430 min, 450 min, or 480 min, or a value within a range of values ​​defined by any two of the above specific values ​​as endpoints.

[0133] In some embodiments of this application, the multi-step crystallization process includes a two-step crystallization process. In some embodiments of this application, the temperature of the first crystallization step in the two-step crystallization process is 500℃-560℃, and the temperature of the second crystallization step is 560℃-800℃. In some embodiments of this application, the temperature of the first crystallization step in the two-step crystallization process can be 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, or 560℃, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the temperature of the second crystallization step in the two-step crystallization process can be 560℃, 570℃, 580℃, 600℃, 650℃, 700℃, 750℃, or 800℃, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0134] In some embodiments of this application, the time for the first crystallization step in the two-step crystallization process is 30 min to 240 min, and the time for the second crystallization step is 30 min to 240 min. In some embodiments of this application, the time for the first crystallization step in the two-step crystallization process can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, or 240 min, or a value within the range of any two of the above specific values ​​as endpoints. In some embodiments of this application, the time for the second crystallization step in the two-step crystallization process can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, or 240 min, or a value within a range of any two of the above specific values ​​as endpoints.

[0135] Before and / or after heat treatment, those skilled in the art may perform other conventional steps to obtain substrate glass or curved photosensitive glass samples that meet the required specifications or requirements. These steps may include shaping, cutting (e.g., using a multi-wire cutting machine), CNC machining, thinning, or polishing. This application does not limit the size of the substrate glass or curved photosensitive glass samples; for example, they may be 50mm × 50mm × 0.7mm, 300mm × 120mm × 0.7mm, etc.

[0136] In some embodiments of this application, a reinforced curved photosensitive glass with a thickness of t is provided. This glass includes a reinforcing layer extending inward from the surface of the curved photosensitive glass body. The thickness of the reinforcing layer is 0–0.22t. The reinforcing layer, by mass percentage of oxides, comprises the following components: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Na2O: 5.00%–20.00%, K2O: 2.00%–6.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%. The Li2O content is lower than the Li2O content at the center.

[0137] The center of the reinforced curved photosensitive glass contains the following components by mass percentage of oxides: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Li2O: 7.00%–15.00%, Na2O: 1.00%–4.00%, K2O: 1.00%–4.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%.

[0138] The reinforced curved photosensitive glass includes a non-exposed area and an exposed area.

[0139] In some embodiments of this application, a reinforced curved photosensitive glass with a thickness of t is also provided, which is obtained by chemically strengthening the curved photosensitive glass prepared by the above-mentioned curved photosensitive glass or the above-mentioned method for preparing curved photosensitive glass.

[0140] In some embodiments of this application, the above-mentioned reinforced curved photosensitive glass contains a reinforcing layer, which, by mass percentage of oxides, comprises the following components: SiO2: 65.00%–75.00%, Al2O3: 5.00%–10.00%, Na2O: 5.00%–20.00%, K2O: 2.00%–6.00%, ZrO2: 5.00%–8.00%, Ag2O: 0.15%–0.80%, CeO2: 0.05%–0.15%, and Sb2O3: 0.1%–0.50%; the Li2O content is lower than the Li2O content at the center.

[0141] In this application, chemical fortification can be carried out using existing and known methods; for example, chemical fortification includes single-step chemical fortification or multi-step chemical fortification. In some embodiments of this application, the single-step chemical fortification uses a salt bath containing NaNO3; preferably, the content of NaNO3 is 30-100 wt%; more preferably, the single-step chemical fortification uses a mixed salt bath containing NaNO3 and KNO3, preferably, the content of KNO3 in the mixed salt bath is 80-100 wt%, and the content of NaNO3 is 0-20 wt%.

[0142] In some embodiments of this application, the temperature of the single-step chemical enhancement is 380-480°C, and preferably, the ion exchange time of the single-step chemical enhancement is 1-10 h.

[0143] In some embodiments of this application, the multi-step chemical strengthening includes two-step chemical strengthening, wherein the first step of chemical strengthening uses a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%; and the second step of chemical strengthening uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%.

[0144] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380-480°C, and the time of the first step of chemical strengthening is preferably 1-10 h; preferably, the temperature of the second step of chemical strengthening is 380-480°C, and the time of the second step of chemical strengthening is preferably 5-120 min.

[0145] In some embodiments of this application, the aforementioned reinforced curved photosensitive glass includes one or more of reinforced 3D photosensitive glass, reinforced 4D photosensitive glass, reinforced 5D photosensitive glass, reinforced irregularly shaped photosensitive glass, and reinforced four-curved photosensitive glass.

[0146] In some embodiments of this application, the thickness t of the tempered glass is not particularly limited, for example, it can be 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm. In some embodiments of this application, the thickness of the tempered glass can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, or 2.0 mm, or a value within the range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0147] In some embodiments of this application, the surface pressure (CS) of the non-exposed area of ​​the reinforced curved photosensitive glass is 300 MPa or higher, preferably 350 MPa or higher, and more preferably 350 MPa to 600 MPa. In some embodiments of this application, the surface pressure (CS) of the non-exposed area of ​​the reinforced curved photosensitive glass can be 350 MPa, 351 MPa, 395 MPa, 438 MPa, 385 MPa, 391 MPa, 398 MPa, 402 MPa, 422 MPa, 450 MPa, 480 MPa, 500 MPa, 530 MPa, 550 MPa, 580 MPa, or 600 MPa, or a value within a range defined by any two of the above specific values ​​as endpoints; as long as the photosensitive glass with the performance required by this application can be obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the performance required by this application can be obtained.

[0148] In some embodiments of this application, the single-bar static compressive strength of the aforementioned reinforced curved photosensitive glass is 100N or more, preferably 100N to 400N, and more preferably 200N to 400N. In some embodiments of this application, the single-bar static compressive strength of the reinforced curved photosensitive glass can be 294N, 361N, 392N, 301N, 314N, 375N, 376N, 390N, or 400N, or a value within a range defined by any two of the above specific values ​​as endpoints; as long as the photosensitive glass with the performance required by this application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the performance required by this application can be obtained.

[0149] The high-performance curved photosensitive glass and / or strengthened curved photosensitive glass provided in this application can be used in electronic devices, including but not limited to mobile phones, tablets, handheld game consoles, portable digital devices (e.g., digital cameras), smart home devices, and smart wearables (e.g., smart bracelets, smartwatches, smart glasses). They can also be used in vehicles, aircraft, or spacecraft, and in any glass device requiring curved photosensitive glass. For example, they can be used for the back cover glass of mobile phones, the outer casing glass of smartwatches, etc.; and for windshields of vehicles, aircraft, or spacecraft, such as front windshields or side windshields.

[0150] For example, the high-performance curved photosensitive glass and / or reinforced curved photosensitive glass provided in this application can be used to manufacture cover glass, which can be the back cover or camera protection cover of an electronic device such as a mobile phone. For example, the high-performance curved photosensitive glass and / or reinforced curved photosensitive glass provided in this application can be used in electronic devices. In some embodiments of this application, an electronic device is provided, which can be a mobile phone (such as...) Figure 4 As shown, curved photosensitive glass and / or reinforced curved photosensitive glass can be used as the back cover of mobile phones, or as a back cover of tablets, smart wearable devices (such as...). Figure 5 As shown, curved photosensitive glass and / or reinforced curved photosensitive glass can be used as the bottom casing of smartwatches and other electronic products.

[0151] In some embodiments of this application, the electronic device includes a smart wearable device worn on the body, which includes a housing having a top and a bottom, the bottom being designed to contact the user's skin when worn, and the housing of the bottom including the curved photosensitive glass and / or reinforced curved photosensitive glass described above in this application.

[0152] In some embodiments of this application, such as Figure 4As shown, the electronic device also includes a camera assembly 32 located inside the housing. The housing may include a camera protective cover 31, which covers the camera assembly 32 to protect it. The camera protective cover 31 uses the aforementioned curved photosensitive glass and / or reinforced curved photosensitive glass. In some embodiments of this application, the camera protective cover 31 may partially or entirely use the aforementioned curved photosensitive glass and / or reinforced curved photosensitive glass. In some embodiments of this application, the location of the camera protective cover 31 depends on the location of the camera assembly 32; it may be located on the front side of the electronic device or on the rear side. In some embodiments of this application, the camera protective cover 31 may be a separate structure from the rear cover 33. In other embodiments of this application, the camera protective cover 31 may be an integral structure with the rear cover 33.

[0153] The technical solutions of this application will be further described in detail below with reference to the embodiments. The embodiments of this application described in detail below are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0154] Example 1

[0155] (1) Prepare each raw material according to the proportion of each component in Table 1. The total mass of the prepared raw materials is 2000g. Add 10g of clarifying agent sodium chloride (NaCl) to the prepared raw materials, and then mix with a V-type mixer for 30 minutes to obtain a uniformly mixed raw material mixture.

[0156] The uniformly mixed raw material was transferred in small batches to a platinum crucible at 1450°C, with each addition spaced 40 minutes apart. After all the raw material had been added, the temperature was raised to 1500°C, and the mixture was stirred and clarified using a platinum stirring rod for a total of 10 hours. The mixture was then drawn and shaped continuously to produce glass bricks of the desired specifications. The glass bricks were then placed in an annealing furnace at 450°C for 12 hours, and then allowed to cool naturally to room temperature to obtain the substrate glass sample brick.

[0157] The obtained substrate glass brick is then subjected to cold working processes including cutting, CNC machining (the CNC instrument used in this application is model RCG500S), and polishing to obtain substrate glass that meets the required specifications and requirements. The dimensions of the substrate glass are 50mm × 50mm × 0.7mm.

[0158] (2) The glass substrate was ultrasonically cleaned sequentially in deionized water, anhydrous ethanol, propanol, and deionized water for 10 minutes, and then dried in a drying oven; after cleaning, masking ink was applied to local areas of the upper and lower main surfaces of the photosensitive glass substrate, such as... Figure 1As shown, the black area is the masked area; subsequently, it was subjected to double-sided irradiation for a total of 20 minutes under parallel ultraviolet light (UVHX800*850 drawer type) with a wavelength of 310nm, and the irradiation light energy density was 200mw / cm². 2 The UV-irradiated glass was heat-treated according to the heat treatment process in Table 1 to obtain photosensitive glass. The heat treatment included nucleation and crystallization. The heating rate for both nucleation and crystallization was 10℃ / min. The photosensitive glass was then subjected to cold working processes such as laser cutting, cleaving, polishing, and chamfering to obtain a glass with dimensions of [missing information]. Photosensitive glass, such as Figure 2 As shown.

[0159] (3) The above photosensitive glass is subjected to a hot bending process to obtain 3D photosensitive glass, which contains an exposure area and a non-exposure area, and the glass shape is as follows. Figure 3 As shown.

[0160] The hot bending process consists of 4 preheating stations, 3 hot pressing stations, and 3 cooling stations; the specific hot bending process is shown in Table 2 below.

[0161] The crystal phase and transmittance of the exposed area of ​​the 3D photosensitive glass (transmittance at 550nm wavelength T1, transmittance at 850nm wavelength T3, and transmittance at 900nm wavelength T5) were tested, and the crystal phase and transmittance of the unexposed area of ​​the 3D photosensitive glass (transmittance at 550nm wavelength T2, transmittance at 850nm wavelength T4, and transmittance at 900nm wavelength T6) were tested. The results are shown in Table 3.

[0162] (4) The 3D photosensitive glass obtained in (3) is subjected to chemical strengthening treatment. The chemical strengthening treatment is to sequentially pass through a salt bath of 100wt% NaNO3 at 450℃ for 3h and then through a salt bath of 100wt% KNO3 at 430℃ for 15min to obtain strengthened 3D photosensitive glass.

[0163] The surface CS and monobar static compressive strength of the non-exposed area of ​​the reinforced 3D photosensitive glass were tested, and the results are shown in Table 4.

[0164] Examples 2 to 7

[0165] Each of these experiments was conducted with reference to Example 1, except that the raw material composition, process parameters, and corresponding test results for each example are shown in Tables 1 to 4.

[0166] Comparative Examples 1 to 3

[0167] Each of these experiments was conducted with reference to Example 1, except that the raw material composition, process parameters, and corresponding test results for each example are shown in Tables 1 to 4.

[0168] Table 1

[0169]

[0170]

[0171] Table 2

[0172]

[0173] Table 3

[0174]

[0175]

[0176] Table 4

[0177] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Non-exposed area CS / MPa 351 395 438 385 391 398 402 Single bar static compressive strength / N 294 361 392 301 314 375 376

[0178] As shown in the table above, the 3D photosensitive glass prepared using the embodiments of this application has good shielding performance in its exposed area, especially in the infrared wavelength range, and displays a beautiful black appearance; at the same time, its non-exposed area has good light transmittance in the visible light and infrared wavelength range, which can meet the requirements of mobile phone cover plates, smartwatch back covers, and other fields.

[0179] A comparison of the data from Example 4 and Comparative Example 1 shows that, when both are processed using Process 1, the 3D photosensitive glass of Comparative Example 1 has too little Sb₂O₃ content, which falls outside the scope of this application, and therefore cannot generate sufficient Ce in its glass. 3+ Therefore, under ultraviolet irradiation, it is unable to release enough Ag. + Reduced to silver atoms Ag 0 This results in the light-blocking effect in the exposed area not meeting the requirements, and the area has a brown appearance.

[0180] By comparing Example 4 and Comparative Example 1, it can be seen that when the hot bending process is the same as Process 2, the 3D photosensitive glass of Comparative Example 1 cannot achieve the required light-blocking effect in the exposed area after hot bending, and phase separation occurs in the non-exposed area, resulting in a significant reduction in transmittance and failing to meet the light transmission performance requirements.

[0181] A comparison of Example 4 and Comparative Example 2 shows that in Comparative Example 2, an excessive amount of CeO2 in the 3D photosensitive glass leads to a decrease in the penetration depth of ultraviolet light in the exposure area of ​​the glass. Figure 6 As shown, there is not enough Ce 3+ Sufficient Ag will be excited by ultraviolet light + Reduced to silver atoms Ag 0 This results in the light-blocking effect in the exposed area not meeting the requirements.

[0182] A comparison between Example 4 and Comparative Example 3 shows that the 3D photosensitive glass in Comparative Example 3, due to its insufficient Ag₂O content, cannot reduce enough silver atoms (Ag). 0 This results in the light-blocking effect in the exposed area not meeting the requirements.

[0183] The above description is merely a specific embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing curved photosensitive glass, characterized in that, It includes: Obtain the substrate glass; The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain a masked substrate glass. After processing the masked substrate glass, a curved photosensitive glass with a non-exposed area and an exposed area is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area; the processing includes radiation treatment and subsequent heat treatment and hot bending treatment; the heat treatment includes two-step crystallization treatment, wherein the temperature of the first crystallization treatment is 500℃-560℃ and the temperature of the second crystallization treatment is 560℃-800℃; and the temperature of the hot bending treatment is 250℃~630℃. The curved photosensitive glass comprises the following components by mass percentage of oxides: SiO2: 65.00%~75.00%, Al2O3: 5.00%~10.00%, Li2O: 7.00%~15.00%, Na2O: 1.00%~4.00%, K2O: 1.00%~4.00%, ZrO2: 5.00%~8.00%, Ag2O: 0.15%~0.80%, CeO2: 0.05%~0.15%, and Sb2O3: 0.1%~0.50%.

2. The method for preparing curved photosensitive glass according to claim 1, characterized in that, The composition of the substrate glass is the same as or basically the same as that of the curved photosensitive glass.

3. The method for preparing curved photosensitive glass according to claim 1 or 2, characterized in that, The thickness of the substrate glass is 0.3~2.0mm.

4. The method for preparing curved photosensitive glass according to claim 3, characterized in that, The thickness of the substrate glass is 0.3~1.0mm.

5. The method for preparing curved photosensitive glass according to claim 1 or 2, characterized in that, Masking processes include masking using masking inks and / or photomasks.

6. The method for preparing curved photosensitive glass according to claim 1 or 2, characterized in that, The heat treatment includes nucleation and crystallization.

7. The method for preparing curved photosensitive glass according to claim 6, characterized in that, The heating rate of the nucleation treatment is 1℃ / min-10℃ / min; and / or, The nucleation treatment is performed at a temperature of 430℃-500℃; and / or, The nucleation treatment time is 30 min-360 min; and / or, The temperature rise rate for the crystallization treatment is 1℃ / min-10℃ / min; and / or, The crystallization treatment temperature is higher than the nucleation treatment temperature; and / or, The crystallization process takes 30-480 minutes.

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